Title of Invention	DETERGENT GRANULES AND METHOD FOR PRODUCING THE SAME AND A HIGH BULK DENSITY DETERGENT COMPOSITION
Abstract	The present invention relates to a method for producing detergent granules, comprising the step of dry-neutralizing a liquid acid precursor of a non-soap, anionic surfactant with a water-soluble, solid, alkali inorganic substance, wherein the dry-neutralizing step is carried out in the presence of 0.1 to 1.0 mol of sulfuric acid per mol of said liquid acid precursor of a non-soap, anionic surfactant, whereit:l the sulfuric acid is added to the starting material components, including the liquid acid precursor of a non-soap, anionic surfactant, wherein the amount of sulfuric acid preexisting in the liquid acid precursor of a non-soap, anionic surfactant is 0.09 mol or less per mol of said liquid acid precursor, wherein the non-soap, anionic surfactant is contained in the detergent granules in an amount of 28 % by weight or more and less than 50 % by weight, wherein the molar ratio of [inorganic salt undetectable by X -ray diffraction method]/[ non-soap, anionic surfactant] is from 0.1 to 1.0, and wherein the inorganic salt undetectable by X-ray diffraction method is sodium sulfate.

Title of Invention

DETERGENT GRANULES AND METHOD FOR PRODUCING THE SAME AND A HIGH BULK DENSITY DETERGENT COMPOSITION

Abstract

The present invention relates to a method for producing detergent granules, comprising the step of dry-neutralizing a liquid acid precursor of a non-soap, anionic surfactant with a water-soluble, solid, alkali inorganic substance, wherein the dry-neutralizing step is carried out in the presence of 0.1 to 1.0 mol of sulfuric acid per mol of said liquid acid precursor of a non-soap, anionic surfactant, whereit:l the sulfuric acid is added to the starting material components, including the liquid acid precursor of a non-soap, anionic surfactant, wherein the amount of sulfuric acid preexisting in the liquid acid precursor of a non-soap, anionic surfactant is 0.09 mol or less per mol of said liquid acid precursor, wherein the non-soap, anionic surfactant is contained in the detergent granules in an amount of 28 % by weight or more and less than 50 % by weight, wherein the molar ratio of [inorganic salt undetectable by X -ray diffraction method]/[ non-soap, anionic surfactant] is from 0.1 to 1.0, and wherein the inorganic salt undetectable by X-ray diffraction method is sodium sulfate.

Full Text	DESCRIPTION DETERGENT GRANULES AND METHOD FOR PRODUCING THE SAME. AND HIGH-BULK DENSITY DETERGENT COMPOSITION i TECHNICAL FIELD The present invention relates to detergent granules i comprising a non-soap, anionic surfactant and an inorganic salt, and a method for producing the above detergent granules by a dry-neutralization process. The prejsent. invention further relates to a high-bulk density detergent composition containing the above detergent granules. i BACKGROUND ART In the detergent industries, recently, methods for producing powder detergents having relatively high bulk densities are remarked. Such powdery detergents containing anionic surfactants, such as alkylbenzenesulfonates, are prepared in situ neutralization of an acid precursor of the anionic surfactant with an alkali, such as sodium hydroxide, sodium carbonate, or the like. For instance, Japanese Patent Laid-Open No. 60-72999 and GB-2,166,452B disclose a process comprising the steps of blending detergent sulfonic acid, sodium carbonate, and %rater with a strong shearing device; cooling the resultin solid substances to 40°C or lower; finely pulverizing the cooled product; and then forming the fine powders into- i I granules. This method is a typical one of those I conventionally proposed methods, in which the ! ! neutralization reaction product is a doughy mass, which necessitates a kneading device, such as a kneader, capable of supplying extremely large energy required for th£ j neutralization reaction. GB-1,369,269 discloses a method for producing an anionic detergent comprising vigorously mixing detergent sulfonic acid with sodium carbonate powder by using a mixer equipped with a shearing device, such as Lodige PLOUGH SHARE Mixer. By this method, in order to obtain products of particulate forms, not a doughy mass, it is necessary to blow a gas into the two-component mixture mentioned above, to thereby suitably make the reaction substances flowable and blend the reaction mixture. In order to carry out this treatment, the mixer has to be made notably complicated. Also, since water serving to accelerate the neutralization reaction is not added, the progress of this reaction is mild, so that relatively coarse products are formed. Japanese Patent Laid-Open No. 3-33199 discloses a method of producing a detergent composition comprising the steps of dry-neutralizing components in .a high speed i mixer/granulator at a temperature of 55°C or less, and I then'adding a liquid binder thereto to carry out granulation, Japanese Patent Laid-Open No. 4-363398 l discloses a method of producing a detergent composition comprising the steps of dry-neutralizing components in a high speed mixer/granulator at a temperature of 55°C or more, and then adding a liquid binder thereto to carry out granulation. Japanese Patent Laid-Open No. 3-146599 discloses a method of producing a detergent composition comprising the steps of dry-neutralizing components in a continuous high speed mixer; then increasing to a high * bulk density using a moderate speed mixer; and then cooling and/or drying the resulting product to carry out granulation. The detergent compositions obtainable by the methods described above include granules having small particle sizes. However, for practical purposes, the yield of the detergent composition comprising granules of a desired, even smaller particle size is yet to be improved. Also, in the above methods, such factors in operating conditions as the powder temperature, the water content, the powder blending efficiency, and the like, are optimally selected simply for the purpose of preparing detergent compositions comprising granules having even smaller particle sizes, never attempting to fundamentally l improve the tackiness ascribed to the anionic surfactants, which cause agglomeration of the granules and formation of coarse granules. Japanese Patent Unexamined Publication No. 7-503750 discloses a method of producing detergent granules comprising neutralizing an anionic surfactant in an acid form with a granular neutralizing agent (sodium carbonate) of which has 50% by volume of particles of less than 5 pm in diameter in a high shearing mixer. However, in this publication, no disclosures or suggestions concerning the improvements of the yield of the detergent composition comprising granules having a desired particle size are made. One object of the present invention is to provide detergent granules with suppressed tackiness and small particle size. Another object of the present invention is to provide a method for producing the above detergent granules,. Still another object of the present invention is to provide a high-bulk density detergent composition comprising the above detergent granules. These and other objects of the present invention will be apparent from the following description. DISCLOSURE OF THE INVENTION The present invention is concerned with the following: (1) Detergent granules comprising one or more non-soap, anionic surfactants and one or more inorganic salts undetectable by X-ray diffraction method, wherein the molar ratio of [inorganic salts undetectable by X-ray diffraction method]/[non-soap, anionic surfactants] is from 0.1 to 1.0; (2) The detergent granules described in item (1) above, wherein the non-soap, anionic surfactant is contained in the detergent granules in an amount of 28% by weight or more and less than 50% by weight; (3) The detergent granules described in item (1) above, wherein the non-soap, anionic surfactant is contained in the detergent granules in an amount of 10% by weight or more and less than 28% by weight, and wherein the molar ratio of [inorganic salts undetectable by X-ray diffraction method]/[non-soap, anionic surfactants] is from 0.3 to 1.0; (4) A method for producing detergent granules, comprising the step of dry-neutralizing a liquid acid precursor of a non-soap, anionic surfactant with a water-soluble, solid, alkali inorganic substance, wherein a dry neutralizing step is carried out in the presence of 0.1 to 1.0 mol of an inorganic acid per mol of the liquid acid precursor of a non-soap, anionic surfactant; (5) The method described in item (4) above, further comprising the step of adding a free-flowing aid after the dry-neutralizing step, to surface-modify the detergent granules; (6) The method described in item (4) above, further comprising the step of adding one or more liquid components after the dry-neutralizing step; (7) The method described in item (6) above, further comprising the step of adding a free-flowing aid after the step of adding one or more liquid components, to surface-modify the detergent granules; (8) The method described in any one of items (4) to (7) above, wherein the liquid acid precursor of a non-soap, anionic surfactant is a linear alkylbenzenesulfonic acid obtained by S03 gas sulfonation method; i (9) The method described in any one of items (4) to (8) j above, wherein an amount of an inorganic acid preexisting i in the liquid acid precursor of a non-soap, anionijc i surfactant is 0.09 mol or less per mol of the liquid acid precursor of a non-soap, anionic surfactant; (10) The method described in any one of items (4) to (9) .above, wherein the inorganic acid is sulfuric acid1 or phosphoric acid; (11) The method described in any one of items (4) to (10) above, wherein the resulting detergent granules contain the non-soap, anionic surfactant in an amount of 28% by weight or more and less than 50% by weight, and have a molar ratio of [inorganic salts undetectable by X-ray diffraction method]/[non-soap, anionic surfactants] of from 0.1 to 1.0; (12) The method described in any one of items (4) to (10) above, wherein the resulting detergent granules contain the non-soap-, anionic surfactant in an amount of 10% by weight or more and less than 28% by weight in the detergent granules, and have a molar ratio of [inorganic salts undetectable by X-ray diffraction method]/[non-soap, anionic surfactants] of from 0.3 to 1.0; and (13) A high-bulk density detergent composition havijng a i ] bulk density of 500 g/L or more, comprising the detergent granules according to any one of items (1) to (3), ;or the detergent granules obtainable by the method of any ;one of items (4) to (12). BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a graph showing X-ray diffraction patterns of the detergent granules obtained in Comparative Example 13. Its measurement is taken by X-ray diffraction analyzer "RAD-RC" (manufactured by Rigaku Co., Ltd.). Figure 2 is a graph showing X-ray diffraction patterns of the powdery sodium sulfate. Figure 3 is a graph showing the relationship between the amount of the sodium sulfate added as the starting material in the preparation of the detergent compositions and the peak intensity at d=2.78 in the X-ray diffraction analysis. This graph can be used as a calibration curve for determining the "powdery sodium sulfate" added as the starting material in the preparation of the detergent composition from the peak intensity obtained by X-ray diffraction analysis of the detergent composition. [ Figure 4 is a graph showing X-ray diffraction j i patterns of the detergent composition obtained in Example 12. i Figure 5 is a graph showing the relationship between the entire amount of the sodium sulfate in the detejrgent composition calculated from the starting material composition and the amount of sodium sulfate in the detergent composition determined by ion chromatography. The graph is prepared by the chemically .determined amounts of sodium sulfate in the detergent compositions of Examples 11, 12, 13, 16, 17, 18, and 21 and Comparative Examples 11, 16, and 19. This graph can be used as a calibration curve for obtaining the "entire amount of sodium sulfate" contained in the detergent composition. Figure 6 is a graph showing the relationship between the depths from the surface of the granules of the detergent compositions and the relative intensity of the i ! peaks ascribed to sodium sulfate, an inorganic salt (namely, the ratio between the peak intensity of sodium i sulfate and.the peak intensity of the LAS-Na), as determined by FT-IR/PAS analysis of the detergent j f i compositions obtained in Example 11 and in Comparative i Example 11. In the figure, bold line represents data of Example 11, and solid line represents data of Comparative » . i Example 11. j Figure 7 is a graph showing the relationship q>f the i microporous diameter and the microporous capacity of the detergent compositions obtained in Example 18 and in Comparative Example 16. In the figure, bold line represents data of Example 18, and solid line represents data of Comparative Example 16. BEST MODE FOR CARRYING OUT THE INVENTION The method for producing detergent granules of the present invention comprises the step of dry-neutralizing a liquid acid precursor of a non-soap, anionic surfactant with a water-soluble, solid, alkali inorganic substance, wherein a dry-neutralizing step is carried out in the presence of 0.1 to 1.0 mol of an inorganic acid per mol of the liquid acid precursor of a non-soap, anionic surfactant. In the present invention, it is possible to produce detergent granules and high-bulk density detergent i i composition by the above method. In other words, jsince the granules prepared by the step of dry-neutralising a i liquid acid precursor of the non-soap, anionic surtfactant with a water-soluble, solid, alkali inorganic substance in the intentional presence of the inorganic acid coniprise ! neutralized salts ascribed to the inorganic acids !in relatively larger amounts at near the surfaces of the granules than at the inner portion of the granules, the resulting granules have low tackiness with small particle sizes. Also, since the tackiness of the granules is suppressed, the granules with a high surfactant content can be obtained without causing agglomeration of the granules. The dry-neutralization process usable in the method of the present invention are not particularly limited as long as the dry-neutralization process is carried out in the presence of a given amount of an inorganic acid. In a preferred embodiment, for instance, the dry-neutralization process may be carried out by blending a mixture of a liquid acid precursor of a non-soap, anionic surfactant and an inorganic acid with a water-soluble, solid, alkali inorganic substance to carry out the dry-neutralization i l i process. The present invention will be further explained in detail below by taking the above embodiment as one i example of the method of the present invention. i This embodiment comprises 1) a blending step and 2) a dry-neutralizing step. Each of the steps will be detailed below. 1) Blending step This process precedes the dry-neutralizing step and comprises blending a liquid acid precursor of a non-soap, anionic surfactant and an inorganic acid in advance. The liquid acid precursors of non-soap, anionic surfactants refer to the precursors of the non-soap, anionic surfactants in the form of acids in a liquid state, which are formed into salts by neutralization reaction. Therefore, the liquid acid precursors of non-soap, anionic surfactants may be precursors having the above properties of any of known anionic surfactants acids without particular limitations. Concrete examples thereof include linear alkylbenzenesulfonic acids (LAS), ct-olefin sulfonic acids (AOS), alkyl sulfuric acids (AS), and internal olefin sulfonic acids, sulfonic acids of fatty acid esters, alkylether sulfuric acids, dialkyl sulfosuccinic acids, and the like. The liquid acid precursors may be used singly or in a combination of two or more components. The preferred inorganic acids usable in the priesent invention include sulfuric acid and phosphoric acid. More preferred inorganic acid includes sulfuric acid. Also, there are some cases where sulfuric acid is contained in the liquid acid precursor of a non-soap, anionic surfactant usable in the present invention by the production process of the liquid acid precursor. The linear alkylbenzenesulfonates listed as the preferred liquid acid precursors of a non-soap, anionic surfactant may be prepared by one of the following two typical methods. (1) Oleum sulfonation method. (2) S03 gas sulfonation method. (1) is a classical method for producing linear alkylbenzenesulfonic acids, wherein sulfuric acid may be contained in the resulting product in an amount of about 0.3 mol per mol of the linear alkylbenzenesulfonic acid. Also, in (2), the purity of the linear alkylbenzenesulfonic acids in the resulting product is high, and the amount of sulfuric acid preexisting is relatively low, wherein the amount of sulfuric acid preexisting is usually at a level of 0.2 mol or less per mol of the linear alkylbenzenesulfonic acid. Presently, from the aspects of quality and production efficiency, the method (2) is mainly employed as the method of giving high-purity linear alkylbenzenesulfonic acids. In the present invention, the linear alkylbenzenesulfonates prepared by (2) are suitably used. As mentioned above, the inorganic acid may preexist in the precursors of non-soap, anionic surfactants in some cases. The amount of the inorganic acid, namely the amount of the inorganic acid preexisting in the liquid acid precursors of the non-soap, anionic surfactants, is not particularly limited. From the aspect of giving good hue in the resulting detergent granules, the amount of the inorganic acid preexisting in the liquid acid precursor of a non-soap, anionic surfactant is preferably 0.09 mol or less, more preferably 0.06 mol or less, per mol of the liquid acid precursor of a non-soap, anionic surfactant. The amount of the inorganic acid in the method of the present invention is from 0,1 to 1.0 mol per mol of the liquid acid precursor of a non-soap, anionic surfactant, preferably from 0.1 to 0.8 mol, more preferably from 0.15 to 0.65 mol, still more preferably from 0.2 to 0.6 mol, still more preferably from 0.25 to 0.55 mol, per mol of j the liquid acid precursor of a non-soap, anionic \| i surfactant. From the aspect of inhibiting the formation i of coarse granules of the detergent granules, the amount of the inorganic acid is preferably 0.1 mol or more per mol of the liquid acid precursor, and from the aspect of securing the compositional freedom of the detergent composition, the amount of the inorganic acid is preferably 1.0 mol or less per mol of the liquid acid precursor. In particular, from the aspect of the microporosity of the detergent granules as detailed below, the amount of the inorganic acid is preferably 0.3 mol or more, more preferably from 0.3 to 1.0 mol, still more preferably from 0.3 to 0.8 mol, still more preferably 0.35 to 0.7 mol, per mol of the liquid acid precursor. Also, as clearly described in Examples set forth below, by changing the compositional ratios between the liquid acid precursor of a non-soap, anionic surfactant and the inorganic acid, the tackiness and/or the microporosity of the resulting neutralized granules can be j varied. Therefore, a suitable compositional ratio between the liquid acid precursor of a non-soap, anionic surfaqtant and the inorganic acid may be selected and controlled by contents of the non-soap, anionic surfactant in thd i granules, kinds of inorganic acids used, different Ikinds of additives incorporated in the granules, or the like.. In other words, it is desired that the inorgariic acid is added to the starting material components, including the liquid acid precursor of a non-soap, anionic surfactant, in the case where the amount of the inorganic acid preexisting in the liquid acid precursor of a non-soap, anionic surfactant is not in the above range. Alternatively, it is also desired that the inorganic acid is added to the starting material components in the case where further improvements in the tackiness and/or the microporosity of the granules is to be made, or the neutralized granules are to be made even smaller, even when the amount of the inorganic acid preexisting in the liquid acid precursor is in the above range. The mixers usable in this step are not particularly limited. Concrete examples thereof include mixing vessel for liquid components equipped with an agitating device. Also, the mixing may be carried out to an extent such that the each of the components are uniformly mixed. 2) Dry-Neutralizing Step This step comprises adding a mixture of the liquid acid precursor of a non-soap, anionic surfactant dnd an i inorganic acid obtained in the previous step to a water-soluble, solid, alkali inorganic substance, to dry-neutralize of the liquid.acid precursor of a non-soap, anionic surfactant. Incidentally, in this step, by adding the liquid acid precursor of a non-soap, anionic surfactant and an inorganic acid, the neutralization reaction and the granulation process concurrently take place, to form the neutralized granules. Concretely, the dry-neutralizing step includes the following steps: (a) blending one or more water-soluble, solid, alkali inorganic substances and/or and optional known substances generally employed in detergent compositions, wherein the water-soluble, solid, alkali inorganic substance is used in an amount of equal to or greater than that necessary for neutralizing a mixture comprising a liquid acid precursor of a non-soap, anionic surfactant and an inorganic acid obtained in the blending step i described above; and ! (b) adding the mixture comprising the liquid acid precursor of a non-soap, anionic surfactant and the inorganic acid obtained in above blending step to the mixture obtained in step (a) to t I neutralize the mixture obtained in step (a) while the mixture remains in a particulate form. Step (a) The water-soluble, solid, alkali inorganic substances may be any one usually used as alkalizing agents in detergent compositions, which may be used alone or in combination. Concrete examples thereof include sodium carbonate, sodium hydrogencarbor^ate, sodium silicate, potassium carbonate, calcium carbonate, and the like. ■ Among the water-soluble, solid, alkali inorganic substances, preference is given to sodium carbonate because the sodium carbonate can act as a detergent i builder and an alkalizing agent in the final detergent composition. Therefore, by adding and blending thfe water-soluble, solid, alkali inorganic substance components in this step, in amounts sufficient to neutralize a mixture of the liquid acid precursor of anionic surfactants and i the inorganic acid in addition to the amount of sodium carbonate acting as builders and alkalizing agents mentioned above, the neutralization reaction can be favorably carried out in this step. Specifically, it is preferred that the water-soluble, solid, alkali inorganic substances is added in an amount of equal to or greater than that required for neutralization of the liquid acid precursor of a non-soap, anionic surfactant and the inorganic aci,d (amount required for neutralization), for example, 1 to 20 times the amount required for neutralization, more preferably 2 to 10 times the amount required for neutralization, particularly 3 to 8 times the amount required for neutralization. Also, the average particle size of the water-soluble, solid, alkali inorganic substance is not particularly limited. From the viewpoint of further increase in yield and storage stability, the average particle size is preferably 30 pm or more, more preferably from 40 to 200 pm, particularly from 50 to 100 pm. Here, in the present specification, the average particle size of the water-soluble, solid, alkali inorganic substance is evaluated based on volume using a laser diffraction particle size distribution analyzer ("LA-500," manufactured by H0RIBA Ltd.). Further, in the present invention, any of the following known substances generally employed in detergent i compositions may be also optionally blended. Concrete examples thereof include tripolyphosphates; crystalline or amorphous alkali metal aluminosilicates; crystalline silicates; fluorescers; pigments; anti-redeposition agents, such as polycarboxylate polymers and sodium salt of carboxymethyl cellulose; granular surfactants, such as fatty acids, salts thereof, linear alkylbenzenesulfonates, alkyl sulfates; spray-dried powders, diatomaceous earth, i calcite, kaolin, bentonite, sodium sulfate, sodium: sulfite, and the like. The above substances may be * i optionally used depending upon the function of the' granules. When these substances are added, it is clesired that they are used as a mixture with the water-soluble, solid, alkali inorganic substance. In the case where the detergent compositions . comprising the tripolyphosphates as main components are prepared, the average particle size of the i tripolyphosphates is not particularly limited, and\| the i average particle size may be preferably frdm 1 to 00 pm, more preferably from 5 to 20 pm, still more preferably from 6 to 15 pm. Smaller the average particle size of the tripolyphosphate, higher the yields because of inhibition •of the agglomeration of the detergent granules. On the other hand, from the aspect of productivity for preparing the detergent granules with small particle sizes in an industrial scale, the average particle size of the tripolyphosphates is preferably 1 pm or more. From the aspect of inhibiting the agglomeration of the detergent granules, the average particle size is preferably 30 pm or less. Here, in the present specification, the average particle size of the tripolyphosphate is evaluated based on volume using a laser diffraction particle size distribution analyzer ("LA-500," manufactured by HORIBA Ltd.). When the tripolyphosphate is added, the amount of the tripolyphosphate is not particularly limited. The tripolyphosphate is preferably contained in the final granular product in an amount of 1 to 50-k oy weignc, raore i i -. . preferably from 10 to 40% by weight, particularly j preferably from 15 to 35% by weight. Here, the finhl i granular product may mean the detergent granules themselves when the detergent granules of the present i invention are directly used as the detergent composition, or it may mean the final product of the detergent j composition in a case where the detergent granules of the present invention are included as a constituting element of a different detergent composition. Erom the aspect of inhibiting the agglomeration of the detergent granules, the amount of the tripolyphosphate is preferably 2% by weight or more. From the aspect of securing the compositional freedom of the resulting detergent composition, the amount is preferably 50% by weight or less. Further, in cases where detergent compositions having the alkali metal aluminosilicates as main builder components are prepared, an excess agglomeration can be inhibited by the addition of the alkali metal aluminosilicates in this step. Moreover, the alkali metal aluminosilicate also acts as an aid for disintegrating the agglomerated product with the chopper of the agitation granulator. The alkali metal aluminosilicates have an average particle size of from 1 to 30 pm. 1 Here, in the present specification, the average particle size of the aluminosilicate is evaluated based on i t volume using a laser diffraction particle size ! distribution analyzer ("LA-500," manufactured by HORIBA Ltd.). Also, the amounts of fluorescers, pigments, anti-redeposition agents, granular surfactants, spray-dried powders, diatomaceous earth, calcite, kaolin, bentonite, sodium sulfate, sodium sulfite, and the like are not particularly limited. The mixers usable in step (a) for blending each of the above components are not particularly limited, and an agitation granulator may be suitably used. The agitation granulators are not particularly limited, and it is preferred that the agitation granulators are equipped with agitation blades and a chopper for disintegration and dispersion. Here, the blades or chopper may be replaced with a functionally equivalent means. Concrete examples of the agitation granulators usable in the present invention for a batch process include Vertical Granulator (manufactured by Powrex Corp.); High-Speed Mixer (manufactured by Fukae Powtec Kogyo Corp.); L5dige Mixer (manufactured by Matsubo Co., Ltd.); and PLOUGH SHARE Mixer (manufactured by PACIFIC MACHINERY & ENGINEERING Co., LTD.); Gericke Mixer (manufactured by t I Meiji Machine Co., Ltd.)/ and the like. Here, preference is given to the LSdige Mixer and the PLOUGH SHARE Mixer. i i Concrete examples of the agitation granulators usable for a continuous process include continuous Lodige Mixer (moderate speed mixer: those having relatively long resistance time); CB recycler (manufactured by Lodige; high-speed mixer: those having relatively short resistance time); Turbilizer (manufactured by Hosokawa Micron Corporation); Shugi Mixer (manufactured by Powrex Corp.); Flow Jet Mixer (manufactured by Funken Powtechs, Inc.), and the like. Incidentally, in the present invention, the above mixers may be suitably used in combination. Also, it is more preferred that the agitation granulators are equipped with a jacket for adjusting the internal temperature of the granulator and a nozzle for blowing a gas into the agitation granulator. The extent of mixing in step (a) is not particularly limited, and mixing may be preferably carried out to an extent such that each of the components is uniformly mixed. For instance, in the case where the agitation granulators are used in this jstep, the operating conditions of the agitation granulators may be, for example, the blending time is preferably within five minutes. The agitating speed of the main shaft and the chopper speed for disintegration and dispersion may be suitably set depending on the kinds of the mixers used. For instance, in the case of mixers for a batch process, the peripheral agitating speed of the main shaft is preferably from 2 to 15 m/s, and the peripheral chopper speed for disintegration and dispersion is preferably from 20 to 60 m/s. Incidentally, during or after the blending, or at the completion of blending in step (a), water may be added as a reaction initiating agent. By adding the reaction initiating agent, the neutralization reaction can be favorably accelerated. The amount of water added is not particularly limited, and water is added in an amount of preferably from 0.2 to 3 parts by weight, more preferably from 0.5 to 1.5 parts by weight, based on 100 parts by weight of the powdery mixture in step (a). From the viewpoint of initiating the neutralization reaction, the amount of water is preferably 0.2 parts by weight or more, and from the viewpoint of inhibiting the agglomeration of the detergent granules, the amount is preferably 3 parts by weight or less. Incidentally, in cases where the above components, such as the liquid acid precursor of a non-soap, anionic surfactant, contain water, or in!cases where other aqueous starting material solutions are used, or in cases where water-containing powdery starting materials are used, the amount of water to be added may be determined by considering the water contents of these components. In addition, as still more preferred reaction initiating agents, an aqueous solution of alkalis may be added. By using an aqueous solution of alkalis as a reaction initiating agent, when compared with water, not only the neutralization reaction can be further favorably accelerated, but also the particle size of the resulting detergent granules can be made small and thus the bulk density of the resulting detergent granules can be made large. The amount of the aqueous solution of alkalis is preferably from 0.05 to 0.5 times the amount, more preferably from 0.10 to 0.45 times the amount, particularly preferably from 0.15 to 0.40 times the amount, required for neutralizing the liquid acid precursor of a non-soap, anionic surfactant. From the aspect of initiating the neutralization reaction to obtain ! - - ■ desired effects, the amount of the aqueous solution of alkalis is preferably equal to or greater than 0.05 times i the amount required for neutralization, and from the aspect of inhibiting the agglomeration of the detergent granules, the amount is preferably equal to or less than I i 0.5 times the amount required for neutralization, t Incidentally, although the concentration of the aqueous solution of alkalis is not particularly limited, in cases of low concentrations, excess amount of water is supplied to the mixture along with the given amount of the aqueous solution of alkalis, so that the agglomeration of the detergent granules is liable to take place. Therefore, the concentration of the aqueous solution of alkalis is preferably from 20 to 50% by weight, more preferably 30 to 50% by weight, particularly preferably from 40 to 50% by weight. Also, the kinds of the aqueous solutions of alkalis usable in the present invention are not particularly limited. Concrete examples thereof include aqueous sodium hydroxide, aqueous potassium hydroxide, and the like, which are aqueous solutions of strong-alkalis which easily cause neutralization reaction with the liquid acid precursors of the non-soap, anionic surfactants. Among them, the aqueous sodium hydroxide is suitably used from the viewpoint of reduced costs. Also, it is more preferred that the aqueous solutions of alkalis mentioned above have a pH of 12 or more. I In addition, mixing in this step may be preferably carried out to an extent such that added the aqueous solution of alkalis is uniformly dispersed. Step (b) In step (b), in order to carry out the dry-neutralization process of the non-soap, anionic surfactant, the liquid acid precursor or a mixture of the liquid acid precursor and the inorganic acid is gradually added to the water-soluble, solid alkali inorganic substance. The time required for the addition of the liquid acid precursor or the above mixture depends upon the amount of the liquid acid precursor or the above mixture added and thus cannot be generalized. In the case of employing mixing in a batch process, the time required is generally one minute or more, more preferably from 1 to j 10 minutes, still more preferably 2 to 7 minutes. Here, when the liquid acid precursor or the above mixture is i added in an extremely short time, the liquid acids, remain ! -- unreacted accumulate, thereby making it likely to pause i i excess agglomeration. Therefore, it is preferred that the liquid acid precursor or the above mixture is added in' one i minute or longer ■. ! Also, the liquid acid precursor or the above mixture I i ] may be added continuously or added in multiple stages in separate portions. Also, a plurality of addition means may be provided. Incidentally, the mixers usable in step (b) are not particularly limited, with a preference given to the agitation granulators exemplified in step (a). After the addition of the liquid acid precursor or the above mixture, it is desired that the agitation granulator is operated for additional 30 seconds or more, more preferably one minute or more. By having this additional step, the neutralization reaction and the granulation process can be favorably completed. In step (b), it is preferred that the neutralization is carried out while blowing a gas into an agitatipn l granulator. By blowing a gas into the agitation > i i granulator, the excess water produced in the i neutralization reaction can be evaporated and the granular product can be cooled with the gas, to thereby inhibit the a laser diffraction particle size distribution analyzer ("LA-500," manufactured by HORIBA Ltd.). Also, the operating time of the agitation granulator in cases where the surface modifiers are added is not i .. particularly limited, and the operating time may bej i i preferably from 1 to 5 minutes. ! Incidentally, in the method of the present invention, the optional liquid components may be added depending upon i the composition of the detergent compositions to be • ! obtained (step of adding liquid components). The addition of the liquid components may be carried out at any stage without particular limitation. For instance, the addition of the liquid components may be carried out prior to or during the process of the dry-neutralization, or the addition may be alternatively carried out after the dry-neutralization. For instance, it is preferred that the step of adding the liquid components prior to the addition of the surface modifiers. However, in certain cases where the detergent granules obtained after the step of adding the liquid components have excellent free-flowability and/or excellent storage stability, it is not necessary to add the surface modifier as a free-flowing aid. Examples of the optional liquid components include any given liquid components usually used in detergent producing the detergent granules of the present invention i may further comprise the step of adding a free-flowing aid to the detergent granules obtained after the dry-neutralizing step, to surface-modify the detergent granules. By surface-modifying the detergent granules, since further improvements in the free-flowability and the storage stability of the resulting detergent granules can be attained, the surface-modifying step is suitably provided, for instance, in a case where the detergbnt i granules of the present invention are included as ja constituting element of a different detergent composition. Specifically, the surface modification can be carried out by adding a given amount of a surface modifier added as a free-flowing aid while blending the detergent granules, in an agitation granulator (surface-modifying step). The surface modifiers may be any of conventionally known ones, and crystalline or amorphous alkali metal aluminosilicates (zeolite), calcite, diatomaceous earth, silica, and the like may be suitably used. The above aluminosilicates preferably have an average particle size of 10 pm or less. Also, the amount of the surface modifiers in the final detergent composition product is preferably from 2 to 15% by weight, more preferably from 4 to 12% by weight. Incidentally, the average particle size of the surface modifier is evaluated based on volume using compositions, including liquid nonionic surfactants; i .water-soluble polymers, such as polyethylene glycol, acrylic acid-maleic acid copolymers, and the like; fatty acids, and the like. The liquid components may be used singly or a combination of two or more kinds. From the aspect of inhibiting the agglomeration of the detergent composition, the amount of the liquid components may be preferably 15% by weight or less, more preferably 10% by weight or less, of the final detergent composition product. Further, in the present invention, any of the following known substances generally employed in detergent compositions may be also optionally blended to the detergent granules obtained after the dry-neutralizing step. For instance, these substances may be added prior to the step of adding liquid components and/or to the surface-modifying step. Concrete examples thereof include tripolyphosphates; crystalline or amorphous alkali metal aluminosilicates; crystalline silicates; fluorescers; pigments; anti-redeposition agents, such as polycarboxylate polymers and sodium salt of carboxymethyl cellulose; granular surfactants, such as fatty acids, salts thereof, linear alkylbenzenesulfonates, alkyl sulfates; spray-dried powders, diatomaceous earth, calcite, kaolin, bentonite, sodium sulfate, sodium sulfite, and the like. The above substances may be optionally used depending upon the function of the granules. Also, the operating time of the agitation granulator in cases where the step of adding the liquid components precedes the addition of the surface modifiers is not particularly limited, and the operating time may be preferably from 0.5 to 8 minutes. The methods for producing the detergent granules of the present invention also have the following embodiments as preferred embodiments: [1] Embodiment further comprising the step of adding one or more liquid components after the dry-neutralizing step. [2] Embodiment further comprising the step of adding a free-flowing aid after the step of adding one or more liquid components in Embodiment [1], to surface-modify the detergent granules. The hue of the surface-modified, detergent granules obtained by the method described above is not particularly limited. For instance, in the case where the particle size of the surface-modified, detergent granules is evenly sized at 350 to 500 pm and the above detergent granules is analyzed by photoelectric colorimeter, the Hunter Lab coloration is desirably 90 or more in its L value. In the present invention, the following optional components may be also included in the detergent composition. The optional components include, for instance, enzymes, perfumes, bleaching agents, pigments, and the like. Such optional components may be formulated by blending the detergent granules obtainable by the method of the present invention with optional components using mixers, such as a rotary mixer. Modes for carrying out the present invention are not limited to the above methods. In other words, the present invention is applicable for the known methods for producing powdery detergent compositions having high bulk density obtained by the dry-neutralization process of the liquid acid precursor of an anionic surfactant and for known methods for producing the commercial products of the high-bulk density detergent compositions. In general, the particle size of the detergent granules obtained by the dry-neutralization process increases as the proportion of the non-soap, anionic surfactant increases. Also, similarly, the particle size tends to increase as the proportions of the other liquid starting materials, such as nonionic surfactants and polymer solutions, increase. For instance, among 'the detergent granules obtainable by the dry-neutralization process having extremely high proportion of the anionic surfactant, in the case where the proportion of the detergent granules having suitably small particle size is low, by entirely pulverizing all of the obtained neutralized granules in the presence of a pulverizing aid, and then classifying the granules, the detergent granules of the desired particle size range can be obtained at high yields. Also, when the proportions of the other liquid starting materials, such as nonionic surfactants and polymer solutions, are increased, the detergent granules having suitably small particle size can be obtained at high yieldsi Also, the detergent granules obtainable by the method of the present invention may be included as a constituting element of a different detergent composition. In addition, in the present invention, the liquid acid precursor of a non-soap, anionic surfactant, the water-soluble, solid alkali inorganic substance, and the inorganic acid may be blended by adding all of the components at once. In this case, the blending process and the neutralization and granulation process are concurrently carried out. This embodiment is highly suitable for the method of blending in a continuous process. The detergent granules of the present invention thus obtained comprise one or more non-soap, anionic surfactants and one or more inorganic salts undetectable by X-ray diffraction method, wherein the molar ratio of [inorganic salts undetectable by X-ray diffraction method]/[non-soap, anionic surfactants] is from 0.1 to 1.0. The biggest feature of the detergent granules of the present invention is in that the above inorganic salt is undetectable by X-ray diffraction method. In the present specification, the phrase "undetectable by X-ray diffraction method" means that the material does not have a definite diffraction peak in X-ray diffraction patterns, and that the identification of peaks cannot be made even when using any of diffraction patterns reported, for instance, in Japan Committee on Powder Diffraction Standards (JCPDS). Incidentally, in X-ray diffraction patterns, in certain cases, no definite diffraction peaks but indefinite diffraction halo patterns may be observed. However, even in such cases it cannot be said to be detectable by X-ray diffraction method. Typical examples of the inorganic salts include sodium sulfate (Glauber's salt). For instance, since the detergent granules of Comparative Example 13, which can be produced without using the method of the present invention, contain powdery sodium sulfate (Na2S04) obtained without using a method of the present.invention, diffraction peaks shown in Figure 1 are detectable in X-ray diffraction patterns of the detergent granules. These diffraction peaks are identified as sodium sulfate, for instance, by No. 37-1465 of JCPDS (Figure 2). Also, as shown in Figure 3, the amount of the powdery sodium sulfate can be determined by preparing a calibration curve of the powdery sodium sulfate and the peak intensities of the X-ray diffraction peaks. By contrast, as typically exemplified by Example 12, in the detergent granules of the present invention, diffraction peaks ascribed to any of the diffraction i V patterns of sodium sulfate are undetectable by X-ray diffraction method even though sodium sulfate can be chemically determined by the method described above (Figure 4), thereby making it impossible to identify the sodium sulfate by X-ray diffraction method. On the other hand, the content of the inorganic salt in the detergent granules can be chemically determined, for instance, by analyzing means, such as ion chromatography. For example, in a case where the inorganic salt is a sulfate, it is possible to determine the sulfate contained in the detergent granules by using a calibration curve of sulfate ions prepared in advance. Similarly in the detergent granules of the present invention, the sulfate contained in the detergent granules can be determined as shown in Figure 5. Also, the non- soap, anionic surfactant can be determined, for instance, by carrying out a qualitative analysis method and a quantitative analysis method of the anionic surfactants in a synthetic detergent testing method (according to JIS K3362). In the case where inorganic salts, such as powdery i sodium sulfate and powdery sodium phosphate, obtained by the process other than the dry-neutralization process in the method of the present invention, are not used at all as the starting material, since the inorganic salts, such as sodium sulfate and sodium phosphate, contained in the detergent granules and formed by the method of the present invention are undetectable by X-ray diffraction method, the amount of the inorganic salts chemically determined would be considered as "the amount of the inorganic salts undetectable by X-ray diffraction method." Therefore, the molar ratio of [inorganic salts undetectable by X-ray diffraction method]/[non-soap, anionic surfactants] can be calculated from the amount of the inorganic salts and the amount of the non-soap, anionic surfactant determined by the methods described above. Incidentally, even in cases where, for instance, the powdery sodium sulfate mentioned above and the detergent granules of the present invention are mixed to give a desired detergent composition, the amount of the inorganic salt undetectable by X-ray diffraction method can be calculated by the difference in the amounts of sodium sulfate shown in Figure 5 and Figure 3, and the above molar ratio can be calculated from this value. The detergent granules of the present invention comprise one or more non-soap, anionic surfactants and one or more inorganic salts undetectable by X-ray diffraction method, wherein the molar ratio of [inorganic salts undetectable by X-ray diffraction method]/[non-soap, anionic surfactants] is from 0.1 to 1.0. From the aspect of suppressing the tackiness of the granules, the molar ratio is preferably 0.1 or more, and from the aspect of securing the compositional freedom of the detergent composition, the molar ratio is preferably 1.0 or less. The detergent granules of the present invention mentioned above have the properties of (1) having extremely low tackiness of the granules, and (2) having a large number of micropores. The properties of the detergent granules of the present invention will be described in detail below. (1) Low Tackiness The detergent granules of the present invention show extremely low tackiness of the granules. This tackiness * is dependent upon the molar ratio of the inorganic salt to the non-soap, anionic surfactant: Larger the molar ratio of the inorganic salt to the non-soap, anionic surfactant, lower the tackiness of the granules. In the present specification, the tackiness of the granules can be evaluated by a fracture load of the compression molding product of the granules as detailed below. A cylinder having 40 mm in diameter is uniformly charged with a 40 g sample, and a 1 kg load is applied with a piston, and the piston-charged cylinder is allowed to stand for three minutes, to thereby mold the granules into cylindrical.shapes. The molded samples are taken out of the cylinder. Thereafter, a force required for breaking the molded sample is measured by using a rheometer (manufactured by Fudohkogyo K.K.), and this force is defined as the fracture load. In general, smaller the value of the fracture load, smaller the tackiness of the granules and less the agglomeration being caused. The fracture load varies depending upon the amounts formulated, and the values of the fracture load of the detergent granules of the present invention are lower than those of the detergent granules with similar compositions to the present invention except for not using the inorganic salt used in the method of the present invention, thereby showing improvements of the tackiness of the granules in the detergent granules of the present invention. The detergent granules obtained by the method of the present invention comprise a composite layer containing the inorganic salt and the non-soap, anionic surfactant in the outer layer of the granules. Also, since the inorganic salts are present in relatively larger amounts i at near the surface of the detergent granules than in the inner portion of the detergent granules, the tackiness of the granules can be suppressed. As an example of methods of confirming the states of the above detergent granules includes a method of utilizing both Fourier transform infrared spectroscopy (FT-IR) and photoacoustic spectroscopy (PAS) (simply abbreviated as "FT-IR/PAS"). FT-IR/PAS is described in "APPLIED SPECTROSCOPY," Vol.47, p.1311-1316 (1993). In this method, spectra taken in the direction of from the surface to the depths of the samples can be measured without changing the shapes of the samples, so that it is possible to identify the distribution states of the substances at any given depths from the surface of the detergent granules. The concrete measurement method is as follows. A cell is charged with samples to conduct FT-IR/PAS measurement, and the measurement points taken at any depths up to about 20 pm from the surface are analyzed. More concretely, in the phase modulation FT-IR/PAS:spectra at a constant phase modulation frequency, a magnitude speqtrum at given phase angle is obtained, by synchronously analyzing PAS spectral components at a given phase angle and at an angle with a 90° phase shift from the given phase angle. The FT-IR spectrum is measured, for instance, by using an infrared spectrometer "FTS-60A/896" (manufactured by Bio-Rad Laboratories), and the PAS cell includes an acoustic detector "Model 300" manufactured by MTEC Corporation. Scanning with an interferometer is conducted by a step-scan method, and the modulation frequency is set at 2.5 kHz. Peak intensities can be detectable from the typical spectra for the sodium linear alkylbenzenesulfonate (LAS-Na) and sodium sulfate respectively detectable at 1222 cm"1 (S03 anti-symmetric stretching vibration) and 1149 cm"1 (S04 stretching vibration). A typical example of the FT-IR/PAS measurement is shown in Figure 6. As is clear from in Figure 6, in the case of the detergent granules obtainable in Example 11, the relative intensity of the peaks ascribed to sodium sulfate, an inorganic salt (namely, the ratio between the peak intensity of sodium sulfate and the peak intensity of the LAS-Na) is high in the surface layer of the granules when compared to the sodium sulfate which is present in the inner portion of the granules, i.e. the detergent granules have relatively large contents of the inorganic salt in the surface layer. By contrast, in the case of the detergent granules obtainable in Comparative Example 11, the peak intensity ascribed to the inorganic salt shows substantially no changes in the direction of,from the depths of the inner portion of the granules to the outer layer of the granules, and when compared with Example 11, the peak intensity value is low and cohstant. i In addition, the tackiness of the granules (evaluated by i the Values of the fracture load) of each of the detergent granules is 673 gf for the detergent granules of Example i 11 in contrast to 1124 gf for the detergent granules of Comparative Example 11, showing that the detergent granules of the present invention are low-tackiness granules by forming an inorganic salt on the surfaces of the granules by dry neutralization. (2) Microporosity The detergent granules of the present invention feature in having a large number of micropores in the granules as well as having the low tackiness mentioned above. By having a larger number of micropores in the granules, the liquid content which can be retained in the micropores in the granules increases, so that excess agglomeration of the granules owing to the bleeding out of t i the liquid starting materials during the production of granules can be presumably suppressed. The microporous capacity in the granules can be measured, for instance, by i known mercury pressure method (for example, a mercury porosimeter "PORESIZER 9320," manufactured by Shimadzu Corporation). The detergent granules of the present invention have a microporous capacity larger than that of the detergent granules obtained by conventional method of dry neutralization. In order to illustrate the effects of amount of the microporous capacity, Example 18 and Comparative Example 16 may be compared as shown in Figure 7. Figure 7 is a graph showing the relationship of the microporous diameter and the microporous capacity of the detergent compositions obtained in Example 18 and in Comparative Example 16. The microporous diameter is measured by a mercury porosimeter "PORESIZER 9320," manufactured by Shimadzu Corporation, and the microporous capacity is measured by mercury pressure method. The entire microporous capacity of the detergent composition obtained in Example 18 is 0.402 mL/g, and the entire microporous surface areas of the detergent composition are 0.711 m2/g. Also, the entire microporous capacity of the detergent composition obtained in Comparative Example 16 is 0.327 mL/g, and the entire microporous surface areas of the detergent composition are i 0.547 m2/g. In Comparative Example 16, the molar ratio of the inorganic acid to the liquid acid precursor of a non-soap, anionic surfactant is 0.04, smaller than the lower limit in the present invention. On the other hand, in Example 18, the detergent granules are produced by dry neutralization under the conditions that the molar ratio of the inorganic acid to the liquid acid precursor of a non-soap, anionic surfactant is 0.44. When the entire microporous capacity and the microporous surface areas of both of the detergent granules are compared, all of the values are larger in the detergent granules of Example 18 than those in the detergent granules of Comparative Example 16. Also, the average particle size of the detergent granules is 493 \im for Example 18 whereas the average particle size is 1313 pm for Comparative Example 16. From these results, since the detergent granules of Example 18 have larger entire microporous capacity and entire microporous surface area than those of Comparative Example 16, the liquid content which can be retained in the micropores in the granules increases, so that excess agglomeration of the granules owing to the bleeding out of the liquid starting materials during the production of granules can be presumably suppressed. In the case where the detergent granules are designed or produced utilizing the above features of the detergent granules of the present invention, the detergent granules of the following embodiments can be suitably used according to its utility. Specifically, the preferred embodiments are as follows. (1) The detergent granules comprising one or more non-soap, anionic surfactants and one or more inorganic salts undetectable by X-ray diffraction method, wherein the amount of the non-soap, anionic surfactant is in an amount of 28% by weight or more and less than 50% by weight, and a molar ratio of [inorganic salts undetectable by X-ray diffraction method]/[non-soap, anionic surfactants] is from 0.1 to 1.0. (2) The detergent granules comprising one or more non-soap, anionic surfactants and one or more inorganic salts undetectable by X-ray diffraction method, wherein the amount of the non-soap, anionic surfactant in an amount of 10% by weight or more and less than 28% by weight in the detergent granules, and a molar ratio of [inorganic salts undetectable by X-ray diffraction method]/[non-soap, anionic surfactants] is from 0.3 to 1.0. Detergent Granules of Embodiment (1) In general, in the detergent granules containing large amounts of the non-soap, anionic surfactant, it is difficult to produce the granules having excellent free-flowability with small particle sizes, because the agglomeration of the granules is likely to take place owing to the tackiness inherently owned by the non-soap, anionic surfactant. Therefore, in the case, for instance, where the detergent granules are produced by conventional method, the tackiness of the granules is likely to be impaired during the production of the detergent granules when the content of the non-soap, anionic surfactant is relatively large, for example, when the content is 20%" by weight or more in the granules, more remarkably 28% by weight or more and less than 50% by weight, particularly remarkably 30% by weight or more and less than 50% by 1 weight. Therefore, it is preferred from the aspect of strongly exhibiting the effects of suppressing the i ; tackiness of the granules that the detergent granules of the present invention comprise one or more non-soap, anionic surfactants and one or more inorganic salts: i undetectable by X-ray diffraction method, wherein the t 1 amount of the non-soap, anionic surfactant is in an; amount of 28% by weight or more and less than 50% by weight, and a molar ratio of [inorganic salts undetectable by X-ray diffraction method]/[non-soap, anionic surfactants] is from 0.1 to 1.0. Also, in the detergent granules, the molar ratio of [inorganic salts undetectable by X-ray diffraction method]/[non-soap, anionic surfactant] is more preferably from 0.1 to 0.8, still more preferably from 0.15 to 0.65, still more preferably from 0.2 to 0.6, still more preferably from 0.25 to 0.55. Detergent Granules of Embodiment (2) Also, when the microporous capacity of the granules is studied, since the detergent granules of the present invention have a large microporous capacity, the liquid components, such as nonionic surfactants, can be included in larger amounts in the micropores. From the above aspect of containing larger amounts of the liquid components, such as nonionic surfactants, the detergent granules comprise one or more non-soap, anionic j surfactants and one or more inorganic salts undetectable by X-ray diffraction method, wherein the amount of 'the non-soap, anionic surfactant in an amount of 10% by weight or more and less than 28% by weight in the detergent granules, and a molar ratio of [inorganic salts undetectable by X-ray diffraction method]/[non-soap, anionic surfactants] is from 0.3 to 1.0, may be used in a preferred embodiment. In the detergent granules, the non- soap, anionic surfactant is contained in the detergent granules in an amount of more preferably 15% by weight or more and less than 28% by weight, still -more preferably from 15 to 26% by weight. From the aspect of giving high washing power, the amount of the non-soap, anionic surfactant in the detergent granules is preferably 10% by weight or more. From the aspect of suppressing the foaming of the detergent composition upon use, the amount is preferably less than 28% by weight. Also, the detergent granules in this embodiment have a molar ratio [inorganic salts undetectable by X-ray diffraction method]/[non-soap, anionic surfactants] of more preferably from 0.3 to 0.8, still more preferably 0.35 to 0.7. i _ The detergent granules of the present invention i i having the properties mentioned above may be used as such i i as a high-bulk density detergent composition, or they i detergent granules may be used as one of components constituting a detergent composition. The amount of the liquid acid precursors of a \ non-soap, anionic surfactants can be suitably set depending upon the composition of the desired detergent composition. The amount of the liquid acid precursors of anionic surfactants may be so added to include the anionic surfactants produced by the neutralization reaction in the final detergent composition product in an amount of preferably from 5 to 50% by weight, more preferably from 5 to 45% by weight, still more preferably from 10 to 40% by weight, particularly preferably from 20 to 40% by weight, within which range the effects of the present invention can be remarkably exhibited, which become particularly remarkable when the amount of the anionic surfactant is large. Also, it is more desired that the detergent granules of the present invention or the high-bulk density detergent composition containing the detergent granules i obtainable by the method of the present invention having a i bulk density of 500 g/L or more have the following properties. Having a bulk density of preferably from 650 to 950 g/L, more preferably from 700 to 900 g/L. In the present specification, the bulk density is a value evaluated by the method defined in JIS K 3362; Having an average particle size, from the aspect of solubility rate of the detergent granules, of preferably 850 pm or less, more preferably from 300 to 800 pm. The proportion of the particles of 1400 pm or less, namely the percentage of 1400 pm-pass particles, may vary in their suitable ranges depending upon the concentration of the non-soap, anionic surfactant in the resulting high-bulk density detergent composition. For instance, when the concentration of the non-soap, anionic surfactant ijs from 35 to 40% by weight, the percentage of 1400 pm-pass i particles is preferably 60% or more, more preferably 70% or more. When the concentration of the non-soap, anionic i surfactant is less than 35% by weight, the percentage of 1400 pm-pass particles is preferably 75% or more, more preferably 80% or more. In the present specification, the l average particle size is evaluated from the weight i percentages depending on the sizes of the sieves after vibrating a standard sieve according to JIS K 8801 for five minutes, and the percentage of 1400 pm-pass particles means the weight percentage of the proportion occupied by the particles of 1400 pm or less; and Having a free-flowability in terms of flow time of preferably 8 seconds or less, more preferably 7 seconds or less. In the present specification, the free-flowability is defined as a time period required for discharging 100 ml of powder from a hopper used in a measurement of bulk density according to JIS K 3362. EXAMPLES The present invention will be explained in further detail by means of the following working examples, without intending to limit the scope of the present invention thereto. Example 1 The detergent composition having the composition shown in Table 1 was prepared in an amount of 35 kg for each unit using a high speed mixer "Lodige Mixer FIJM-130D" i (manufactured by Matsubo Co., Ltd.). This mixer was equipped with agitator blades and a shearing device, the shearing device corresponding to a chopper for disintegration and dispersion. Here, the detergent composition was prepared by the following procedures as detailed below. Powder Blending The solid ingredients consisting of 7.0 parts by weight of sodium tripolyphosphate (STPP; average particle size: 11.2 pm), 12.61 parts by weight of sodium carbonate ("LIGHT ASH," manufactured by Central Glass Co., Ltd.; average particle size: 56.1 \xm), and 0.11 parts by weight of a fluorescer were blended for one minute under the conditions of a rotational speed of agitator blades of 130 rpm (peripheral speed: 3.4 m/s) and a rotational speed of shearing device of 2850 rpm (peripheral speed: 27 m/s) by the Lodige Mixer. Addition of Reaction Initiating Agent Water was added to the contents in the mixer in an amount of 0.20 parts by weight as a reaction initiating agent, and the blending was carried out for one minute and thirty seconds under the same blending conditions as above. Neutralization While the mixer was operated under the same conditions as above, a mixture of 10.92 parts by weight of a linear alkylbenzenesulfonic acid (LAS; molecular weight: 322) and 0.23 parts by weight of 98% by weight sulfuric acid were added to the contents in the mixer in four minutes, the mixture being prepared in advance. During the addition, the ingredients were cooled by allowing water to flow through the mixer jacket at 25 °C. At this stage, the temperature rose to 75°C. Incidentally, during this stage, the reaction mixture remained in a particulate form. Incidentally, the LAS mentioned above, obtained by S03 gas sulfonation method, contained 0.16 parts by weight of sulfuric acid. In other words, the resulting mixture contained 0.05 mol of sulfuric acid per mol of the LAS. Also, the proportion of sulfuric acid to the LAS during neutralization reaction was such that the reaction mixture contained 0.12 mol of sulfuric acid per mol of the LAS. The amount of sodium carbonate was about six times the amount required for neutralizing the LAS and sulfuric acid. After the addition of the LAS, the mixer was continuously operated under the same conditions for one minute to complete the neutralization reaction and the granulation process. Addition of Liquid Ingredients and Surface Modification At a point where the neutralization reaction and the granulation process were completed, an aqueous solution of a 40% by weight acrylic acid-maleic acid copolymer was added to the mixer with an effective amount of the copolymer being 0.18 parts by weight, while the mixer was operated under the same conditions as above, and the ingredients were mixed for one minute and thirty seconds. Thereafter, the resulting mixture was subjected to a surface modification by adding 4.20 parts by weight of zeolite having an average particle size of 4 ym to the mixer as a surface modifier, and operating the mixture for additional two minutes. Incidentally, the zeolite contained 0.84 parts by weight, of a crystal water. The resulting granules of the detergent composition, prior to the after-blending step, had the following properties: Percentage of particles with 1400 pm-pass: 75.3%; Average particle size: 633 jam; properties. After-Blending Using a rotary mixer, 0.18 parts by weight of enzyme granules and the detergent composition prepared above were blended, and thereafter 0.07 parts by weight of perfume were sprayed, to give a final powdery product of the high-bulk density detergent composition. Example 2 Similar procedures to those in Example 1 were carried out except for respectively changing the amounts of LIGHT ASH and sulfuric acid to 12.45 parts by weight and I i 0.57 parts by weight, to give a detergent composition. The resulting granules of the detergent composition, i prior to the after-blending step, had the following i properties: i i Incidentally, the proportion of sulfuric acid to the LAS during neutralization reaction was such that the reaction mixture contained 0.23 mol of sulfuric acid per mol of the LAS. The amount of sodium carbonate was about five times the amount required for neutralizing the LAS and sulfuric acid. l Example 3 . ; Similar procedures to those in Example 1 were carried out except for respectively changing the amounts of LIGHT ASH and sulfuric acid to 12.33 parts by weight and ' i i 0.82 parts by weight, to give a detergent compositipn. The resulting granules of the detergent composition, prior to the after-blending step, had the following! properties: Accordingly, the granules showed excellent properties. Incidentally, the proportion of sulfuric acid to the LAS during neutralization reaction was such that the reaction mixture contained 0.3 mol of sulfuric acid per mol of the LAS. The amount of sodium carbonate was about four times the amount required for neutralizing the LAS and sulfuric acid. Example 4 . i i Similar procedures to those in Example 1 were; carried out except for respectively changing the amounts of LIGHT ASH, the LAS, and sulfuric acid to 11.11 parts by weight, 12.29 parts by weight, and 0.80 parts by weight, to give a detergent composition. Incidentally, the LAS mentioned i i above contained 0.18 parts by weight of sulfuric acid. The resulting granules of the detergent composition, prior to the after-blending step, had the following properties: Percentage of particles with 1400 pm-pass: 70.0%; Average particle size: 703 pun; Bulk density: 694 g/L; Incidentally, the proportion of sulfuric acid to the LAS during neutralization reaction was such that the reaction mixture contained 0.27 mol of sulfuric acid per mol of the LAS. The amount of sodium carbonate was about four times the amount required for neutralizing the LAS and fiul furic ncid. Example 5 The detergent composition having the composition shown in Table 1 was prepared in an amount of 35 kg for each unit using a high speed mixer "LOdige Mixer FKM-130D" (manufactured by Matsubo Co., Ltd.). This mixer was equipped with agitator blades and a shearing device, the shearing device corresponding to a chopper for di .'j In Ley ration and dispersion. Here, the detergent composition was prepared by the following procedures as detailed below. Powder Blending The solid ingredients consisting of 20.06 parts by weight of sodium carbonate ("LIGHT ASH/' manufactured by Central Glass Co., Ltd.; average particle size: 56.1 pm) were blended for one minute under the conditions of a rotational speed of agitator blades of 130 rpm and a rotational speed of shearing device of 2850 rpm by the LOdige Mixer. Addition of Reaction Initiating Agent Water was added to the contents in the mixer in an amount of 0.25 parts by weight as a reaction initiating agent, and the blending was carried out for one minute and thirty seconds under the same blending conditions as above. mixture remained in a particulate form. Incidentally, the LAS mentioned above contained 0.16 parts by weight of sulfuric acid. Also, the proportion of sulfuric acid to the LAS during neutralization reaction was such Jhat the reaction mixture contained 0.3 mol of sulfuric acid per mol of the LAS. The amount of sodium carbonate was about seven times the amount required for neutralizing the LAS and sulfuric acid. After the addition of the LAS, the mixer was continuously operated under the same conditions for one minute to complete the neutralization reaction and the granulation process. The resulting granules of the detergent composition had the following properties: Percentage of particles with 1400 pm-pass: 81.0%; Average particle size: 604 prn; Bulk density: 707 g/L; Free-flowability: 6.5 seconds; and Hue: 91.1. Accordingly, the granules showed excellent properties. Example 6 Similar procedures to those in Example 3 were carried out except for not containing sodium tripolyphosphate at all and thus making zeolite as a main builder component, to give a detergent composition. The resulting granules of the detergent composition, prior to the after-blending step, had the following i properties: Percentage of particles with 1400 pm-pass: 83,9%; * Average particle size: 536 pm; Bulk density: 737 g/L; Free-flowability: 6.3 seconds; and Hue: 90.2. Accordingly, the granules showed excellent; properties. Example 7 Similar procedures to those in Example 3 were carrxeu out except for using sodium tripolyphosphate having an average particle uixe of 58.4 pin, to give a detergent oonipou I V I on - The ruttultliuj grunulaa o£ the detergent composition, prior to the after-blending step, had the following properties: Percentage of particles with 1400 pnwpase: 82.3%; Average particle size: 532 pm; Bulk density: 760 g/L; Free-flowability: 6,3 seconds; and Hue: 90-8. Accordingly, the granules showed excellent properties. Comparative Example 1 powder Blending '"'■■" Gv The solid ingredients consisting of 7,0 parts by weight of sodium tripolyphosphate (STPP? average particle size: 11,2 pm), 12.6& parts py weight of sodium carbonate ("LIGHT ASH/' manufacture^ by Central Glass Co., Ltd.; average particle size: 56.1 pro), and 0.11 parts by weight of a fluorescer were blended for one minute under the 1 i conditions of a rotational speed of agitator blades of 130 rpm and a rotational speed of shearing device of 2850 rpm by the L6dige Mixer. Addition of Reaction Initiating Agent Water was added to the contents in the mixer in an amount of 0.20 parts by weight as a reaction initiating agent, and the blinding was carried out for one minute and thirty seconds under the same blending conditions as above. Neutralization While the mixer was operated under the same conditions as above, 10.92 parts by weight of a linear alkylbensenesulfonic acid (LAS) were added to the contents in the mixer in four minutes. During the addition, the ingredients were cooled by allowing water to flow through the mixer jacket at 25°C. At this stage, the temperature rose to 73°C. Incidentally, during this stage, the reaction mixture remained in a particulate form. Incidentally, the LAS mentioned above contained 0.16 parts by weight of sulfuric acid. Also, the proportion of sulfuric acid to the LAS during neutralization reaction was such that the reaction mixture contained 0.05 mol of sulfuric acid per mol of the LAS. After the addition of the LAS, the mixer was continuously operated under the same conditions for one minute to complete the neutralization reaction and the granulation process. The breaking load of the granules obtained in this Example was 1215 gf, and the average particle size of the granules was 1114 pm. Addition of Liquid Ingredients and Surface; Modification At a point where the neutralization reaction and the granulation process were completed, an aqueous solution of a 40% by weight acrylic acid-maleic acid copolymer was added to the mixer with an effective amount of the copolymer being 0.18 parts by weight, while the mixer was operated under the same conditions as above, and the ingredients were mixed for one minute and thirty seconds. Thereafter, the resulting mixture was subjected to a surface modification by adding 4.20 parts by weight of zeolite having an average particle size of 4 pm to the mixer as a surface modifier, and operating the mixture for additional two minutes. Incidentally, the zeolite contained 0.84 parts by weight of a crystal water. The resulting granules of the detergent composition, prior to the after-blending step, had the following properties: Percentage of particles with 1400 pm-pass: 67.4%-; Average particle size: 739 pm; Bulk density: 830 g/L; Free-flowability: 6.1 seconds; and Hue: 91.6. Accordingly, the granules gave notably poorer results in the percentage of particles with 1400 pm-pass and in the average particle size than the granules of Examples. After-Blending Using a rotary mixer, 0.18 parts by weight of enzyme granules and the detergent composition prepared above were blended, and thereafter 0.07 parts by weight of perfume were sprayed, to give a final powdery product of the high-bulk density detergent composition. Inc.; J dentally, the amount oi t;od i uiu cuboiui te w.i.s about seven times the amount required for neutralizing the liAJi ciml HUHUI UJ Comparative Example 2 The detergent composition having the composition shown in Table 2 was prepared in an amount of 35 kg for each unit using a high speed mixer "LOdige Mixer FKM-130D" (manufactured by Matsubo Co., Ltd.). This mixer was equipped with agitator blades and a shearing device, the shearing device corresponding to a chopper for disintegration and dispersion. Here, the detergent composition was prepared by the following procedures as detailed below. Powder Blending The solid ingredients consisting of 7.0 parts by weight of sodium tripolyphosphate (STPP; average particle size: 11.2 pm), 11.53 parts by weight of sodium carbonate ("LIGHT ASH," manufactured by Central Glass Co., Ltd.; average particle size: 56.1 pm), 0.11 parts by weight of a fluorescer, and 1.16 parts by weight of sodium sulfate (prepared by pulverizing to an average particle size of 8.22 pm by a hammer mill) were blended fox- one minute . under the conditions of a rotational speed of agitator blades of 130 rpm and a rotational speed of shearing device of 2850 rpm by the LGdige Mixer. Addition of Reaction Initiating Agent Water was added to the contents in the mixer in an amount of 0.20 parts by weight as a reaction initiating agent, and the blending was carried out for one minute and thirty seconds under the same blending conditions as above. Neutralization While the mixer was operated under the same conditions as above, 10.92 parts by weight of a linear alkylbenzenesulfonic acid (LAS) were added to the contents in the mixer in four minutes. During the addition, the Inyrodlpiil n WPIO finnlorl by nl Irjwlny wnlor \o flow through the mixer jacket cit 25°C. At this stage, the temperature rose to 72°C. Incidentally, during this stage, the reaction mixture remained in a particulate form. Incidentally, the LAS mentioned above contained 0.16 parts by weight of sulfuric acid. Also, the proportion of sulfuric acid to the LAS duriny neutralization react.on was such that the reaction mixture contained 0.05 mol of sulfuric acid per mol of the LAS. After the addition of the LAS, the mixer was continuously operated under the same conditions for one minute to complete the neutralization reaction and the granulation process. Addition of Liquid Ingredients and Surface Modification At a point where the neutralization reaction and the granulation process were completed, an aqueous 'solution of a 40% by weight acrylic acid-maleic acid copolymer was added to the mixer with an effective amount of the copolymer being 0.18 parts by weight, while the mixer was operated under the same conditions as above, and the ingredients were mixed for one minute and thirty seconds. Thereafter, the resulting mixture was subjected to a surface modification by adding 4.20 parts by weight of /,ool i to hnviruj nn nvorngo pnrtfole ni 7,o of 4 pin to tho mlxor OB a surface modifier, and oporatincj the mixture for additional two minutes. Incidentally, the zeolite contained 0.84 parts by weight of a crystal water. The resulting granules of the detergent composition, prior to the after-blending step, had the following properties: Percentage of particles with 1400 pm~pass: 68.0%; Average particle size: 720 pm; Bulk density: 786 g/L; Free-flowability: 6.3 seconds; and Hue: 90.8. Accordingly, the granules gave notably poorer results in the percentage of particles with 1400 pm-pass and in the average particle size than the granules of Examples. After-Blending Using a rotary mixer, 0.18 parts by weight of enzyme granules and the detergent composition prepared above were blended, and thereafter 0.07 parts by weight of perfume were sprayed, to give a final powdery product of the high-bulk density detergent composition. f n<: dmi t rt i y l.hn ninoui j o nod win cnr honntc w.irt nhntil wiwun muu nun mint cmjti cul f n itm in-> LAS and sulfuric acid. Comparative Example 3 The detergent composition having the composition shown in Table 2 was prepared in an amount of 35 kg for each unit using a high speed mixer "Lttdigo Mixer FKM-130D" (manufactured by Matsubo Co., Ltd.)* This mixer was equipped with agitator blades and a shearing device, the shearing device corresponding to a chopper for disintegration and dispersion. e Here, the detergent composition was prepared by the following procedures as detailed below* Powder Blending The solid ingredients consisting of 7.0 parts by weight of sodium tripolyphosphate (STPP; average particle size: 11.2 pm), 11.43 parts by weight of sodium carbonate ("LIGHT ASH," manufactured by Central Glass Co., Ltd.; average particle size: 56.1 pm), and 0.11 parts by weight r of a fluorescer were blended for one minute under the i ■ conditions of a rotational speed of agitator blades of 130 rpm and a rotational speed of shearing device of 2850 rpm by the LOdige Mixer• Addition of Reaction Initiating Agent Water was added to the contents in the mixer in an amount of 0.20 parts by weight as a reaction initiating agent, and the blending was carried out for one minute, and thirty seconds under the same blending conditions as above. Neutralization While the mixer was operated under the same conditions as above, 12.29 parts by weight of a linear alkylbenzenesulfonic acid (LAS) were added to the contents in the mixer in four minutes. During the addition, the ingredients were cooled by allowing water to flow through the mixer jacket at 25°C. At this stage, the temperature rose to 73°C. Incidentally, during this stage, the reaction mixture remained in a particulate form. Incidentally, the LAS mentioned above contained 0.18 parts by weight of sulfuric acid. Also, the proportion of sulfuric acid to the LAS during neutralization reaction was such that the reaction mixture contained 0.05 mol of sulfuric acid per mol of the LAS. After the addition of the LAS, the mixer was continuously operated under the &ame condi tionn for ono minute to complete the neutralization reaction and the granulation process. Addition of Liquid Ingredients and Surface Modification At a point where the neutralization reaction and the granulation process were completed, an aqueous solut on of a 40% by weight acrylic acid-maleic acid copolymer was added to the mixex" with an effective amount of the copolymer being 0.18 parts by weight, while the mixer was operated under the same conditions as above, and the ingredients were mixed for one minute and thirty seconds. Thereafter, the resulting mixture was subjected to a surface modification by adding 4.20 parts by weight of zeolite having an average particle size of 4 pm to the mixer as a surface modifier, and operating the mixture for additional two minutes. Incidentally, the zeolite contained 0.84 parts by weight of a crystal water. The resulting granules of the detergent composition, prior to the after-blending step, had the following properties: Percentage of particles with 1400 pm~pass: 32.5%; Average particle size: 1469 pm; Bulk density: 736 g/L; Free-flowability: 6.4 seconds; and Huts: 91.4. Accordingly, the granules gave notably poorer results in the percentage of particles with 1400 pm-pass than the granules of the present invention, having a large proportion of coarse particles. After-Blending Using a rotary mixer, 0.18 parts by weight Bf enzyme granules and the detergent composition prepared above were blended, and thereafter 0.07 parts by weight of perfume were sprayed, to give a final powdery product of the high-bulk density detergent composition. In this Comparative Example, the amount of sodium carbonate was about five times the amount required for neutralizing the LAS and sulfuric acid. Comparative Example 4 The detergent composition having the composition shown in Table 2 was prepared in an amount of 35 kg for each unit using a high speed mixer "LOdige Mixer FKM-130D" (manufactured by Matsubo Co., Ltd.). This mixer was equipped with agitator blades and a shearing device, the shearing device corresponding to a chopper for disintegration and dispersion. Here, the detergent composition was prepared by the following procedures as detailed below. Powder Blending The uolid ingredients cons it* ting of 7. 0 parts by wolyht. of ttotl J urn t r 1 polyphosphate* ( BTl'S'; ovtunya prtrtlola size: 58.4 ym), 12.69 parts by weight of sodium carbonate ("LIGHT ASH," manufactured by Central Glass Co., Ltd.; average particle size: 56.1 pm), and 0.11 parts by weight of a fluorescer wore blended for one minute under the conditions of a rotational speed of agitator blades of 130 rpm and a rotational speed of shearing device of 2850 rpm by the Lttdige Mixer. * Addition of Reaction Initiating Agent Water was added to the contents in the mixer in an amount of 0.20 parts by weight as a reaction initiating agent, and the blending was carried out for one minute and thirty seconds under the same blending conditions as above. Neutralization While the mixer was operated under the same conditions as above, 10.92 parts by weight of a linear alkylbenzenesulfonic acid (LAS) were added to the contents in the mixer in four minutes. During the addition, the ingredients were cooled by allowing water to flow through the mixer jacket at 25°C. At this stage, the temperature rose to 71°C. Incidentally, during this stage, the reaction mixture remained in a particulate form. Incidentally, the LAS mentioned above contained 0.16 parts by weight of sulfuric acid. After the addition of the LAS, the mixer was continuously operated under the same conditions for one minute to complete the neutralization reaction and the granulation procesjs. c Addition of Liquid Ingredients and Surface Modification At a point where /\|h§jn§utralization reaction an$ tlie granulation process were completed, an aqueous solution of a 40% by weight acrylic acid-maleic acid copolymer was added to the mixer with an effective amount of the copolymer being 0.18 parts by weight, while the mixer was operated under the same conditions as above, and the ingredients were mixed for one minute and thirty seconds. Thereafter, the resulting mixture was subjected to a surface modification by adding 4.20 parts by weight of zeolite having an average particle size of 4 pm to the mixer as a surface modifier, and operating the mixture for additional two minutes. Incidentally, the zeolite contained 0.84 parts by weight of a crystal water. The resulting granules of the detergent composition, prior to I hn n f I f«r h I mid I nq n I pp, )\n Percentage of particles with 1400 pm-pass: 34.2%; Average particle size: 1013 ym; Bulk density: 712 g/L; and Free-flowability: 7.8 seconds. Accordingly, the granules gave lower bulk density and notably poorer results in the percentage of particles with 1400 iim-pass than those of the present invention1; having a large proportion in coarse particles. After-Blending Using a rotary mixer, 0.18 parts by weight of enzyme granules and the detergent composition prepared above were blended, and thereafter 0.07 parts by weight of perfume were sprayed, to give a final powdery product of the high-bulk density detergent composition. Incidentally, the amount of sodium carbonate was about seven times the amount required for neutralizing the LAS and sulfuric acid. Incidentally, Tables 1 and 2 show the compositions of the final powdery product of each of the detergent compositions in Examples and Comparative Examples. Also, Tables 3 and 4 show the properties of the detergent compositions after granulation. As is clearly illustrated by the above results, by dry- npwt-rnl i 7.1nq the nomponont^ in the prirs of n yivtMi ciiuount oi ouliuric: dcidr thu high-buLk dnnu I ty detergent compositions having small particle sizes can be obtained at high yields (Examples 1 to 7). Also, as illustrated by Example 5 and Example 6, the method of the present invention can be suitably utilized to give desired effects without being limitative in the detergent composi tlons* Altio, tho method is particularly applicable for production of phosphorus-free detergent*. On the other hand, in the case of Comparative Example 1 where a smaller amount of sulfuric acid is used during neutralization, the granules are large, showing notably poorer results in the percentage of particles with 1400 urn-pass and in the average particle size as compared to Examples- Also, in the case of Comparative Example. 2 where pulverized sodium sulfate is added, the resulting detergent granules have large particle size. By comparing Example 4 with Comparative Example 3, remarkable differences in the percentage of particles with 1400 pm-pass and in the average particle size can be noted when the concentration of the anionic surfactant (LAS-Na) in the resulting detergent composition is as high as 36.00% by weight. Therefore, the method of the present invention can be suitably applied in cases where the anionic surfactant is contained at a high concentration in the dnLortjcmt, componi t ion . Hy compnri nq l\Knnif)l o 7 nnd Comparative Example 4, uvea when LI it par Lie lo ulze ot Llie tripolyphosphate is relatively large (58.4 yim), the effects of the method of the present invention can be clearly observed, Incidentally, in Example 1, Example 2, and Example 3, a decrease in the bulk densities.can be observed by an increase in the amount of sulfuric acid, thereby suggesting that the bulk densities! of the resulting detergent compositions can be controlled to desired values by the amount of sulfuric acid added. Incidentally, the detergent compositions obtained in Each of Examples were subjected to X-ray diffraction analysis, but no diffraction peaks ascribed to sodium sulfate were detectable. Example 11 The detergent composition having the composition shown in Table 5 was prepared in an amount of 35 kg for each unit using a high speed mixer "Lttdige Mixer FKM-130D" (manufactured by Matsubo Co., Ltd.)* This mixer was equipped with agitator blades and a shearing device, the shearing device corresponding to a chopper for disintegration and dispersion. Here, the detergent composition was prepared by the following procedures as detailed below. Powder Blending The solid ingredients consisting of 7.0 parts by weight of sodium tripolyphosphate (STPP; average particle size: 11.2 pm), 12.72 parts by weight of sodium carbonate ("LIGHT ASH," manufactured by Central Glass Co.,. Ltd.; average particle size: 56.1 pm), and 0.11 parts by weight of a fluorescer were blended for one minute under the conditions of a rotational speed of agitator blades of 130 rpm (peripheral speed: 3.4 m/s) and a rotational speed of shearing device of 2850 rpm (peripheral speed: 27 m/s) by the Lbdige Mixer. Addition of Reaction Initiating Agent A 48% by weight aqueous NaOH solution was added to the contents in the mixer in an amount of 0.51 parts by wniqht. i\r. a rc.nnt. Ion I n 1 tl n t; I nq nqnnt, nnd Lhn blending wnn cm r I tu'\ on t for onn in i nu to nrul thirty fjncondf! undnr the same blending conditions as above. Neutralization While the mixer was operated under the same conditions as above, a mixture of 10,19 parts by weight of a linear alkylbenzenesulfonic acid (LAS; molecular weight: 322) and 0.58 parts by weight of 98% by weight sulfuric acid were added to the contents in the mixer in four minutes, the mixture being prepared in advance. During the addition, the ingredients were cooled by allowing water to flow through the mixer jacket at 25°C. Incidentally, during this stage, the reaction mixture remained in a particulate form. Incidentally, the LAS mentioned above, which was prepared by S03 gas sulfonation method, contained 0.16 parts by weight of sulfuric acid. In other words, the resulting mixture contained 0.05 mol of sulfuric acid per mol of the LAS. Also, the proportion of sulfuric acid to the LAS during neutralization reaction was such that the reaction mixture contained 0.24 mol of sulfuric acid per mol of the LAS. The amount of sodium carbonate was about five times the amount required for neutralizing the LAS and sulfuric acid. After the addition of the LAS, the mixer was continuously operated under the same conditions for three minutes to complete the neutralization reaction and the granulation process;. Also, air was blown at a rate of 300 L/min immediately after the addition of the mixed acid. Addition of Liquid Ingredients and Surface Modification At a point where the neutralization reaction and the granulation process were completed, an aqueous solution of a 40% by weight acrylic acid-maleic acid copolymer was added to the mixei with an effective amount of the copolymer being 0.18 parts by weight, while the mixer was operated under the same conditions as above, and the ingredients were mixed for one minute and thirty seconds. Thereafter, the resulting mixture was subjected to a surface modification by adding 4.20 parts by weight of zeolite having an average particle size of 4 \xm to the. mixer as a surface modifier, and operating the mixture for additional two minutes. Incidentally, the zeolite contained 0.84 parts by weight of a crystal water. The resulting granules of the detergent composition, prior to the after-blending step, had the following properties: Percentage of particles with 1400 pm-pass: 83.8%; Average particle size: 469 pm; Bulk density: 753 g/L; Free-flowability: 6.3 seconds. Accordingly, the* granules showed excellent properties. After-Blending Using a rotary mixer, 0.18 parts by weight of enzyme granules nnd tho cJotorgonl; aomponit Ion prcpnrcul nbovo worn blended, and thereaftur 0,07 parts by weight of perfume were sprayed, to give a final powdery product of the high-bulk density detergent composition. Examples 12-22 and Comparative Examples 11-19 Similar procedures to those in Example 11 were carried out except for using the respective kinds and e amounts of starting materials listed in Tobies 5 and 6, to give each of the final powdery products of the high-bulk density detergent compositions. Here, in Examples 18 to 20, after completing the neutralization process, additional components of fatty acid (having 14 to 18 carbon atoms) and a nonionic surfactant (having ethylene oxide moiety with 6 addition molar number) were added to the ingredients in the mixture in given amounts shown in Table 5, and the ingredients were blended for one minute. The composition and the properties of each of the resulting final powdery products of the high-bulk density detergent compositions are listed in Tables 7 through 10. Incidentally, the breaking load is measured by using a rheometer "NRA-3002DM (manufactured by Fudohkogyo K.K.). Table 6 Composition Comparative Examples (parts by weight) 11 12 13 • 1U 15 16 17 18 19 Powder Blending STEP 7.00 7.00 7.00 7.00 7.00 7.70 7-70 - Sodium Carbonate 13.05 13.68 12.20 11.06 10.10 13.26 14.34 14.34 13.22 Zeolite . . ____.___7.70 7-70 Powdery Sodium Sulfate - -0.90— - - - — - Fluorescer 0.11 0.11 0.11 0.11 0.11 0.11 0.11 0.11 0.11 Addition of Reaction Initiating Agent 4b vti-Aqueous NaOH Solution 0.51 - 0.51 0.61 0.66 0.37 0.27 0.27 300 0.49 1.40 Neutralization D_ 10.19 10.19 10.19 12.22 13.24 98 wt* Sulfuric Acid - - - - - 85 wt (Amount of Gas Blown) [L/min] 300 300 300 300 300 Fatty Acid _____ Nonionic Surfactant _____ 7.47 5.43 5.43 10.19 300 300 0.49 2.45 300 0.49 2.45 Addition of Liquid Ingredients and Surface Modification Acrylic Acid-Maieic Acid Copolymer 0.44 0.44 0.44 0.44 0.44 _ _ _ o:44 Zeolite 4.20 4.20 4.20 4.20 4.20 4.20 4.20 4.20 4.20 After-Blending _ Enzvme 0.18 0.18 0.18 0.18 0.18 0.18 Q,18 0.-18 0.18 Perfume 0.07 0.07 0.07 0.07 0.07 0.07 o".07 0.07 0.07 Molar Ratio of Inorganic Acid/ Liquid Acid 0.04 0.04 0.34 0.04 • 0.04 0.04 0.03 0.03 0.04 Precursor [mol/mol] Table 7 Properties 11 12 13 14 15 Examples 16 17 16 19 20 21 22 After NeutralizationPowder Temp. [°C] Breaking Load [gf] Average Particle Size [ ii m ] and Granulation80.1 87.3 673 520560 488 Process92.3 470450 79.2 690583 73.7 930570 84.3 850850 90.0 9501785 79.-22629C 72.0 57241 68.8 51339 80.8 502580 79.5 659545 After Surface Modification Process Powder Temp. [°Cl 69.5 71.1 74.5 68.1 64.2 70.9 75-4 66.5 53.2 58.5 61.0 68.2 Average Particle Size [(in } 469 400 380 490 470 670 1567 493 ^45 494 450 458 Percentage of Particles with 1400 ^m-pass [%] 83.8 86.0 87.0 83.1 79.2 73.0 30.0 87-9 78.9 78.8 79.1 84.0 Bulk Density [g/L] 753 723 '724 731 816 725 719 79' 331 818 747 748 Free Flowability [sec] 6.3 6.6 6.8 6.4 6.1 6.4 6.8 6.C 5.1 6.6 6.8 6.5 Table 8 Properties 11 12 Comparative Examples 14 15 16 17 18 19 After Neutralization and Granulation Process Powder Temp. [°C] 73.0 68.9 76.8 * 68.1 60.1 56.7 67.8 Breaking Load [gf] 112U 1163 1606 •:• 723 130 147 948 Average Particle Size [ p,m. ] 879 970 QlXZ 3055 390 299 463 750 After Surface Modification Process Powder Temp. [°C] 6U.5 62.6 63.5 * 58.5 55.1 54.3 55.4 Average Particle Size [ p,m ] 670 710 ~2C 2033 * 1313 1173 964 590 Percentage of Particles with 1H00 #M-pass [%] 69.8 63.7 12.0 * 53.2 32.9 57.4 76.3 Bulk Density [g/L] 841 788 53' 692 ■& 847 864 848 769 Free Flowability [sec] 6.2 6.U •~i ■« 6.7 X O. 1 6.6 6.9 6.9 Remarks ••: The neutralized product became r - -— #■« sticky, and thus no measurments could be taken. Table 9 Composition / Examples (parts by weight) 11 '2 _3 1U 15 .16 17 18 19 20 21 22 Las-Na 30.00 3C00 30.00 30.00 30.00 36.00 39.00 22.00 16.00 16.00 30.00 30.00 Soap 0.00 COO 0.00 0.00 0.00 0.00 0.00 1.50 1.50 1.50 0.00 0.00 STPP 20.00 2C.00 2C.00 20.00 17.00 20.00 20.00 22.00 22.00 0.00 0.00 20.00 Zeolite 12.00 12.00 12.00 12.00 12.00 12.00 12.00 12.00 12.00 34.00 32.00 12.00 Sodi'js Carbonate 30. 40 2-.80 22.50 31.30 32.30 20.80 17.10 31.30 35.00 35.00 28.70 25.40 Sodium Sulfate* 3.00 5.00 10.00 3.00 0.50 6.00 6.50 U.00 4.00 4.00 5. CO 0W Sodium Phosphate 0.00 COO COO 0.00 3-00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Acrylic Acid-Maleic Acid Copolymer 0.50 C.5C C.50 0.50 0.50 0.50 0.50 0.00 0.00 0.00 0.50 0.50 Nonionic Surfactant 0.00 COO 0.00 0.00 0.00 0.00 0.00 4.00 7.00 7.00 0.00 0.00 Fluorescer 0.30 C.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 Enzyme 0.50 C.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 Perfume 0.20 C.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 Water 3.10 370 J--00 2.20 3.70 3.70 3.90 2.20 1.50 1.50 .2.80 3.10 Sodium Sulfate ■ 3.14 5.42 ".14 # •• 6.114 6.57 4.55 •« •«« 5.43 •» Remarks : Amount calculated fron starting material composition. : Amount chemically derersiined by ion chromatography. * : Undetermined. Table 10 Composition Comparative Exairles (parts by weight) 11 12 13 1U 15 • ■' 17 18 19 Las-Na 30.00 30.00 30.00 36.00 39.00 22-CO 16.00 16.00 30.00 Soap 0.00 0.00 0.00 0.00 0.00 '.50 1.50 1.50 0.00 STPP 20.00 20.00 20.00 20.00 20.00 22.00 22.00 0.00 0.00 Zeolite 12.00 12.00 12.00 12.00 12.00 2.C0 12.00 34.00 32.00 Sodium Carbonate 33.20 34.10 30.20 26.75 23-60 3-. 50 38.65 38.65 33.70 Sodium Sulfate* 0.50 0.50 3.00 0.55 0.60 0.45 0.45 0.50 Acrylic Acid-Maleic Acid Copolymer 0.50 0.50 0.50 0.50 0.50 :.so 0.00 0.00 0.50 Nonionic Surfactant 0.00 0.00 0.50 0.00 0.00 7.00 7.00 0.00 Fluorescer 0.30 0.30 0-30 0.30 0.30 -■30 0.30 0.30 0.30 Enzyme 0.50 0.50 0.50 0.50 0.50 :.50 0.50 0.50 0.50 Perfume 0.20 0.20 0.20 0.20 0.20 -.20 0.20 0.20 0.20 Water 2.80 1.90 2.80 3.20 3.30 2.20 1.40 1.40 2.30 Sodium Sulfate 0.54 * ••• «•• «• 2.34 •• #«« 0.50 Remarks Amount calculated from starting material composition. Amount cheaically determined by ion chromatography. Undetermined. AR 1R nlpnr from Ihp rPHiil tR In TnhlPR !i to 10, by dry-neutralizing the liquid acid precursor in the presence of a given amount of an inorganic acid, high-bulk density detergent compositions comprising granules with small particle sizes can be obtained at high yields in Examples 11 to 22. Also, as is clear from Examples 18 to 21, according to the method of the present invention, the resulting detergent compositions exhibit desired effects without limiting their compositions, and the method is particularly suitably applicable in the production of phosphorus-free detergents. Particularly in the case of Examples 11 to 13, it is found that as the molar ratio of the inorganic acid to the liquid acid precursor increases, the particle size of the resulting detergent granules become smaller, so that the detergent granules with a desired particle rsize can be obtained by controlling the above molar ratio. On the other hand, in the case of Comparative Example 11 where the amount of the inorganic acid at neutralization is small, the resulting detergent granules are large, having notably lower percentages of particles with 1400 pm-pass and larger average particle size. Also, in the case of Comparative Example 13 where pulverized sodium sulfate is added, the resulting detergent granules have large particle sizes, so that similar effects to those attained by addition of sulfuric acid cannot be obtained. By comparing the results of Example 16 with those of Comparative Example 14 and the results of Example 17 with those of Comparative Example 15, even more remarkable differences in the percentages of particles with 1400 jim-pass and the average particle sizes can be observed in cases where the anionic surfactant (LAS-Na) is contained in the resulting detergent composition in high concentrations. Therefore, the method of the present invention is suitably applicable in cases where the concentrations of the anionic surfactant in the detergent composition are high. Also, when comparing the results of Example 18 with those of Comparative Example 16, in the case where the concentration of the anionic surfactant (LAS-Na) is low, the microporous surface areas of the detergent composition increase by addition of the inorganic acid, so that large amounts of the liquid starting material, such as nonionic surfactants, can he formulated while maintaining a small particle size in the detergent granules. Also, the detergent compositions obtained in each of t Examples 11 to 21 are subjected to X-ray diffraction analysis, but no diffraction pejaks ascribed to inorganic salts, such as sodium sulfate, are detectable. INDUSTRIAL APPLICABILITY By neutralizing the a liquid acid precursor of a . non-soap, anionic surfactant with a water-soluble, solid, alkali inorganic substance in the presence of a given amount of the organic acid, high-bulk density detergent compositions compiising granules having smal1 particle sizes can be obtained at high yields. The present invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as v/ould be obvious to one skilled in the art are intended to be included within the scope of the following claims. CLAIMs 1. Detergent granules comprising one or more non-soap, anionic surfactants and one or more inorganic salts undetectable by X-ray diffraction method, wherein the molar ratio of [inorganic salts undetectable by X-ray diffraction method]/[non-soap, anionic surfactants] is from 0.1 to 1.0. 2. The detergent granules according to claim 1, wherein the non-soap, anionic surfactant is contained in the detergent granules in an amount of 28% by weight or more and less than 50% by weight. 3. The detergent granules according to claim 1, wherein the non-soap, anionic surfactant is contained in the detergent granules in an amount of 10% by v/eight or more and less than 28% by weight, and wherein the molar ratio of [inorganic salts undetectable by X-ray diffraction method]/[non-soap, anionic surfactants] is from 0.3 to 1.0. 4. A method for producing detergent granules, comprising the step of dry-neutralizing a liquid acid precursor of a non-soap, anionic surfactant with a water- soluble, solid, alkali inorganic substance, wherein a dry-neutralizing step is carried out in the presence of 0.1 to 1.0 mol of an inorganic acid per mol of said liquid acid precursor of a non-soap, anionic surfactant. 5. The method according to claim 4, further comprising the step of adding a free-flowing aid after the dry-neutralizing step, to surface-modify the detergent granules. 6. The method according to claim 4, further comprising the stop of adding one or more liquid components after the dry-neutralizing step. 7. . The method according to claim 6, further comprising the step of adding a free-flowing aid after the step of adding one or more liquid components, to surface-modify the detergent granules. • 8. The method according to any one of claims 4 to 7, wherein said liquid acid precursor of a non-soap, anionic surfactant is a linear1 alkylbenzenesulfonic acid obtained by S03 gas sulfonation method. 9. The method according to any one of claims 4 to 8, wherein an amount of an inorganic acid preexisting in the liquid acid precursor of a non-soap, anionic surfactant is 0.09 mol or less per mol of said liquid acid precursor of a non-soap, anionic surfactant. 10. The method according to any one of claims 4 to 9, wherein said inorganic acid is sulfuric acid or phosphoric acid. 11. Tho muthod according to nny OHM of clnlmii 4 to 10, wherein the resulting detergent granules contain the non-soap, anionic surfactant in an amount of 28% by weight or more and less than 50% by weight, and have a molar ratio of [inorganic salts undetectable by X-ray diffraction method]/[non-soap, anionic surfactants] of from 0.1 to 1.0. 12. The method according to any one of claims 4 to 10, wherein the resulting detergent granules contain the non-soap, anionic surfactant in an amount of 10% by weight or more and less than 28% by weight in the detergent granules, and have a molar ratio of [inorganic salts undetectable by X-ray diffraction method]/[non-soap, anionic surfactants] of from 0.3 to 1.0. 13. A high-bulk density detergent composition having a bulk density of 500 g/L or more, comprising the detergent granules according to any one of claims 1 to 3, or the detergent granules obtainable by the method of any one of claims 4 to 12*

Full Text

DESCRIPTION
DETERGENT GRANULES AND METHOD FOR PRODUCING THE SAME. AND HIGH-BULK DENSITY DETERGENT COMPOSITION
i
TECHNICAL FIELD
The present invention relates to detergent granules
i
comprising a non-soap, anionic surfactant and an inorganic salt, and a method for producing the above detergent granules by a dry-neutralization process. The prejsent. invention further relates to a high-bulk density detergent composition containing the above detergent granules.
i
BACKGROUND ART
In the detergent industries, recently, methods for producing powder detergents having relatively high bulk densities are remarked. Such powdery detergents containing anionic surfactants, such as alkylbenzenesulfonates, are prepared in situ neutralization of an acid precursor of the anionic surfactant with an alkali, such as sodium hydroxide, sodium carbonate, or the like.
For instance, Japanese Patent Laid-Open No. 60-72999 and GB-2,166,452B disclose a process comprising the steps of blending detergent sulfonic acid, sodium carbonate, and

%rater with a strong shearing device; cooling the resultin solid substances to 40°C or lower; finely pulverizing the cooled product; and then forming the fine powders into-
i I
granules. This method is a typical one of those I conventionally proposed methods, in which the !
!
neutralization reaction product is a doughy mass, which necessitates a kneading device, such as a kneader, capable
of supplying extremely large energy required for th£
j
neutralization reaction.
GB-1,369,269 discloses a method for producing an anionic detergent comprising vigorously mixing detergent sulfonic acid with sodium carbonate powder by using a mixer equipped with a shearing device, such as Lodige PLOUGH SHARE Mixer. By this method, in order to obtain products of particulate forms, not a doughy mass, it is necessary to blow a gas into the two-component mixture mentioned above, to thereby suitably make the reaction substances flowable and blend the reaction mixture. In order to carry out this treatment, the mixer has to be made notably complicated. Also, since water serving to accelerate the neutralization reaction is not added, the progress of this reaction is mild, so that relatively coarse products are formed.
Japanese Patent Laid-Open No. 3-33199 discloses a method of producing a detergent composition comprising the

steps of dry-neutralizing components in .a high speed
i
mixer/granulator at a temperature of 55°C or less, and
I then'adding a liquid binder thereto to carry out
granulation, Japanese Patent Laid-Open No. 4-363398
l
discloses a method of producing a detergent composition comprising the steps of dry-neutralizing components in a high speed mixer/granulator at a temperature of 55°C or more, and then adding a liquid binder thereto to carry out granulation. Japanese Patent Laid-Open No. 3-146599 discloses a method of producing a detergent composition comprising the steps of dry-neutralizing components in a continuous high speed mixer; then increasing to a high
*
bulk density using a moderate speed mixer; and then cooling and/or drying the resulting product to carry out granulation.
The detergent compositions obtainable by the methods described above include granules having small particle sizes. However, for practical purposes, the yield of the detergent composition comprising granules of a desired, even smaller particle size is yet to be improved.
Also, in the above methods, such factors in operating conditions as the powder temperature, the water content, the powder blending efficiency, and the like, are optimally selected simply for the purpose of preparing detergent compositions comprising granules having even

smaller particle sizes, never attempting to fundamentally
l
improve the tackiness ascribed to the anionic surfactants, which cause agglomeration of the granules and formation of coarse granules.
Japanese Patent Unexamined Publication No. 7-503750 discloses a method of producing detergent granules comprising neutralizing an anionic surfactant in an acid form with a granular neutralizing agent (sodium carbonate) of which has 50% by volume of particles of less than 5 pm in diameter in a high shearing mixer. However, in this publication, no disclosures or suggestions concerning the improvements of the yield of the detergent composition comprising granules having a desired particle size are made.
One object of the present invention is to provide detergent granules with suppressed tackiness and small particle size.
Another object of the present invention is to provide a method for producing the above detergent granules,.
Still another object of the present invention is to provide a high-bulk density detergent composition comprising the above detergent granules.
These and other objects of the present invention will be apparent from the following description.

DISCLOSURE OF THE INVENTION
The present invention is concerned with the following:
(1) Detergent granules comprising one or more non-soap, anionic surfactants and one or more inorganic salts undetectable by X-ray diffraction method, wherein the molar ratio of [inorganic salts undetectable by X-ray diffraction method]/[non-soap, anionic surfactants] is from 0.1 to 1.0;
(2) The detergent granules described in item (1) above, wherein the non-soap, anionic surfactant is contained in the detergent granules in an amount of 28% by weight or more and less than 50% by weight;
(3) The detergent granules described in item (1) above, wherein the non-soap, anionic surfactant is contained in the detergent granules in an amount of 10% by weight or more and less than 28% by weight, and wherein the molar ratio of [inorganic salts undetectable by X-ray diffraction method]/[non-soap, anionic surfactants] is from 0.3 to 1.0;
(4) A method for producing detergent granules, comprising the step of dry-neutralizing a liquid acid precursor of a non-soap, anionic surfactant with a water-soluble, solid, alkali inorganic substance, wherein a dry neutralizing step is carried out in the presence of 0.1 to

1.0 mol of an inorganic acid per mol of the liquid acid precursor of a non-soap, anionic surfactant;
(5) The method described in item (4) above, further comprising the step of adding a free-flowing aid after the dry-neutralizing step, to surface-modify the detergent granules;
(6) The method described in item (4) above, further comprising the step of adding one or more liquid components after the dry-neutralizing step;
(7) The method described in item (6) above, further comprising the step of adding a free-flowing aid after the step of adding one or more liquid components, to surface-modify the detergent granules;
(8) The method described in any one of items (4) to (7) above, wherein the liquid acid precursor of a non-soap, anionic surfactant is a linear alkylbenzenesulfonic acid obtained by S03 gas sulfonation method; i
(9) The method described in any one of items (4) to (8)
j
above, wherein an amount of an inorganic acid preexisting
i
in the liquid acid precursor of a non-soap, anionijc
i
surfactant is 0.09 mol or less per mol of the liquid acid precursor of a non-soap, anionic surfactant;
(10) The method described in any one of items (4) to (9)
.above, wherein the inorganic acid is sulfuric acid1 or
phosphoric acid;

(11) The method described in any one of items (4) to (10) above, wherein the resulting detergent granules contain the non-soap, anionic surfactant in an amount of 28% by weight or more and less than 50% by weight, and have a molar ratio of [inorganic salts undetectable by X-ray diffraction method]/[non-soap, anionic surfactants] of from 0.1 to 1.0;
(12) The method described in any one of items (4) to (10) above, wherein the resulting detergent granules contain the non-soap-, anionic surfactant in an amount of 10% by weight or more and less than 28% by weight in the detergent granules, and have a molar ratio of [inorganic salts undetectable by X-ray diffraction method]/[non-soap, anionic surfactants] of from 0.3 to 1.0; and
(13) A high-bulk density detergent composition havijng a
i ]
bulk density of 500 g/L or more, comprising the detergent granules according to any one of items (1) to (3), ;or the detergent granules obtainable by the method of any ;one of items (4) to (12).
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a graph showing X-ray diffraction patterns of the detergent granules obtained in Comparative Example 13. Its measurement is taken by X-ray diffraction analyzer "RAD-RC" (manufactured by Rigaku Co., Ltd.).

Figure 2 is a graph showing X-ray diffraction patterns of the powdery sodium sulfate.
Figure 3 is a graph showing the relationship between the amount of the sodium sulfate added as the starting material in the preparation of the detergent compositions and the peak intensity at d=2.78 in the X-ray diffraction analysis. This graph can be used as a calibration curve for determining the "powdery sodium sulfate" added as the starting material in the preparation of the detergent composition from the peak intensity obtained by X-ray diffraction analysis of the detergent composition. [
Figure 4 is a graph showing X-ray diffraction j
i
patterns of the detergent composition obtained in Example
12. i
Figure 5 is a graph showing the relationship between the entire amount of the sodium sulfate in the detejrgent composition calculated from the starting material composition and the amount of sodium sulfate in the detergent composition determined by ion chromatography. The graph is prepared by the chemically .determined amounts of sodium sulfate in the detergent compositions of Examples 11, 12, 13, 16, 17, 18, and 21 and Comparative Examples 11, 16, and 19. This graph can be used as a calibration curve for obtaining the "entire amount of sodium sulfate" contained in the detergent composition.

Figure 6 is a graph showing the relationship between the depths from the surface of the granules of the
detergent compositions and the relative intensity of the
i
! peaks ascribed to sodium sulfate, an inorganic salt
(namely, the ratio between the peak intensity of sodium i sulfate and.the peak intensity of the LAS-Na), as
determined by FT-IR/PAS analysis of the detergent j
f
i
compositions obtained in Example 11 and in Comparative
i
Example 11. In the figure, bold line represents data of
Example 11, and solid line represents data of Comparative
» . i
Example 11. j
Figure 7 is a graph showing the relationship q>f the
i microporous diameter and the microporous capacity of the
detergent compositions obtained in Example 18 and in
Comparative Example 16. In the figure, bold line
represents data of Example 18, and solid line represents
data of Comparative Example 16.
BEST MODE FOR CARRYING OUT THE INVENTION
The method for producing detergent granules of the present invention comprises the step of dry-neutralizing a liquid acid precursor of a non-soap, anionic surfactant with a water-soluble, solid, alkali inorganic substance, wherein a dry-neutralizing step is carried out in the presence of 0.1 to 1.0 mol of an inorganic acid per mol of

the liquid acid precursor of a non-soap, anionic surfactant.
In the present invention, it is possible to produce
detergent granules and high-bulk density detergent
i
i
composition by the above method. In other words, jsince
the granules prepared by the step of dry-neutralising a
i liquid acid precursor of the non-soap, anionic surtfactant
with a water-soluble, solid, alkali inorganic substance in
the intentional presence of the inorganic acid coniprise
!
neutralized salts ascribed to the inorganic acids !in relatively larger amounts at near the surfaces of the granules than at the inner portion of the granules, the resulting granules have low tackiness with small particle sizes. Also, since the tackiness of the granules is suppressed, the granules with a high surfactant content can be obtained without causing agglomeration of the granules.
The dry-neutralization process usable in the method of the present invention are not particularly limited as long as the dry-neutralization process is carried out in the presence of a given amount of an inorganic acid. In a preferred embodiment, for instance, the dry-neutralization process may be carried out by blending a mixture of a liquid acid precursor of a non-soap, anionic surfactant and an inorganic acid with a water-soluble, solid, alkali

inorganic substance to carry out the dry-neutralization
i l i
process. The present invention will be further explained
in detail below by taking the above embodiment as one
i example of the method of the present invention. i
This embodiment comprises 1) a blending step and 2) a dry-neutralizing step. Each of the steps will be detailed below. 1) Blending step
This process precedes the dry-neutralizing step and comprises blending a liquid acid precursor of a non-soap, anionic surfactant and an inorganic acid in advance.
The liquid acid precursors of non-soap, anionic surfactants refer to the precursors of the non-soap, anionic surfactants in the form of acids in a liquid state, which are formed into salts by neutralization reaction. Therefore, the liquid acid precursors of non-soap, anionic surfactants may be precursors having the above properties of any of known anionic surfactants acids without particular limitations. Concrete examples thereof include linear alkylbenzenesulfonic acids (LAS), ct-olefin sulfonic acids (AOS), alkyl sulfuric acids (AS), and internal olefin sulfonic acids, sulfonic acids of fatty acid esters, alkylether sulfuric acids, dialkyl sulfosuccinic acids, and the like. The liquid acid precursors may be used singly or in a combination of two

or more components.
The preferred inorganic acids usable in the priesent invention include sulfuric acid and phosphoric acid. More preferred inorganic acid includes sulfuric acid. Also, there are some cases where sulfuric acid is contained in the liquid acid precursor of a non-soap, anionic surfactant usable in the present invention by the production process of the liquid acid precursor.
The linear alkylbenzenesulfonates listed as the preferred liquid acid precursors of a non-soap, anionic surfactant may be prepared by one of the following two typical methods.
(1) Oleum sulfonation method.
(2) S03 gas sulfonation method.
(1) is a classical method for producing linear alkylbenzenesulfonic acids, wherein sulfuric acid may be contained in the resulting product in an amount of about 0.3 mol per mol of the linear alkylbenzenesulfonic acid. Also, in (2), the purity of the linear
alkylbenzenesulfonic acids in the resulting product is high, and the amount of sulfuric acid preexisting is relatively low, wherein the amount of sulfuric acid preexisting is usually at a level of 0.2 mol or less per mol of the linear alkylbenzenesulfonic acid. Presently,

from the aspects of quality and production efficiency, the method (2) is mainly employed as the method of giving high-purity linear alkylbenzenesulfonic acids. In the present invention, the linear alkylbenzenesulfonates prepared by (2) are suitably used.
As mentioned above, the inorganic acid may preexist in the precursors of non-soap, anionic surfactants in some cases. The amount of the inorganic acid, namely the amount of the inorganic acid preexisting in the liquid acid precursors of the non-soap, anionic surfactants, is not particularly limited. From the aspect of giving good hue in the resulting detergent granules, the amount of the inorganic acid preexisting in the liquid acid precursor of a non-soap, anionic surfactant is preferably 0.09 mol or less, more preferably 0.06 mol or less, per mol of the liquid acid precursor of a non-soap, anionic surfactant.
The amount of the inorganic acid in the method of the present invention is from 0,1 to 1.0 mol per mol of the liquid acid precursor of a non-soap, anionic surfactant, preferably from 0.1 to 0.8 mol, more preferably from 0.15 to 0.65 mol, still more preferably from 0.2 to 0.6 mol, still more preferably from 0.25 to 0.55 mol, per mol of
j
the liquid acid precursor of a non-soap, anionic |
i
surfactant. From the aspect of inhibiting the formation
i
of coarse granules of the detergent granules, the amount

of the inorganic acid is preferably 0.1 mol or more per mol of the liquid acid precursor, and from the aspect of securing the compositional freedom of the detergent composition, the amount of the inorganic acid is preferably 1.0 mol or less per mol of the liquid acid precursor. In particular, from the aspect of the microporosity of the detergent granules as detailed below, the amount of the inorganic acid is preferably 0.3 mol or more, more preferably from 0.3 to 1.0 mol, still more preferably from 0.3 to 0.8 mol, still more preferably 0.35 to 0.7 mol, per mol of the liquid acid precursor.
Also, as clearly described in Examples set forth below, by changing the compositional ratios between the liquid acid precursor of a non-soap, anionic surfactant and the inorganic acid, the tackiness and/or the microporosity of the resulting neutralized granules can be j varied.
Therefore, a suitable compositional ratio between the liquid acid precursor of a non-soap, anionic surfaqtant and the inorganic acid may be selected and controlled by
contents of the non-soap, anionic surfactant in thd
i granules, kinds of inorganic acids used, different Ikinds
of additives incorporated in the granules, or the like..
In other words, it is desired that the inorgariic acid
is added to the starting material components, including

the liquid acid precursor of a non-soap, anionic surfactant, in the case where the amount of the inorganic acid preexisting in the liquid acid precursor of a non-soap, anionic surfactant is not in the above range. Alternatively, it is also desired that the inorganic acid is added to the starting material components in the case where further improvements in the tackiness and/or the microporosity of the granules is to be made, or the neutralized granules are to be made even smaller, even when the amount of the inorganic acid preexisting in the liquid acid precursor is in the above range.
The mixers usable in this step are not particularly limited. Concrete examples thereof include mixing vessel for liquid components equipped with an agitating device. Also, the mixing may be carried out to an extent such that the each of the components are uniformly mixed.
2) Dry-Neutralizing Step
This step comprises adding a mixture of the liquid
acid precursor of a non-soap, anionic surfactant dnd an
i inorganic acid obtained in the previous step to a
water-soluble, solid, alkali inorganic substance, to dry-neutralize of the liquid.acid precursor of a non-soap, anionic surfactant. Incidentally, in this step, by adding the liquid acid precursor of a non-soap, anionic

surfactant and an inorganic acid, the neutralization reaction and the granulation process concurrently take place, to form the neutralized granules.
Concretely, the dry-neutralizing step includes the following steps:
(a) blending one or more water-soluble, solid,
alkali inorganic substances and/or and optional
known substances generally employed in detergent
compositions, wherein the water-soluble, solid,
alkali inorganic substance is used in an amount
of equal to or greater than that necessary for
neutralizing a mixture comprising a liquid acid
precursor of a non-soap, anionic surfactant and
an inorganic acid obtained in the blending step
i
described above; and !
(b) adding the mixture comprising the liquid acid
precursor of a non-soap, anionic surfactant and
the inorganic acid obtained in above blending
step to the mixture obtained in step (a) to
t I
neutralize the mixture obtained in step (a) while the mixture remains in a particulate form.
Step (a)
The water-soluble, solid, alkali inorganic substances may be any one usually used as alkalizing agents in

detergent compositions, which may be used alone or in
combination. Concrete examples thereof include sodium
carbonate, sodium hydrogencarbor^ate, sodium silicate,
potassium carbonate, calcium carbonate, and the like. ■
Among the water-soluble, solid, alkali inorganic
substances, preference is given to sodium carbonate
because the sodium carbonate can act as a detergent
i builder and an alkalizing agent in the final detergent
composition. Therefore, by adding and blending thfe water-soluble, solid, alkali inorganic substance components in this step, in amounts sufficient to neutralize a mixture
of the liquid acid precursor of anionic surfactants and
i
the inorganic acid in addition to the amount of sodium carbonate acting as builders and alkalizing agents mentioned above, the neutralization reaction can be favorably carried out in this step.
Specifically, it is preferred that the water-soluble, solid, alkali inorganic substances is added in an amount of equal to or greater than that required for neutralization of the liquid acid precursor of a non-soap, anionic surfactant and the inorganic aci,d (amount required for neutralization), for example, 1 to 20 times the amount required for neutralization, more preferably 2 to 10 times the amount required for neutralization, particularly 3 to 8 times the amount required for neutralization.

Also, the average particle size of the water-soluble, solid, alkali inorganic substance is not particularly limited. From the viewpoint of further increase in yield and storage stability, the average particle size is preferably 30 pm or more, more preferably from 40 to 200 pm, particularly from 50 to 100 pm. Here, in the present specification, the average particle size of the water-soluble, solid, alkali inorganic substance is evaluated based on volume using a laser diffraction particle size distribution analyzer ("LA-500," manufactured by H0RIBA Ltd.).
Further, in the present invention, any of the
following known substances generally employed in detergent
i
compositions may be also optionally blended. Concrete examples thereof include tripolyphosphates; crystalline or amorphous alkali metal aluminosilicates; crystalline silicates; fluorescers; pigments; anti-redeposition agents, such as polycarboxylate polymers and sodium salt of carboxymethyl cellulose; granular surfactants, such as fatty acids, salts thereof, linear alkylbenzenesulfonates,
alkyl sulfates; spray-dried powders, diatomaceous earth,
i calcite, kaolin, bentonite, sodium sulfate, sodium:
sulfite, and the like. The above substances may be
* i
optionally used depending upon the function of the' granules. When these substances are added, it is clesired

that they are used as a mixture with the water-soluble, solid, alkali inorganic substance.
In the case where the detergent compositions . comprising the tripolyphosphates as main components are prepared, the average particle size of the
i
tripolyphosphates is not particularly limited, and| the
i
average particle size may be preferably frdm 1 to 00 pm, more preferably from 5 to 20 pm, still more preferably from 6 to 15 pm. Smaller the average particle size of the tripolyphosphate, higher the yields because of inhibition •of the agglomeration of the detergent granules. On the other hand, from the aspect of productivity for preparing the detergent granules with small particle sizes in an industrial scale, the average particle size of the tripolyphosphates is preferably 1 pm or more. From the aspect of inhibiting the agglomeration of the detergent granules, the average particle size is preferably 30 pm or less. Here, in the present specification, the average particle size of the tripolyphosphate is evaluated based on volume using a laser diffraction particle size distribution analyzer ("LA-500," manufactured by HORIBA Ltd.).
When the tripolyphosphate is added, the amount of the tripolyphosphate is not particularly limited. The tripolyphosphate is preferably contained in the final

granular product in an amount of 1 to 50-k oy weignc, raore
i
i -. .
preferably from 10 to 40% by weight, particularly j
preferably from 15 to 35% by weight. Here, the finhl
i granular product may mean the detergent granules
themselves when the detergent granules of the present
i
invention are directly used as the detergent composition, or it may mean the final product of the detergent j composition in a case where the detergent granules of the present invention are included as a constituting element of a different detergent composition. Erom the aspect of inhibiting the agglomeration of the detergent granules, the amount of the tripolyphosphate is preferably 2% by weight or more. From the aspect of securing the compositional freedom of the resulting detergent composition, the amount is preferably 50% by weight or less.
Further, in cases where detergent compositions having the alkali metal aluminosilicates as main builder components are prepared, an excess agglomeration can be inhibited by the addition of the alkali metal aluminosilicates in this step. Moreover, the alkali metal aluminosilicate also acts as an aid for disintegrating the agglomerated product with the chopper of the agitation granulator. The alkali metal aluminosilicates have an average particle size of from 1 to 30 pm.

1 Here, in the present specification, the average
particle size of the aluminosilicate is evaluated based on
i
t
volume using a laser diffraction particle size ! distribution analyzer ("LA-500," manufactured by HORIBA
Ltd.).
Also, the amounts of fluorescers, pigments, anti-redeposition agents, granular surfactants, spray-dried powders, diatomaceous earth, calcite, kaolin, bentonite, sodium sulfate, sodium sulfite, and the like are not particularly limited.
The mixers usable in step (a) for blending each of the above components are not particularly limited, and an agitation granulator may be suitably used. The agitation granulators are not particularly limited, and it is preferred that the agitation granulators are equipped with agitation blades and a chopper for disintegration and dispersion. Here, the blades or chopper may be replaced with a functionally equivalent means.
Concrete examples of the agitation granulators usable in the present invention for a batch process include Vertical Granulator (manufactured by Powrex Corp.); High-Speed Mixer (manufactured by Fukae Powtec Kogyo Corp.); L5dige Mixer (manufactured by Matsubo Co., Ltd.); and PLOUGH SHARE Mixer (manufactured by PACIFIC MACHINERY & ENGINEERING Co., LTD.); Gericke Mixer (manufactured by

t I
Meiji Machine Co., Ltd.)/ and the like. Here, preference
is given to the LSdige Mixer and the PLOUGH SHARE Mixer.
i i
Concrete examples of the agitation granulators usable for a continuous process include continuous Lodige Mixer (moderate speed mixer: those having relatively long resistance time); CB recycler (manufactured by Lodige; high-speed mixer: those having relatively short resistance time); Turbilizer (manufactured by Hosokawa Micron Corporation); Shugi Mixer (manufactured by Powrex Corp.); Flow Jet Mixer (manufactured by Funken Powtechs, Inc.), and the like. Incidentally, in the present invention, the above mixers may be suitably used in combination.
Also, it is more preferred that the agitation granulators are equipped with a jacket for adjusting the internal temperature of the granulator and a nozzle for blowing a gas into the agitation granulator.
The extent of mixing in step (a) is not particularly limited, and mixing may be preferably carried out to an extent such that each of the components is uniformly mixed. For instance, in the case where the agitation granulators are used in this jstep, the operating conditions of the agitation granulators may be, for example, the blending time is preferably within five minutes. The agitating speed of the main shaft and the

chopper speed for disintegration and dispersion may be suitably set depending on the kinds of the mixers used. For instance, in the case of mixers for a batch process, the peripheral agitating speed of the main shaft is preferably from 2 to 15 m/s, and the peripheral chopper speed for disintegration and dispersion is preferably from 20 to 60 m/s.
Incidentally, during or after the blending, or at the completion of blending in step (a), water may be added as a reaction initiating agent. By adding the reaction initiating agent, the neutralization reaction can be favorably accelerated. The amount of water added is not particularly limited, and water is added in an amount of preferably from 0.2 to 3 parts by weight, more preferably from 0.5 to 1.5 parts by weight, based on 100 parts by weight of the powdery mixture in step (a). From the viewpoint of initiating the neutralization reaction, the amount of water is preferably 0.2 parts by weight or more, and from the viewpoint of inhibiting the agglomeration of the detergent granules, the amount is preferably 3 parts by weight or less. Incidentally, in cases where the above components, such as the liquid acid precursor of a non-soap, anionic surfactant, contain water, or in!cases where other aqueous starting material solutions are used, or in cases where water-containing powdery starting

materials are used, the amount of water to be added may be determined by considering the water contents of these components.
In addition, as still more preferred reaction initiating agents, an aqueous solution of alkalis may be added. By using an aqueous solution of alkalis as a reaction initiating agent, when compared with water, not only the neutralization reaction can be further favorably accelerated, but also the particle size of the resulting detergent granules can be made small and thus the bulk density of the resulting detergent granules can be made large.
The amount of the aqueous solution of alkalis is preferably from 0.05 to 0.5 times the amount, more preferably from 0.10 to 0.45 times the amount, particularly preferably from 0.15 to 0.40 times the amount, required for neutralizing the liquid acid precursor of a non-soap, anionic surfactant. From the aspect of initiating the neutralization reaction to obtain
! - - ■
desired effects, the amount of the aqueous solution of
alkalis is preferably equal to or greater than 0.05 times
i
the amount required for neutralization, and from the aspect of inhibiting the agglomeration of the detergent
granules, the amount is preferably equal to or less than
I i
0.5 times the amount required for neutralization, t

Incidentally, although the concentration of the aqueous solution of alkalis is not particularly limited, in cases of low concentrations, excess amount of water is supplied to the mixture along with the given amount of the aqueous solution of alkalis, so that the agglomeration of the detergent granules is liable to take place. Therefore, the concentration of the aqueous solution of alkalis is preferably from 20 to 50% by weight, more preferably 30 to 50% by weight, particularly preferably from 40 to 50% by weight.
Also, the kinds of the aqueous solutions of alkalis
usable in the present invention are not particularly
limited. Concrete examples thereof include aqueous sodium
hydroxide, aqueous potassium hydroxide, and the like,
which are aqueous solutions of strong-alkalis which easily
cause neutralization reaction with the liquid acid
precursors of the non-soap, anionic surfactants. Among
them, the aqueous sodium hydroxide is suitably used from
the viewpoint of reduced costs. Also, it is more preferred that the aqueous solutions of alkalis mentioned
above have a pH of 12 or more. I
In addition, mixing in this step may be preferably carried out to an extent such that added the aqueous solution of alkalis is uniformly dispersed.

Step (b)
In step (b), in order to carry out the dry-neutralization process of the non-soap, anionic surfactant, the liquid acid precursor or a mixture of the liquid acid precursor and the inorganic acid is gradually added to the water-soluble, solid alkali inorganic substance. The time required for the addition of the liquid acid precursor or the above mixture depends upon the amount of the liquid acid precursor or the above mixture added and thus cannot be generalized. In the case of employing mixing in a batch process, the time required is generally one minute or more, more preferably from 1 to j 10 minutes, still more preferably 2 to 7 minutes. Here, when the liquid acid precursor or the above mixture is
i
added in an extremely short time, the liquid acids, remain
! --
unreacted accumulate, thereby making it likely to pause
i i
excess agglomeration. Therefore, it is preferred that the liquid acid precursor or the above mixture is added in' one
i
minute or longer ■. !
Also, the liquid acid precursor or the above mixture
I
i ]
may be added continuously or added in multiple stages in separate portions. Also, a plurality of addition means may be provided.
Incidentally, the mixers usable in step (b) are not particularly limited, with a preference given to the

agitation granulators exemplified in step (a).
After the addition of the liquid acid precursor or the above mixture, it is desired that the agitation granulator is operated for additional 30 seconds or more, more preferably one minute or more. By having this additional step, the neutralization reaction and the granulation process can be favorably completed.
In step (b), it is preferred that the neutralization is carried out while blowing a gas into an agitatipn
l
granulator. By blowing a gas into the agitation >
i i
granulator, the excess water produced in the
i
neutralization reaction can be evaporated and the granular product can be cooled with the gas, to thereby inhibit the
a laser diffraction particle size distribution analyzer ("LA-500," manufactured by HORIBA Ltd.).
Also, the operating time of the agitation granulator
in cases where the surface modifiers are added is not
i ..
particularly limited, and the operating time may bej
i i
preferably from 1 to 5 minutes. !
Incidentally, in the method of the present invention,
the optional liquid components may be added depending upon
i
the composition of the detergent compositions to be •
!
obtained (step of adding liquid components). The addition
of the liquid components may be carried out at any stage without particular limitation. For instance, the addition of the liquid components may be carried out prior to or
during the process of the dry-neutralization, or the
addition may be alternatively carried out after the
dry-neutralization. For instance, it is preferred that
the step of adding the liquid components prior to the
addition of the surface modifiers. However, in certain
cases where the detergent granules obtained after the step
of adding the liquid components have excellent
free-flowability and/or excellent storage stability, it is
not necessary to add the surface modifier as a
free-flowing aid.
Examples of the optional liquid components include
any given liquid components usually used in detergent

producing the detergent granules of the present invention
i may further comprise the step of adding a free-flowing aid
to the detergent granules obtained after the dry-neutralizing step, to surface-modify the detergent granules. By surface-modifying the detergent granules, since further improvements in the free-flowability and the storage stability of the resulting detergent granules can be attained, the surface-modifying step is suitably
provided, for instance, in a case where the detergbnt
i
granules of the present invention are included as ja constituting element of a different detergent composition. Specifically, the surface modification can be carried out by adding a given amount of a surface modifier added as a free-flowing aid while blending the detergent granules, in an agitation granulator (surface-modifying step).
The surface modifiers may be any of conventionally known ones, and crystalline or amorphous alkali metal aluminosilicates (zeolite), calcite, diatomaceous earth, silica, and the like may be suitably used. The above aluminosilicates preferably have an average particle size of 10 pm or less. Also, the amount of the surface modifiers in the final detergent composition product is preferably from 2 to 15% by weight, more preferably from 4 to 12% by weight. Incidentally, the average particle size of the surface modifier is evaluated based on volume using

compositions, including liquid nonionic surfactants;
i
.water-soluble polymers, such as polyethylene glycol, acrylic acid-maleic acid copolymers, and the like; fatty acids, and the like. The liquid components may be used singly or a combination of two or more kinds. From the aspect of inhibiting the agglomeration of the detergent composition, the amount of the liquid components may be preferably 15% by weight or less, more preferably 10% by weight or less, of the final detergent composition product.
Further, in the present invention, any of the following known substances generally employed in detergent compositions may be also optionally blended to the detergent granules obtained after the dry-neutralizing step. For instance, these substances may be added prior to the step of adding liquid components and/or to the surface-modifying step. Concrete examples thereof include tripolyphosphates; crystalline or amorphous alkali metal aluminosilicates; crystalline silicates; fluorescers; pigments; anti-redeposition agents, such as polycarboxylate polymers and sodium salt of carboxymethyl cellulose; granular surfactants, such as fatty acids, salts thereof, linear alkylbenzenesulfonates, alkyl sulfates; spray-dried powders, diatomaceous earth, calcite, kaolin, bentonite, sodium sulfate, sodium

sulfite, and the like. The above substances may be optionally used depending upon the function of the granules.
Also, the operating time of the agitation granulator in cases where the step of adding the liquid components precedes the addition of the surface modifiers is not particularly limited, and the operating time may be preferably from 0.5 to 8 minutes.
The methods for producing the detergent granules of the present invention also have the following embodiments as preferred embodiments:
[1] Embodiment further comprising the step of adding one or more liquid components after the dry-neutralizing step. [2] Embodiment further comprising the step of adding a free-flowing aid after the step of adding one or more liquid components in Embodiment [1], to surface-modify the detergent granules.
The hue of the surface-modified, detergent granules obtained by the method described above is not particularly limited. For instance, in the case where the particle size of the surface-modified, detergent granules is evenly sized at 350 to 500 pm and the above detergent granules is analyzed by photoelectric colorimeter, the Hunter Lab coloration is desirably 90 or more in its L value.
In the present invention, the following optional

components may be also included in the detergent composition. The optional components include, for instance, enzymes, perfumes, bleaching agents, pigments, and the like. Such optional components may be formulated by blending the detergent granules obtainable by the method of the present invention with optional components using mixers, such as a rotary mixer.
Modes for carrying out the present invention are not limited to the above methods. In other words, the present invention is applicable for the known methods for producing powdery detergent compositions having high bulk density obtained by the dry-neutralization process of the liquid acid precursor of an anionic surfactant and for known methods for producing the commercial products of the high-bulk density detergent compositions.
In general, the particle size of the detergent granules obtained by the dry-neutralization process increases as the proportion of the non-soap, anionic surfactant increases. Also, similarly, the particle size tends to increase as the proportions of the other liquid starting materials, such as nonionic surfactants and polymer solutions, increase. For instance, among 'the detergent granules obtainable by the dry-neutralization process having extremely high proportion of the anionic surfactant, in the case where the proportion of the

detergent granules having suitably small particle size is low, by entirely pulverizing all of the obtained neutralized granules in the presence of a pulverizing aid, and then classifying the granules, the detergent granules of the desired particle size range can be obtained at high yields. Also, when the proportions of the other liquid starting materials, such as nonionic surfactants and polymer solutions, are increased, the detergent granules having suitably small particle size can be obtained at high yieldsi
Also, the detergent granules obtainable by the method of the present invention may be included as a constituting element of a different detergent composition.
In addition, in the present invention, the liquid acid precursor of a non-soap, anionic surfactant, the water-soluble, solid alkali inorganic substance, and the inorganic acid may be blended by adding all of the components at once. In this case, the blending process and the neutralization and granulation process are concurrently carried out. This embodiment is highly suitable for the method of blending in a continuous process.
The detergent granules of the present invention thus obtained comprise one or more non-soap, anionic surfactants and one or more inorganic salts undetectable

by X-ray diffraction method, wherein the molar ratio of [inorganic salts undetectable by X-ray diffraction method]/[non-soap, anionic surfactants] is from 0.1 to
1.0.
The biggest feature of the detergent granules of the present invention is in that the above inorganic salt is undetectable by X-ray diffraction method. In the present specification, the phrase "undetectable by X-ray diffraction method" means that the material does not have a definite diffraction peak in X-ray diffraction patterns, and that the identification of peaks cannot be made even when using any of diffraction patterns reported, for instance, in Japan Committee on Powder Diffraction Standards (JCPDS). Incidentally, in X-ray diffraction patterns, in certain cases, no definite diffraction peaks but indefinite diffraction halo patterns may be observed. However, even in such cases it cannot be said to be detectable by X-ray diffraction method. Typical examples of the inorganic salts include sodium sulfate (Glauber's salt).
For instance, since the detergent granules of Comparative Example 13, which can be produced without using the method of the present invention, contain powdery sodium sulfate (Na2S04) obtained without using a method of the present.invention, diffraction peaks shown in Figure 1

are detectable in X-ray diffraction patterns of the detergent granules. These diffraction peaks are identified as sodium sulfate, for instance, by No. 37-1465 of JCPDS (Figure 2). Also, as shown in Figure 3, the amount of the powdery sodium sulfate can be determined by preparing a calibration curve of the powdery sodium sulfate and the peak intensities of the X-ray diffraction peaks. By contrast, as typically exemplified by Example 12, in the detergent granules of the present invention,
diffraction peaks ascribed to any of the diffraction
i
V
patterns of sodium sulfate are undetectable by X-ray diffraction method even though sodium sulfate can be chemically determined by the method described above (Figure 4), thereby making it impossible to identify the sodium sulfate by X-ray diffraction method.
On the other hand, the content of the inorganic salt in the detergent granules can be chemically determined, for instance, by analyzing means, such as ion chromatography. For example, in a case where the inorganic salt is a sulfate, it is possible to determine the sulfate contained in the detergent granules by using a calibration curve of sulfate ions prepared in advance. Similarly in the detergent granules of the present invention, the sulfate contained in the detergent granules can be determined as shown in Figure 5. Also, the non-

soap, anionic surfactant can be determined, for instance, by carrying out a qualitative analysis method and a quantitative analysis method of the anionic surfactants in a synthetic detergent testing method (according to JIS K3362).
In the case where inorganic salts, such as powdery
i
sodium sulfate and powdery sodium phosphate, obtained by the process other than the dry-neutralization process in the method of the present invention, are not used at all as the starting material, since the inorganic salts, such as sodium sulfate and sodium phosphate, contained in the detergent granules and formed by the method of the present invention are undetectable by X-ray diffraction method, the amount of the inorganic salts chemically determined would be considered as "the amount of the inorganic salts undetectable by X-ray diffraction method." Therefore, the molar ratio of [inorganic salts undetectable by X-ray diffraction method]/[non-soap, anionic surfactants] can be calculated from the amount of the inorganic salts and the amount of the non-soap, anionic surfactant determined by the methods described above. Incidentally, even in cases where, for instance, the powdery sodium sulfate mentioned above and the detergent granules of the present invention are mixed to give a desired detergent composition, the amount of the inorganic salt undetectable by X-ray

diffraction method can be calculated by the difference in the amounts of sodium sulfate shown in Figure 5 and Figure 3, and the above molar ratio can be calculated from this value.
The detergent granules of the present invention comprise one or more non-soap, anionic surfactants and one or more inorganic salts undetectable by X-ray diffraction method, wherein the molar ratio of [inorganic salts undetectable by X-ray diffraction method]/[non-soap, anionic surfactants] is from 0.1 to 1.0. From the aspect of suppressing the tackiness of the granules, the molar ratio is preferably 0.1 or more, and from the aspect of securing the compositional freedom of the detergent composition, the molar ratio is preferably 1.0 or less.
The detergent granules of the present invention mentioned above have the properties of (1) having extremely low tackiness of the granules, and (2) having a large number of micropores. The properties of the detergent granules of the present invention will be described in detail below.
(1) Low Tackiness
The detergent granules of the present invention show
extremely low tackiness of the granules. This tackiness
* is dependent upon the molar ratio of the inorganic salt to

the non-soap, anionic surfactant: Larger the molar ratio of the inorganic salt to the non-soap, anionic surfactant, lower the tackiness of the granules.
In the present specification, the tackiness of the granules can be evaluated by a fracture load of the compression molding product of the granules as detailed below. A cylinder having 40 mm in diameter is uniformly charged with a 40 g sample, and a 1 kg load is applied with a piston, and the piston-charged cylinder is allowed to stand for three minutes, to thereby mold the granules into cylindrical.shapes. The molded samples are taken out of the cylinder. Thereafter, a force required for breaking the molded sample is measured by using a rheometer (manufactured by Fudohkogyo K.K.), and this force is defined as the fracture load. In general, smaller the value of the fracture load, smaller the tackiness of the granules and less the agglomeration being caused. The fracture load varies depending upon the amounts formulated, and the values of the fracture load of the detergent granules of the present invention are lower than those of the detergent granules with similar compositions to the present invention except for not using the inorganic salt used in the method of the present invention, thereby showing improvements of the tackiness of the granules in the detergent granules of the present

invention.
The detergent granules obtained by the method of the present invention comprise a composite layer containing the inorganic salt and the non-soap, anionic surfactant in the outer layer of the granules. Also, since the
inorganic salts are present in relatively larger amounts
i at near the surface of the detergent granules than in the
inner portion of the detergent granules, the tackiness of
the granules can be suppressed.
As an example of methods of confirming the states of the above detergent granules includes a method of utilizing both Fourier transform infrared spectroscopy (FT-IR) and photoacoustic spectroscopy (PAS) (simply abbreviated as "FT-IR/PAS"). FT-IR/PAS is described in "APPLIED SPECTROSCOPY," Vol.47, p.1311-1316 (1993). In this method, spectra taken in the direction of from the surface to the depths of the samples can be measured without changing the shapes of the samples, so that it is possible to identify the distribution states of the substances at any given depths from the surface of the detergent granules.
The concrete measurement method is as follows.
A cell is charged with samples to conduct FT-IR/PAS measurement, and the measurement points taken at any depths up to about 20 pm from the surface are analyzed.

More concretely, in the phase modulation FT-IR/PAS:spectra at a constant phase modulation frequency, a magnitude speqtrum at given phase angle is obtained, by synchronously analyzing PAS spectral components at a given phase angle and at an angle with a 90° phase shift from the given phase angle. The FT-IR spectrum is measured, for instance, by using an infrared spectrometer "FTS-60A/896" (manufactured by Bio-Rad Laboratories), and the PAS cell includes an acoustic detector "Model 300" manufactured by MTEC Corporation. Scanning with an interferometer is conducted by a step-scan method, and the modulation frequency is set at 2.5 kHz. Peak intensities can be detectable from the typical spectra for the sodium linear alkylbenzenesulfonate (LAS-Na) and sodium sulfate respectively detectable at 1222 cm"1 (S03 anti-symmetric stretching vibration) and 1149 cm"1 (S04 stretching vibration).
A typical example of the FT-IR/PAS measurement is shown in Figure 6. As is clear from in Figure 6, in the case of the detergent granules obtainable in Example 11, the relative intensity of the peaks ascribed to sodium sulfate, an inorganic salt (namely, the ratio between the peak intensity of sodium sulfate and the peak intensity of the LAS-Na) is high in the surface layer of the granules when compared to the sodium sulfate which is present in

the inner portion of the granules, i.e. the detergent granules have relatively large contents of the inorganic salt in the surface layer. By contrast, in the case of the detergent granules obtainable in Comparative Example 11, the peak intensity ascribed to the inorganic salt shows substantially no changes in the direction of,from the depths of the inner portion of the granules to the outer layer of the granules, and when compared with
Example 11, the peak intensity value is low and cohstant.
i
In addition, the tackiness of the granules (evaluated by
i
the Values of the fracture load) of each of the detergent
granules is 673 gf for the detergent granules of Example
i
11 in contrast to 1124 gf for the detergent granules of Comparative Example 11, showing that the detergent granules of the present invention are low-tackiness granules by forming an inorganic salt on the surfaces of the granules by dry neutralization.
(2) Microporosity
The detergent granules of the present invention feature in having a large number of micropores in the granules as well as having the low tackiness mentioned above. By having a larger number of micropores in the granules, the liquid content which can be retained in the micropores in the granules increases, so that excess

agglomeration of the granules owing to the bleeding out of
t i
the liquid starting materials during the production of granules can be presumably suppressed. The microporous
capacity in the granules can be measured, for instance, by
i known mercury pressure method (for example, a mercury
porosimeter "PORESIZER 9320," manufactured by Shimadzu
Corporation). The detergent granules of the present
invention have a microporous capacity larger than that of
the detergent granules obtained by conventional method of
dry neutralization.
In order to illustrate the effects of amount of the
microporous capacity, Example 18 and Comparative Example
16 may be compared as shown in Figure 7. Figure 7 is a
graph showing the relationship of the microporous diameter
and the microporous capacity of the detergent compositions
obtained in Example 18 and in Comparative Example 16. The
microporous diameter is measured by a mercury porosimeter
"PORESIZER 9320," manufactured by Shimadzu Corporation,
and the microporous capacity is measured by mercury
pressure method. The entire microporous capacity of the
detergent composition obtained in Example 18 is
0.402 mL/g, and the entire microporous surface areas of
the detergent composition are 0.711 m2/g. Also, the entire
microporous capacity of the detergent composition obtained
in Comparative Example 16 is 0.327 mL/g, and the entire

microporous surface areas of the detergent composition are
i
0.547 m2/g.
In Comparative Example 16, the molar ratio of the inorganic acid to the liquid acid precursor of a non-soap, anionic surfactant is 0.04, smaller than the lower limit in the present invention. On the other hand, in Example 18, the detergent granules are produced by dry neutralization under the conditions that the molar ratio of the inorganic acid to the liquid acid precursor of a non-soap, anionic surfactant is 0.44. When the entire microporous capacity and the microporous surface areas of both of the detergent granules are compared, all of the values are larger in the detergent granules of Example 18 than those in the detergent granules of Comparative Example 16. Also, the average particle size of the detergent granules is 493 \im for Example 18 whereas the average particle size is 1313 pm for Comparative Example 16. From these results, since the detergent granules of Example 18 have larger entire microporous capacity and entire microporous surface area than those of Comparative Example 16, the liquid content which can be retained in the micropores in the granules increases, so that excess agglomeration of the granules owing to the bleeding out of the liquid starting materials during the production of granules can be presumably suppressed.

In the case where the detergent granules are designed or produced utilizing the above features of the detergent granules of the present invention, the detergent granules of the following embodiments can be suitably used according to its utility. Specifically, the preferred embodiments are as follows.
(1) The detergent granules comprising one or more non-soap, anionic surfactants and one or more inorganic salts undetectable by X-ray diffraction method, wherein the amount of the non-soap, anionic surfactant is in an amount of 28% by weight or more and less than 50% by weight, and a molar ratio of [inorganic salts undetectable by X-ray diffraction method]/[non-soap, anionic surfactants] is from 0.1 to 1.0.
(2) The detergent granules comprising one or more non-soap, anionic surfactants and one or more inorganic salts undetectable by X-ray diffraction method, wherein the amount of the non-soap, anionic surfactant in an amount of 10% by weight or more and less than 28% by weight in the detergent granules, and a molar ratio of [inorganic salts undetectable by X-ray diffraction method]/[non-soap, anionic surfactants] is from 0.3 to 1.0.
Detergent Granules of Embodiment (1)

In general, in the detergent granules containing large amounts of the non-soap, anionic surfactant, it is difficult to produce the granules having excellent free-flowability with small particle sizes, because the agglomeration of the granules is likely to take place owing to the tackiness inherently owned by the non-soap, anionic surfactant. Therefore, in the case, for instance, where the detergent granules are produced by conventional method, the tackiness of the granules is likely to be impaired during the production of the detergent granules when the content of the non-soap, anionic surfactant is relatively large, for example, when the content is 20%" by weight or more in the granules, more remarkably 28% by weight or more and less than 50% by weight, particularly remarkably 30% by weight or more and less than 50% by 1 weight.
Therefore, it is preferred from the aspect of
strongly exhibiting the effects of suppressing the
i
; tackiness of the granules that the detergent granules of the present invention comprise one or more non-soap, anionic surfactants and one or more inorganic salts:
i
undetectable by X-ray diffraction method, wherein the
t
1 amount of the non-soap, anionic surfactant is in an; amount
of 28% by weight or more and less than 50% by weight, and
a molar ratio of [inorganic salts undetectable by X-ray

diffraction method]/[non-soap, anionic surfactants] is from 0.1 to 1.0. Also, in the detergent granules, the molar ratio of [inorganic salts undetectable by X-ray diffraction method]/[non-soap, anionic surfactant] is more preferably from 0.1 to 0.8, still more preferably from 0.15 to 0.65, still more preferably from 0.2 to 0.6, still more preferably from 0.25 to 0.55.
Detergent Granules of Embodiment (2)
Also, when the microporous capacity of the granules is studied, since the detergent granules of the present invention have a large microporous capacity, the liquid components, such as nonionic surfactants, can be included in larger amounts in the micropores. From the above aspect of containing larger amounts of the liquid components, such as nonionic surfactants, the detergent granules comprise one or more non-soap, anionic j surfactants and one or more inorganic salts undetectable by X-ray diffraction method, wherein the amount of 'the non-soap, anionic surfactant in an amount of 10% by weight or more and less than 28% by weight in the detergent granules, and a molar ratio of [inorganic salts undetectable by X-ray diffraction method]/[non-soap, anionic surfactants] is from 0.3 to 1.0, may be used in a preferred embodiment. In the detergent granules, the non-

soap, anionic surfactant is contained in the detergent granules in an amount of more preferably 15% by weight or more and less than 28% by weight, still -more preferably from 15 to 26% by weight. From the aspect of giving high washing power, the amount of the non-soap, anionic surfactant in the detergent granules is preferably 10% by weight or more. From the aspect of suppressing the foaming of the detergent composition upon use, the amount is preferably less than 28% by weight. Also, the detergent granules in this embodiment have a molar ratio [inorganic salts undetectable by X-ray diffraction method]/[non-soap, anionic surfactants] of more preferably
from 0.3 to 0.8, still more preferably 0.35 to 0.7.
i _
The detergent granules of the present invention
i i
having the properties mentioned above may be used as such
i i
as a high-bulk density detergent composition, or they
i
detergent granules may be used as one of components constituting a detergent composition.
The amount of the liquid acid precursors of a \ non-soap, anionic surfactants can be suitably set depending upon the composition of the desired detergent composition. The amount of the liquid acid precursors of anionic surfactants may be so added to include the anionic surfactants produced by the neutralization reaction in the final detergent composition product in an amount of

preferably from 5 to 50% by weight, more preferably from 5 to 45% by weight, still more preferably from 10 to 40% by weight, particularly preferably from 20 to 40% by weight, within which range the effects of the present invention can be remarkably exhibited, which become particularly remarkable when the amount of the anionic surfactant is large.
Also, it is more desired that the detergent granules of the present invention or the high-bulk density
detergent composition containing the detergent granules
i
obtainable by the method of the present invention having a
i
bulk density of 500 g/L or more have the following properties.
Having a bulk density of preferably from 650 to 950 g/L, more preferably from 700 to 900 g/L. In the present specification, the bulk density is a value evaluated by the method defined in JIS K 3362;
Having an average particle size, from the aspect of solubility rate of the detergent granules, of preferably 850 pm or less, more preferably from 300 to 800 pm. The proportion of the particles of 1400 pm or less, namely the percentage of 1400 pm-pass particles, may vary in their suitable ranges depending upon the concentration of the non-soap, anionic surfactant in the resulting high-bulk density detergent composition. For instance, when the

concentration of the non-soap, anionic surfactant ijs from
35 to 40% by weight, the percentage of 1400 pm-pass
i
particles is preferably 60% or more, more preferably 70%
or more. When the concentration of the non-soap, anionic
i
surfactant is less than 35% by weight, the percentage of 1400 pm-pass particles is preferably 75% or more, more
preferably 80% or more. In the present specification, the
l
average particle size is evaluated from the weight i percentages depending on the sizes of the sieves after vibrating a standard sieve according to JIS K 8801 for five minutes, and the percentage of 1400 pm-pass particles means the weight percentage of the proportion occupied by the particles of 1400 pm or less; and
Having a free-flowability in terms of flow time of preferably 8 seconds or less, more preferably 7 seconds or less. In the present specification, the free-flowability is defined as a time period required for discharging 100 ml of powder from a hopper used in a measurement of bulk density according to JIS K 3362.
EXAMPLES The present invention will be explained in further detail by means of the following working examples, without intending to limit the scope of the present invention thereto.

Example 1
The detergent composition having the composition shown in Table 1 was prepared in an amount of 35 kg for
each unit using a high speed mixer "Lodige Mixer FIJM-130D"
i
(manufactured by Matsubo Co., Ltd.). This mixer was equipped with agitator blades and a shearing device, the shearing device corresponding to a chopper for disintegration and dispersion.
Here, the detergent composition was prepared by the following procedures as detailed below.
Powder Blending
The solid ingredients consisting of 7.0 parts by weight of sodium tripolyphosphate (STPP; average particle size: 11.2 pm), 12.61 parts by weight of sodium carbonate ("LIGHT ASH," manufactured by Central Glass Co., Ltd.; average particle size: 56.1 \xm), and 0.11 parts by weight of a fluorescer were blended for one minute under the conditions of a rotational speed of agitator blades of 130 rpm (peripheral speed: 3.4 m/s) and a rotational speed of shearing device of 2850 rpm (peripheral speed: 27 m/s) by the Lodige Mixer.
Addition of Reaction Initiating Agent
Water was added to the contents in the mixer in an

amount of 0.20 parts by weight as a reaction initiating
agent, and the blending was carried out for one minute and
thirty seconds under the same blending conditions as
above.
Neutralization
While the mixer was operated under the same conditions as above, a mixture of 10.92 parts by weight of a linear alkylbenzenesulfonic acid (LAS; molecular weight: 322) and 0.23 parts by weight of 98% by weight sulfuric acid were added to the contents in the mixer in four minutes, the mixture being prepared in advance. During the addition, the ingredients were cooled by allowing water to flow through the mixer jacket at 25 °C. At this stage, the temperature rose to 75°C. Incidentally, during this stage, the reaction mixture remained in a particulate form. Incidentally, the LAS mentioned above, obtained by S03 gas sulfonation method, contained 0.16 parts by weight of sulfuric acid. In other words, the resulting mixture contained 0.05 mol of sulfuric acid per mol of the LAS. Also, the proportion of sulfuric acid to the LAS during neutralization reaction was such that the reaction mixture contained 0.12 mol of sulfuric acid per mol of the LAS. The amount of sodium carbonate was about six times the amount required for neutralizing the LAS and sulfuric

acid.
After the addition of the LAS, the mixer was continuously operated under the same conditions for one minute to complete the neutralization reaction and the granulation process.
Addition of Liquid Ingredients and Surface Modification
At a point where the neutralization reaction and the granulation process were completed, an aqueous solution of a 40% by weight acrylic acid-maleic acid copolymer was added to the mixer with an effective amount of the copolymer being 0.18 parts by weight, while the mixer was operated under the same conditions as above, and the ingredients were mixed for one minute and thirty seconds. Thereafter, the resulting mixture was subjected to a surface modification by adding 4.20 parts by weight of zeolite having an average particle size of 4 ym to the mixer as a surface modifier, and operating the mixture for additional two minutes. Incidentally, the zeolite contained 0.84 parts by weight, of a crystal water.
The resulting granules of the detergent composition, prior to the after-blending step, had the following properties:
Percentage of particles with 1400 pm-pass: 75.3%;
Average particle size: 633 jam;

properties.
After-Blending
Using a rotary mixer, 0.18 parts by weight of enzyme granules and the detergent composition prepared above were blended, and thereafter 0.07 parts by weight of perfume were sprayed, to give a final powdery product of the high-bulk density detergent composition.
Example 2
Similar procedures to those in Example 1 were carried
out except for respectively changing the amounts of LIGHT
ASH and sulfuric acid to 12.45 parts by weight and I
i 0.57 parts by weight, to give a detergent composition.
The resulting granules of the detergent composition,
i prior to the after-blending step, had the following
i
properties: i
i

Incidentally, the proportion of sulfuric acid to the LAS during neutralization reaction was such that the reaction mixture contained 0.23 mol of sulfuric acid per mol of the LAS. The amount of sodium carbonate was about five times the amount required for neutralizing the LAS and sulfuric acid.
l
Example 3 . ;
Similar procedures to those in Example 1 were carried
out except for respectively changing the amounts of LIGHT
ASH and sulfuric acid to 12.33 parts by weight and '
i i
0.82 parts by weight, to give a detergent compositipn.
The resulting granules of the detergent composition, prior to the after-blending step, had the following! properties:

Accordingly, the granules showed excellent properties.
Incidentally, the proportion of sulfuric acid to the LAS during neutralization reaction was such that the reaction mixture contained 0.3 mol of sulfuric acid per mol of the LAS. The amount of sodium carbonate was about four times the amount required for neutralizing the LAS
and sulfuric acid.
Example 4 . i
i Similar procedures to those in Example 1 were; carried
out except for respectively changing the amounts of LIGHT
ASH, the LAS, and sulfuric acid to 11.11 parts by weight,
12.29 parts by weight, and 0.80 parts by weight, to give a
detergent composition. Incidentally, the LAS mentioned
i i
above contained 0.18 parts by weight of sulfuric acid.
The resulting granules of the detergent composition, prior to the after-blending step, had the following properties:
Percentage of particles with 1400 pm-pass: 70.0%;
Average particle size: 703 pun;
Bulk density: 694 g/L;

Incidentally, the proportion of sulfuric acid to the LAS during neutralization reaction was such that the reaction mixture contained 0.27 mol of sulfuric acid per mol of the LAS. The amount of sodium carbonate was about four times the amount required for neutralizing the LAS and fiul furic ncid.
Example 5
The detergent composition having the composition shown in Table 1 was prepared in an amount of 35 kg for each unit using a high speed mixer "LOdige Mixer FKM-130D" (manufactured by Matsubo Co., Ltd.). This mixer was equipped with agitator blades and a shearing device, the shearing device corresponding to a chopper for di .'j In Ley ration and dispersion.
Here, the detergent composition was prepared by the following procedures as detailed below.
Powder Blending

The solid ingredients consisting of 20.06 parts by weight of sodium carbonate ("LIGHT ASH/' manufactured by Central Glass Co., Ltd.; average particle size: 56.1 pm) were blended for one minute under the conditions of a rotational speed of agitator blades of 130 rpm and a rotational speed of shearing device of 2850 rpm by the LOdige Mixer.
Addition of Reaction Initiating Agent
Water was added to the contents in the mixer in an amount of 0.25 parts by weight as a reaction initiating agent, and the blending was carried out for one minute and thirty seconds under the same blending conditions as above.

mixture remained in a particulate form. Incidentally, the LAS mentioned above contained 0.16 parts by weight of sulfuric acid. Also, the proportion of sulfuric acid to the LAS during neutralization reaction was such Jhat the reaction mixture contained 0.3 mol of sulfuric acid per mol of the LAS. The amount of sodium carbonate was about seven times the amount required for neutralizing the LAS and sulfuric acid.
After the addition of the LAS, the mixer was continuously operated under the same conditions for one minute to complete the neutralization reaction and the granulation process.
The resulting granules of the detergent composition had the following properties:
Percentage of particles with 1400 pm-pass: 81.0%;
Average particle size: 604 prn;
Bulk density: 707 g/L;
Free-flowability: 6.5 seconds; and
Hue: 91.1.
Accordingly, the granules showed excellent properties.
Example 6
Similar procedures to those in Example 3 were carried

out except for not containing sodium tripolyphosphate at all and thus making zeolite as a main builder component, to give a detergent composition.
The resulting granules of the detergent composition,
prior to the after-blending step, had the following
i properties:
Percentage of particles with 1400 pm-pass: 83,9%;
*
Average particle size: 536 pm;
Bulk density: 737 g/L; Free-flowability: 6.3 seconds; and Hue: 90.2.
Accordingly, the granules showed excellent; properties.
Example 7
Similar procedures to those in Example 3 were carrxeu
out except for using sodium tripolyphosphate having an
average particle uixe of 58.4 pin, to give a detergent oonipou I V I on -
The ruttultliuj grunulaa o£ the detergent composition, prior to the after-blending step, had the following properties:
Percentage of particles with 1400 pnwpase: 82.3%;
Average particle size: 532 pm;

Bulk density: 760 g/L; Free-flowability: 6,3 seconds; and Hue: 90-8.
Accordingly, the granules showed excellent properties.
Comparative Example 1

powder Blending
'"'■■" Gv
The solid ingredients consisting of 7,0 parts by
weight of sodium tripolyphosphate (STPP? average particle size: 11,2 pm), 12.6& parts py weight of sodium carbonate ("LIGHT ASH/' manufacture^ by Central Glass Co., Ltd.; average particle size: 56.1 pro), and 0.11 parts by weight
of a fluorescer were blended for one minute under the 1 i

conditions of a rotational speed of agitator blades of 130 rpm and a rotational speed of shearing device of 2850 rpm by the L6dige Mixer.
Addition of Reaction Initiating Agent
Water was added to the contents in the mixer in an amount of 0.20 parts by weight as a reaction initiating agent, and the blinding was carried out for one minute and thirty seconds under the same blending conditions as above.
Neutralization
While the mixer was operated under the same conditions as above, 10.92 parts by weight of a linear alkylbensenesulfonic acid (LAS) were added to the contents in the mixer in four minutes. During the addition, the ingredients were cooled by allowing water to flow through the mixer jacket at 25°C. At this stage, the temperature rose to 73°C. Incidentally, during this stage, the reaction mixture remained in a particulate form. Incidentally, the LAS mentioned above contained 0.16 parts by weight of sulfuric acid. Also, the proportion of sulfuric acid to the LAS during neutralization reaction was such that the reaction mixture contained 0.05 mol of sulfuric acid per mol of the LAS.

After the addition of the LAS, the mixer was continuously operated under the same conditions for one minute to complete the neutralization reaction and the granulation process. The breaking load of the granules obtained in this Example was 1215 gf, and the average particle size of the granules was 1114 pm.
Addition of Liquid Ingredients and Surface; Modification
At a point where the neutralization reaction and the granulation process were completed, an aqueous solution of a 40% by weight acrylic acid-maleic acid copolymer was added to the mixer with an effective amount of the copolymer being 0.18 parts by weight, while the mixer was operated under the same conditions as above, and the ingredients were mixed for one minute and thirty seconds.
Thereafter, the resulting mixture was subjected *to a surface modification by adding 4.20 parts by weight of zeolite having an average particle size of 4 pm to the mixer as a surface modifier, and operating the mixture for additional two minutes. Incidentally, the zeolite contained 0.84 parts by weight of a crystal water.
The resulting granules of the detergent composition, prior to the after-blending step, had the following properties:
Percentage of particles with 1400 pm-pass: 67.4%-;

Average particle size: 739 pm; Bulk density: 830 g/L; Free-flowability: 6.1 seconds; and Hue: 91.6.
Accordingly, the granules gave notably poorer results in the percentage of particles with 1400 pm-pass and in the average particle size than the granules of Examples.
After-Blending
Using a rotary mixer, 0.18 parts by weight of enzyme granules and the detergent composition prepared above were blended, and thereafter 0.07 parts by weight of perfume were sprayed, to give a final powdery product of the high-bulk density detergent composition.
Inc.; J dentally, the amount oi t;od i uiu cuboiui te w.i.s about seven times the amount required for neutralizing the liAJi ciml HUHUI UJ Comparative Example 2
The detergent composition having the composition shown in Table 2 was prepared in an amount of 35 kg for each unit using a high speed mixer "LOdige Mixer FKM-130D" (manufactured by Matsubo Co., Ltd.). This mixer was equipped with agitator blades and a shearing device, the

shearing device corresponding to a chopper for disintegration and dispersion.
Here, the detergent composition was prepared by the following procedures as detailed below.
Powder Blending
The solid ingredients consisting of 7.0 parts by weight of sodium tripolyphosphate (STPP; average particle size: 11.2 pm), 11.53 parts by weight of sodium carbonate ("LIGHT ASH," manufactured by Central Glass Co., Ltd.; average particle size: 56.1 pm), 0.11 parts by weight of a fluorescer, and 1.16 parts by weight of sodium sulfate (prepared by pulverizing to an average particle size of 8.22 pm by a hammer mill) were blended fox- one minute . under the conditions of a rotational speed of agitator blades of 130 rpm and a rotational speed of shearing device of 2850 rpm by the LGdige Mixer.
Addition of Reaction Initiating Agent
Water was added to the contents in the mixer in an amount of 0.20 parts by weight as a reaction initiating agent, and the blending was carried out for one minute and thirty seconds under the same blending conditions as above.

Neutralization
While the mixer was operated under the same conditions as above, 10.92 parts by weight of a linear alkylbenzenesulfonic acid (LAS) were added to the contents in the mixer in four minutes. During the addition, the Inyrodlpiil n WPIO finnlorl by nl Irjwlny wnlor \o flow through the mixer jacket cit 25°C. At this stage, the temperature
rose to 72°C. Incidentally, during this stage, the reaction mixture remained in a particulate form. Incidentally, the LAS mentioned above contained 0.16 parts by weight of sulfuric acid. Also, the proportion of sulfuric acid to the LAS duriny neutralization react.on was such that the reaction mixture contained 0.05 mol of sulfuric acid per mol of the LAS.
After the addition of the LAS, the mixer was continuously operated under the same conditions for one minute to complete the neutralization reaction and the granulation process.
Addition of Liquid Ingredients and Surface Modification
At a point where the neutralization reaction and the
granulation process were completed, an aqueous 'solution of
a 40% by weight acrylic acid-maleic acid copolymer was added to the mixer with an effective amount of the copolymer being 0.18 parts by weight, while the mixer was

operated under the same conditions as above, and the ingredients were mixed for one minute and thirty seconds. Thereafter, the resulting mixture was subjected to a surface modification by adding 4.20 parts by weight of /,ool i to hnviruj nn nvorngo pnrtfole ni 7,o of 4 pin to tho mlxor OB a surface* modifier, and oporatincj the mixture for additional two minutes. Incidentally, the zeolite contained 0.84 parts by weight of a crystal water.
The resulting granules of the detergent composition, prior to the after-blending step, had the following properties:
Percentage of particles with 1400 pm~pass: 68.0%;
Average particle size: 720 pm;
Bulk density: 786 g/L;
Free-flowability: 6.3 seconds; and
Hue: 90.8.
Accordingly, the granules gave notably poorer results in the percentage of particles with 1400 pm-pass and in the average particle size than the granules of Examples.
After-Blending
Using a rotary mixer, 0.18 parts by weight of enzyme
granules and the detergent composition prepared above were
blended, and thereafter 0.07 parts by weight of perfume

were sprayed, to give a final powdery product of the high-bulk density detergent composition.
f n<: dmi t rt i y l.hn ninoui j o nod win cnr honntc w.irt nhntil wiwun muu nun mint cmjti cul f n itm in-> LAS and sulfuric acid.
Comparative Example 3
The detergent composition having the composition shown in Table 2 was prepared in an amount of 35 kg for each unit using a high speed mixer "Lttdigo Mixer FKM-130D" (manufactured by Matsubo Co., Ltd.)* This mixer was equipped with agitator blades and a shearing device, the shearing device corresponding to a chopper for
disintegration and dispersion.
e Here, the detergent composition was prepared by the
following procedures as detailed below*
Powder Blending
The solid ingredients consisting of 7.0 parts by weight of sodium tripolyphosphate (STPP; average particle size: 11.2 pm), 11.43 parts by weight of sodium carbonate ("LIGHT ASH," manufactured by Central Glass Co., Ltd.; average particle size: 56.1 pm), and 0.11 parts by weight
r
of a fluorescer were blended for one minute under the
i ■
conditions of a rotational speed of agitator blades of

130 rpm and a rotational speed of shearing device of 2850 rpm by the LOdige Mixer•
Addition of Reaction Initiating Agent
Water was added to the contents in the mixer in an amount of 0.20 parts by weight as a reaction initiating agent, and the blending was carried out for one minute, and thirty seconds under the same blending conditions as above.
Neutralization
While the mixer was operated under the same conditions as above, 12.29 parts by weight of a linear alkylbenzenesulfonic acid (LAS) were added to the contents in the mixer in four minutes. During the addition, the ingredients were cooled by allowing water to flow through the mixer jacket at 25°C. At this stage, the temperature rose to 73°C. Incidentally, during this stage, the reaction mixture remained in a particulate form. Incidentally, the LAS mentioned above contained 0.18 parts by weight of sulfuric acid. Also, the proportion of sulfuric acid to the LAS during neutralization reaction was such that the reaction mixture contained 0.05 mol of sulfuric acid per mol of the LAS.
After the addition of the LAS, the mixer was

continuously operated under the &ame condi tionn for ono minute to complete the neutralization reaction and the
granulation process.
Addition of Liquid Ingredients and Surface Modification
At a point where the neutralization reaction and the granulation process were completed, an aqueous solut on of a 40% by weight acrylic acid-maleic acid copolymer was added to the mixex" with an effective amount of the copolymer being 0.18 parts by weight, while the mixer was operated under the same conditions as above, and the ingredients were mixed for one minute and thirty seconds. Thereafter, the resulting mixture was subjected to a surface modification by adding 4.20 parts by weight of zeolite having an average particle size of 4 pm to the mixer as a surface modifier, and operating the mixture for
additional two minutes. Incidentally, the zeolite contained 0.84 parts by weight of a crystal water.
The resulting granules of the detergent composition, prior to the after-blending step, had the following properties:
Percentage of particles with 1400 pm~pass: 32.5%;
Average particle size: 1469 pm;
Bulk density: 736 g/L;
Free-flowability: 6.4 seconds; and

Huts: 91.4.
Accordingly, the granules gave notably poorer results in the percentage of particles with 1400 pm-pass than the granules of the present invention, having a large proportion of coarse particles.
After-Blending
Using a rotary mixer, 0.18 parts by weight Bf enzyme granules and the detergent composition prepared above were blended, and thereafter 0.07 parts by weight of perfume were sprayed, to give a final powdery product of the high-bulk density detergent composition.
In this Comparative Example, the amount of sodium carbonate was about five times the amount required for neutralizing the LAS and sulfuric acid.
Comparative Example 4
The detergent composition having the composition shown in Table 2 was prepared in an amount of 35 kg for each unit using a high speed mixer "LOdige Mixer FKM-130D" (manufactured by Matsubo Co., Ltd.). This mixer was
equipped with agitator blades and a shearing device, the shearing device corresponding to a chopper for disintegration and dispersion.

Here, the detergent composition was prepared by the following procedures as detailed below.
Powder Blending
The uolid ingredients cons it* ting of 7. 0 parts by wolyht. of ttotl J urn t r 1 polyphosphate* ( BTl'S'; ovtunya prtrtlola size: 58.4 ym), 12.69 parts by weight of sodium carbonate
("LIGHT ASH," manufactured by Central Glass Co., Ltd.; average particle size: 56.1 pm), and 0.11 parts by weight of a fluorescer wore blended for one minute under the conditions of a rotational speed of agitator blades of 130 rpm and a rotational speed of shearing device of 2850 rpm by the Lttdige Mixer.
*
Addition of Reaction Initiating Agent
Water was added to the contents in the mixer in an amount of 0.20 parts by weight as a reaction initiating agent, and the blending was carried out for one minute and thirty seconds under the same blending conditions as above.
Neutralization
While the mixer was operated under the same conditions as above, 10.92 parts by weight of a linear alkylbenzenesulfonic acid (LAS) were added to the contents

in the mixer in four minutes. During the addition, the ingredients were cooled by allowing water to flow through the mixer jacket at 25°C. At this stage, the temperature rose to 71°C. Incidentally, during this stage, the reaction mixture remained in a particulate form. Incidentally, the LAS mentioned above contained 0.16 parts by weight of sulfuric acid.
After the addition of the LAS, the mixer was
continuously operated under the same conditions for one
minute to complete the neutralization reaction and the
granulation procesjs. c
Addition of Liquid Ingredients and Surface Modification
At a point where /|h§jn§utralization reaction an$ tlie granulation process were completed, an aqueous solution of a 40% by weight acrylic acid-maleic acid copolymer was added to the mixer with an effective amount of the copolymer being 0.18 parts by weight, while the mixer was operated under the same conditions as above, and the ingredients were mixed for one minute and thirty seconds. Thereafter, the resulting mixture was subjected to a surface modification by adding 4.20 parts by weight of zeolite having an average particle size of 4 pm to the mixer as a surface modifier, and operating the mixture for additional two minutes. Incidentally, the zeolite

contained 0.84 parts by weight of a crystal water.
The resulting granules of the detergent composition,
prior to I hn n f I f«r h I mid I nq n I pp, )\n Percentage of particles with 1400 pm-pass: 34.2%;
Average particle size: 1013 ym;
Bulk density: 712 g/L; and
Free-flowability: 7.8 seconds.
Accordingly, the granules gave lower bulk density and notably poorer results in the percentage of particles with 1400 iim-pass than those of the present invention1; having a large proportion in coarse particles.
After-Blending
Using a rotary mixer, 0.18 parts by weight of enzyme granules and the detergent composition prepared above were blended, and thereafter 0.07 parts by weight of perfume were sprayed, to give a final powdery product of the high-bulk density detergent composition.
Incidentally, the amount of sodium carbonate was about seven times the amount required for neutralizing the LAS and sulfuric acid.
Incidentally, Tables 1 and 2 show the compositions of the final powdery product of each of the detergent

compositions in Examples and Comparative Examples. Also, Tables 3 and 4 show the properties of the detergent compositions after granulation.

As is clearly illustrated by the above results, by dry- npwt-rnl i 7.1nq the nomponont^ in the prirs of n yivtMi ciiuount oi ouliuric: dcidr thu high-buLk dnnu I ty detergent compositions having small particle sizes can be obtained at high yields (Examples 1 to 7). Also, as illustrated by Example 5 and Example 6, the method of the present invention can be suitably utilized to give desired effects without being limitative in the detergent composi tlons* Altio, tho method is particularly applicable for production of phosphorus-free detergent**.
On the other hand, in the case of Comparative Example 1 where a smaller amount of sulfuric acid is used during neutralization, the granules are large, showing notably poorer results in the percentage of particles with 1400 urn-pass and in the average particle size as compared to Examples- Also, in the case of Comparative Example. 2 where pulverized sodium sulfate is added, the resulting detergent granules have large particle size. By comparing Example 4 with Comparative Example 3, remarkable differences in the percentage of particles with 1400 pm-pass and in the average particle size can be noted when the concentration of the anionic surfactant (LAS-Na) in the resulting detergent composition is as high as 36.00% by weight. Therefore, the method of the present invention can be suitably applied in cases where the anionic

surfactant is contained at a high concentration in the dnLortjcmt, componi t ion . Hy compnri nq l\Knnif)l o 7 nnd Comparative Example 4, uvea when LI it* par Lie lo ulze ot Llie
tripolyphosphate is relatively large (58.4 yim), the
effects of the method of the present invention can be clearly observed, Incidentally, in Example 1, Example 2, and Example 3, a decrease in the bulk densities.can be observed by an increase in the amount of sulfuric acid, thereby suggesting that the bulk densities! of the resulting detergent compositions can be controlled to desired values by the amount of sulfuric acid added.
Incidentally, the detergent compositions obtained in Each of Examples were subjected to X-ray diffraction analysis, but no diffraction peaks ascribed to sodium sulfate were detectable.
Example 11
The detergent composition having the composition shown in Table 5 was prepared in an amount of 35 kg for each unit using a high speed mixer "Lttdige Mixer FKM-130D" (manufactured by Matsubo Co., Ltd.)* This mixer was
equipped with agitator blades and a shearing device, the shearing device corresponding to a chopper for disintegration and dispersion.
Here, the detergent composition was prepared by the

following procedures as detailed below.
Powder Blending
The solid ingredients consisting of 7.0 parts by weight of sodium tripolyphosphate (STPP; average particle size: 11.2 pm), 12.72 parts by weight of sodium carbonate ("LIGHT ASH," manufactured by Central Glass Co.,. Ltd.; average particle size: 56.1 pm), and 0.11 parts by weight of a fluorescer were blended for one minute under the conditions of a rotational speed of agitator blades of 130 rpm (peripheral speed: 3.4 m/s) and a rotational speed of shearing device of 2850 rpm (peripheral speed: 27 m/s) by the Lbdige Mixer.
Addition of Reaction Initiating Agent
A 48% by weight aqueous NaOH solution was added to the contents in the mixer in an amount of 0.51 parts by wniqht. i\r. a rc.nnt. Ion I n 1 tl n t; I nq nqnnt, nnd Lhn blending wnn cm r I tu'\ on t for onn in i nu to nrul thirty fjncondf! undnr the same blending conditions as above.
Neutralization
While the mixer was operated under the same conditions as above, a mixture of 10,19 parts by weight of a linear alkylbenzenesulfonic acid (LAS; molecular weight:

322) and 0.58 parts by weight of 98% by weight sulfuric acid were added to the contents in the mixer in four minutes, the mixture being prepared in advance. During the addition, the ingredients were cooled by allowing water to flow through the mixer jacket at 25°C. Incidentally, during this stage, the reaction mixture remained in a particulate form. Incidentally, the LAS mentioned above, which was prepared by S03 gas sulfonation method, contained 0.16 parts by weight of sulfuric acid. In other words, the resulting mixture contained 0.05 mol of sulfuric acid per mol of the LAS. Also, the proportion of sulfuric acid to the LAS during neutralization reaction was such that the reaction mixture contained 0.24 mol of sulfuric acid per mol of the LAS. The amount of sodium carbonate was about five times the amount required for neutralizing the LAS and sulfuric acid.
After the addition of the LAS, the mixer was continuously operated under the same conditions for three minutes to complete the neutralization reaction and the granulation process;. Also, air was blown at a rate of 300 L/min immediately after the addition of the mixed acid.
Addition of Liquid Ingredients and Surface Modification
At a point where the neutralization reaction and the

granulation process were completed, an aqueous solution of a 40% by weight acrylic acid-maleic acid copolymer was added to the mixei with an effective amount of the copolymer being 0.18 parts by weight, while the mixer was operated under the same conditions as above, and the ingredients were mixed for one minute and thirty seconds. Thereafter, the resulting mixture was subjected to a surface modification by adding 4.20 parts by weight of zeolite having an average particle size of 4 \xm to the. mixer as a surface modifier, and operating the mixture for additional two minutes. Incidentally, the zeolite contained 0.84 parts by weight of a crystal water.
The resulting granules of the detergent composition, prior to the after-blending step, had the following properties:
Percentage of particles with 1400 pm-pass: 83.8%;
Average particle size: 469 pm;
Bulk density: 753 g/L;
Free-flowability: 6.3 seconds.
Accordingly, the* granules showed excellent properties.
After-Blending
Using a rotary mixer, 0.18 parts by weight of enzyme

granules nnd tho cJotorgonl; aomponit Ion prcpnrcul nbovo worn blended, and thereaftur 0,07 parts by weight of perfume were sprayed, to give a final powdery product of the high-bulk density detergent composition.
Examples 12-22 and Comparative Examples 11-19
Similar procedures to those in Example 11 were
carried out except for using the respective kinds and
e amounts of starting materials listed in Tobies 5 and 6, to
give each of the final powdery products of the high-bulk
density detergent compositions. Here, in Examples 18 to 20, after completing the neutralization process, additional components of fatty acid (having 14 to 18 carbon atoms) and a nonionic surfactant (having ethylene oxide moiety with 6 addition molar number) were added to the ingredients in the mixture in given amounts shown in Table 5, and the ingredients were blended for one minute.
The composition and the properties of each of the resulting final powdery products of the high-bulk density detergent compositions are listed in Tables 7 through 10.
Incidentally, the breaking load is measured by using a rheometer "NRA-3002DM (manufactured by Fudohkogyo K.K.).

Table 6
Composition Comparative Examples
(parts by weight) 11 12 13 • 1U 15 16 17 18 19
Powder Blending
STEP 7.00 7.00 7.00 7.00 7.00 7.70 7-70 -
Sodium Carbonate 13.05 13.68 12.20 11.06 10.10 13.26 14.34 14.34 13.22
Zeolite . . ____.___7.70 7-70
Powdery Sodium Sulfate - -0.90— - - - — -
Fluorescer 0.11 0.11 0.11 0.11 0.11 0.11 0.11 0.11 0.11
Addition of Reaction Initiating Agent
4b vti-Aqueous
NaOH Solution 0.51 - 0.51 0.61 0.66 0.37 0.27 0.27

300
0.49
1.40
Neutralization
D_ 10.19 10.19 10.19 12.22 13.24
98 wt* Sulfuric Acid - - - - -
85 wt (Amount of Gas Blown)
[L/min] 300 300 300 300 300
Fatty Acid _____
Nonionic Surfactant _____

7.47 5.43 5.43 10.19
300
300
0.49
2.45
300
0.49
2.45

Addition of Liquid Ingredients and Surface Modification Acrylic Acid-Maieic
Acid Copolymer 0.44 0.44 0.44 0.44 0.44 _ _ _ o:44
Zeolite 4.20 4.20 4.20 4.20 4.20 4.20 4.20 4.20 4.20
After-Blending _
Enzvme 0.18 0.18 0.18 0.18 0.18 0.18 Q,18 0.-18 0.18
Perfume 0.07 0.07 0.07 0.07 0.07 0.07 o".07 0.07 0.07
Molar Ratio of Inorganic
Acid/ Liquid Acid 0.04 0.04 0.34 0.04 • 0.04 0.04 0.03 0.03 0.04 Precursor [mol/mol]

Table 7

Properties 11 12 13 14 15 Examples 16 17 16 19 20 21 22
After NeutralizationPowder Temp. [°C] Breaking Load [gf] Average Particle Size [ ii m ] and Granulation80.1 87.3 673 520560 488 Process92.3 470450 79.2 690583 73.7 930570 84.3 850850 90.0 9501785 79.-22629C 72.0 57241 68.8 51339 80.8 502580 79.5 659545
After Surface Modification Process
Powder Temp. [°Cl 69.5 71.1 74.5 68.1 64.2 70.9 75-4 66.5 53.2 58.5 61.0 68.2
Average Particle
Size [(in } 469 400 380 490 470 670 1567 493 ^45 494 450 458
Percentage of Particles
with 1400 ^m-pass [%] 83.8 86.0 87.0 83.1 79.2 73.0 30.0 87-9 78.9 78.8 79.1 84.0
Bulk Density [g/L] 753 723 '724 731 816 725 719 79' 331 818 747 748
Free Flowability [sec] 6.3 6.6 6.8 6.4 6.1 6.4 6.8 6.C 5.1 6.6 6.8 6.5

Table 8

Properties

11

12

Comparative Examples 14 15 16

17

18

19

After Neutralization and Granulation Process
Powder Temp. [°C] 73.0 68.9 76.8 * 68.1 60.1 56.7 67.8
Breaking Load [gf] 112U 1163 1606 •*:• 723 130 147 948
Average Particle
Size [ p,m. ] 879 970 QlXZ 3055 * 390 299 463 750
After Surface Modification Process
Powder Temp. [°C] 6U.5 62.6 63.5 * 58.5 55.1 54.3 55.4
Average Particle
Size [ p,m ] 670 710 ~2C 2033 * 1313 1173 964 590
Percentage of Particles
with 1H00 #M-pass [%] 69.8 63.7 12.0 * 53.2 32.9 57.4 76.3
Bulk Density [g/L] 841 788 53' 692 ■& 847 864 848 769
Free Flowability [sec] 6.2 6.U •~i ■« 6.7 X O. 1 6.6 6.9 6.9
Remarks •*•: The neutralized product became r* - -— #■« sticky, and thus no measurments could be taken.

Table 9
Composition / Examples
(parts by weight) 11 '2 _3 1U 15 .16 17 18 19 20 21 22
Las-Na 30.00 3C00 30.00 30.00 30.00 36.00 39.00 22.00 16.00 16.00 30.00 30.00
Soap 0.00 COO 0.00 0.00 0.00 0.00 0.00 1.50 1.50 1.50 0.00 0.00
STPP 20.00 2C.00 2C.00 20.00 17.00 20.00 20.00 22.00 22.00 0.00 0.00 20.00
Zeolite 12.00 12.00 12.00 12.00 12.00 12.00 12.00 12.00 12.00 34.00 32.00 12.00
Sodi'js Carbonate 30. 40 2-.80 22.50 31.30 32.30 20.80 17.10 31.30 35.00 35.00 28.70 25.40
Sodium Sulfate* 3.00 5.00 10.00 3.00 0.50 6.00 6.50 U.00 4.00 4.00 5. CO 0*W
Sodium Phosphate 0.00 COO COO 0.00 3-00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Acrylic Acid-Maleic
Acid Copolymer 0.50 C.5C C.50 0.50 0.50 0.50 0.50 0.00 0.00 0.00 0.50 0.50
Nonionic Surfactant 0.00 COO 0.00 0.00 0.00 0.00 0.00 4.00 7.00 7.00 0.00 0.00
Fluorescer 0.30 C.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30
Enzyme 0.50 C.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50
Perfume 0.20 C.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20
Water 3.10 3*70 J--00 2.20 3.70 3.70 3.90 2.20 1.50 1.50 .2.80 3.10
Sodium Sulfate** ■ 3.14 5.42 ".14 **# •*• 6.114 6.57 4.55 *•« •«« 5.43 *•»
Remarks * : Amount calculated fron starting material composition. ** : Amount chemically derersiined by ion chromatography. *** : Undetermined.

Table 10

Composition Comparative Exairles
(parts by weight) 11 12 13 1U 15 • *■' 17 18 19
Las-Na 30.00 30.00 30.00 36.00 39.00 22-CO 16.00 16.00 30.00
Soap 0.00 0.00 0.00 0.00 0.00 '.50 1.50 1.50 0.00
STPP 20.00 20.00 20.00 20.00 20.00 22.00 22.00 0.00 0.00
Zeolite 12.00 12.00 12.00 12.00 12.00 *2.C0 12.00 34.00 32.00
Sodium Carbonate 33.20 34.10 30.20 26.75 23-60 3-. 50 38.65 38.65 33.70
Sodium Sulfate* 0.50 0.50 3.00 0.55 0.60 0.45 0.45 0.50
Acrylic Acid-Maleic
Acid Copolymer 0.50 0.50 0.50 0.50 0.50 :.so 0.00 0.00 0.50
Nonionic Surfactant 0.00 0.00 0.50 0.00 0.00 7.00 7.00 0.00
Fluorescer 0.30 0.30 0-30 0.30 0.30 -■30 0.30 0.30 0.30
Enzyme 0.50 0.50 0.50 0.50 0.50 :.50 0.50 0.50 0.50
Perfume 0.20 0.20 0.20 0.20 0.20 -.20 0.20 0.20 0.20
Water 2.80 1.90 2.80 3.20 3.30 2.20 1.40 1.40 2.30
Sodium Sulfate** 0.54 *** ••• «•• «*• 2.34 *•• #«« 0.50

Remarks

Amount calculated from starting material composition. Amount cheaically determined by ion chromatography. Undetermined.

AR 1R nlpnr from Ihp rPHiil tR In TnhlPR !i to 10, by
dry-neutralizing the liquid acid precursor in the presence of a given amount of an inorganic acid, high-bulk density detergent compositions comprising granules with small particle sizes can be obtained at high yields in Examples 11 to 22. Also, as is clear from Examples 18 to 21, according to the method of the present invention, the resulting detergent compositions exhibit desired effects without limiting their compositions, and the method is particularly suitably applicable in the production of phosphorus-free detergents. Particularly in the case of Examples 11 to 13, it is found that as the molar ratio of the inorganic acid to the liquid acid precursor increases, the particle size of the resulting detergent granules become smaller, so that the detergent granules with a desired particle rsize can be obtained by controlling the above molar ratio.
On the other hand, in the case of Comparative Example 11 where the amount of the inorganic acid at neutralization is small, the resulting detergent granules are large, having notably lower percentages of particles with 1400 pm-pass and larger average particle size. Also, in the case of Comparative Example 13 where pulverized sodium sulfate is added, the resulting detergent granules have large particle sizes, so that similar effects to

those attained by addition of sulfuric acid cannot be
obtained.
By comparing the results of Example 16 with those of Comparative Example 14 and the results of Example 17 with those of Comparative Example 15, even more remarkable differences in the percentages of particles with 1400 jim-pass and the average particle sizes can be observed in cases where the anionic surfactant (LAS-Na) is contained in the resulting detergent composition in high concentrations. Therefore, the method of the present invention is suitably applicable in cases where the concentrations of the anionic surfactant in the detergent composition are high.
Also, when comparing the results of Example 18 with those of Comparative Example 16, in the case where the concentration of the anionic surfactant (LAS-Na) is low, the microporous surface areas of the detergent composition increase by addition of the inorganic acid, so that large amounts of the liquid starting material, such as nonionic surfactants, can he formulated while maintaining a small particle size in the detergent granules.
Also, the detergent compositions obtained in each of t Examples 11 to 21 are subjected to X-ray diffraction analysis, but no diffraction pejaks ascribed to inorganic salts, such as sodium sulfate, are detectable.

INDUSTRIAL APPLICABILITY
By neutralizing the a liquid acid precursor of a . non-soap, anionic surfactant with a water-soluble, solid, alkali inorganic substance in the presence of a given amount of the organic acid, high-bulk density detergent compositions compiising granules having smal1 particle sizes can be obtained at high yields.
The present invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as v/ould be obvious to one skilled in the art are intended to be included within the scope of the following claims.

CLAIMs
1. Detergent granules comprising one or more non-soap, anionic surfactants and one or more inorganic salts undetectable by X-ray diffraction method, wherein the molar ratio of [inorganic salts undetectable by X-ray diffraction method]/[non-soap, anionic surfactants] is from 0.1 to 1.0.
2. The detergent granules according to claim 1, wherein the non-soap, anionic surfactant is contained in the detergent granules in an amount of 28% by weight or more and less than 50% by weight.
3. The detergent granules according to claim 1, wherein the non-soap, anionic surfactant is contained in the detergent granules in an amount of 10% by v/eight or more and less than 28% by weight, and wherein the molar ratio of [inorganic salts undetectable by X-ray diffraction method]/[non-soap, anionic surfactants] is from 0.3 to 1.0.
4. A method for producing detergent granules, comprising the step of dry-neutralizing a liquid acid precursor of a non-soap, anionic surfactant with a water-

soluble, solid, alkali inorganic substance, wherein a dry-neutralizing step is carried out in the presence of 0.1 to 1.0 mol of an inorganic acid per mol of said liquid acid precursor of a non-soap, anionic surfactant.
5. The method according to claim 4, further comprising the step of adding a free-flowing aid after the dry-neutralizing step, to surface-modify the detergent granules.
6. The method according to claim 4, further comprising the stop of adding one or more liquid components after the dry-neutralizing step.
7. . The method according to claim 6, further
comprising the step of adding a free-flowing aid after the
step of adding one or more liquid components, to
surface-modify the detergent granules.
• 8. The method according to any one of claims 4 to 7, wherein said liquid acid precursor of a non-soap, anionic surfactant is a linear1 alkylbenzenesulfonic acid obtained by S03 gas sulfonation method.
9. The method according to any one of claims 4 to

8, wherein an amount of an inorganic acid preexisting in
the liquid acid precursor of a non-soap, anionic
surfactant is 0.09 mol or less per mol of said liquid acid
precursor of a non-soap, anionic surfactant.
10. The method according to any one of claims 4 to
9, wherein said inorganic acid is sulfuric acid or
phosphoric acid.
11. Tho muthod according to nny OHM of clnlmii 4 to
10, wherein the resulting detergent granules contain the
non-soap, anionic surfactant in an amount of 28% by weight
or more and less than 50% by weight, and have a molar
ratio of [inorganic salts undetectable by X-ray
diffraction method]/[non-soap, anionic surfactants] of
from 0.1 to 1.0.
12. The method according to any one of claims 4 to 10, wherein the resulting detergent granules contain the non-soap, anionic surfactant in an amount of 10% by weight or more and less than 28% by weight in the detergent granules, and have a molar ratio of [inorganic salts undetectable by X-ray diffraction method]/[non-soap, anionic surfactants] of from 0.3 to 1.0.

13. A high-bulk density detergent composition having a bulk density of 500 g/L or more, comprising the detergent granules according to any one of claims 1 to 3, or the detergent granules obtainable by the method of any
one of claims 4 to 12*

Documents:

1941-mas-1997-abstract.pdf

1941-mas-1997-claims duplicate.pdf

1941-mas-1997-claims original.pdf

1941-mas-1997-correspondence others.pdf

1941-mas-1997-correspondence po.pdf

1941-mas-1997-description complete duplicate.pdf

1941-mas-1997-description complete original.pdf

1941-mas-1997-drawings.pdf

1941-mas-1997-form 1.pdf

1941-mas-1997-form 26.pdf

1941-mas-1997-form 3.pdf

1941-mas-1997-form 4.pdf

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Patent Number

207949

Indian Patent Application Number

1941/MAS/1997

PG Journal Number

29/2007

Publication Date

20-Jul-2007

Grant Date

02-Jul-2007

Date of Filing

02-Sep-1997

Name of Patentee

KAO CORPORATION

Applicant Address

14-10, 1-CHOME, KAYABA-CHO, NIHONBASHI, CHUO-KU, TOKYO.

Inventors:

#	Inventor's Name	Inventor's Address
1	HIDEICHI NITTA	C/O KAO CORPORATION, RESEARCH LABORATORIES, 1334,MINATO, WAKAYAMA-SHI, WAKAYAMA-KEN.
2	HIROYUKI YAMASHITA	C/O KAO CORPORATION, RESEARCH LABORATORIES, 1334,MINATO, WAKAYAMA-SHI, WAKAYAMA-KEN.
3	JUN SAITO	C/O KAO CORPORATION, RESEARCH LABORATORIES, 1334,MINATO, WAKAYAMA-SHI, WAKAYAMA-KEN.

PCT International Classification Number

C11D3/04

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	8-257416	1996-09-06	Japan