Title of Invention	A POLYGLYCEROL HAVING A CYCLIC STRUCTURE IN LOW CONTENT AND A PROCESS FOR PREPARING THE SAME, AND A FATTY ACID ESTER OF THE POLYGLYCEROL AND A PROCESS FOR PREPARING SAME .
Abstract	The present invention relates to a polyglycerol significantly reduced in content of a polyglycerol having a cyclic structure formed by removal of a water molecule from a polyglycerol molecule, and to a fatty acid ester of a polyglycerol having excellent surface activity. 2 mole or more of glycidol and a catalyst are successively added to 1 mole of glycerol for a reaction to obtain a polyglycerol, in which a ratio of [total polyglycerol (1)] to [total polyglycerol (2) having a cyclic structure] is [70% or more]/[30% or less] (the total of both is 100% by weight) in terms of an intensity ratio determined by liquid chromatography/mass spectrometry; and an average polymerization degree "n" is 2 or more. A reaction of a polyglycerol with a fatty acid provides the corresponding a fatty acid ester of the polyglycerol.

Title of Invention

A POLYGLYCEROL HAVING A CYCLIC STRUCTURE IN LOW CONTENT AND A PROCESS FOR PREPARING THE SAME, AND A FATTY ACID ESTER OF THE POLYGLYCEROL AND A PROCESS FOR PREPARING SAME .

Abstract

The present invention relates to a polyglycerol significantly reduced in content of a polyglycerol having a cyclic structure formed by removal of a water molecule from a polyglycerol molecule, and to a fatty acid ester of a polyglycerol having excellent surface activity. 2 mole or more of glycidol and a catalyst are successively added to 1 mole of glycerol for a reaction to obtain a polyglycerol, in which a ratio of [total polyglycerol (1)] to [total polyglycerol (2) having a cyclic structure] is [70% or more]/[30% or less] (the total of both is 100% by weight) in terms of an intensity ratio determined by liquid chromatography/mass spectrometry; and an average polymerization degree "n" is 2 or more. A reaction of a polyglycerol with a fatty acid provides the corresponding a fatty acid ester of the polyglycerol.

Full Text	DESCRIPTION POLYGLYCEROL, FATTY ACID ESTER OF POLYGLYCEROL, AND PROCESSES FOR PRODUCING THE SAME Technical Field The present invention relates to a fatty acid ester of a polyglycerol having a cyclic structure in low content, to a polyglycerol having a cyclic structure in low content used as a raw material for the fatty acid ester of a polyglycerol, and to processes for producing the same. The fatty acid ester of a polyglycerol having a cyclic structure in low content obtained by the present invention has high surface activity because of low content of a dehydrated cyclic structure, and it can be used as a food additive or a cosmetic, medical, or industrial surfactant for the purpose of emulsification, solubilization, dispersion, washing, anticorrosion, lubrication, static protection, wetting, and so on. Moreover, the polyglycerol itself can be used as humectants, thickeners, plasticizers, and for hydrophilic treatment, and so on. Background Art Examples of various compounds, conventionally known as emulsif iers or solubilizers include : ethylene oxide-based non-ionic surfactants such as a polyoxyethylene alkyl ether, a polyoxyethylene polyhydric alcohol/fatty acid ester, and a polyoxyethylene alkyl phenyl ether; and food surfactants such as a sorbitan/fatty acid ester, a sucrose/fatty acid ester, and a fatty acid ester of a polyglycerol (including a polyglycerol ester of interesterified ricinoleic acid). Of those, the fatty acid ester of a polyglycerol is one of the most useful surfactants because the fatty acid ester of a polyglycerol ensures safety to a human body and to the environment, can have diverse compositions, and has high versatility. The fatty acid ester of a polyglycerol is produced by polymerizing glycerol as one of raw materials at high temperatures in the presence of an alkali catalyst such as caustic soda, deodorizing and decolorizing the resultant to obtain a polyglycerol reaction product, and subjecting the polyglycerol reaction product and a fatty acid as raw materials to an esterification reaction. Meanwhile, known processes for industrial production of a polyglycerol used as a raw material are as follows: (i) a process for producing a polyglycerol through recovery from a distillation residue of glycerol; (ii) aprocess for producing a polyglycerol through dehydration condensation of glycerol; (iii) a process for producing a polyglycerol through direct polymerization of epichlorohydrin, hydrolysis, and then dechlorination; and (iv) a process for producing a polyglycerol through addition of glycidol to glycerol or a polyglycerol in the presence of an alkali catalyst such as NaOH or amines, or an acidic catalyst such as acetic acid. However, analysis of a composition distribution of the polyglycerol reaction product obtained through each of the above processes by liquid chromatography/mass spectrometry as described below confirms that produced through intramolecular dehydration are not only cyclic low molecular compounds but also a polyglycerol having a cyclic structure in considerably high content with a molecular weight ranging from several hundreds to several thousands, which are formed through removal of one to several water molecule (s) from a polyglycerol molecule. The inventors of the present invention have found that a polyglycerol containing the above-described polyglycerol having a cyclic structure in high content has inhibited properties in hydrophilicity and the like . The inventors of the present invention have also found that deterioration of properties such as water solubility, surface activity, and the like is caused in a fatty acid ester of a polyglycerol obtained from the above-described polyglycerol and a fatty acid ester. As a polyglycerol produced through a reaction, a reaction product obtained by reacting glycerol with epichlorohydrin or glycidol, or by reacting glycerol or a polyglycerol with epichlorohydrin, monochlorohydrin, dichlorohydrin, or glycidol has been heretofore used as it is or used after having been optionally purified. Example of a purification process include: purification by heating under reduced pressure of several Torr in a stream of a gas such as nitrogen or water vapor for deodorization or removal of unreacted raw materials; purification by removing ionic components such as a catalyst used with an ion-exchange resin, an ion-exchange membrane, or the like; purification by removing color components or odor components using an absorbent such as active carbon; and purification by reduction treatment through hydrogenation or the like. However, in the purification processes for a polyglycerol reaction product, the composition distribution of the resulting a polyglycerol reaction product has not been discussed in detail. Regarding a polyglycerol reaction product obtained by polymerizing the most generally used glycerol at high temperatures in the presence of an alkali catalyst such as caustic soda, and deodorizing and decolorizing the resultant, cyclic compounds having a low molecular weight such as cyclic, diglycerol have been discussed extensively. However, actually, analysis on the composition distribution of a polyglycerol having a molecular weight in the range of several hundreds to several thousands has been hardly discussed in spite of a fact that a dehydration reaction is known to take place in a polyglycerol molecule. Commercially distributed a polyglycerol is called tetraglycerol, hexaglycerol, or decaglycerol according to an average polymerization degree calculated from a hydroxyl value. However, in fact, the polyglycerol is a mixture of various glycerol polymers each having a polymerization degree from 2 to 10 or more, and may include unreacted glycerol (polymerization degree of 1). It has been revealed that a polyglycerol of a relatively low molecular weight such as glycerol, diglycerol, or triglycerol may exist in high content in a polyglycerol containing such a mixture of various glycerols in order to adjust the average polymerization degree calculated from hydroxyl values to the same value. JP-B 5-1291 (claim 1, lines 12-22 in the 3rd column, and Examples) discloses slightly colored polyglycerol having a large polymerization degree obtained by: adding a phosphoric acid catalyst to glycerol or a polyglycerol; and subjecting the resultant to an addition reaction with glycidol at 115 to 125°C. JP-A7-216082 (claiml, paragraph 0008, and Examples) discloses a process for producing a polyglycerol in which glycerol is polycondensed in a boiling state of a reaction mixture at 200 to 270°C in the presence of an alkali. JP-A 2002-30144 (claim 1, and Examples 1 to 12) discloses a process for producing a polyglycerol in which glycidol alone is added and allowed to react in the presence of an alkali metal halide without the use of glycerol as an initiator. Regarding a fatty acid ester of a polyglycerol, JP-A 7-308560 [claim 1 and Comparative Example 1 (Production of a polyglycerol used in each Example)] discloses a process in which a polyglycerol obtained by distilling off low molecular weight polymers from a polyglycerol produced through polycondensation of glycerol at 240°C in the presence of sodium hydroxide is allowed to react with a fatty acid. Alternatively, JP-A 8-109153 (claim 1 and Examples) discloses a process for producing a fatty acid ester of a polyglycerol obtained through an addition polymerization reaction of glycidol with a fatty acid. However, a product obtained through this process is restricted to a polyglycerol/mono-fatty acid ester alone. Disclosure of the Invention An object of the present invention is to provide : a polyglycerol significantly reduced in content of a polyglycerol having a cyclic structure formed through removal of a water molecule from a polyglycerol molecule and a production process thereof; and a fatty acid ester of a polyglycerol having excellent surface activity and a production process thereof. A polyglycerol has not been thoroughly studied so far because a polyglycerol has physical properties of high viscosity and high boiling point and thus because of difficulties in handling. In particular, significance of the presence of a polyglycerol having a cyclic structure in a polyglycerol reaction product and significance of its removal have not been recognized. However, the inventors of the present invention have realized that reduction in content of a polyglycerol having a cyclic structure is necessary. Thus, the inventors of the present invention have devoted themselves to extensive studies and have found that glycidol and a catalyst are added dropwise for a reaction with glycerol as a starting material, to thereby give a polyglycerol having a cyclic structure in low content. Thus, the inventors of the present invention have completed the present invention. That is, a first aspect of the present invention provides a polyglycerol having a cyclic structure in low content, in which a ratio of total polyglycerol (1) represented by the following general formula [1] to total polyglycerol (2) having a cyclic structure that contains at least one cyclic structure in a molecule, that is, [the total polyglycerol (1) ]: [the total polyglycerol (2) having a cyclic structure] is [70% or more]:[30% or less](the total of both is 100 % by weight) in terms of an intensity ratio determined by liquid chromatography/mass spectrometry; and an average polymerization degree (repeating unit of a glycerol residue) "n" is 2 or more: (in the formula [1], "p" represents a repeating portion of a glycerol residue and is an integer of 0 or more; and the polyglycerol molecule has a polymerization degree of "p+2"). A second aspect of the present invention provides a polyglycerol having a cyclic structure in low content according to the first aspect of the present invention, in which the polyglycerol (2) having a cyclic structure is a polyglycerol having a cyclic structure that contains a structure represented by the following general formula [2]: (in the formula [2], "p" represents a repeating portion of a glycerol residue and is an integer of 0 or more; "q" represents a cyclic structure portion and is an integer of 1 or more; the polyglycerol molecule has a polymerization degree of "p+2q+l"; the cyclic structure portion (s) may be inserted randomly or continuously between the glycerol residues; and the polyglycerol having a cyclic structure in low content, which is a mixture of the polyglycerol molecules, has an average polymerization degree "n" of 2 or more). A third aspect of the present invention provides a polyglycerol having a cyclic structure in low content according to the first aspect of the present invention, in which the polyglycerol (2) having a cyclic structure is a polyglycerol having a cyclic structure containing a structure represented by the following general formula [3] : (in the formula [3], "p" represents a repeating portion of a glycerol residue and is an integer of 0 or more; and the polyglycerol molecule has a polymerization degree of "p+3"). A fourth aspect of the present invention provides a polyglycerol having a cyclic structure in low content according to the first aspect of the present invention, in which an average polymerization degree "n" is 3 to 60. A fifth aspect of the present invention provides a polyglycerol having a cyclic structure in low content according to the first aspect of the present invention, in which: a ratio of [the total polyglycerol (l)]:[the total polyglycerol (2) having a cyclic structure] is [80% or more]:[20% or less] (the total of both is 100% by weight); and an average polymerization degree "n" is 2 to 10. A sixth aspect of the present invention provides a polyglycerol having a cyclic structure in low content according to the first aspect of the present invention, in which a ratio of [the total polyglycerol (l)]:[the total polyglycerol (2) having a cyclic structure] is [70% or more] : [30% or less] (the total of both is 100% by weight); and an average polymerization degree "n" is greater than 10. A seventh aspect of the present invention provides a polyglycerol having a cyclic structure in low content according to any one of the first to sixth aspects of the present invention, in which: a ratio of a component with a polymerization degree "n-1" to a polyglycerol showing the highest distribution rate (polymerization degree "n") in terms of an intensity ratio distribution determined by liquid chromatography/mass spectrometry, that is, (component with a polymerization degree "n-1") /(component with a polymerization degree "n") is 0.4 or more. An eighth aspect of the present invention provides a process for producing a polyglycerol having a cyclic structure in low content according to the first aspect of the present invention, characterized by including successively adding 2 mole or more of glycidol and a catalyst to 1 mole of glycerol for a reaction. An ninth aspect of the present invention provides a process for producing a polyglycerol having a cyclic structure in low content according to the eighth aspect of the present invention, in which the catalyst is a phosphoric acid-based acidic catalyst. A tenth aspect of the present invention provides a process for producing a polyglycerol having a cyclic structure in low content according to the ninth aspect of the present invention, in which the phosphoric acid-based acidic catalyst is phosphoric acid or acidic phosphate. A eleventh aspect of the present invention provides a process for producing a polyglycerol having a cyclic structure in low content according to any one of the eighth to tenth aspects of the present invention, in which a reaction temperature is in a range of 80 to 130°C. A twelfth aspect of the present invention provides a polyglycerol having a cyclic structure in low content obtained through the process for producing a polyglycerol having a cyclic structure in low content according to any one of the eighth to tenth aspects of the present invention, in which a fluctuation trend of ratio of (component with a polymerization degree "n-1") / (component with a polymerization degree "n") and of (component with a polymerization degree "n+1")/(component with a polymerization degree "n") in terms of intensity ratio determined by liquid chromatography/mass spectrometry corresponds to a distribution obtained through a successive reaction of glycidol using glycerol as an initiator. A thirteenth aspect of the present invention provides a polyglycerol having a cyclic structure in low content obtained through the process for producing a polyglycerol having a cyclic structure in low content according to the eleventh aspect of the present invention, in whicha fluctuation trendof ratio of (component with a polymerization degree "n-1") / (component with a polymerization degree "n") and of (component with a polymerization degree "n+1")/(component with a polymerization degree "n") in terms of intensity ratio determined by liquid chromatography/mass spectrometry corresponds to a distribution obtained through a successive reaction of glycidol using glycerol as an initiator. A fourteenth aspect of the present invention provides a fatty acid ester of a polyglycerol having a cyclic structure in low content, including an ester structure formed through a dehydration reaction of a polyglycerol having a cyclic structure in low content according to any one of the first to sixth aspects of the present invention with a fatty acid having 2 to 30 carbons. A fifteenth aspect of the present invention provides a fatty acid ester of a polyglycerol having a cyclic structure in low content, including an ester structure formed through a dehydration reaction of a polyglycerol having a cyclic structure in low content according to the seventh aspect of the present invention with a fatty acid having 2 to 30 carbons. A sixteenth aspect of the present invention provides a fatty acid ester of a polyglycerol having a cyclic structure in low content, including an ester structure formed through a dehydration reaction of a polyglycerol having a cyclic structure in low content according to the twelfth aspect of the present invention with a fatty acid having 2 to 30 carbons. A seventeenth aspect of the present invention provides a fatty acid ester of a polyglycerol having a cyclic structure in low content, including an ester structure formed through a dehydration reaction of a polyglycerol having a cyclic structure in low content according to the thirteenth aspect of the present invention with a fatty acid having 2 to 30 carbons. A eighteenth aspect of the present invention provides a process for producing a fatty acid ester of a polyglycerol having a cyclic structure in low content, including carrying out a dehydration reaction of a polyglycerol having a cyclic structure in low content according to any one of the first to sixth aspects of the present invention with a fatty acid having 2 to 30 carbons. A nineteenth aspect of the present invention provides a process for producing a fatty acid ester of a polyglycerol having a cyclic structure in low content, including carrying out a dehydration reaction of a polyglycerol having a cyclic structure in low content according to the seventh aspect of the present invention with a fatty acid having 2 to 30 carbons. A twentieth aspect of the present invention provides a process for producing a fatty acid ester of a polyglycerol having a cyclic structure in low content, including carrying out a dehydration reaction of a polyglycerol having a cyclic structure in low content according to the twelfth aspect of the present invention with a fatty acid having 2 to 30 carbons. A twenty-first aspect of the present invention provides a process for producing a fatty acid ester of a polyglycerol having a cyclic structure in low content, including carrying out a dehydration reaction of a polyglycerol having a cyclic structure in low content according to the thirteenth aspect of the present invention with a fatty acid having 2 to 30 carbons. Brief Description of the Accompanying Drawings Fig. 1 is a chart showing a composition distribution of a reaction product according to Example 1. Fig. 2 is a chart showing a composition distribution of a reaction product according to Example 2. Fig. 3 is a chart showing a composition distribution of a reaction product according to Example 3. Fig. 4 is a chart showing a composition distribution of a reaction product according to Example 4. Fig. 5 is a chart showing a composition distribution of a reaction product according to Comparative Example 1. Fig. 6 is a chart showing a composition distribution of a reaction product according to Comparative Example 2. Fig. 7 is a chart showing a composition distribution of a reaction product according to Comparative Example 3. Fig. 8 (a) is a liquid chromatogram of a reaction product according to Example 3. Fig. 8(b) is a liquid chromatogram of a reaction product according to Comparative Example 1. Fig. 8(c) is a liquid chromatogram of a reaction product according to Comparative Example 2. Fig. 9 is a chart showing a composition distribution of a reaction product according to Comparative Example 4. Best Mode for carrying out the Invention Hereinafter, the present invention will be described indetail. I. A polyglycerol having a cyclic structure in low content A polyglycerol having a cyclic structure in low content of the present invention is composed of a polyglycerol (1) represented by the general formula [1] and a polyglycerol(2) having a cyclic structure containing at least one cyclic structure in a polyglycerol molecule. In the formula [1], "p" represents a repeating portion of a glycerol residue and is an integer of 0 or more, and the polyglycerol molecule has a polymerization degree of "p+2". Thus, the formula [1] represents diglycerol having a polymerization degree of 2 if "p" is 0, triglycerol having a polymerization degree of 3 if "p" is 1, or tetraglycerol having a polymerization degree of 4 if "p" is 2, for example. The cyclic structure portion in the polyglycerol (2) having a cyclic structure is formed through a dehydration reaction of any two hydroxyl groups of a glycerol residue in the polyglycerol (1) . The cyclic structure can include various structures depending on reaction conditions and so on, and is therefore not particularly limited. Examples of a cyclic structure formed under general reaction conditions include a 1,4-dioxahe structure (6-membered ring), a 1, 4-dioxepane structure (7-membered ring), and a 1,5-dioxocane structure (8-membered ring). For example, in a polyglycerol having a cyclic structure represented by the following formula [2] , "p" represents a repeating portion of a glycerol residue and is an integer of 0 or more. The "q" represents a cyclic structure portion and is an integer of 1 or more. The polyglycerol molecule has a polymerization degree of "p+2q+1". The cyclic structure portion(s) may be inserted between the glycerol residues randomly or continuously, into a chain, or at a terminal. Thus, the formula [2] is composed of 1 unit of dehydrated cyclic diglycerol and 1 unit of glycerol if "p" is 0 and "q" is 1, or 2 units of glycerol and 1 unit of dehydrated cyclic diglycerol if "p" is 1 and "q" is 1, for example. Further, the formula [2] is composed of 3 units of glycerol and 1 unit of dehydrated cyclic diglycerol if "p" is 2 and "q" is 1, or 4 units of glycerol and 2 units of dehydrated cyclic diglycerol if "p" is 3 and "q" is 2, for example. A polyglycerol having a cyclic structure in low content of the present invention is characterized in that a ratio of [total polyglycerol (1)]: [total polyglycerol (2) having a cyclic structure containing at least one cyclic structure, preferably one or two of cyclic structure(s) in the polyglycerol molecule] is [70% or more] : [30% or less] (the total of both is 100 % by weight) , preferably [80% or more]:[20% or less] by liquid chromatography/mass spectrometry (abbreviated as LC/MS) described below. In a polyglycerol having a cyclic structure in low content of the present invention, the total polyglycerol having one cyclic structure is 30% or less, preferably 20% or less with respect to the total polyglycerol (1) . The total polyglycerol having two cyclic structures is one third or less of the total polyglycerol having one cyclic structure, and the total polyglycerol having three cyclic structures is one fifth or less of the total polyglycerol having two cyclic structures. Thus, the polyglycerol having three cyclic structures, if any, is present in the polyglycerol in very low content. The polyglycerol (1) in the polyglycerol having a cyclic structure in low content of the present invention has an average polymerization degree (repeating unit of a glycerol residue) "n" of 2 or more, preferably 3 to 60, particularly preferably 3 to 50. In the polyglycerol having a cyclic structure in low content of the present invention, the ratio of a polyglycerol (2) having a cyclic structure tends to increase gradually with increasing average polymerization degree "n" of a polyglycerol (1) . If the average polymerization degree "n" of a polyglycerol (1) is from 2 to 10, the ratio of [the total polyglycerol (l)]:[the total polyglycerol (2) having a cyclic structure] is [80% or more]: [20% or less], preferably [85% or more]:[15% or less], more preferably [90% or more]:[10% or less]. If the average polymerization degree "n" of a polyglycerol (1) is greater than 10, the ratio of [the total polyglycerol (1) ]: [the total polyglycerol (2) having a cyclic structure] is [70% or more]:[30% or less], preferably [75% or more]: [25% or less], more preferably [80% or more]: [20% or less] . Moreover, in a polyglycerol having a cyclic structure in low content of the present invention, the ratio of a component with a polymerization degree "n-1" to a polyglycerol showing the highest distribution rate (polymerization degree "n") in terms of an intensity ratio distribution determined by liquid chromatography/mass spectrometry, that is, (component with a polymerization degree "n-1")/(component with a polymerization degree "n") is 0.4 or more, and 0.5 or more and even 0.7 or more with increasing average polymerization degree "n" of a polyglycerol (1) . Furthermore, in a polyglycerol having a cyclic structure in small amount obtained through a production process of the present invention, a fluctuation trend of ratio of (component with a polymerization degree "n-1")/(component with a polymerization degree "n") and of (component with a polymerization degree "n+1")/(component with a polymerization degree "n") in terms of intensity ratio determined by liquid chromatography/mass spectrometry corresponds to a distribution obtained through a successive reaction of glycidol using glycerol as an initiator. A polyglycerol having such a distribution easily improves solvency and acquires required HLB (hydrophilicity-lipophilicity balance) . A polyglycerol (1) may contain a low content of a branched structure having glycidol added to a secondary hydroxyl group. A reaction product contains approximately 1 to 15%, preferably 10% or less of other compounds (e.g. , a polyglycerol having a double bond in the polyglycerol molecule) in addition to the above-described polyglycerol (1) and a polyglycerol (2) , andglycerol as a rawmaterial. The content of other compounds increases with increasing average polymerization degree of a polyglycerol (1). An LC/MS analysis system is composed of LC and MS portions, and an interface connecting them. The MS portion as a detection system operates on a principle common with that of a GC/MS analysis system, which employs a technique of detecting and identifying ionized target substances on the basis of a mass number/charge (m/z) ratio. Processes for obtaining information from MS connected to chromatography include a mass chromatogram showing a time distribution of an intensity of an arbitrary m/z, a mass spectrum showing a relative intensity distribution of each m/z at an arbitrary time, and a total ion chromatogram (TIC) showing a time change of total intensity, not of an intensity of individual m/z, obtained by adding intensities (quantities of electricity) of all ions. Of those processes, the total ion chromatogram is preferably used. Processes for obtaining the mass chromatogram include a scanning method for extracting a time distribution of required m/z intensity from intensity information in a time axis direction obtained through magnetic field scanning within a certain m/z range at a constant time interval, and a selected ion monitoring (SIM) method with high sensitivity for selectively detecting only an intensity of a target single m/z or intensities of a plurality of m/z's. Examples of a basic principle of a mass spectrometer in practical use include a magnetic sector type, a quadrupole type, an ion trap type, a flying time, and a Fourier transform type. Of those spectrometers, the ion trap type spectrometer is preferred. A polyglycerol having a cyclic structure in low content of the present invention is obtained by successively adding a catalyst and glycidol to a reactor charged with water or glycerol as an initiator for an addition polymerization reaction. The catalyst is preferably a phosphoric acid-based acidic catalyst. Examples of the above-described phosphoric acid-based acidic catalyst include phosphoric acids and phosphates. Specific examples thereof include: phosphoric acids such as phosphoric acid, phosphoric anhydride, polyphosphoric acid, orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, and tetraphosphoric acid; and acidic phosphates such as methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, and 2-ethylhexyl acid phosphate. It is noted that those acidic phosphates can be used in any forms such as a monoester, a diester, and a mixture thereof. Of those, phosphoric acid and acidic phosphate are preferably used. One of the above-described catalysts may be used alone, or two or more of them may be used as a mixture. An addition amount of the catalyst is 0.001 to 1% by weight, preferably 0.01 to 0.5% by weight with respect to a resulting polyglycerol. The addition amount of less than 0.001% by weight provides a small reaction rate. On the other hand, the addition amount of more than 1% by weight easily promotes hydrolysis in esterification with a fatty acid due to the remaining phosphoric acid. As a result, the addition amount of more than 1% by weight causes a deleterious effect on the performance of a product such as insufficient stability of an aqueous solution. Glycerol is placed in a reactor and 2 mole or more of glycidol and a catalyst are successively added to 1 mole of the glycerol for a reaction, to name one example of a reaction process. Alternatively, in the case of using water as an initiator, water is placed in a reactor and a reaction is carried out in the same manner as that described above. The catalyst and glycidol may be separately added dropwise (separately charged), or may be added dropwise in a mixed state. It is not preferred that the dropping of the catalyst be terminated too early compared with that of glycidol. Although the rate of dropping thereof is not particularly limited, it is preferred that the catalyst and glycidol be added dropwise at a uniform rate as a whole. A reaction temperature is in the range of 80°C to 130°C, preferably 85°C to 125°C, more preferably 90°C to 120°C. When the temperature is lower than 80°C, the reaction rate is small. When the temperature is higher than 130°C, intramolecular dehydration takes place easily, thereby increasing the content of a polyglycerol having a cyclic structure. Moreover, the reaction is desirably carried out under an inert gas atmosphere such as nitrogen gas, and may be optionally carried out under compressed or reduced pressure conditions. The reaction rate can be increased in a reaction under compressed conditions. A conversion of glycidol is 98% or more, preferably 99.5% or more, more preferably 99.9% or more. The obtained polyglycerol having a cyclic structure in low content may be purified as required for use of a product. A purification process is not particularly limited, and any of processes known in the art may be employed. For example, a polyglycerol may be purified through an absorption treatment with active carbon, activated clay, or the like, a treatment under reduced pressure using water vapor, nitrogen, or the like as a carrier gas, washing with an acid or an alkali, or molecular distillation. Alternatively, unreacted polyglycerol and the like may be separated and removed through liquid-liquid distribution, or using an absorbent, a resin, a molecular sieve, a loose reverse osmosis membrane, an ultrafiltration membrane, or the like. Furthermore, lowmolecular weight substances such as unreacted glycerol and glycerol dimer in the above-described reaction product may be optionally removed through distillation or the like from a polyglycerol having a cyclic structure in low content of the present invention. II. Fatty acid ester of a polyglycerol having a cyclic structure in low content A fatty acid ester of a polyglycerol having a cyclic structure in low content according to the present invention is a fatty acid ester of a polyglycerol having a cyclic structure in low content, which has an ester structure formed through dehydration of the above-described polyglycerol having a cyclic structure in low content of the present invention and a fatty acid. Examples of a process for producing the fatty acid ester of a polyglycerol having a cyclic structure in low content according to the present invention can include a process through dehydration esterification of a polyglycerol having a cyclic structure in low content with a fatty acid, a process through removal of low molecular weight alcohol from an ester of a fatty acid with a low molecular weight alcohol and a polyglycerol having a cyclic structure in low content, a process through removal of a low molecular weight fatty acid from an ester of a low molecular weight fatty acid with a polyglycerol having a cyclic structure in low content and a higher fatty acid, and a process through removal of an alkali halide from a fatty acid halide, a polyglycerol having a cyclic structure in low content, and caustic alkali. Of those processes, there is economical the process through dehydration esterification of a polyglycerol having a cyclic structure in low content with a fatty acid. In the process through dehydration esterif ication, for example, the dehydration esterification can be carried out under normal pressure or reduced pressure in the presence of an alkali catalyst or an acid catalyst, or in the absence of a catalyst. A polyglycerol having a cyclic structure in low content and a fatty acid must be added in an amount appropriately selected according to the purpose of a product. For example, in the case of intending to obtain a hydrophilic surfactant, a polyglycerol having a cyclic structure in low content and a fatty acid may be added in equimolar amounts by calculating weights thereof from a hydroxyl value (also referred to as an OH value) of a polyglycerol having a cyclic structure in low content and a molecular weight of a fatty acid. In the case of intending to obtain a lipophilic surfactant, mole number of the fatty acid may be increased. The obtained fatty acid ester of a polyglycerol having a cyclic structure in low content may be purified as required for use of a product. The purification process is not particularly limited, and any of processes known in the art may be employed. For example, the fatty acid ester of a polyglycerol may be purified through an absorption treatment with activated carbon, activated clay, or the like, a treatment under reduced pressure using water vapor, nitrogen, or the like as a carrier gas, washing with an acid or an alkali or molecular distillation. Alternatively, unreacted polyglycerol and the like may be separated and removed through liquid-liquid distribution, or using an absorbent, a resin, a molecular sieve, a loose reverse osmosis membrane, an ultrafiltration membrane, or the like. Additive An additive may be added to the fatty acid ester of a polyglycerol having a cyclic structure in low content of the present invention to allow easy handling of a product. Examples of the additive include ethanol, propylene glycol, glycerol, a polyglycerol, water, liquid sugar, and oils and fats for reducing a viscosity of a product. One additive or two or more additives may be added to dissolve or emulsify the fatty acid ester of a polyglycerol. Alternatively, polysaccharide such as lactose or dextrin, or a protein such as caseinate may be added to pulverize the fatty acid ester of a polyglycerol. Depending on the purpose for use, the fatty acid ester of a polyglycerol having a cyclic structure in low content of the present invention may be mixed with other surfactants as additives to produce a product of a surfactant. Examples of the other surfactants that can be used include nonionic surfactants, amphoteric surfactants, anionic surfactants, and cationic surfactants. Examples of the nonionic surfactants include: lecithin such as soybean lecithin, yolk lecithin, or rapeseed lecithin, or a partial hydrolysate thereof; monoglycerides such as monoglycerides of caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, elaidic acid, ricinoleic acid, and interesterified ricinoleic acid, a monoglyceride mixture thereof, or a monoglyceride of an organic acid which is an organic acid ester of the monoglyceride with an organic acid such as acetic acid, citric acid, succinic acid, malic acid, and tartaric acid; a fatty acid ester of sorbitan such as a sorbitan ester of caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, elaidic acid, ricinoleic acid, and interesterif ied ricinoleic acid; propylene glycol/fatty acid esters such as propylene glycols of caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, elaidic acid, ricinoleic acid, and interesterified ricinoleic acid; and sucrose/fatty acid esters such as sucrose esters of caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, elaidic acid, ricinoleic acid, and interesterified ricinoleic acid. [Examples] Hereinafter, the present invention will be more specifically described with reference to examples, but the present invention is not limited thereto. It is to be noted that throughout Examples and Comparative Examples, analysis conditions for LC/MS (Liquid Chromatography/Mass Spectrometry) are as follows. (Conditions for LC separation) Column: TSKgel a-2500 (7.8 x 300 mm) (aqueous polymeric gel column) Temperature: 40°C Eluent: water/acetonitrile = 7/3 Flow rate: 0.8 ml/min Injection volume: 10 µl (sample concentration of 100 ppm) Analysis time: 20 minutes (Conditions for MS analysis) Apparatus: LCQ (manufactured by ThermoQuest, ion trap type) Ionization mode: APCI (Atmospheric Pressure Chemical Ionization), negative Measurement range: m/z = 90 to 2,000 Method for intensity ratio measurement: through a mass spectrometric analysis indicating a relative intensity distribution of each m/z at an arbitrary time. (Example 1) Into a 1 L four-neck flask equipped with a nitrogen introduction pipe, a stirrer, a cooling pipe, a thermoregulator, and a dropping cylinder, 4 . 0 mole (368.4 g) of glycerol was added, and the glycerol was heated to 100°C. While a reaction temperature was maintained at 100°C, 8.0 mole (592.6 g) of glycidol and 1.922 g of phosphoric acid (a product of 85%) were separately dropped therein over 6 hours to continue a reaction until a concentration of oxirane in the system reached less than 0.1%. After cooling, a reaction product was taken out to obtain approximately 950 g of a polyglycerol (PGL 3: average polymerization degree of approximately 3) . The polyglycerol showed an OH value of 1,170mg-KOH/g. The obtained polyglycerol was analyzed by the above LC/MS. Fig. 1 shows the results of componential analysis . In each of figures below showing the results of componential analysis, the numbers of a horizontal axis represent degrees of polymerization of a polyglycerol, and a vertical axis indicates a relative intensity with a bar graph. On the horizontal axis, a polyglycerol (1), a polyglycerol (2) having one cyclic structure that contains one cyclic structure, and a polyglycerol (2) having a cyclic structure that contains two cyclic structures are indicated with the bar graphs drawn side by side for each polymerization degree. In each of the figures, Ideal PGL Groups (PGL) represents a polyglycerol (1), and PGL-H2O, PGL-2H2O, and the like, represent a polyglycerol having a cyclic structure formed through removal of one water molecule, a polyglycerol having a cyclic structure formed through removal of two water molecules, and the like, respectively. In the intensity ratio distribution of a polyglycerol of Fig. 1, the polymerization degree "n" of a polyglycerol showing the mode (the highest distribution rate) was 4, and the ratio of (component with a polymerization degree "n-1") / (component with a polymerization degree "n") was 0.5327. Table 1 Intensity ratio in componential analysis of a polyglycerol in Example 1 [The polymerization degree "n" of a polyglycerol showing the highest distribution rate (mode) was 4] As Table 1 shows, in the reaction product obtained in the polymerization step according to the process of the present invention, components with varying degrees of polymerization except unreacted glycerol provided a distribution corresponding to that obtained through a successive reaction of glycidol using glycerol as an initiator. The reaction product having such a distribution can have improved solvency and so on, though depending on kinds of solutes. (Example 2) Into a 2 liter four-neck flask having equipment similar to those of Example 1, 4.4 mole (405.2 g) of glycerol was added, and the glycerol was heated to 120°C. Subsequently, while a reaction temperature was maintained at 120 °C, 22.0mole (l,629.8g) of glycidol and 2.035 g of phosphoric acid (a product of 85%) were separately dropped therein over 6 hours to continue the reaction until the concentration of oxirane in the system reached less than 0.1%. After cooling, a reaction product was taken out to obtain approximately 2,000 g of a polyglycerol (PGL 6: average polymerization degree of approximately 6). The polyglycerol showed an OH value of 970 mg-KOH/g. Fig. 2 shows the LC/MS analysis results of the obtained polyglycerol. As Table 2 shows, in the reaction product obtained in the polymerization step according to the process of the present invention, components with varying degrees of polymerization except unreacted glycerol provided a preferred distribution as that in Example 1. Table 2 Intensity ratio in componential analysis of a polyglycerol in Example 2 [The polymerization degree "n" of a polyglycerol showing the highest distribution rate (mode) was 8] (Example 3) Into the same flask as that used in Example 2, 2.0 mole (188 g) of glycerol was added, and the glycerol was heated to 100°C. Subsequently, while a reaction temperature was maintained at 100°C, 18.0 mole (1,332 g) of glycidol and 1.525 g of phosphoric acid (a product of 85%) were separately dropped therein over 6 hours to continue the reaction until the concentration of oxirane in the system reached less than 0.1%. After cooling, a reaction product was taken out to obtain approximately 1,500 g of a polyglycerol (PGL 10: average polymerization degree of approximately 10). The polyglycerol showed an OH value of 885 mg-KOH/g. Fig. 3 shows the LC/MS analysis results of the obtained polyglycerol. As Table 3 shows, in the reaction product obtained in the polymerization step according to the process of the present invention, components with varying degrees of polymerization except unreacted glycerol provided a preferred distribution as that in Example 1. Fig. 8(a) shows a liquid chromatogram of the reaction product of Example 3. In each of the liquid chromatograms shown below, the horizontal axis represents an elution time and the vertical axis represents a peak intensity (unit mV) of the chromatogram. Table 3 Intensity ratio in componential analysis of a polyglycerol in Example 3 [The polymerization degree "n" of a polyglycerol showing the highest distribution rate (mode) was 8] (Example 4) Into the same flask as that used in Example 2, 0.5 mole (47 g) of glycerol was added, and the glycerol was heated to 120°C. Subsequently, while a reaction temperature was maintained at 120°C, 19.5 mole (1,443 g) of glycidol and 1.525 g of phosphoric acid (a product of 85%) were separately dropped therein over 12 hours to continue the reaction until the concentration of oxirane in the system reached less than 0.1%. After cooling, a reaction product was taken out to obtain approximately 1,500 g of a polyglycerol (PGL 40: average polymerization degree of approximately 40) . The polyglycerol showed an OH value of 787 mg-KOH/g. Fig. 4 shows the LC/MS analysis results of the obtained polyglycerol. As Table 4 shows, in the reaction product obtained in the polymerization step according to the process of the present invention, components with varying degrees of polymerization except unreacted glycerol provided a preferred distribution as that in Example 1. Table 4 Intensity ratio in componential analysis of a polyglycerol in Example 4. [The polymerization degree "n" of a polyglycerol showing the highest distribution rate (mode) was 8] (Comparative Example 1) Commercially available decaglycerol (available from Sakamoto Yakuhin Co., Ltd., Decaglycerol #750; a polyglycerol obtained through dehydration condensation of glycerol, OH value of 8 90 mg-KOH/g) was analyzed by the above LC/MS. Fig. 5 shows the results of componential analysis . The decaglycerol contains a polyglycerol (2) having a cyclic structure in very high content. (Comparative Example 2) Commercially available decaglycerol (available from Kashima Chemical Co., Ltd., KCOL-IV-750; a polyglycerol obtained from epichlorohydrin, OH value of 882 mg-KOH/g) was analyzed by the above LC/MS. Fig. 6 shows the results of componential analysis. The decaglycerol contains a polyglycerol (2) having a cyclic structure in high content. (Comparative Example 3) Into the same flask as that used in Example 2, 2.0 mole (188 g) of glycerol was added, and the glycerol was heated to 140°C. Subsequently, while a reaction temperature was maintained at 140°C, 18.0 mole (1,332 g) of glycidol and 1.525 g of phosphoric acid (a product of 85%) were separately dropped therein over 6 hours to continue the reaction until the concentration of oxirane in the system reached less than 0.1%. After cooling, a reaction product was taken out to obtain approximately 1,500 g of a polyglycerol (PGL 10 of Comparative Example 3: average polymerization degree of approximately 10) . The polyglycerol showed an OH value of 887 mg-KOH/g. Fig. 7 shows the LC/MS analysis results of the obtained polyglycerol. The polyglycerol contains a polyglycerol (2) having a cyclic structure and other compounds in high content. (Comparative Example 4) A reaction was carried out in the same manner as in Example 3 except that 18.0 mole (1,332 g) of glycidol was added dropwise over 6 hours into a flask charged with 2.0 mole (188 g) of glycerol and 1.525 g of phosphoric acid (a product of 85%). The resulting polyglycerol showed an OH value of 885 mg-KOH/g. Approximately 1,500 g of a polyglycerol (PGL 10 of Comparative Example 4: average polymerization of approximately 10) was obtained. Fig. 9 shows the LC/MS analysis results of the obtained polyglycerol. The polyglycerol contains a polyglycerol (2) having a cyclic structure and other compounds in high content. As described above, glycidol and a catalyst are successively added for a reaction with glycerol, to thereby significantly reduce the amounts of the by-products of a polyglycerol having a cyclic structure. Meanwhile, in the process involving dropping of either glycidol or a catalyst, the amounts of the by-products of a polyglycerol having a cyclic structure are large. Moreover, when a reaction temperature exceeds 130°C, the amounts of the by-products of a polyglycerol having a cyclic structure increase. Hereinafter, the production of a fatty acid ester of a polyglycerol and its evaluation will be shown. (Example 5) Into a reactor with a volume of 2 liter equipped with a stirrer, a thermometer, a heating jacket, a gas-feed port, and a raw material-feed port, 1,200 g of a polyglycerol obtained in Example 3 (PGL 10: average polymerization degree of approximately 10) was added. Subsequently, lauric acid (99% purity) and a 10% sodium hydroxide aqueous solution were added thereto. The addition amount of lauric acid was adjusted such that a molar ratio of lauric acid/a polyglycerol was 1/1. The amount of sodium hydroxide was 0.0025% by weight with respect to the total amount of a polyglycerol and lauric acid. After an internal temperature was elevated to 240°C under normal pressure in a stream of a nitrogen gas for a 3-hour reaction, the internal temperature was further elevated to 260°C for a reaction for 4 hours . After completion of the reaction, the reactor was cooled to normal temperature to obtain a lauric acid ester of a polyglycerol (PGLE-1). (Comparative Example 5) Esterif ication was carried out in the same manner as in Example 5 to obtain a lauric acid ester of polyglycerol(PGLE-2), except that the Decaglycerol #750 of Comparative Example 1 was used instead of the polyglycerol (PGL 10:average polymerization degree of approximately 10). (Evaluation of a fatty acid ester of a polyglycerol) PGLE-1 obtained in Example 5 and PGLE-2 obtained in Comparative Example 5 were respectively dissolved in desalted water to prepare 10% aqueous solutions. The states of the solutions stored at 5°C were observed with time. Table 5 shows the results. Table 5 Industrial Applicability A polyglycerol having a cyclic structure in low content according to the present invention has a reduced content of a polyglycerol having a cyclic structure formed through intramolecular dehydration, and thus has a large OH value. As a result, the polyglycerol having a cyclic structure in low content can be used in humectants, thickeners, plasticizers, hydrophilic treatment, and so on. Moreover, a fatty acid ester of a polyglycerol obtained from the polyglycerol and a fatty acid ester has enhanced properties such as emulsification, solubilization, dispersion, washing, anticorrosion, lubrication, static protection, wetting, and can be used as additives for foods and cosmetic, medical, and industrial surfactants. Furthermore, the polyglycerol itself can be used in humectants, thickeners, plasticizers, hydrophilic treatment, and so on. We Claim: 1. A polyglycerol having a cyclic structure in low content, wherein: a ratio of [total polyglycerol (1) represented by the following general formula [1]] to [total polyglycerol (2) having a cyclic structure that contains at least one cyclic structure in a molecule] , that is, [the total polyglycerol (1)] : [the total polyglycerol (2) having a cyclic structure] is 70% or more : 30% or less (the total of both is 100% by weight) in terms of an intensity ratio determined by liquid chromatography/mass spectrometry; and an average polymerization degree (repeating unit of a glycerol residue) "n" is 2 or more: (in the formula [1], "p" represents a repeating portion of a glycerol residue and is an integer of 0 or more, and a polyglycerol molecule has a polymerization degree of "p+2"). 2. A polyglycerol having a cyclic structure in low content according to claim 1, wherein the polyglycerol (2) having a cyclic structure comprises a polyglycerol having a cyclic structure containing a structure represented by the following general formula [2] : (in the formula [2], "p" represents a repeating portion of a glycerol residue and is an integer of 0 or more; "q" represents a cyclic structure portion and is an integer of 1 or more; the polyglycerol molecule has a polymerization degree of "p+2q+l"; the cyclic structure portion (s) may be inserted randomly or continuously between the glycerol residues; and the polyglycerol having a cyclic structure in low content, which is a mixture of the polyglycerol molecules, has an average polymerization degree "n" of 2 or more). 3. A polyglycerol having a cyclic structure in low content according to claim 1, wherein the polyglycerol (2) having a cyclic structure comprises a polyglycerol having a cyclic structure containing a structure represented by the following general formula [3]: (in the formula [3], "p" represents a repeating portion of a glycerol residue and is an integer of 0 or more; and the polyglycerol molecule has a polymerization degree of "p+3"). 4. A polyglycerol having a cyclic structure in low content according to claim 1, wherein an average polymerization degree "n" is 3 to 60. 5. A polyglycerol having a cyclic structure in low content according to claim 1, wherein a ratio of [the total polyglycerol (1) ] : [the total polyglycerol (2) having a cyclic structure] is [80% or more] : [20% or less] (the total of both is 100% by weight); and an average polymerization degree "n" is 2 to 10. 6. A polyglycerol having a cyclic structure in low content according to claim 1, wherein a ratio of [the total polyglycerol (1) ] : [the total polyglycerol (2) having a cyclic structure] is [70% or more]: [30% or less] (the total of both is 100% by weight); and an average polymerization degree "n" is greater than 10. 7. A polyglycerol having a cyclic structure in low content according to any one of claims 1 to 6, wherein a ratio of a component with a polymerization degree "n-l" to a polyglycerol showing the highest distribution rate (with a polymerization degree "n") in terms of an intensity ratio distribution determined by liquid chromatography/mass spectrometry, that is, (component with a polymerization degree "n- 1") / (component with a polymerization degree "n") is 0.4 or more. 8. A process for producing a polyglycerol having a cyclic structure in low content according to claim 1, wherein comprising successively adding 2 mole or more of glycidol and a catalyst to 1 more of glycerol for a reaction wherein a reaction temperature is in a range of 80 to 130°C. 9. A process for producing a polyglycerol having a cyclic structure in low content according to claim 8 , wherein the catalyst comprises a phosphoric acid-based acidic catalyst. 10. A process for producing a polyglycerol having a cyclic structure in low content according to claim 9, wherein the phosphoric acid- based acidic catalyst comprises phosphoric acid or acidic phosphate. 11. A process for producing a polyglycerol having a cyclic structure in low content according to any one of claims 8 to 10, wherein a reaction temperature is in a range of 80 to 130°C. 12. A polyglycerol having a cyclic structure in low content obtained through the process for producing a polyglycerol having a cyclic structure in low content according to any one of claims 8 to 10, wherein a fluctuation trend of ratio of (component with a polymerization degree "n-1") / (component with a polymerization degree "n") and of (component with a polymerization degree "n+1") / (component with a polymerization degree "n") in terms of intensity ratio determined by liquid chromatography/mass spectrometry corresponds to a distribution obtained through a successive reaction of glycidol using glycerol as an initiator. 13. A polyglycerol having a cyclic structure in low content obtained through the process for producing a polyglycerol having a cyclic structure in low content according to claim 11, wherein a fluctuation trend of ratio of (component with a polymerization degree "n-1") / (component with a polymerization degree "n") and of (component with a polymerization degree "n+1") / (component with a polymerization degree "n") in terms of intensity ratio determined by liquid chromatography/mass spectrometry corresponds to a distribution obtained through a successive reaction of glycidol using glycerol as an initiator. 14. A fatty acid ester of a polyglycerol having a cyclic structure in low content, comprising an ester structure formed through a dehydration reaction of a polyglycerol having a cyclic structure in low content according to any one of claims 1 to 6 with a fatty acid having 2 to 30 carbons. 15. A fatty acid ester of a polyglycerol having a cyclic structure in low content, comprising an ester structure formed through a dehydration reaction of a polyglycerol having a cyclic structure in low content according to claim 7 with a fatty acid having 2 to 30 carbons. 16. A fatty acid ester of a polyglycerol having a cyclic structure in low content, comprising an ester structure formed through a dehydration reaction of a polyglycerol having a cyclic structure in low content according to claim 12 with a fatty acid having 2 to 30 carbons. 17. A fatty acid ester of a polyglycerol having a cyclic structure in low content, comprising an ester structure formed through a dehydration reaction of a polyglycerol having a cyclic structure in low content according to claim 13 with a fatty acid having 2 to 30 carbons. 18. A process for producing a fatty acid ester of a polyglycerol having a cyclic structure in low content, comprising carrying out a dehydration reaction of a polyglycerol having a cyclic structure in low content according to any one of claims 1 to 6 with a fatty acid having 2 to 30 carbons, wherein the dehydration reaction is conducted under elevated temperature. 19. A process for producing a fatty acid ester of a polyglycerol having a cyclic structure in low content, comprising carrying out a dehydration reaction of a polyglycerol having a cyclic structure in low content according to claim 7 with a fatty acid having 2 to 3 carbons. 20. A process for producing a fatty acid ester of a polyglycerol having a cyclic structure in low content, comprising carrying out a dehydration reaction of a polyglycerol having a cyclic structure in low content according to claim 12 with a fatty acid having 2 to 30 carbons. 21. A process for producing a fatty acid ester of a polyglycerol having a cyclic structure in low content, comprising carrying out a dehydration reaction of a polyglycerol having a cyclic structure in low content according to claim 13 with a fatty acid having 2 to 30 carbons. The present invention relates to a polyglycerol significantly reduced in content of a polyglycerol having a cyclic structure formed by removal of a water molecule from a polyglycerol molecule, and to a fatty acid ester of a polyglycerol having excellent surface activity. 2 mole or more of glycidol and a catalyst are successively added to 1 mole of glycerol for a reaction to obtain a polyglycerol, in which a ratio of [total polyglycerol (1)] to [total polyglycerol (2) having a cyclic structure] is [70% or more]/[30% or less] (the total of both is 100% by weight) in terms of an intensity ratio determined by liquid chromatography/mass spectrometry; and an average polymerization degree "n" is 2 or more. A reaction of a polyglycerol with a fatty acid provides the corresponding a fatty acid ester of the polyglycerol.

Full Text

DESCRIPTION
POLYGLYCEROL, FATTY ACID ESTER OF POLYGLYCEROL, AND PROCESSES FOR
PRODUCING THE SAME
Technical Field
The present invention relates to a fatty acid ester of a
polyglycerol having a cyclic structure in low content, to a
polyglycerol having a cyclic structure in low content used as a
raw material for the fatty acid ester of a polyglycerol, and to
processes for producing the same. The fatty acid ester of a
polyglycerol having a cyclic structure in low content obtained by
the present invention has high surface activity because of low content
of a dehydrated cyclic structure, and it can be used as a food additive
or a cosmetic, medical, or industrial surfactant for the purpose
of emulsification, solubilization, dispersion, washing,
anticorrosion, lubrication, static protection, wetting, and so on.
Moreover, the polyglycerol itself can be used as humectants,
thickeners, plasticizers, and for hydrophilic treatment, and so
on.
Background Art
Examples of various compounds, conventionally known as
emulsif iers or solubilizers include : ethylene oxide-based non-ionic
surfactants such as a polyoxyethylene alkyl ether, a polyoxyethylene
polyhydric alcohol/fatty acid ester, and a polyoxyethylene alkyl
phenyl ether; and food surfactants such as a sorbitan/fatty acid
ester, a sucrose/fatty acid ester, and a fatty acid ester of a
polyglycerol (including a polyglycerol ester of interesterified
ricinoleic acid).
Of those, the fatty acid ester of a polyglycerol is one of
the most useful surfactants because the fatty acid ester of a
polyglycerol ensures safety to a human body and to the environment,
can have diverse compositions, and has high versatility. The fatty
acid ester of a polyglycerol is produced by polymerizing glycerol
as one of raw materials at high temperatures in the presence of
an alkali catalyst such as caustic soda, deodorizing and decolorizing
the resultant to obtain a polyglycerol reaction product, and
subjecting the polyglycerol reaction product and a fatty acid as
raw materials to an esterification reaction.
Meanwhile, known processes for industrial production of a
polyglycerol used as a raw material are as follows:
(i) a process for producing a polyglycerol through recovery
from a distillation residue of glycerol;
(ii) aprocess for producing a polyglycerol through dehydration
condensation of glycerol;
(iii) a process for producing a polyglycerol through direct
polymerization of epichlorohydrin, hydrolysis, and then
dechlorination; and
(iv) a process for producing a polyglycerol through addition
of glycidol to glycerol or a polyglycerol in the presence of an
alkali catalyst such as NaOH or amines, or an acidic catalyst such
as acetic acid.
However, analysis of a composition distribution of the
polyglycerol reaction product obtained through each of the above
processes by liquid chromatography/mass spectrometry as described
below confirms that produced through intramolecular dehydration
are not only cyclic low molecular compounds but also a polyglycerol
having a cyclic structure in considerably high content with a
molecular weight ranging from several hundreds to several thousands,
which are formed through removal of one to several water molecule (s)
from a polyglycerol molecule.
The inventors of the present invention have found that a
polyglycerol containing the above-described polyglycerol having
a cyclic structure in high content has inhibited properties in
hydrophilicity and the like . The inventors of the present invention
have also found that deterioration of properties such as water
solubility, surface activity, and the like is caused in a fatty
acid ester of a polyglycerol obtained from the above-described
polyglycerol and a fatty acid ester.
As a polyglycerol produced through a reaction, a reaction
product obtained by reacting glycerol with epichlorohydrin or
glycidol, or by reacting glycerol or a polyglycerol with
epichlorohydrin, monochlorohydrin, dichlorohydrin, or glycidol has
been heretofore used as it is or used after having been optionally
purified.
Example of a purification process include: purification by
heating under reduced pressure of several Torr in a stream of a
gas such as nitrogen or water vapor for deodorization or removal
of unreacted raw materials; purification by removing ionic
components such as a catalyst used with an ion-exchange resin, an
ion-exchange membrane, or the like; purification by removing color
components or odor components using an absorbent such as active
carbon; and purification by reduction treatment through
hydrogenation or the like.
However, in the purification processes for a polyglycerol
reaction product, the composition distribution of the resulting
a polyglycerol reaction product has not been discussed in detail.
Regarding a polyglycerol reaction product obtained by polymerizing
the most generally used glycerol at high temperatures in the presence
of an alkali catalyst such as caustic soda, and deodorizing and
decolorizing the resultant, cyclic compounds having a low molecular
weight such as cyclic, diglycerol have been discussed extensively.
However, actually, analysis on the composition distribution of a
polyglycerol having a molecular weight in the range of several
hundreds to several thousands has been hardly discussed in spite
of a fact that a dehydration reaction is known to take place in
a polyglycerol molecule.
Commercially distributed a polyglycerol is called
tetraglycerol, hexaglycerol, or decaglycerol according to an average
polymerization degree calculated from a hydroxyl value. However,
in fact, the polyglycerol is a mixture of various glycerol polymers
each having a polymerization degree from 2 to 10 or more, and may
include unreacted glycerol (polymerization degree of 1).
It has been revealed that a polyglycerol of a relatively low
molecular weight such as glycerol, diglycerol, or triglycerol may
exist in high content in a polyglycerol containing such a mixture
of various glycerols in order to adjust the average polymerization
degree calculated from hydroxyl values to the same value.
JP-B 5-1291 (claim 1, lines 12-22 in the 3rd column, and
Examples) discloses slightly colored polyglycerol having a large
polymerization degree obtained by: adding a phosphoric acid catalyst
to glycerol or a polyglycerol; and subjecting the resultant to an
addition reaction with glycidol at 115 to 125°C.
JP-A7-216082 (claiml, paragraph 0008, and Examples) discloses
a process for producing a polyglycerol in which glycerol is
polycondensed in a boiling state of a reaction mixture at 200 to
270°C in the presence of an alkali.
JP-A 2002-30144 (claim 1, and Examples 1 to 12) discloses a
process for producing a polyglycerol in which glycidol alone is
added and allowed to react in the presence of an alkali metal halide
without the use of glycerol as an initiator.
Regarding a fatty acid ester of a polyglycerol, JP-A 7-308560
[claim 1 and Comparative Example 1 (Production of a polyglycerol
used in each Example)] discloses a process in which a polyglycerol
obtained by distilling off low molecular weight polymers from a
polyglycerol produced through polycondensation of glycerol at 240°C
in the presence of sodium hydroxide is allowed to react with a fatty
acid.
Alternatively, JP-A 8-109153 (claim 1 and Examples) discloses
a process for producing a fatty acid ester of a polyglycerol obtained
through an addition polymerization reaction of glycidol with a fatty
acid. However, a product obtained through this process is restricted
to a polyglycerol/mono-fatty acid ester alone.
Disclosure of the Invention
An object of the present invention is to provide : a polyglycerol
significantly reduced in content of a polyglycerol having a cyclic
structure formed through removal of a water molecule from a
polyglycerol molecule and a production process thereof; and a fatty
acid ester of a polyglycerol having excellent surface activity and
a production process thereof.
A polyglycerol has not been thoroughly studied so far because
a polyglycerol has physical properties of high viscosity and high
boiling point and thus because of difficulties in handling. In
particular, significance of the presence of a polyglycerol having
a cyclic structure in a polyglycerol reaction product and
significance of its removal have not been recognized. However, the
inventors of the present invention have realized that reduction
in content of a polyglycerol having a cyclic structure is necessary.
Thus, the inventors of the present invention have devoted themselves
to extensive studies and have found that glycidol and a catalyst
are added dropwise for a reaction with glycerol as a starting material,
to thereby give a polyglycerol having a cyclic structure in low
content. Thus, the inventors of the present invention have completed
the present invention.
That is, a first aspect of the present invention provides a
polyglycerol having a cyclic structure in low content, in which
a ratio of total polyglycerol (1) represented by the following general
formula [1] to total polyglycerol (2) having a cyclic structure
that contains at least one cyclic structure in a molecule, that
is, [the total polyglycerol (1) ]: [the total polyglycerol (2) having
a cyclic structure] is [70% or more]:[30% or less](the total of
both is 100 % by weight) in terms of an intensity ratio determined
by liquid chromatography/mass spectrometry; and an average
polymerization degree (repeating unit of a glycerol residue) "n"
is 2 or more:
(in the formula [1], "p" represents a repeating portion of
a glycerol residue and is an integer of 0 or more; and the polyglycerol
molecule has a polymerization degree of "p+2").
A second aspect of the present invention provides a
polyglycerol having a cyclic structure in low content according
to the first aspect of the present invention, in which the polyglycerol
(2) having a cyclic structure is a polyglycerol having a cyclic
structure that contains a structure represented by the following
general formula [2]:
(in the formula [2], "p" represents a repeating portion of
a glycerol residue and is an integer of 0 or more; "q" represents
a cyclic structure portion and is an integer of 1 or more; the
polyglycerol molecule has a polymerization degree of "p+2q+l"; the
cyclic structure portion (s) may be inserted randomly or continuously
between the glycerol residues; and the polyglycerol having a cyclic
structure in low content, which is a mixture of the polyglycerol
molecules, has an average polymerization degree "n" of 2 or more).
A third aspect of the present invention provides a polyglycerol
having a cyclic structure in low content according to the first
aspect of the present invention, in which the polyglycerol (2) having
a cyclic structure is a polyglycerol having a cyclic structure
containing a structure represented by the following general formula
[3] :
(in the formula [3], "p" represents a repeating portion of
a glycerol residue and is an integer of 0 or more; and the polyglycerol
molecule has a polymerization degree of "p+3").
A fourth aspect of the present invention provides a
polyglycerol having a cyclic structure in low content according
to the first aspect of the present invention, in which an average
polymerization degree "n" is 3 to 60.
A fifth aspect of the present invention provides a polyglycerol
having a cyclic structure in low content according to the first
aspect of the present invention, in which: a ratio of [the total
polyglycerol (l)]:[the total polyglycerol (2) having a cyclic
structure] is [80% or more]:[20% or less] (the total of both is
100% by weight); and an average polymerization degree "n" is 2 to
10.
A sixth aspect of the present invention provides a polyglycerol
having a cyclic structure in low content according to the first
aspect of the present invention, in which a ratio of [the total
polyglycerol (l)]:[the total polyglycerol (2) having a cyclic
structure] is [70% or more] : [30% or less] (the total of both is 100%
by weight); and an average polymerization degree "n" is greater
than 10.
A seventh aspect of the present invention provides a
polyglycerol having a cyclic structure in low content according
to any one of the first to sixth aspects of the present invention,
in which: a ratio of a component with a polymerization degree "n-1"
to a polyglycerol showing the highest distribution rate
(polymerization degree "n") in terms of an intensity ratio
distribution determined by liquid chromatography/mass spectrometry,
that is, (component with a polymerization degree "n-1") /(component
with a polymerization degree "n") is 0.4 or more.
An eighth aspect of the present invention provides a process
for producing a polyglycerol having a cyclic structure in low content
according to the first aspect of the present invention, characterized
by including successively adding 2 mole or more of glycidol and
a catalyst to 1 mole of glycerol for a reaction.
An ninth aspect of the present invention provides a process
for producing a polyglycerol having a cyclic structure in low content
according to the eighth aspect of the present invention, in which
the catalyst is a phosphoric acid-based acidic catalyst.
A tenth aspect of the present invention provides a process
for producing a polyglycerol having a cyclic structure in low content
according to the ninth aspect of the present invention, in which
the phosphoric acid-based acidic catalyst is phosphoric acid or
acidic phosphate.
A eleventh aspect of the present invention provides a process
for producing a polyglycerol having a cyclic structure in low content
according to any one of the eighth to tenth aspects of the present
invention, in which a reaction temperature is in a range of 80 to
130°C.
A twelfth aspect of the present invention provides a
polyglycerol having a cyclic structure in low content obtained
through the process for producing a polyglycerol having a cyclic
structure in low content according to any one of the eighth to tenth
aspects of the present invention, in which a fluctuation trend of
ratio of (component with a polymerization degree "n-1") / (component
with a polymerization degree "n") and of (component with a
polymerization degree "n+1")/(component with a polymerization
degree "n") in terms of intensity ratio determined by liquid
chromatography/mass spectrometry corresponds to a distribution
obtained through a successive reaction of glycidol using glycerol
as an initiator.
A thirteenth aspect of the present invention provides a
polyglycerol having a cyclic structure in low content obtained
through the process for producing a polyglycerol having a cyclic
structure in low content according to the eleventh aspect of the
present invention, in whicha fluctuation trendof ratio of (component
with a polymerization degree "n-1") / (component with a polymerization
degree "n") and of (component with a polymerization degree
"n+1")/(component with a polymerization degree "n") in terms of
intensity ratio determined by liquid chromatography/mass
spectrometry corresponds to a distribution obtained through a
successive reaction of glycidol using glycerol as an initiator.
A fourteenth aspect of the present invention provides a fatty
acid ester of a polyglycerol having a cyclic structure in low content,
including an ester structure formed through a dehydration reaction
of a polyglycerol having a cyclic structure in low content according
to any one of the first to sixth aspects of the present invention
with a fatty acid having 2 to 30 carbons.
A fifteenth aspect of the present invention provides a fatty
acid ester of a polyglycerol having a cyclic structure in low content,
including an ester structure formed through a dehydration reaction
of a polyglycerol having a cyclic structure in low content according
to the seventh aspect of the present invention with a fatty acid
having 2 to 30 carbons.
A sixteenth aspect of the present invention provides a fatty
acid ester of a polyglycerol having a cyclic structure in low content,
including an ester structure formed through a dehydration reaction
of a polyglycerol having a cyclic structure in low content according
to the twelfth aspect of the present invention with a fatty acid
having 2 to 30 carbons.
A seventeenth aspect of the present invention provides a fatty
acid ester of a polyglycerol having a cyclic structure in low content,
including an ester structure formed through a dehydration reaction
of a polyglycerol having a cyclic structure in low content according
to the thirteenth aspect of the present invention with a fatty acid
having 2 to 30 carbons.
A eighteenth aspect of the present invention provides a process
for producing a fatty acid ester of a polyglycerol having a cyclic
structure in low content, including carrying out a dehydration
reaction of a polyglycerol having a cyclic structure in low content
according to any one of the first to sixth aspects of the present
invention with a fatty acid having 2 to 30 carbons.
A nineteenth aspect of the present invention provides a process
for producing a fatty acid ester of a polyglycerol having a cyclic
structure in low content, including carrying out a dehydration
reaction of a polyglycerol having a cyclic structure in low content
according to the seventh aspect of the present invention with a
fatty acid having 2 to 30 carbons.
A twentieth aspect of the present invention provides a process
for producing a fatty acid ester of a polyglycerol having a cyclic
structure in low content, including carrying out a dehydration
reaction of a polyglycerol having a cyclic structure in low content
according to the twelfth aspect of the present invention with a
fatty acid having 2 to 30 carbons.
A twenty-first aspect of the present invention provides a
process for producing a fatty acid ester of a polyglycerol having
a cyclic structure in low content, including carrying out a
dehydration reaction of a polyglycerol having a cyclic structure
in low content according to the thirteenth aspect of the present
invention with a fatty acid having 2 to 30 carbons.
Brief Description of the Accompanying Drawings
Fig. 1 is a chart showing a composition distribution of a
reaction product according to Example 1.
Fig. 2 is a chart showing a composition distribution of a
reaction product according to Example 2.
Fig. 3 is a chart showing a composition distribution of a
reaction product according to Example 3.
Fig. 4 is a chart showing a composition distribution of a
reaction product according to Example 4.
Fig. 5 is a chart showing a composition distribution of a
reaction product according to Comparative Example 1.
Fig. 6 is a chart showing a composition distribution of a
reaction product according to Comparative Example 2.
Fig. 7 is a chart showing a composition distribution of a
reaction product according to Comparative Example 3.
Fig. 8 (a) is a liquid chromatogram of a reaction product
according to Example 3.
Fig. 8(b) is a liquid chromatogram of a reaction product
according to Comparative Example 1.
Fig. 8(c) is a liquid chromatogram of a reaction product
according to Comparative Example 2.
Fig. 9 is a chart showing a composition distribution of a
reaction product according to Comparative Example 4.
Best Mode for carrying out the Invention
Hereinafter, the present invention will be described indetail.
I. A polyglycerol having a cyclic structure in low content
A polyglycerol having a cyclic structure in low content of
the present invention is composed of a polyglycerol (1) represented
by the general formula [1] and a polyglycerol(2) having a cyclic
structure containing at least one cyclic structure in a polyglycerol
molecule.
In the formula [1], "p" represents a repeating portion of a
glycerol residue and is an integer of 0 or more, and the polyglycerol
molecule has a polymerization degree of "p+2". Thus, the formula
[1] represents diglycerol having a polymerization degree of 2 if
"p" is 0, triglycerol having a polymerization degree of 3 if "p"
is 1, or tetraglycerol having a polymerization degree of 4 if "p"
is 2, for example.
The cyclic structure portion in the polyglycerol (2) having
a cyclic structure is formed through a dehydration reaction of any
two hydroxyl groups of a glycerol residue in the polyglycerol (1) .
The cyclic structure can include various structures depending on
reaction conditions and so on, and is therefore not particularly
limited. Examples of a cyclic structure formed under general
reaction conditions include a 1,4-dioxahe structure (6-membered
ring), a 1, 4-dioxepane structure (7-membered ring), and a
1,5-dioxocane structure (8-membered ring).
For example, in a polyglycerol having a cyclic structure
represented by the following formula [2] , "p" represents a repeating
portion of a glycerol residue and is an integer of 0 or more. The
"q" represents a cyclic structure portion and is an integer of 1
or more. The polyglycerol molecule has a polymerization degree of
"p+2q+1". The cyclic structure portion(s) may be inserted between
the glycerol residues randomly or continuously, into a chain, or
at a terminal. Thus, the formula [2] is composed of 1 unit of
dehydrated cyclic diglycerol and 1 unit of glycerol if "p" is 0
and "q" is 1, or 2 units of glycerol and 1 unit of dehydrated cyclic
diglycerol if "p" is 1 and "q" is 1, for example. Further, the formula
[2] is composed of 3 units of glycerol and 1 unit of dehydrated
cyclic diglycerol if "p" is 2 and "q" is 1, or 4 units of glycerol
and 2 units of dehydrated cyclic diglycerol if "p" is 3 and "q"
is 2, for example.
A polyglycerol having a cyclic structure in low content of
the present invention is characterized in that a ratio of [total
polyglycerol (1)]: [total polyglycerol (2) having a cyclic structure
containing at least one cyclic structure, preferably one or two
of cyclic structure(s) in the polyglycerol molecule] is [70% or
more] : [30% or less] (the total of both is 100 % by weight) , preferably
[80% or more]:[20% or less] by liquid chromatography/mass
spectrometry (abbreviated as LC/MS) described below.
In a polyglycerol having a cyclic structure in low content
of the present invention, the total polyglycerol having one cyclic
structure is 30% or less, preferably 20% or less with respect to
the total polyglycerol (1) . The total polyglycerol having two cyclic
structures is one third or less of the total polyglycerol having
one cyclic structure, and the total polyglycerol having three cyclic
structures is one fifth or less of the total polyglycerol having
two cyclic structures. Thus, the polyglycerol having three cyclic
structures, if any, is present in the polyglycerol in very low content.
The polyglycerol (1) in the polyglycerol having a cyclic
structure in low content of the present invention has an average
polymerization degree (repeating unit of a glycerol residue) "n"
of 2 or more, preferably 3 to 60, particularly preferably 3 to 50.
In the polyglycerol having a cyclic structure in low content
of the present invention, the ratio of a polyglycerol (2) having
a cyclic structure tends to increase gradually with increasing
average polymerization degree "n" of a polyglycerol (1) . If the
average polymerization degree "n" of a polyglycerol (1) is from
2 to 10, the ratio of [the total polyglycerol (l)]:[the total
polyglycerol (2) having a cyclic structure] is [80% or more]: [20%
or less], preferably [85% or more]:[15% or less], more preferably
[90% or more]:[10% or less]. If the average polymerization degree
"n" of a polyglycerol (1) is greater than 10, the ratio of [the
total polyglycerol (1) ]: [the total polyglycerol (2) having a cyclic
structure] is [70% or more]:[30% or less], preferably [75% or
more]: [25% or less], more preferably [80% or more]: [20% or less] .
Moreover, in a polyglycerol having a cyclic structure in low
content of the present invention, the ratio of a component with
a polymerization degree "n-1" to a polyglycerol showing the highest
distribution rate (polymerization degree "n") in terms of an
intensity ratio distribution determined by liquid
chromatography/mass spectrometry, that is, (component with a
polymerization degree "n-1")/(component with a polymerization
degree "n") is 0.4 or more, and 0.5 or more and even 0.7 or more
with increasing average polymerization degree "n" of a polyglycerol
(1) .
Furthermore, in a polyglycerol having a cyclic structure in
small amount obtained through a production process of the present
invention, a fluctuation trend of ratio of (component with a
polymerization degree "n-1")/(component with a polymerization
degree "n") and of (component with a polymerization degree
"n+1")/(component with a polymerization degree "n") in terms of
intensity ratio determined by liquid chromatography/mass
spectrometry corresponds to a distribution obtained through a
successive reaction of glycidol using glycerol as an initiator.
A polyglycerol having such a distribution easily improves solvency
and acquires required HLB (hydrophilicity-lipophilicity balance) .
A polyglycerol (1) may contain a low content of a branched
structure having glycidol added to a secondary hydroxyl group.
A reaction product contains approximately 1 to 15%, preferably
10% or less of other compounds (e.g. , a polyglycerol having a double
bond in the polyglycerol molecule) in addition to the above-described
polyglycerol (1) and a polyglycerol (2) , andglycerol as a rawmaterial.
The content of other compounds increases with increasing average
polymerization degree of a polyglycerol (1).
An LC/MS analysis system is composed of LC and MS portions,
and an interface connecting them. The MS portion as a detection
system operates on a principle common with that of a GC/MS analysis
system, which employs a technique of detecting and identifying
ionized target substances on the basis of a mass number/charge (m/z)
ratio.
Processes for obtaining information from MS connected to
chromatography include a mass chromatogram showing a time
distribution of an intensity of an arbitrary m/z, a mass spectrum
showing a relative intensity distribution of each m/z at an arbitrary
time, and a total ion chromatogram (TIC) showing a time change of
total intensity, not of an intensity of individual m/z, obtained
by adding intensities (quantities of electricity) of all ions. Of
those processes, the total ion chromatogram is preferably used.
Processes for obtaining the mass chromatogram include a
scanning method for extracting a time distribution of required m/z
intensity from intensity information in a time axis direction
obtained through magnetic field scanning within a certain m/z range
at a constant time interval, and a selected ion monitoring (SIM)
method with high sensitivity for selectively detecting only an
intensity of a target single m/z or intensities of a plurality of
m/z's.
Examples of a basic principle of a mass spectrometer in
practical use include a magnetic sector type, a quadrupole type,
an ion trap type, a flying time, and a Fourier transform type. Of
those spectrometers, the ion trap type spectrometer is preferred.
A polyglycerol having a cyclic structure in low content of
the present invention is obtained by successively adding a catalyst
and glycidol to a reactor charged with water or glycerol as an
initiator for an addition polymerization reaction.
The catalyst is preferably a phosphoric acid-based acidic
catalyst. Examples of the above-described phosphoric acid-based
acidic catalyst include phosphoric acids and phosphates. Specific
examples thereof include: phosphoric acids such as phosphoric acid,
phosphoric anhydride, polyphosphoric acid, orthophosphoric acid,
metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, and
tetraphosphoric acid; and acidic phosphates such as methyl acid
phosphate, ethyl acid phosphate, isopropyl acid phosphate, butyl
acid phosphate, and 2-ethylhexyl acid phosphate. It is noted that
those acidic phosphates can be used in any forms such as a monoester,
a diester, and a mixture thereof. Of those, phosphoric acid and
acidic phosphate are preferably used. One of the above-described
catalysts may be used alone, or two or more of them may be used
as a mixture.
An addition amount of the catalyst is 0.001 to 1% by weight,
preferably 0.01 to 0.5% by weight with respect to a resulting
polyglycerol. The addition amount of less than 0.001% by weight
provides a small reaction rate. On the other hand, the addition
amount of more than 1% by weight easily promotes hydrolysis in
esterification with a fatty acid due to the remaining phosphoric
acid. As a result, the addition amount of more than 1% by weight
causes a deleterious effect on the performance of a product such
as insufficient stability of an aqueous solution.
Glycerol is placed in a reactor and 2 mole or more of glycidol
and a catalyst are successively added to 1 mole of the glycerol
for a reaction, to name one example of a reaction process.
Alternatively, in the case of using water as an initiator,
water is placed in a reactor and a reaction is carried out in the
same manner as that described above.
The catalyst and glycidol may be separately added dropwise
(separately charged), or may be added dropwise in a mixed state.
It is not preferred that the dropping of the catalyst be terminated
too early compared with that of glycidol. Although the rate of
dropping thereof is not particularly limited, it is preferred that
the catalyst and glycidol be added dropwise at a uniform rate as
a whole.
A reaction temperature is in the range of 80°C to 130°C,
preferably 85°C to 125°C, more preferably 90°C to 120°C. When the
temperature is lower than 80°C, the reaction rate is small. When
the temperature is higher than 130°C, intramolecular dehydration
takes place easily, thereby increasing the content of a polyglycerol
having a cyclic structure.
Moreover, the reaction is desirably carried out under an inert
gas atmosphere such as nitrogen gas, and may be optionally carried
out under compressed or reduced pressure conditions. The reaction
rate can be increased in a reaction under compressed conditions.
A conversion of glycidol is 98% or more, preferably 99.5% or
more, more preferably 99.9% or more.
The obtained polyglycerol having a cyclic structure in low
content may be purified as required for use of a product. A
purification process is not particularly limited, and any of
processes known in the art may be employed. For example, a
polyglycerol may be purified through an absorption treatment with
active carbon, activated clay, or the like, a treatment under reduced
pressure using water vapor, nitrogen, or the like as a carrier gas,
washing with an acid or an alkali, or molecular distillation.
Alternatively, unreacted polyglycerol and the like may be separated
and removed through liquid-liquid distribution, or using an
absorbent, a resin, a molecular sieve, a loose reverse osmosis
membrane, an ultrafiltration membrane, or the like.
Furthermore, lowmolecular weight substances such as unreacted
glycerol and glycerol dimer in the above-described reaction product
may be optionally removed through distillation or the like from
a polyglycerol having a cyclic structure in low content of the present
invention.
II. Fatty acid ester of a polyglycerol having a cyclic structure
in low content
A fatty acid ester of a polyglycerol having a cyclic structure
in low content according to the present invention is a fatty acid
ester of a polyglycerol having a cyclic structure in low content,
which has an ester structure formed through dehydration of the
above-described polyglycerol having a cyclic structure in low
content of the present invention and a fatty acid.
Examples of a process for producing the fatty acid ester of
a polyglycerol having a cyclic structure in low content according
to the present invention can include a process through dehydration
esterification of a polyglycerol having a cyclic structure in low
content with a fatty acid, a process through removal of low molecular
weight alcohol from an ester of a fatty acid with a low molecular
weight alcohol and a polyglycerol having a cyclic structure in low
content, a process through removal of a low molecular weight fatty
acid from an ester of a low molecular weight fatty acid with a
polyglycerol having a cyclic structure in low content and a higher
fatty acid, and a process through removal of an alkali halide from
a fatty acid halide, a polyglycerol having a cyclic structure in
low content, and caustic alkali. Of those processes, there is
economical the process through dehydration esterification of a
polyglycerol having a cyclic structure in low content with a fatty
acid.
In the process through dehydration esterif ication, for example,
the dehydration esterification can be carried out under normal
pressure or reduced pressure in the presence of an alkali catalyst
or an acid catalyst, or in the absence of a catalyst. A polyglycerol
having a cyclic structure in low content and a fatty acid must be
added in an amount appropriately selected according to the purpose
of a product. For example, in the case of intending to obtain a
hydrophilic surfactant, a polyglycerol having a cyclic structure
in low content and a fatty acid may be added in equimolar amounts
by calculating weights thereof from a hydroxyl value (also referred
to as an OH value) of a polyglycerol having a cyclic structure in
low content and a molecular weight of a fatty acid. In the case
of intending to obtain a lipophilic surfactant, mole number of the
fatty acid may be increased.
The obtained fatty acid ester of a polyglycerol having a cyclic
structure in low content may be purified as required for use of
a product. The purification process is not particularly limited,
and any of processes known in the art may be employed. For example,
the fatty acid ester of a polyglycerol may be purified through an
absorption treatment with activated carbon, activated clay, or the
like, a treatment under reduced pressure using water vapor, nitrogen,
or the like as a carrier gas, washing with an acid or an alkali
or molecular distillation. Alternatively, unreacted polyglycerol
and the like may be separated and removed through liquid-liquid
distribution, or using an absorbent, a resin, a molecular sieve,
a loose reverse osmosis membrane, an ultrafiltration membrane, or
the like.
Additive
An additive may be added to the fatty acid ester of a polyglycerol
having a cyclic structure in low content of the present invention
to allow easy handling of a product. Examples of the additive include
ethanol, propylene glycol, glycerol, a polyglycerol, water, liquid
sugar, and oils and fats for reducing a viscosity of a product.
One additive or two or more additives may be added to dissolve or
emulsify the fatty acid ester of a polyglycerol. Alternatively,
polysaccharide such as lactose or dextrin, or a protein such as
caseinate may be added to pulverize the fatty acid ester of a
polyglycerol.
Depending on the purpose for use, the fatty acid ester of a
polyglycerol having a cyclic structure in low content of the present
invention may be mixed with other surfactants as additives to produce
a product of a surfactant. Examples of the other surfactants that
can be used include nonionic surfactants, amphoteric surfactants,
anionic surfactants, and cationic surfactants. Examples of the
nonionic surfactants include: lecithin such as soybean lecithin,
yolk lecithin, or rapeseed lecithin, or a partial hydrolysate
thereof; monoglycerides such as monoglycerides of caprylic acid,
capric acid, lauric acid, myristic acid, palmitic acid, stearic
acid, behenic acid, oleic acid, elaidic acid, ricinoleic acid, and
interesterified ricinoleic acid, a monoglyceride mixture thereof,
or a monoglyceride of an organic acid which is an organic acid ester
of the monoglyceride with an organic acid such as acetic acid, citric
acid, succinic acid, malic acid, and tartaric acid; a fatty acid
ester of sorbitan such as a sorbitan ester of caprylic acid, capric
acid, lauric acid, myristic acid, palmitic acid, stearic acid,
behenic acid, oleic acid, elaidic acid, ricinoleic acid, and
interesterif ied ricinoleic acid; propylene glycol/fatty acid esters
such as propylene glycols of caprylic acid, capric acid, lauric
acid, myristic acid, palmitic acid, stearic acid, behenic acid,
oleic acid, elaidic acid, ricinoleic acid, and interesterified
ricinoleic acid; and sucrose/fatty acid esters such as sucrose esters
of caprylic acid, capric acid, lauric acid, myristic acid, palmitic
acid, stearic acid, behenic acid, oleic acid, elaidic acid,
ricinoleic acid, and interesterified ricinoleic acid.
[Examples]
Hereinafter, the present invention will be more specifically
described with reference to examples, but the present invention
is not limited thereto.
It is to be noted that throughout Examples and Comparative
Examples, analysis conditions for LC/MS (Liquid Chromatography/Mass
Spectrometry) are as follows.
(Conditions for LC separation)
Column: TSKgel a-2500 (7.8 x 300 mm) (aqueous polymeric gel
column)
Temperature: 40°C
Eluent: water/acetonitrile = 7/3
Flow rate: 0.8 ml/min
Injection volume: 10 µl (sample concentration of 100 ppm)
Analysis time: 20 minutes
(Conditions for MS analysis)
Apparatus: LCQ (manufactured by ThermoQuest, ion trap type)
Ionization mode: APCI (Atmospheric Pressure Chemical
Ionization), negative
Measurement range: m/z = 90 to 2,000
Method for intensity ratio measurement: through a mass
spectrometric analysis indicating a relative intensity distribution
of each m/z at an arbitrary time.
(Example 1)
Into a 1 L four-neck flask equipped with a nitrogen introduction
pipe, a stirrer, a cooling pipe, a thermoregulator, and a dropping
cylinder, 4 . 0 mole (368.4 g) of glycerol was added, and the glycerol
was heated to 100°C. While a reaction temperature was maintained
at 100°C, 8.0 mole (592.6 g) of glycidol and 1.922 g of phosphoric
acid (a product of 85%) were separately dropped therein over 6 hours
to continue a reaction until a concentration of oxirane in the system
reached less than 0.1%. After cooling, a reaction product was taken
out to obtain approximately 950 g of a polyglycerol (PGL 3: average
polymerization degree of approximately 3) . The polyglycerol showed
an OH value of 1,170mg-KOH/g. The obtained polyglycerol was analyzed
by the above LC/MS. Fig. 1 shows the results of componential analysis .
In each of figures below showing the results of componential analysis,
the numbers of a horizontal axis represent degrees of polymerization
of a polyglycerol, and a vertical axis indicates a relative intensity
with a bar graph. On the horizontal axis, a polyglycerol (1), a
polyglycerol (2) having one cyclic structure that contains one cyclic
structure, and a polyglycerol (2) having a cyclic structure that
contains two cyclic structures are indicated with the bar graphs
drawn side by side for each polymerization degree. In each of the
figures, Ideal PGL Groups (PGL) represents a polyglycerol (1), and
PGL-H2O, PGL-2H2O, and the like, represent a polyglycerol having
a cyclic structure formed through removal of one water molecule,
a polyglycerol having a cyclic structure formed through removal
of two water molecules, and the like, respectively.
In the intensity ratio distribution of a polyglycerol of Fig.
1, the polymerization degree "n" of a polyglycerol showing the mode
(the highest distribution rate) was 4, and the ratio of (component
with a polymerization degree "n-1") / (component with a polymerization
degree "n") was 0.5327.
Table 1 Intensity ratio in componential analysis of a polyglycerol
in Example 1
[The polymerization degree "n" of a polyglycerol showing the highest
distribution rate (mode) was 4]
As Table 1 shows, in the reaction product obtained in the
polymerization step according to the process of the present invention,
components with varying degrees of polymerization except unreacted
glycerol provided a distribution corresponding to that obtained
through a successive reaction of glycidol using glycerol as an
initiator. The reaction product having such a distribution can have
improved solvency and so on, though depending on kinds of solutes.
(Example 2)
Into a 2 liter four-neck flask having equipment similar to
those of Example 1, 4.4 mole (405.2 g) of glycerol was added, and
the glycerol was heated to 120°C. Subsequently, while a reaction
temperature was maintained at 120 °C, 22.0mole (l,629.8g) of glycidol
and 2.035 g of phosphoric acid (a product of 85%) were separately
dropped therein over 6 hours to continue the reaction until the
concentration of oxirane in the system reached less than 0.1%. After
cooling, a reaction product was taken out to obtain approximately
2,000 g of a polyglycerol (PGL 6: average polymerization degree
of approximately 6). The polyglycerol showed an OH value of 970
mg-KOH/g. Fig. 2 shows the LC/MS analysis results of the obtained
polyglycerol. As Table 2 shows, in the reaction product obtained
in the polymerization step according to the process of the present
invention, components with varying degrees of polymerization except
unreacted glycerol provided a preferred distribution as that in
Example 1.
Table 2 Intensity ratio in componential analysis of a polyglycerol
in Example 2
[The polymerization degree "n" of a polyglycerol showing the highest
distribution rate (mode) was 8]
(Example 3)
Into the same flask as that used in Example 2, 2.0 mole (188
g) of glycerol was added, and the glycerol was heated to 100°C.
Subsequently, while a reaction temperature was maintained at 100°C,
18.0 mole (1,332 g) of glycidol and 1.525 g of phosphoric acid (a
product of 85%) were separately dropped therein over 6 hours to
continue the reaction until the concentration of oxirane in the
system reached less than 0.1%. After cooling, a reaction product
was taken out to obtain approximately 1,500 g of a polyglycerol
(PGL 10: average polymerization degree of approximately 10). The
polyglycerol showed an OH value of 885 mg-KOH/g. Fig. 3 shows the
LC/MS analysis results of the obtained polyglycerol. As Table 3
shows, in the reaction product obtained in the polymerization step
according to the process of the present invention, components with
varying degrees of polymerization except unreacted glycerol provided
a preferred distribution as that in Example 1.
Fig. 8(a) shows a liquid chromatogram of the reaction product
of Example 3. In each of the liquid chromatograms shown below, the
horizontal axis represents an elution time and the vertical axis
represents a peak intensity (unit mV) of the chromatogram.
Table 3 Intensity ratio in componential analysis of a polyglycerol
in Example 3
[The polymerization degree "n" of a polyglycerol showing the highest
distribution rate (mode) was 8]
(Example 4)
Into the same flask as that used in Example 2, 0.5 mole (47
g) of glycerol was added, and the glycerol was heated to 120°C.
Subsequently, while a reaction temperature was maintained at 120°C,
19.5 mole (1,443 g) of glycidol and 1.525 g of phosphoric acid (a
product of 85%) were separately dropped therein over 12 hours to
continue the reaction until the concentration of oxirane in the
system reached less than 0.1%. After cooling, a reaction product
was taken out to obtain approximately 1,500 g of a polyglycerol
(PGL 40: average polymerization degree of approximately 40) . The
polyglycerol showed an OH value of 787 mg-KOH/g. Fig. 4 shows the
LC/MS analysis results of the obtained polyglycerol. As Table 4
shows, in the reaction product obtained in the polymerization step
according to the process of the present invention, components with
varying degrees of polymerization except unreacted glycerol provided
a preferred distribution as that in Example 1.
Table 4 Intensity ratio in componential analysis of a polyglycerol
in Example 4.
[The polymerization degree "n" of a polyglycerol showing the highest
distribution rate (mode) was 8]
(Comparative Example 1)
Commercially available decaglycerol (available from Sakamoto
Yakuhin Co., Ltd., Decaglycerol #750; a polyglycerol obtained
through dehydration condensation of glycerol, OH value of 8 90
mg-KOH/g) was analyzed by the above LC/MS. Fig. 5 shows the results
of componential analysis . The decaglycerol contains a polyglycerol
(2) having a cyclic structure in very high content.
(Comparative Example 2)
Commercially available decaglycerol (available from Kashima
Chemical Co., Ltd., KCOL-IV-750; a polyglycerol obtained from
epichlorohydrin, OH value of 882 mg-KOH/g) was analyzed by the above
LC/MS. Fig. 6 shows the results of componential analysis. The
decaglycerol contains a polyglycerol (2) having a cyclic structure
in high content.
(Comparative Example 3)
Into the same flask as that used in Example 2, 2.0 mole (188
g) of glycerol was added, and the glycerol was heated to 140°C.
Subsequently, while a reaction temperature was maintained at 140°C,
18.0 mole (1,332 g) of glycidol and 1.525 g of phosphoric acid (a
product of 85%) were separately dropped therein over 6 hours to
continue the reaction until the concentration of oxirane in the
system reached less than 0.1%. After cooling, a reaction product
was taken out to obtain approximately 1,500 g of a polyglycerol
(PGL 10 of Comparative Example 3: average polymerization degree
of approximately 10) . The polyglycerol showed an OH value of 887
mg-KOH/g. Fig. 7 shows the LC/MS analysis results of the obtained
polyglycerol. The polyglycerol contains a polyglycerol (2) having
a cyclic structure and other compounds in high content.
(Comparative Example 4)
A reaction was carried out in the same manner as in Example
3 except that 18.0 mole (1,332 g) of glycidol was added dropwise
over 6 hours into a flask charged with 2.0 mole (188 g) of glycerol
and 1.525 g of phosphoric acid (a product of 85%). The resulting
polyglycerol showed an OH value of 885 mg-KOH/g. Approximately 1,500
g of a polyglycerol (PGL 10 of Comparative Example 4: average
polymerization of approximately 10) was obtained. Fig. 9 shows the
LC/MS analysis results of the obtained polyglycerol. The
polyglycerol contains a polyglycerol (2) having a cyclic structure
and other compounds in high content.
As described above, glycidol and a catalyst are successively
added for a reaction with glycerol, to thereby significantly reduce
the amounts of the by-products of a polyglycerol having a cyclic
structure. Meanwhile, in the process involving dropping of either
glycidol or a catalyst, the amounts of the by-products of a
polyglycerol having a cyclic structure are large. Moreover, when
a reaction temperature exceeds 130°C, the amounts of the by-products
of a polyglycerol having a cyclic structure increase.
Hereinafter, the production of a fatty acid ester of a
polyglycerol and its evaluation will be shown.
(Example 5)
Into a reactor with a volume of 2 liter equipped with a stirrer,
a thermometer, a heating jacket, a gas-feed port, and a raw
material-feed port, 1,200 g of a polyglycerol obtained in Example
3 (PGL 10: average polymerization degree of approximately 10) was
added. Subsequently, lauric acid (99% purity) and a 10% sodium
hydroxide aqueous solution were added thereto. The addition amount
of lauric acid was adjusted such that a molar ratio of lauric acid/a
polyglycerol was 1/1. The amount of sodium hydroxide was 0.0025%
by weight with respect to the total amount of a polyglycerol and
lauric acid.
After an internal temperature was elevated to 240°C under
normal pressure in a stream of a nitrogen gas for a 3-hour reaction,
the internal temperature was further elevated to 260°C for a reaction
for 4 hours . After completion of the reaction, the reactor was cooled
to normal temperature to obtain a lauric acid ester of a polyglycerol
(PGLE-1).
(Comparative Example 5)
Esterif ication was carried out in the same manner as in Example
5 to obtain a lauric acid ester of polyglycerol(PGLE-2), except
that the Decaglycerol #750 of Comparative Example 1 was used instead
of the polyglycerol (PGL 10:average polymerization degree of
approximately 10).
(Evaluation of a fatty acid ester of a polyglycerol)
PGLE-1 obtained in Example 5 and PGLE-2 obtained in Comparative
Example 5 were respectively dissolved in desalted water to prepare
10% aqueous solutions. The states of the solutions stored at 5°C
were observed with time. Table 5 shows the results.
Table 5
Industrial Applicability
A polyglycerol having a cyclic structure in low content
according to the present invention has a reduced content of a
polyglycerol having a cyclic structure formed through intramolecular
dehydration, and thus has a large OH value. As a result, the
polyglycerol having a cyclic structure in low content can be used
in humectants, thickeners, plasticizers, hydrophilic treatment,
and so on. Moreover, a fatty acid ester of a polyglycerol obtained
from the polyglycerol and a fatty acid ester has enhanced properties
such as emulsification, solubilization, dispersion, washing,
anticorrosion, lubrication, static protection, wetting, and can
be used as additives for foods and cosmetic, medical, and industrial
surfactants. Furthermore, the polyglycerol itself can be used in
humectants, thickeners, plasticizers, hydrophilic treatment, and
so on.
We Claim:
1. A polyglycerol having a cyclic structure in low content,
wherein:
a ratio of [total polyglycerol (1) represented by the following
general formula [1]] to [total polyglycerol (2) having a cyclic
structure that contains at least one cyclic structure in a molecule] ,
that is, [the total polyglycerol (1)] : [the total polyglycerol (2)
having a cyclic structure] is 70% or more : 30% or less (the total
of both is 100% by weight) in terms of an intensity ratio determined
by liquid chromatography/mass spectrometry; and
an average polymerization degree (repeating unit of a glycerol
residue) "n" is 2 or more:
(in the formula [1], "p" represents a repeating portion of
a glycerol residue and is an integer of 0 or more, and a polyglycerol
molecule has a polymerization degree of "p+2").
2. A polyglycerol having a cyclic structure in low content
according to claim 1, wherein the polyglycerol (2) having a cyclic
structure comprises a polyglycerol having a cyclic structure
containing a structure represented by the following general formula
[2] :
(in the formula [2], "p" represents a repeating portion of
a glycerol residue and is an integer of 0 or more; "q" represents
a cyclic structure portion and is an integer of 1 or more; the
polyglycerol molecule has a polymerization degree of "p+2q+l"; the
cyclic structure portion (s) may be inserted randomly or continuously
between the glycerol residues; and the polyglycerol having a cyclic
structure in low content, which is a mixture of the polyglycerol
molecules, has an average polymerization degree "n" of 2 or more).
3. A polyglycerol having a cyclic structure in low content
according to claim 1, wherein the polyglycerol (2) having a cyclic
structure comprises a polyglycerol having a cyclic structure
containing a structure represented by the following general formula
[3]:
(in the formula [3], "p" represents a repeating portion of
a glycerol residue and is an integer of 0 or more; and the polyglycerol
molecule has a polymerization degree of "p+3").
4. A polyglycerol having a cyclic structure in low content
according to claim 1, wherein an average polymerization degree "n"
is 3 to 60.
5. A polyglycerol having a cyclic structure in low content
according to claim 1, wherein a ratio of [the total polyglycerol
(1) ] : [the total polyglycerol (2) having a cyclic structure] is [80%
or more] : [20% or less] (the total of both is 100% by weight); and
an average polymerization degree "n" is 2 to 10.
6. A polyglycerol having a cyclic structure in low content
according to claim 1, wherein a ratio of [the total polyglycerol
(1) ] : [the total polyglycerol (2) having a cyclic structure] is [70%
or more]: [30% or less] (the total of both is 100% by weight); and
an average polymerization degree "n" is greater than 10.
7. A polyglycerol having a cyclic structure in low content
according to any one of claims 1 to 6, wherein
a ratio of a component with a polymerization degree "n-l" to
a polyglycerol showing the highest distribution rate (with a
polymerization degree "n") in terms of an intensity ratio
distribution determined by liquid chromatography/mass
spectrometry, that is, (component with a polymerization degree "n-
1") / (component with a polymerization degree "n") is 0.4 or more.
8. A process for producing a polyglycerol having a cyclic structure
in low content according to claim 1, wherein comprising
successively adding 2 mole or more of glycidol and a catalyst to 1
more of glycerol for a reaction wherein a reaction temperature is in
a range of 80 to 130°C.
9. A process for producing a polyglycerol having a cyclic structure in
low content according to claim 8 , wherein the catalyst comprises a
phosphoric acid-based acidic catalyst.
10. A process for producing a polyglycerol having a cyclic structure in
low content according to claim 9, wherein the phosphoric acid-
based acidic catalyst comprises phosphoric acid or acidic
phosphate.
11. A process for producing a polyglycerol having a cyclic structure in
low content according to any one of claims 8 to 10, wherein a
reaction temperature is in a range of 80 to 130°C.
12. A polyglycerol having a cyclic structure in low content
obtained through the process for producing a polyglycerol having
a cyclic structure in low content according to any one of claims
8 to 10, wherein a fluctuation trend of ratio of (component with
a polymerization degree "n-1") / (component with a polymerization
degree "n") and of (component with a polymerization degree "n+1")
/ (component with a polymerization degree "n") in terms of intensity
ratio determined by liquid chromatography/mass spectrometry
corresponds to a distribution obtained through a successive reaction
of glycidol using glycerol as an initiator.
13. A polyglycerol having a cyclic structure in low content
obtained through the process for producing a polyglycerol having
a cyclic structure in low content according to claim 11, wherein
a fluctuation trend of ratio of (component with a polymerization
degree "n-1") / (component with a polymerization degree "n") and
of (component with a polymerization degree "n+1") / (component with
a polymerization degree "n") in terms of intensity ratio determined
by liquid chromatography/mass spectrometry corresponds to a
distribution obtained through a successive reaction of glycidol
using glycerol as an initiator.
14. A fatty acid ester of a polyglycerol having a cyclic
structure in low content, comprising an ester structure formed
through a dehydration reaction of a polyglycerol having a cyclic
structure in low content according to any one of claims 1 to 6 with
a fatty acid having 2 to 30 carbons.
15. A fatty acid ester of a polyglycerol having a cyclic structure in low
content, comprising an ester structure formed through a
dehydration reaction of a polyglycerol having a cyclic structure in
low content according to claim 7 with a fatty acid having 2 to 30
carbons.
16. A fatty acid ester of a polyglycerol having a cyclic structure in low
content, comprising an ester structure formed through a
dehydration reaction of a polyglycerol having a cyclic structure in
low content according to claim 12 with a fatty acid having 2 to 30
carbons.
17. A fatty acid ester of a polyglycerol having a cyclic structure in low
content, comprising an ester structure formed through a
dehydration reaction of a polyglycerol having a cyclic structure in
low content according to claim 13 with a fatty acid having 2 to 30
carbons.
18. A process for producing a fatty acid ester of a polyglycerol having
a cyclic structure in low content, comprising carrying out a
dehydration reaction of a polyglycerol having a cyclic structure in
low content according to any one of claims 1 to 6 with a fatty acid
having 2 to 30 carbons, wherein the dehydration reaction is
conducted under elevated temperature.
19. A process for producing a fatty acid ester of a polyglycerol having
a cyclic structure in low content, comprising carrying out a
dehydration reaction of a polyglycerol having a cyclic structure in
low content according to claim 7 with a fatty acid having 2 to 3
carbons.
20. A process for producing a fatty acid ester of a polyglycerol having
a cyclic structure in low content, comprising carrying out a
dehydration reaction of a polyglycerol having a cyclic structure in
low content according to claim 12 with a fatty acid having 2 to 30
carbons.
21. A process for producing a fatty acid ester of a polyglycerol having
a cyclic structure in low content, comprising carrying out a
dehydration reaction of a polyglycerol having a cyclic structure in
low content according to claim 13 with a fatty acid having 2 to 30
carbons.
The present invention relates to a polyglycerol significantly reduced in
content of a polyglycerol having a cyclic structure formed by removal of a
water molecule from a polyglycerol molecule, and to a fatty acid ester of a
polyglycerol having excellent surface activity. 2 mole or more of glycidol
and a catalyst are successively added to 1 mole of glycerol for a reaction to
obtain a polyglycerol, in which a ratio of [total polyglycerol (1)] to [total
polyglycerol (2) having a cyclic structure] is [70% or more]/[30% or less]
(the total of both is 100% by weight) in terms of an intensity ratio
determined by liquid chromatography/mass spectrometry; and an average
polymerization degree "n" is 2 or more. A reaction of a polyglycerol with a
fatty acid provides the corresponding a fatty acid ester of the polyglycerol.

Documents:

1218-KOLNP-2005-FORM-27.pdf

1218-kolnp-2005-granted-abstract.pdf

1218-kolnp-2005-granted-claims.pdf

1218-kolnp-2005-granted-correspondence.pdf

1218-kolnp-2005-granted-description (complete).pdf

1218-kolnp-2005-granted-drawings.pdf

1218-kolnp-2005-granted-examination report.pdf

1218-kolnp-2005-granted-form 1.pdf

1218-kolnp-2005-granted-form 2.pdf

1218-kolnp-2005-granted-form 26.pdf

1218-kolnp-2005-granted-form 3.pdf

1218-kolnp-2005-granted-form 5.pdf

1218-kolnp-2005-granted-reply to examination report.pdf

1218-kolnp-2005-granted-specification.pdf

1218-kolnp-2005-granted-translated copy of priority document.pdf

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Patent Number

227662

Indian Patent Application Number

1218/KOLNP/2005

PG Journal Number

03/2009

Publication Date

16-Jan-2009

Grant Date

14-Jan-2009

Date of Filing

23-Jun-2005

Name of Patentee

DAICEL CHEMICAL INDUSTRIES, LTD

Applicant Address

1, TEPPOCHO, SAKAI-SHI, OSAKA

Inventors:

#	Inventor's Name	Inventor's Address
1	ENDO TOSHIO	13-5, KUBA 4-CHOME, OHTAKE-SHI HIROSHIMA 739-0651
2	OMORI HIDETOSHI	12-21, MONZEN-CHO 1-CHOME, IWAKUNI-SHI, YAMAGUCHI 740-0031

PCT International Classification Number

C07C 41/03

PCT International Application Number

PCT/JP2003/015295

PCT International Filing date

2003-11-28

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	2002 346431	2002-11-28	Japan