Title of Invention	" A DETERGENT COMPOSITION "
Abstract	A detergent composition comprising from about 70% of a surfactant, and from about 0.05% to about 10% of a dye maintenance polymer or oligomer having at least three net positive charges per molecule. The dye maintenance polymer should have a Dye Maintenance Parameter, as determined by the Dye Maintenance Parameter Test defined herein, of greater than about 0.23. Further, the dye maintenance polymer is not a polyethyleneimine or alkoxylated derivative thereof.

Title of Invention

" A DETERGENT COMPOSITION "

Abstract

A detergent composition comprising from about 70% of a surfactant, and from about 0.05% to about 10% of a dye maintenance polymer or oligomer having at least three net positive charges per molecule. The dye maintenance polymer should have a Dye Maintenance Parameter, as determined by the Dye Maintenance Parameter Test defined herein, of greater than about 0.23. Further, the dye maintenance polymer is not a polyethyleneimine or alkoxylated derivative thereof.

Full Text	FIELD OF THE INVENTION The present invention relates to a biaxially oriented transparent holographic film consisting of polypropylene polymer and the process for the manufacture of the said biaxially oriented, transparent holographic film to be used for packaging to avoid the piracy of the said package The film presents a magnificient colour rainbow under any form of light, not only attracting immediate attention but also complimenting the product Other than packaging application the film can also be used as labels. More particularly the subject invention relates to an improved biaxially oriented multilayer holographic film with unique property of being directly embossable and also suitable for mechanical enginnering followed by metalization. The object of the invention is to provide an improved biaxially oriented holographic film having excellent optical properties, enhanced durability and dimentional stability. Another object of the invention is to provide an improved biaxially oriented holographic film having polar polymers and excellent hot slip properties Yet another object of the invention is to provide a novel process for manufacturing a biaxially oriented holographic film comprising co-extruding at least one polypropylene layer and having a third layer containing polar polymers BACKGROUND OF THE INVENTION Conventionally transparent oriented polyolefin films are used widely as packaging materials. Since the film have excellent optical properties, they are used in large quantities in graphic industries for lamination namely solvent lamination, water based lamination, dry lamination, dry lamination etc. of printed products. Given the foregoing, there is clearly an ongoing need to identify materials which could be added to laundry products that would associate themselves with the fibers of the fabrics and textiles laundered using such products and thereby reduce or minimize the tendency of the laundered fabric/textiles to deteriorate in appearance Any such detergent product additive material should, of course, be able to benefit fabric appearance and integrity without undulv interfering with the ability of the laundry product to perform its intended "function The present invention is directed to the use of dye maintenance polymers in laundry applications that perform in this desired manner, and a test for determining the Dye Maintenance Parameter for any given polymer SUMMARY OF THE INVENTION The present invention is directed to a detergent composition comprising. a) from about 4% to about 70% of a surfactant that is preferably selected from the group consisting of nonionic, anionic, cationic, amphoteric, zwittenonic surfactants and mixtures thereof, and is even more preferably an anionic surfactant; b) from about 0.01% to about 10%, preferably from about 0.1% to about 8%, more preferably from about 0.5% to about 6%, and most preferably from about 0.8% to about 5% of a dye maintenance polymer or oligomer having at least three net positnc charges per molecule and having a Dye Maintenance Parameter, as determined by the Dye Maintenance Parameter Test, of greater than about 0.23, preferably greater than about 0.6 more preferably greater than about 0 8 and most preferably greater than about 0 9 The dye maintenance polymer is not a polyethyleneimine or alkoxylated derivative thereof In another aspect of this invention there is provided a fabnc conditioning composition comprising: a) from about 1% to about 80% of a fabnc softening active; and b) from about 0.01 % to about 50%, preferably from about 0.1% to about 40%, more preferably from about 0 5% to about 30%, and most preferably from about 0 8% to about 20% of a dye maintenance polymer or oligomer having at least three net positive charges per molecule and having a Dye Maintenance Parameter, as determined by the Dye Maintenance Parameter Test, of greater than about 0 23, preferably greater than about 0.6 more preferably greater than about 0.8 and most preferably greater than about 0 9 The dye maintenance polymer is not a polyethyleneimine or alkoxylated denvative thereof In yet another aspect of this invention there is provided a laundry additive composition compnsmg- a) from about 1 % to about 99% by weight of water, and b) from about 0 01% to about 50%, preferably from about 0.1% to about 40%, more preferably from about 0.5% to about 30%, and most preferably from about 0 8% to about 20% of a dye maintenance polymer or oligomer having at least three net positive charges per molecule and having a Dye Maintenance Parameter, as determined by the Dye Maintenance Parameter Test, of greater than about 0 23, preferably greater than about 0 6 more preferably greater than about 0 8 and most preferably greater than about 0 9 The dye maintenance polymer is not a polyethyleneimine or alkoxylated derivative thereof In addition to the surfactant and the dye maintenance polymer of this invention, the laundry detergent compositions herein comprise from about 0.01% to 80% by weight of an organic or inorganic detergency builder and other conventional laundry detergent products In addition to the fabric softener and the dye maintenance polymer of this invention, the fabric softener compositions herein comprise pH adjusters, other earners and adjunct ingredients. Aqueous solutions of the dye maintenance polymers of this invention comprise from about 0.05% to about 50% by weight of the dye maintenance polymers of this invention, fabric treatment materials dissolved in water and other ingredients such as stabilizers and pH adjusters. In its method aspect, the present invention relates to the laundering or treating of fabrics and textiles in aqueous washing, rinsing, or treating solutions formed from effective amounts of any of the detergent compositions, fabric softener compositions, or aqueous solution treatments described herein, or formed from the individual components of such compositions. Laundering of fabrics and textiles in such washing, nnsing and/or treatment solutions, followed by drying, imparts fabnc appearance benefits to the fabnc and textile articles so treated. Such benefits can include improved overall appearance, pill/fuzz reduction, antifading, improved abrasion resistance, and/or enhanced softness. It has been surpnsmgly determined that the dye maintenance polymers of this invention impart fabric appearance and integnty benefits that are greater than the benefits achieved by a corresponding amount of either component by itself The components of present compositon are interageting surprisingly and not reacting chemically to input exceptional properties to the composition it is not an admixture According to the present invention there is provided a detergent composition comprising: a) from 5% to 70% of a C10-C20 sulfated or sulfonated anionic surfactant; b) from 0.01% to 10%, of a dye maintenance polymer or oligomer which is a member selected from the group consisting of imidazole-epichlorohydrin adducts, imidazole-piperazine-epichlorohydrin adducts, piperazme-epichlorohydrin adducts, and oxidized imidazole-epichlorohydrm adducts, said polymer or oligomer having at least three net positive charges per molecule and having a Dye Maintenance Parameter, as determined by the Dye Maintenance Parameter Test, of greater than 0.23; and c) optionally conventional detergent component. DETAILED DESCRIPTION OF THE INVENTION As noted, when fabric or textiles are laundered in solutions which comprise the dye maintenance polymers of the present invention fabric appearance and integrity are enhanced. The dye maintenance polymers can be added to wash solutions by incorporating them into a detergent composition, a fabric softener or by adding them separately to the washing solution. The dye maintenance polymers are described herein primarily as liquid or granular detergent additives but the present invention is not meant to be so limited. The dye maintenance polymers, detergent composition components, optional ingredients for such compositions and methods of using such compositions, are described m detail below All percentages are by weight unless other specified Dye Maintenance Polymers The dye maintenance polymers of this invention can be used in any fabric laundering process and provide certain appearance benefits to the fabncs laundered in these processes Such fabric appearance benefits can include, for example, improved overall appearance of the laundered fabrics, reduction of the formation of pills and fuzz, protection against color fading, improved abrasion resistance, etc The dye maintenance polymers used in the compositions and methods herein can provide such fabric appearance benefits with acceptably little or no loss in cleaning performance provided by the laundry detergent compositions into which such materials are incorporated As will be apparent to those skilled m the art, an oligomer is a molecule consisting of only a few monomer units while polymers comprise considerably more monomer units For the present invention, ohgomers are defined as molecules having an average molecular weight below about 1,000 and polymers are molecules having an average molecular weight of greater than about 1,000 Copolymers are polymers or oligomers wherein two or more dissimilar monomers have been simultaneously or sequentially polymerized. Copolymers of the present invention can include, for example, polymers or oligomers polymerized from a polyfunctional alkylating agent such as epichlorohydnn with a mixture of a cyclic amme-based monomer, e.g., piperazine and another cyclic amine-based monomer, e g., morpholine Cationic polymers in general and their method of manufacture are know. For example, a detailed description of cationic polymers can be found m an article by M. Fred Hoover that was published in the Journal of Macromolecular Science-Chemistry, A4(6), pp 1327-1417, October, 1970. The entire disclosure of the Hoover article is incorporated herein by reference The dye maintenance polymers of this invention will be better understood when read m light of the Hoover article, the present disclosure and the Examples herein. Table A lists 6 patent applications that describe various dye maintenance polymers according to this invention, methods of making these polymers and methods of using them The entire disclosure of each of the applications listed m Table A is incorporated herein by reference Table A (Table Removed) In addition to the dye maintenance polymers of the present invention, the present laundry detergent and additive compositions can include common detergent adjuvants as defined m greater detail below. The detergent compositions of this invention include a surfactant selected from the group consisting of nonionic, anionic, cationic, amphotenc, zwittenonic surfactants and mixtures thereof. Preferably, at least about 4% by weight of the surfactant is an anionic surfactant. The most common detergent ingredients that are preferred for use in the present invention include: detersive enzymes, preferably cellulase and preferably an enzyme stabilization system, an inorganic peroxygen bleaching compound, which is preferably selected from the group consisting of alkali metal salts of perborate, percarbonate and mixtures thereof, and a bleach activator, which is preferably nonanoyloxybenzene sulfonate The laundry additive compositions of this invention preferably comprise a pH adjuster and one or more fabric softening components Detersive Surfactant The detergent compositions herein compnse from about 4% to 80% by weight of a detersive surfactant Preferably such compositions compnse from about 5% to 50%> by weight of surfactant Detersive surfactants utilized can be of the anionic, nomonic, zwittenonic, ampholytic or cationic type or can compnse compatible mixtures of these types Detergent surfactants useful herein are described in U.S Patent 3,664,961, Norns, issued May 23, 1972, US Patent 3,919,678, Laughhn et al , issued December 30, 1975, U.S Patent 4,222,905, Cockrell, issued September 16, 1980, and in U.S. Patent 4,239,659, Murphy, issued December 16, 1980 All of these patents are incorporated herein by reference Of all the surfactants, anionics and nomonics are preferred. Useful anionic surfactants can themselves be of several different types For example, water-soluble salts of the higher fatty acids, I e, "soaps", are useful anionic surfactants m the compositions herein. This includes alkali metal soaps such as the sodium, potassium, ammonium, and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms. Additional non-soap anionic surfactants which are suitable for use herein include the water-soluble salts, preferably the alkali metal, and ammonium salts, of organic sulfunc reaction products having m their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfunc acid ester group. (Included in the term "alkyl" is the alkyl portion of acyl groups.) Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as C11-13 LAS. Preferred nomonic surfactants are those of the formula R1(OC2H4)nOH, wherein R. is a C10-C16 alkyl group or a C8-C12 alkyl phenyl group, and n is from 3 to about 80 Particularly preferred are condensation products of C12-C15 alcohols with from about 5 to about 20 moles of ethylene oxide per mole of alcohol, e.g , C12-C13 alcohol condensed with about 6 5 moles of ethylene oxide per mole of alcohol. Additional suitable surfactants, including polyhydroxy fatty acid amides and amine based surfactants, are disclosed in one or more of the co-pending PCT Applications listed in Table A and incorporated herein by reference Determent Builder The detergent compositions herein may also comprise from about 0 1% to 80% by weight of a detergent builder Preferably such compositions in liquid form will comprise from about 1% o 10% by weight of the builder component Preferably such compositions in granular form will comprise from about 1% to 50% by weight of the builder component. Detergent builders are well known in the art and can comprise, for example, phosphate salts as well as various organic and inorganic nonphosphorus builders Water-soluble, nonphosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy sulfonates Suitable polycarboxylates for use herein are the polyacetal carboxylates described in U S. Patent 4,144,226, issued March 13, 1979 to Crutchfield et al, and U S Patent 4,246,495, issued March 27, 1979 to Crutchfield et al, both of which are incorporated herein by reference. Particularly preferred polycarboxylate builders are the oxydisuccinates and the ether carboxylate builder compositions comprising a combination of tartrate monosuccmate and tartrate disuccinate described in U.S Patent 4,663,071, Bush et al., issued May 5, 1987, the disclosure of which is incorporated herein by reference. Examples of suitable nonphosphorus, inorganic builders include the silicates, aluminosilicates, borates and carbonates. Particularly preferred are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicates having a weight ratio of SiC2 to alkali metal oxide of from about 0 5 to about 4.0, preferably from about 1.0 to about 2.4. Also preferred are aluminosilicates including zeolites. Such materials and their use as detergent builders are more fully discussed in Corkill et al., U. S Patent No 4,605,509, the disclosure of which is incorporated herein by reference Also discussed in U. S. Patent No 4,605,509 are crystalline layered silicates which are suitable for use in the detergent compositions of this invention Optional Detergent Ingredients In addition to the surfactants, builders and dye maintenance polymers of the detergent compositions of the present invention can also include any number of additional optional ingredients. These include conventional detergent composition components such as enzymes and enzyme stabilizing agents, suds boosters or suds suppressers, anti-tarnish and anticorrosion agents, bleachmg agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, non-builder alkalinity sources, chelating agents, organic and inorganic fillers, solvents, hydrotropes, optical bnghteners, dyes and perfumes Accordingly the present invention relates to a biaxially oriented transparent holographic film comprising: - an upper skin layer of high crystalline polypropylene of at least 60% crystalhnity having 5 to 25% of the total film thickness, - a core layer of polypropylene polymer sandwiched between the said upper and lower skin layers being more than 80% of the total film thickness; - a lower skin layer of copolymers selected from propylene-ethylene random copolymers, propylene-a-olefin copolymers or ethylene-alpha olefin copolymer or an appropriate blend thereof having 5 to 25% of the total film thickness, wherein the said upper skin and lower skin layers contain antiblocking agents in 0 2 - 1.0% while the lower skin layer contains polar polymers as herein described in the range of 12-13% and additionally with silicone resins in the range of 0.25% to 1.25%. BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS Fig. 1 depicts a general lay out of the manufacture of biaxially oriented polypropylene (BOPP) film on a tenter frame. Fig. 2 depicts the process of embossing on the film. DETAILED DESCRIPTION OF THE INVENTION As shown in Fig. 1 extrusion of the three layer is done through three separate extruders 1, 2 and 3 on a tenter frame followed by melt extrusion. Three melt streams from three extruders, namely main extruder giving the core layer, satellite I for skin I and satellite II for skin II, are pressed together in the slit die (5) and are extruded as a single sheet The said composite sheet after cooling is fed into an apparatus adapted for monoaxial orientation. The film is quenched on a chill roll and/or water bath Issued November 1, 1983 to Chung et al The nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are "ypical and preferred Mixtures thereof can also be used See also the hereinbefore referenced U S 4,634,551 for other typical bleaches and activators useful herein Other useful amido-denved bleach activators are those of the formulae R^RSJCCO^CCCOL or R1C(0)N(R5)R2C(0)L wherein R1 is an alkyl group containing from about 6 to about 12 carbon atoms, R2 is an alkylene containing from 1 to about 6 carbon atoms, R5 is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group A leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion A preferred leaving group is phenol sulfonate Preferred examples of bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzene-sul-fonate, (6-decanamido-caproyl)oxybenzenesulfonate and mixtures thereof as described in the hereinbefore referenced U.S. Patent 4,634,551. Another class of useful bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al. m U.S. Patent 4,966, 723, Issued October 30, 1990, incorporated herein by reference. See also U.S. Patent 4,545,784, Issued to Sanderson, October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate. If utilized, peroxygen bleaching agent will generally comprise from about 2% to 30% by weight of the detergent compositions herein More preferably, peroxygen bleaching agent will comprise from about 2% to 20% by weight of the compositions. Most preferably, peroxygen bleaching agent will be present to the extent of from about 3% to 15% by weight of the compositions herein. If utilized, bleach activators can comprise from about 2% to 10% by weight of the detergent compositions herein Frequently, activators are employed such that the molar ratio of bleaching agent to activator ranges from about 1:1 to 10:1, more preferably from about 1.5:1 to 5:1. Additional suitable bleaching agents and bleach activators are disclosed in one or more of the co-pending PCT Applications listed in Table A and incorporated herein by reference Another highly preferred optional ingredient m the detergent compositions herein is a detersive enzyme component. Enzymes can be included in the present detergent compositions for a variety of purposes, including removal of protein-based, carbohydrate-based, or tnglycende-based stains from substrates, for the prevention of refugee dye transfer in fabric laundering, and for fabric restoration Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin Preferred selections are influenced by factors such as pH-activity and/or stability, optimal thermostability, and stability to active detergents, builders and the like. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases. "Detersive enzyme", as used herein, means any enzyme having a cleaning, stain removing or otherwise beneficial effect in a laundry detergent composition Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases, amylases and peroxidases Enzymes are normally incorporated into' detergent compositions at levels sufficient to provide a "cleaning-effective amount" The term "cleaning-effective amount" refers to any amount capable of producing a cleaning, stain removal, soil removal, whitening, deodonzmg, OT freshness improving effect on substrates such as fabrics. In practical terms for current commercial preparations, typical amounts are up to about 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the detergent composition. Stated otherwise, the compositions herein will typically comprise from 0.001% to 5%, preferably 0.01%-1% by weight of a commercial enzyme preparation. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition. Higher active levels may be desirable in highly concentrated detergent formulations. Cellulases usable herein include those disclosed in U.S. Patent No. 4,435,307, Barbesgoard et al., March 6, 1984, and GB-A-2.075.028, GB-A-2.095.275 and DE-OS-2.247 832 CAREZYME® and CELLUZYME® (Novo) are especially useful. See also WO 9117243 to Novo. The enzyme-containing compositions herein may optionally also comprise from about 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing system. The enzyme stabilizmg system can be any stabilizing system which is compatible with the detersive enzyme. Such a system may be inherently provided by other formulation actives, or be added separately, e.g., by the formulator or by a manufacturer of detergent-ready enzymes. Such stabilizing systems can, for example, compose calcium ion, boric acid, propylene glycol, short chain carboxyhc acids, boronic acids, and mixtures thereof, and are designed to address different stabilization problems depending on the type and physical form of the detergent composition. Detereent Composition Preparation The detergent compositions according to the present invention can be in liquid, paste or granular form Such compositions can be prepared by combining the essential and optional components in the requisite concentrations in any suitable order and by any conventional means The forgoing description of uses for the dye maintenance polymers defined herein are intended to be exemplary and other uses will be apparent to those skilled in the art and are intended to be within the scope of the present invention Granular compositions, for example, are generally made by combining base granule ingredients, e.g , surfactants, builders, water, etc , as a slurry, and spray drying the resulting slurry to a low level of residual moisture (5-12%) The remaining dry ingredients, e g , granules of the essential dye maintenance polymers, can be admixed in granular powder form with the spray dried granules m a rotary mixing drum The liquid ingredients, e.g., solutions of the essential dye maintenance polymers, enzymes, binders and perfumes, can be sprayed onto the resulting granules to form the finished detergent composition. Granular compositions according to the present invention can also be in "compact form", i.e. they may have a relatively higher density than conventional granular detergents, i.e. from 550 to 950 g/1. In such case, the granular detergent compositions according to the present invention will contain a lower amount of "inorganic filler salt", compared to conventional granular detergents; typical filler salts are alkaline earth metal salts of sulphates and chlorides, typically sodium sulphate; "compact" detergents typically comprise not more than 10% filler salt Liquid detergent compositions can be prepared by admixing the essential and optional ingredients thereof in any desired order to provide compositions containing components in the requisite concentrations. Liquid compositions according to the present invention can also be in "compact form", in such case, the liquid detergent compositions according to the present invention will contain a lower amount of water, compared to conventional liquid detergents Addition of the dye maintenance polymers to liquid detergent or other aqueous compositions of this invention may be accomplished by simply mixing into the liquid solutions the desired dye maintenance polymers. Fabric Laundering Method The present invention also provides a method for laundering fabrics in a manner which imparts fabric appearance benefits provided by the dye maintenance polymers used herein Such a method employs contacting these fabrics with an aqueous washing solution formed from an effective amount of the detergent compositions hereinbefore described or formed from the individual components of such compositions Contacting of fabrics with washing solution will generally occur under conditions of agitation although the compositions of the present invention may also be used to form aqueous unagitated soaking solutions for fabric cleaning and treatment As discussed above, it is preferred that the washing solution have a pH of less than about 10 0, preferably it has a pH of about 9 5 and most preferably it has a pH of about 7 5 Agitation is preferably provided in a washing machine for good 'cleaning. Washing is preferably followed by drying the wet fabric in a conventional clothes dryer. An effective amount of a high density liquid or granular detergent composition in the aqueous wash solution in the washing machine is preferably from about 500 to about 7000 ppm, more preferably from about 1000 to about 3000 ppm. Fabric Conditioning and Softening The dye maintenance polymers hereinbefore described as components of the laundry detergent compositions herein may also be used to treat and condition fabrics and textiles in the absence of the detersive surfactant and builder components of the detergent composition embodiments of this invention. Thus, for example, a fabric conditioning composition comprising a fabric softener and the dye maintenance polymer or a fabric treatment composition comprising only the dye maintenance polymers themselves, or comprising an aqueous solution of the dye maintenance polymers, may be added during the nnse cycle of a conventional home laundering operation in order to impart the desired fabric appearance and integrity benefits hereinbefore described. The fabric softener compositions of the present invention comprise at least about 1%, preferably from about 8%, more preferably from about 20% to about 80%, more preferably to about 60%, most preferably to about 45% by weight, of the composition of one or more fabric softener actives. The preferred fabric softening actives according to the present invention are amines having the formula. (Formula Removed) quaternary ammonium compounds having the formula (Formula Removed) and mixtures thereof, wherein each R is independently C1-C6 alkyl, C1-C6 hydroxyalkyl, benzyl, and mixtures thereof; R1 is preferably C11-C22 linear alkyl, C11-C22 branched alkyl, C11-C22 linear alkenyl, C11-C22 branched alkenyl, and mixtures thereof, Q is a carbonyl moiety independently selected from the units having the formula (Formula Removed) wherein R.2 IS hydrogen, C1-C4 alkyl, preferably hydrogen; R3 is C1-C4 alkyl, preferably hydrogen or methyl; preferably Q has the formula: (Formula Removed) X is a softener compatible anion, preferably the anion of a strong acid, for example, chloride, bromide, methylsulfate, ethylsulfate, sulfate, nitrate and mixtures thereof, more preferably chloride and methyl sulfate. The anion can also, but less preferably, carry a double charge, in which case represents half a group. The index m has a value of from 1 to 3, die index n has a value of from 1 to 4, preferably 2 or 3, more preferably 2 One embodiment of the present invention provides for amines and quatemized amines having two or more different values for the index n per molecule, for example, a softener active prepared from the starting amine methyl(3-aminopropyl)(2-hydroxyethyl)amine. More preferred softener actives according to the present invention have the formula wherein the unit having the formula: (Formula Removed) is a fatty acyl moiety. Suitable fatty acyl moieties for use in the softener actives of the present invention are derived from sources of triglycerides including tallow, vegetable oils and/or partially hydrogenated vegetable oils including inter aha canola oil, safflower oil, peanut oil, sunflower oil, com oil, soybean oil, tall oil, rice bran oil. Yet more preferred are the Diester Quaternary Ammonium Compounds (DEQA's) wherein the index m is equal to 2 The formulator, depending upon the desired physical and performance properties of the final fabric softener active, can choose any of the above mentioned sources of fatty acyl moieties, or alternatively, the formulator can mix sources of triglyceride to form a "customized blend" However, those skilled in the art of fats and oils recognize that the fatty acyl composition may vary, as in the case of vegetable oil, from crop to crop, or from variety of vegetable oil source to variety of vegetable oil source. DEQA's which are prepared using fatty acids derived from natural sources are preferred. A preferred embodiment of the present invention provides softener actives comprising R' units which have at least about 3%, preferably at least about 5%, more preferably at least about 10%, most preferably at least about 15% C11-C22 alkenyl, including polyalkenyl (polyunsaturated) units inter alia oleic, hnoleic, linolemc. For the purposes of the present invention the term "mixed chain fatty acyl units" is defined as "a mixture of fatty acyl units comprising alkyl and alkenyl chains having from 10 carbons to 22 carbon atoms including the carbonyl carbon atom, and in the case of alkenyl chains, from one to three double bonds, preferably all double bonds in the cis configuration". With regard to the R.I units of the present invention, it is preferred that at least a substantial percentage of the fatty acyl groups are unsaturated, e.g., from about 25%, preferably from about 50% to about 70%, preferably to about 65%. The total level of fabric softening active containing polyunsaturated fatty acyl groups can be from about 3%, preferably from about 5%, more preferably from about 10% to about 30%, preferably to about 25%, more preferably to about 18%. As stated herein above cis and trans isomers can be used, preferably with a as/trans ratio is of from l-i, prefeiably at least 3:1, and more preferably from about 4:1 to about 501, more preferably about 20 1, however, the minimum being 1 1 The level of unsaturation contained within the tallow, canola, or other fatty acyl unit chain can be measured by the Iodine Value (IV) of the corresponding fatty acid, which in the present case should preferably be in the range of from 5 to 100 with two categories of compounds being distinguished, having a IV below or above 25 Indeed, for compounds having the formula (Formula Removed) derived from tallow fatty acids, when the Iodine Value is from 5 to 25, preferably 15 to 20, it has been found that a cis/trans isomer weight ratio greater than about 30/70, preferably greater than about 50/50 and more preferably greater than about 70/30 provides optimal concentrabihty For compounds of this type made from tallow fatty acids having a Iodine Value of above 25, the ratio of cis to trans isomers has been found to be less critical unless very high concentrations are needed A further preferred embodiment of the present invention comprises DEQA's wherein the average Iodine Value for R1 is approximately 45. The R.1 units suitable for use in the isotropic liquids present invention can be further characterized in that the Iodine Value (IV) of the parent fatty acid, said IV is preferably from about 10, more preferably from about 50, most preferably from about 70, to a value of about 140, preferably to about 130, more preferably to about 115. However, formulators, depending upon which embodiment of the present invention they choose to execute, may wish to add an amount of fatty acyl units which have Iodine Values outside the range listed herein above. For example, "hardened stock" (IV less than or equal to about 10) may be combined with the source of fatty acid admixture to adjust the properties of the final softener active. A prefered source of fatty acyl units, especially fatty acyl units having branching, for example, "Guerbet branching", methyl, ethyl, etc. units substituted along the primary alkyl chain, synthetic sources of fatty acyl units are also suitable. For example, the formulator may with to add one or more fatty acyl units having a methyl branch at a "non-naturally occunng" position, for example, at the third carbon of a C17 chain What is meant herein by the term "non-naturally occunng" is "acyl units whihc are not found m significant (greater than about 0.1%) quantities is common fats and oils which serve as feedstocks for the source of triglycerides described herein " If the desired branched chain fatty acyl unit is unavailable from readily available natural feedstocks, therefore, synthetic fatty acid can be suitably admixed with othei synthetic materials or with other natural triglyceride derived sources of acyl units The following are examples of preferred softener actives according to the present invention. N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride; N,N-di(canolyl-oxy-ethyl)-N,N-dimethyl ammonium chloride; N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate, N,N-di(canolyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate, N,N-di(tallowylamidoethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate, N,N-di(2-tallowyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride, N,N-di(2-canolyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chlonde, N,N-di(2-tallowyloxyethylcarbonyloxyethyl)-N,N-dimethyl ammon'ium chlonde. N,N-di(2-canolyloxyethylcarbonyloxyethyl)-N,N-dimethyl ammonium chlonde, N-(2-tallowoyloxy-2-ethyl)-N-(2-tallowyloxy-2 -oxo-ethyl)-N,N-dimethyl ammonium chlonde; N-(2-canolyloxy-2-ethyl)-N-(2-canolyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chlonde, N,N,N-tn(tallowyl-oxy-ethyl)-N-methyl ammonium chlonde; N,N,N-tn(canolyl-oxy-ethyl)-N-methyl ammonium chlonde; N-(2-tallowyloxy-2-oxoethyl)-N-(tallowyl)-N,N-dimethyl ammonium chlonde; N-(2-canolyloxy-2-oxoethyl)-N-(canolyl)-N,N-dimethyl ammonium chlonde; l,2-ditallowyloxy-3-N,N,N-tnmethylammoniopropane chloride; and 1,2-dicanolyloxy-3-N,N,N-tnmethylammoniopropane chlonde; and mixtures of the above actives. Particularly preferred is N,N-di(tallowoyl-oxy-ethyl)-N,N-dimethyl ammonium chlonde, where the tallow chains are at least partially unsaturated and N,N-di(canoloyl-oxy-ethyl)-N,N-dimethyl ammonium chlonde, N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate; N,N-di(canolyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate, and mixtures thereof. Additional fabric softening agents useful herein are descnbed in U.S. 5,643,865 Mermelstem et al., issued July 1, 1997, U.S 5,622,925 de Buzzaccanni et al., issued Apnl 22, 1997; U.S. 5,545,350 Baker et al., issued August 13, 1996; U.S. 5,474,690 Wahl et al, issued December 12, 1995; U.S. 5,417,868 Turner et al., issued January 27, 1994; U.S. 4,661,269 Tnnh et al., issued Apnl 28, 1987; U.S. 4,439,335 Burns, issued March 27, 1984; U.S. 4,401,578 Verbruggen, issued August 30, 1983; U.S. 4,308,151 Cambre, issued December 29, 1981, U.S 4,237,016 Rudkin et al., issued October 27, 1978; US 4,233,164 Davis, issued November 11, 1980; U.S. 4,045,361 Watt et al., issued August 30, 1977; U.S. 3,974,076 Wiersema et al, issued August 10, 1976; U.S. 3,886,075 Bernadmo, issued May 6, 1975; U.S. 3,861,870 Edwards et al, issued January 21 1975; and European Patent Application publication No. 472,178, by Yamamura et al., all of said documents being incorporated herein by reference. EXAMPLES The following examples illustrate the compositions and methods of the present invention, but are not necessarily meant to limit or otherwise define the scope of the invention EXAMPLE I Dye Maintenance Parameter 1 est To evaluate a dye maintenance polymer, prepare a 10 ppm solution of the dye maintenance polymer in water Add 800ml of this solution to a l000mL beaker Introduce 8 gm+/-50mg of CI 10 fabric (CI 10 is a poplin fabric dyed with Direct Black 112 and supplied by Empirical Manufacturing Company of Cincinnati, OH) swatch in the solution such that it is completely immersed m the liquid Agitate the solution gently with a magnetic stirrer for 120 minutes A portion of the dye from the fabric will slowly bleed into the water After 120 minutes, withdraw an aliquot of the liquor, place it in a 5 cm path length cell and measure its absorbance at wavelength of 600nm with a Hewlett Packard Model 8453 uv-vis spectrophotomer following the general instructions provided by the manufacturer for the use of this instrument This absorbance is called AbsPolymer. Using the procedure outlined above, repeat the procedure with distilled water alone with no added dye maintenance polymer to obtain AbsWtler The Dye Maintenance Parameter ("DMP") is defined as (AbSw„„ - AbsPolymtr) EXAMPLE II Calculation of the Average Charge Per Molecule While there are many ways to calculate the charge density of a polymeric matenal known to those skilled m the analytical arts, one such method is as follows. Specifically, the charge density for molecules with a known chemical structure, is determined by a standard acid-base titration or a potentiometnc titration to give charge to mass ratio Charge density can then be converted to an average charge per molecule by determining the average molecular weight of the matenal and simply dividing the charge density by the average molecular weight to determine the average number of positive charges per molecule For low molecular weight matenals, molecular weight is determined standard techniques such as mass spectrosocpy For polymenc matenals, molecular weight is determined by gel permeation chromatography. These methods are descnbed in analytical text books such as "Instrumental Methods of Analysis" by Willard, Memtt, Dean, and Settle EXAMPLE III TABLE III comprises numerous examples according to the present invention along with some compantive examples of matenal known to the art of laundry detergents The chemical structures shown in the examples below are idealized structures Side reactions expected to occur dunng the condensation are not shown TABLE III (Table Removed) EXAMPLE IV Granular Detergent Test Composition Preparation Several heavy duty granular detergent compositions are prepared containing one or more dye maintenance polymer having a DMP according to this invention. These granular detergent compositions all have the following basic formula: TABLE IV (Table Removed) EXAMPLE V Liquid Detergent Test Composition Preparation Several heavy duty liquid detergent compositions are prepared containing one or more dye maintenance polymer havmg a DMP according to this invention These liquid detergent compositions all have the following basic formula TABLE V (Table Removed) EXAMPLE VI Granular Detergent Test Composition Preparation Several granular detergent compositions are prepared containing one or more dye maintenance polymer having a DMP according to this invention. Such granular detergent compositions all have the following basic formula TABLE VI (Table Removed) EXAMPLE VII Fabnc Softener Test Composition Preparation Several fabnc softener compositions are prepared containing one or more dye maintenance polymer having a DMP according to this invention Such fabnc softener compositions can have any of the following basic formulae TABLE VIIa (Table Removed) 1 N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride (tallowyl having an I V of 50) 2 N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride (tallowyl having an I V of 18) 3 l,2-Ditallowyloxy-3-N,N,N-tnmethylammoniopropane chloride. 4 Ditallow dimethyl ammonium chloride 5. Methyl bis(tallow amidoethyl)-2-hydroxyethyl ammonium methyl sulfate 6. 1 -Tallowamidoethyl-2-imidazoline. 10. N,N,N' ,N'-terakis(2-hydroxypropyl)ethylenediamine. 11. Dimethyl terephthalate, 1,2-propylene glycol, methyl capped PEG polymer. 12. N,N'-bis(3-aminopropyl)-1,3-propylenediamine TABLE Vllb (Table Removed) 1 N,N-di(canoyloxyethyl)-N-2-hydroxyethyl-N-methyl ammonium methyl sulfate available from Witco 2 Monocanolyl tnmethyl ammonium chloride, available as Adogen 417® from Witco 6 N,N'-(3-ammopropyl)ethylenediamine 7 N,N'-(3-ammopropyl)butylenediamine 8 Tnpropylenetetraamme 9 Tnmethyl pentanediol available from Eastman Chemical. 10 1,4-cyclohexane dimethanol available from Eastman Chemical 11 Minors can include perfume, dye, acid, preservatives, etc EXAMPLE Vni Aqueous Treatment Composition Preparation Several aqueous treatment compositions are prepared containing one or more dye maintenance polymer having a DMP according to this invention. Such treatment compositions can have any of the following basic formulae. TABLE VIII (Table Removed) 1. N,N-di-(canolyl-oxy-ethyl)-N-methy l-N-(2- hycIroxyethyl ammonn lm methy sulfate 2. Selected from REWIN SRF, REWIN SRF-O and REWIN DWR ex CHT-Beitlich GMBH 3 Polyalkyleneimine having a molecular weight of 1800 and an average ethoxylation per backbone nitrogen of approximately 4 4 Polyalkyleneimine having a molecular weight of 1800 and an average ethoxylation per backbone nitrogen of approximately 1 5 Polyalkyleneimine having a molecular weight of 1800 and an average ethoxylation per backoone nitrogen of approximately 7 6 Hydroxyethanediphosphonate (HEDP) 7 BAYHIBIT AM ex Baeyer 8 Suitable enzymes include cellulase, lipase, protease, peroxidase, and mixtures thereof 9 N,N' -bis(propyleneammo)-1,4-piperazme We claim: 1. A biaxially oriented transparent holographic film comprising: - an upper skin layer of high crystalline polypropylene of at least 60% crystallinity having 5 to 25% of the total film thickness: - a core layer of polypropylene polymer sandwiched between the said upper and lower skin layers being more than 80% of the total film thickness; - a lower skin layer of copolymers selected from propylene-ethylene random copolymers, propylene-α-olefin copolymers or ethylene-alpha olefin copolymer or an appropriate blend thereof having 5 to 25% of the total film thickness, wherein the said upper skin and lower skin layers contain antiblocking agents in 0.2 - 1.0% while the lower skin layer contains polar polymers as herein described in the range of 12-13% and additionally with silicone resins in the range of 0.25% to 1.25%. 2. A film as claimed in claim 1, wherein the thickness of upper skin layer is 5-12% of the total thickness. 3. A film as claimed in claim 1. wherein the thickness of lower skin layer is 10-12.5% of the total thickness. 4. A film as claimed in claim 1, wherein thickness of said core layer is upto 90% of the total thickness. 5. A film as claimed in claim 1, wherein the said antiblocking agents are polymethylene methacrylate, Nylon, Polyisobutyl methacrylate, silica, silicates and/ or a mixture thereof. 6. A film as claimed in claim 1, wherein the said silicone resins are in the range of 0.5-1.0%. 7. A film as claimed in claim 1, wherein the said polar polymers are acrylic modified or maleic anhydride modified polypropylene. 8. A film as claimed in claim 1, wherein at least one skin layer is made of high crystalline polypropylene with a crystallinity of more than 65%. 9. A film as claimed in claim 1, wherein the isotactic index of said high crystalline polypropylene used is 90%, preferably more than 95%. 10. A process for manufacturing a biaxially oriented transparent holographic film as claimed in claim 1 comprising the steps of: - providing a body of thermoplastic film; - orienting the said film along a first axis by passing the film through a series of powered calender rollers which tension the film in the longitudinal direction; - orienting the film along a second axis, normal to the first axis, by clamping the edges of the film in a tenter frame which tensions the film in the transverse direction; - raising the temperature of the film to a desired annealing temperature above room temperature; - continuing to maintain the film at a temperature above room temperature while embossing a diffraction pattern into a surface of the film, the film being continuously maintained at a temperature above room temperature and under tension along at least one of said first and second axes from the time the film temperature is raised to the desired annealing temperature until the diffraction pattern is embossed into the film; - cooling the film to room temperature; and - depositing a metallic layer as herein described over the diffraction pattern embossed into the surface of the film. 11. A biaxially oriented transparent holographic film substantially as herein before described with reference to the accompanying drawings. 12. A process for manufacturing a biaxially oriented transparent holographic film substantially as herein before described with reference to the accompanying drawings.

Full Text

FIELD OF THE INVENTION
The present invention relates to a biaxially oriented transparent holographic film consisting of polypropylene polymer and the process for the manufacture of the said biaxially oriented, transparent holographic film to be used for packaging to avoid the piracy of the said package The film presents a magnificient colour rainbow under any form of light, not only attracting immediate attention but also complimenting the product Other than packaging application the film can also be used as labels.
More particularly the subject invention relates to an improved biaxially oriented multilayer holographic film with unique property of being directly embossable and also suitable for mechanical enginnering followed by metalization.
The object of the invention is to provide an improved biaxially oriented holographic film having excellent optical properties, enhanced durability and dimentional stability.
Another object of the invention is to provide an improved biaxially oriented holographic film having polar polymers and excellent hot slip properties
Yet another object of the invention is to provide a novel process for manufacturing a biaxially oriented holographic film comprising co-extruding at least one polypropylene layer and having a third layer containing polar polymers
BACKGROUND OF THE INVENTION
Conventionally transparent oriented polyolefin films are used widely as packaging materials. Since the film have excellent optical properties, they are used in large quantities in graphic industries for lamination namely solvent lamination, water based lamination, dry lamination, dry lamination etc. of printed products.
Given the foregoing, there is clearly an ongoing need to identify materials which could be added to laundry products that would associate themselves with the fibers of the fabrics and textiles laundered using such products and thereby reduce or minimize the tendency of the laundered fabric/textiles to deteriorate in appearance Any such detergent product additive material should, of course, be able to benefit fabric appearance and integrity without undulv interfering with the ability of the laundry product to perform its intended "function The present invention is directed to the use of dye maintenance polymers in laundry applications that perform in this desired manner, and a test for determining the Dye Maintenance Parameter for any given polymer
SUMMARY OF THE INVENTION
The present invention is directed to a detergent composition comprising.
a) from about 4% to about 70% of a surfactant that is preferably selected from the group consisting of nonionic, anionic, cationic, amphoteric, zwittenonic surfactants and mixtures thereof, and is even more preferably an anionic surfactant;
b) from about 0.01% to about 10%, preferably from about 0.1% to about 8%, more preferably from about 0.5% to about 6%, and most preferably from about 0.8% to about 5% of a dye maintenance polymer or oligomer having at least three net positnc charges per molecule and having a Dye Maintenance Parameter, as determined by the Dye Maintenance Parameter Test, of greater than about 0.23, preferably greater than about 0.6 more preferably greater than about 0 8 and most preferably greater than about 0 9
The dye maintenance polymer is not a polyethyleneimine or alkoxylated derivative thereof
In another aspect of this invention there is provided a fabnc conditioning composition comprising:
a) from about 1% to about 80% of a fabnc softening active; and
b) from about 0.01 % to about 50%, preferably from about 0.1% to about 40%, more preferably from about 0 5% to about 30%, and most preferably from about 0 8% to about 20% of a dye maintenance polymer or oligomer having at least three net positive charges per molecule and having a Dye Maintenance Parameter, as determined by the Dye Maintenance Parameter Test, of greater than about 0 23, preferably greater than about 0.6 more preferably greater than about 0.8 and most preferably greater than about 0 9
The dye maintenance polymer is not a polyethyleneimine or alkoxylated denvative thereof
In yet another aspect of this invention there is provided a laundry additive composition compnsmg-
a) from about 1 % to about 99% by weight of water, and
b) from about 0 01% to about 50%, preferably from about 0.1% to about 40%, more
preferably from about 0.5% to about 30%, and most preferably from about 0 8% to
about 20% of a dye maintenance polymer or oligomer having at least three net
positive charges per molecule and having a Dye Maintenance Parameter, as
determined by the Dye Maintenance Parameter Test, of greater than about 0 23,
preferably greater than about 0 6 more preferably greater than about 0 8 and most
preferably greater than about 0 9
The dye maintenance polymer is not a polyethyleneimine or alkoxylated derivative thereof
In addition to the surfactant and the dye maintenance polymer of this invention, the laundry detergent compositions herein comprise from about 0.01% to 80% by weight of an organic or inorganic detergency builder and other conventional laundry detergent products
In addition to the fabric softener and the dye maintenance polymer of this invention, the fabric softener compositions herein comprise pH adjusters, other earners and adjunct ingredients.
Aqueous solutions of the dye maintenance polymers of this invention comprise from about 0.05% to about 50% by weight of the dye maintenance polymers of this invention, fabric treatment materials dissolved in water and other ingredients such as stabilizers and pH adjusters.
In its method aspect, the present invention relates to the laundering or treating of fabrics and textiles in aqueous washing, rinsing, or treating solutions formed from effective amounts of any of the detergent compositions, fabric softener compositions, or aqueous solution treatments described herein, or formed from the individual components of such compositions. Laundering of fabrics and textiles in such washing, nnsing and/or treatment solutions, followed by drying, imparts fabnc appearance benefits to the fabnc and textile articles so treated. Such benefits can include improved overall appearance, pill/fuzz reduction, antifading, improved abrasion resistance, and/or enhanced softness. It has been surpnsmgly determined that the dye maintenance polymers of this invention impart fabric appearance and integnty benefits that are greater than the benefits achieved by a corresponding amount of either component by itself
The components of present compositon are interageting surprisingly and not reacting chemically
to input exceptional properties to the composition it is not an admixture

According to the present invention there is provided a detergent composition comprising:
a) from 5% to 70% of a C10-C20 sulfated or sulfonated anionic surfactant;
b) from 0.01% to 10%, of a dye maintenance polymer or oligomer which is a member selected from the group consisting of imidazole-epichlorohydrin adducts, imidazole-piperazine-epichlorohydrin adducts, piperazme-epichlorohydrin adducts, and oxidized imidazole-epichlorohydrm adducts, said polymer or oligomer having at least three net positive charges per molecule and having a Dye Maintenance Parameter, as determined by the Dye Maintenance Parameter Test, of greater than 0.23; and
c) optionally conventional detergent component.
DETAILED DESCRIPTION OF THE INVENTION
As noted, when fabric or textiles are laundered in solutions which comprise the dye maintenance polymers of the present invention fabric appearance and integrity are enhanced. The dye maintenance polymers can be added to wash solutions by incorporating them into a detergent composition, a fabric softener or by adding them separately to the washing solution. The dye maintenance polymers are described herein primarily as liquid or granular detergent additives but the present invention is not meant to be so limited. The dye maintenance polymers, detergent
composition components, optional ingredients for such compositions and methods of using such compositions, are described m detail below All percentages are by weight unless other specified
Dye Maintenance Polymers
The dye maintenance polymers of this invention can be used in any fabric laundering process and provide certain appearance benefits to the fabncs laundered in these processes Such fabric appearance benefits can include, for example, improved overall appearance of the laundered fabrics, reduction of the formation of pills and fuzz, protection against color fading, improved abrasion resistance, etc The dye maintenance polymers used in the compositions and methods herein can provide such fabric appearance benefits with acceptably little or no loss in cleaning performance provided by the laundry detergent compositions into which such materials are incorporated
As will be apparent to those skilled m the art, an oligomer is a molecule consisting of only a few monomer units while polymers comprise considerably more monomer units For the present invention, ohgomers are defined as molecules having an average molecular weight below about 1,000 and polymers are molecules having an average molecular weight of greater than about 1,000 Copolymers are polymers or oligomers wherein two or more dissimilar monomers have been simultaneously or sequentially polymerized. Copolymers of the present invention can include, for example, polymers or oligomers polymerized from a polyfunctional alkylating agent such as epichlorohydnn with a mixture of a cyclic amme-based monomer, e.g., piperazine and another cyclic amine-based monomer, e g., morpholine
Cationic polymers in general and their method of manufacture are know. For example, a detailed description of cationic polymers can be found m an article by M. Fred Hoover that was published in the Journal of Macromolecular Science-Chemistry, A4(6), pp 1327-1417, October, 1970. The entire disclosure of the Hoover article is incorporated herein by reference The dye maintenance polymers of this invention will be better understood when read m light of the Hoover article, the present disclosure and the Examples herein.
Table A lists 6 patent applications that describe various dye maintenance polymers according to this invention, methods of making these polymers and methods of using them The entire disclosure of each of the applications listed m Table A is incorporated herein by reference
Table A
(Table Removed)
In addition to the dye maintenance polymers of the present invention, the present laundry detergent and additive compositions can include common detergent adjuvants as defined m greater detail below. The detergent compositions of this invention include a surfactant selected from the group consisting of nonionic, anionic, cationic, amphotenc, zwittenonic surfactants and mixtures thereof. Preferably, at least about 4% by weight of the surfactant is an anionic surfactant.
The most common detergent ingredients that are preferred for use in the present invention include: detersive enzymes, preferably cellulase and preferably an enzyme stabilization system, an inorganic peroxygen bleaching compound, which is preferably selected from the group
consisting of alkali metal salts of perborate, percarbonate and mixtures thereof, and a bleach activator, which is preferably nonanoyloxybenzene sulfonate The laundry additive compositions of this invention preferably comprise a pH adjuster and one or more fabric softening components
Detersive Surfactant
The detergent compositions herein compnse from about 4% to 80% by weight of a detersive surfactant Preferably such compositions compnse from about 5% to 50%> by weight of surfactant Detersive surfactants utilized can be of the anionic, nomonic, zwittenonic, ampholytic or cationic type or can compnse compatible mixtures of these types Detergent surfactants useful herein are described in U.S Patent 3,664,961, Norns, issued May 23, 1972, US Patent 3,919,678, Laughhn et al , issued December 30, 1975, U.S Patent 4,222,905, Cockrell, issued September 16, 1980, and in U.S. Patent 4,239,659, Murphy, issued December 16, 1980 All of these patents are incorporated herein by reference Of all the surfactants, anionics and nomonics are preferred.
Useful anionic surfactants can themselves be of several different types For example, water-soluble salts of the higher fatty acids, I e, "soaps", are useful anionic surfactants m the compositions herein. This includes alkali metal soaps such as the sodium, potassium, ammonium, and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms.
Additional non-soap anionic surfactants which are suitable for use herein include the water-soluble salts, preferably the alkali metal, and ammonium salts, of organic sulfunc reaction products having m their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfunc acid ester group. (Included in the term "alkyl" is the alkyl portion of acyl groups.) Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as C11-13 LAS.
Preferred nomonic surfactants are those of the formula R1(OC2H4)nOH, wherein R. is a C10-C16 alkyl group or a C8-C12 alkyl phenyl group, and n is from 3 to about 80 Particularly preferred are condensation products of C12-C15 alcohols with from about 5 to about 20 moles of ethylene oxide per mole of alcohol, e.g , C12-C13 alcohol condensed with about 6 5 moles of ethylene oxide per mole of alcohol.
Additional suitable surfactants, including polyhydroxy fatty acid amides and amine based surfactants, are disclosed in one or more of the co-pending PCT Applications listed in Table A and incorporated herein by reference
Determent Builder
The detergent compositions herein may also comprise from about 0 1% to 80% by weight of a detergent builder Preferably such compositions in liquid form will comprise from about 1% o 10% by weight of the builder component Preferably such compositions in granular form will comprise from about 1% to 50% by weight of the builder component. Detergent builders are well known in the art and can comprise, for example, phosphate salts as well as various organic and inorganic nonphosphorus builders
Water-soluble, nonphosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy sulfonates Suitable polycarboxylates for use herein are the polyacetal carboxylates described in U S. Patent 4,144,226, issued March 13, 1979 to Crutchfield et al, and U S Patent 4,246,495, issued March 27, 1979 to Crutchfield et al, both of which are incorporated herein by reference. Particularly preferred polycarboxylate builders are the oxydisuccinates and the ether carboxylate builder compositions comprising a combination of tartrate monosuccmate and tartrate disuccinate described in U.S Patent 4,663,071, Bush et al., issued May 5, 1987, the disclosure of which is incorporated herein by reference.
Examples of suitable nonphosphorus, inorganic builders include the silicates, aluminosilicates, borates and carbonates. Particularly preferred are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicates having a weight ratio of SiC2 to alkali metal oxide of from about 0 5 to about 4.0, preferably from about 1.0 to about 2.4. Also preferred are aluminosilicates including zeolites. Such materials and their use as detergent builders are more fully discussed in Corkill et al., U. S Patent No 4,605,509, the disclosure of which is incorporated herein by reference Also discussed in U. S. Patent No 4,605,509 are crystalline layered silicates which are suitable for use in the detergent compositions of this invention
Optional Detergent Ingredients
In addition to the surfactants, builders and dye maintenance polymers of the detergent compositions of the present invention can also include any number of additional optional ingredients. These include conventional detergent composition components such as enzymes and enzyme stabilizing agents, suds boosters or suds suppressers, anti-tarnish and anticorrosion agents, bleachmg agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, non-builder alkalinity sources, chelating agents, organic and inorganic fillers, solvents, hydrotropes, optical bnghteners, dyes and perfumes
Accordingly the present invention relates to a biaxially oriented transparent holographic film comprising:
- an upper skin layer of high crystalline polypropylene of at least 60% crystalhnity having 5 to 25% of the total film thickness,
- a core layer of polypropylene polymer sandwiched between the said upper and lower skin layers being more than 80% of the total film thickness;
- a lower skin layer of copolymers selected from propylene-ethylene random copolymers, propylene-a-olefin copolymers or ethylene-alpha olefin copolymer or an appropriate blend thereof having 5 to 25% of the total film thickness, wherein the said upper skin and lower skin layers contain antiblocking agents in 0 2 - 1.0% while the lower skin layer contains polar polymers as herein described in the range of 12-13% and additionally with silicone resins in the range of 0.25% to 1.25%.
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS
Fig. 1 depicts a general lay out of the manufacture of biaxially oriented polypropylene (BOPP) film on a tenter frame.
Fig. 2 depicts the process of embossing on the film.
DETAILED DESCRIPTION OF THE INVENTION
As shown in Fig. 1 extrusion of the three layer is done through three separate extruders 1, 2 and 3 on a tenter frame followed by melt extrusion. Three melt streams from three extruders, namely main extruder giving the core layer, satellite I for skin I and satellite II for skin II, are pressed together in the slit die (5) and are extruded as a single sheet
The said composite sheet after cooling is fed into an apparatus adapted for monoaxial orientation. The film is quenched on a chill roll and/or water bath
Issued November 1, 1983 to Chung et al The nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are "ypical and preferred Mixtures thereof can also be used See also the hereinbefore referenced U S 4,634,551 for other typical bleaches and activators useful herein
Other useful amido-denved bleach activators are those of the formulae
R^RSJCCO^CCCOL or R1C(0)N(R5)R2C(0)L
wherein R1 is an alkyl group containing from about 6 to about 12 carbon atoms, R2 is an alkylene containing from 1 to about 6 carbon atoms, R5 is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group A leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion A preferred leaving group is phenol sulfonate
Preferred examples of bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzene-sul-fonate, (6-decanamido-caproyl)oxybenzenesulfonate and mixtures thereof as described in the hereinbefore referenced U.S. Patent 4,634,551.
Another class of useful bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al. m U.S. Patent 4,966, 723, Issued October 30, 1990, incorporated herein by reference. See also U.S. Patent 4,545,784, Issued to Sanderson, October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.
If utilized, peroxygen bleaching agent will generally comprise from about 2% to 30% by weight of the detergent compositions herein More preferably, peroxygen bleaching agent will comprise from about 2% to 20% by weight of the compositions. Most preferably, peroxygen bleaching agent will be present to the extent of from about 3% to 15% by weight of the compositions herein. If utilized, bleach activators can comprise from about 2% to 10% by weight of the detergent compositions herein Frequently, activators are employed such that the molar ratio of bleaching agent to activator ranges from about 1:1 to 10:1, more preferably from about 1.5:1 to 5:1.
Additional suitable bleaching agents and bleach activators are disclosed in one or more of the co-pending PCT Applications listed in Table A and incorporated herein by reference
Another highly preferred optional ingredient m the detergent compositions herein is a detersive enzyme component. Enzymes can be included in the present detergent compositions for a variety of purposes, including removal of protein-based, carbohydrate-based, or tnglycende-based stains from substrates, for the prevention of refugee dye transfer in fabric laundering, and for fabric restoration Suitable enzymes include proteases, amylases, lipases,
cellulases, peroxidases, and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin Preferred selections are influenced by factors such as pH-activity and/or stability, optimal thermostability, and stability to active detergents, builders and the like. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
"Detersive enzyme", as used herein, means any enzyme having a cleaning, stain removing or otherwise beneficial effect in a laundry detergent composition Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases, amylases and peroxidases
Enzymes are normally incorporated into' detergent compositions at levels sufficient to provide a "cleaning-effective amount" The term "cleaning-effective amount" refers to any amount capable of producing a cleaning, stain removal, soil removal, whitening, deodonzmg, OT freshness improving effect on substrates such as fabrics. In practical terms for current commercial preparations, typical amounts are up to about 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the detergent composition. Stated otherwise, the compositions herein will typically comprise from 0.001% to 5%, preferably 0.01%-1% by weight of a commercial enzyme preparation. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition. Higher active levels may be desirable in highly concentrated detergent formulations.
Cellulases usable herein include those disclosed in U.S. Patent No. 4,435,307, Barbesgoard et al., March 6, 1984, and GB-A-2.075.028, GB-A-2.095.275 and DE-OS-2.247 832
CAREZYME® and CELLUZYME® (Novo) are especially useful. See also WO 9117243 to Novo.
The enzyme-containing compositions herein may optionally also comprise from about 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing system. The enzyme stabilizmg system can be any stabilizing system which is compatible with the detersive enzyme. Such a system may be inherently provided by other formulation actives, or be added separately, e.g., by the formulator or by a manufacturer of detergent-ready enzymes. Such stabilizing systems can, for example, compose calcium ion, boric acid, propylene glycol, short chain carboxyhc acids, boronic acids, and mixtures thereof, and are designed to address different stabilization problems depending on the type and physical form of the detergent composition.
Detereent Composition Preparation
The detergent compositions according to the present invention can be in liquid, paste or granular form Such compositions can be prepared by combining the essential and optional components in the requisite concentrations in any suitable order and by any conventional means The forgoing description of uses for the dye maintenance polymers defined herein are intended to be exemplary and other uses will be apparent to those skilled in the art and are intended to be within the scope of the present invention
Granular compositions, for example, are generally made by combining base granule ingredients, e.g , surfactants, builders, water, etc , as a slurry, and spray drying the resulting slurry to a low level of residual moisture (5-12%) The remaining dry ingredients, e g , granules of the essential dye maintenance polymers, can be admixed in granular powder form with the spray dried granules m a rotary mixing drum The liquid ingredients, e.g., solutions of the essential dye maintenance polymers, enzymes, binders and perfumes, can be sprayed onto the resulting granules to form the finished detergent composition. Granular compositions according to the present invention can also be in "compact form", i.e. they may have a relatively higher density than conventional granular detergents, i.e. from 550 to 950 g/1. In such case, the granular detergent compositions according to the present invention will contain a lower amount of "inorganic filler salt", compared to conventional granular detergents; typical filler salts are alkaline earth metal salts of sulphates and chlorides, typically sodium sulphate; "compact" detergents typically comprise not more than 10% filler salt
Liquid detergent compositions can be prepared by admixing the essential and optional ingredients thereof in any desired order to provide compositions containing components in the requisite concentrations. Liquid compositions according to the present invention can also be in "compact form", in such case, the liquid detergent compositions according to the present invention will contain a lower amount of water, compared to conventional liquid detergents Addition of the dye maintenance polymers to liquid detergent or other aqueous compositions of this invention may be accomplished by simply mixing into the liquid solutions the desired dye maintenance polymers.
Fabric Laundering Method
The present invention also provides a method for laundering fabrics in a manner which imparts fabric appearance benefits provided by the dye maintenance polymers used herein Such a method employs contacting these fabrics with an aqueous washing solution formed from an effective amount of the detergent compositions hereinbefore described or formed from the
individual components of such compositions Contacting of fabrics with washing solution will generally occur under conditions of agitation although the compositions of the present invention may also be used to form aqueous unagitated soaking solutions for fabric cleaning and treatment As discussed above, it is preferred that the washing solution have a pH of less than about 10 0, preferably it has a pH of about 9 5 and most preferably it has a pH of about 7 5
Agitation is preferably provided in a washing machine for good 'cleaning. Washing is preferably followed by drying the wet fabric in a conventional clothes dryer. An effective amount of a high density liquid or granular detergent composition in the aqueous wash solution in the washing machine is preferably from about 500 to about 7000 ppm, more preferably from about 1000 to about 3000 ppm.
Fabric Conditioning and Softening
The dye maintenance polymers hereinbefore described as components of the laundry detergent compositions herein may also be used to treat and condition fabrics and textiles in the absence of the detersive surfactant and builder components of the detergent composition embodiments of this invention. Thus, for example, a fabric conditioning composition comprising a fabric softener and the dye maintenance polymer or a fabric treatment composition comprising only the dye maintenance polymers themselves, or comprising an aqueous solution of the dye maintenance polymers, may be added during the nnse cycle of a conventional home laundering operation in order to impart the desired fabric appearance and integrity benefits hereinbefore described.
The fabric softener compositions of the present invention comprise at least about 1%, preferably from about 8%, more preferably from about 20% to about 80%, more preferably to about 60%, most preferably to about 45% by weight, of the composition of one or more fabric softener actives.
The preferred fabric softening actives according to the present invention are amines having the formula.
(Formula Removed)
quaternary ammonium compounds having the formula
(Formula Removed)
and mixtures thereof, wherein each R is independently C1-C6 alkyl, C1-C6 hydroxyalkyl, benzyl, and mixtures thereof; R1 is preferably C11-C22 linear alkyl, C11-C22 branched alkyl, C11-C22 linear alkenyl, C11-C22 branched alkenyl, and mixtures thereof, Q is a carbonyl moiety independently selected from the units having the formula

(Formula Removed)
wherein R.2 IS hydrogen, C1-C4 alkyl, preferably hydrogen; R3 is C1-C4 alkyl, preferably hydrogen or methyl; preferably Q has the formula:
(Formula Removed)
X is a softener compatible anion, preferably the anion of a strong acid, for example, chloride, bromide, methylsulfate, ethylsulfate, sulfate, nitrate and mixtures thereof, more preferably chloride and methyl sulfate. The anion can also, but less preferably, carry a double charge, in which case represents half a group. The index m has a value of from 1 to 3, die index n has a value of from 1 to 4, preferably 2 or 3, more preferably 2
One embodiment of the present invention provides for amines and quatemized amines having two or more different values for the index n per molecule, for example, a softener active prepared from the starting amine methyl(3-aminopropyl)(2-hydroxyethyl)amine.
More preferred softener actives according to the present invention have the formula
wherein the unit having the formula:
(Formula Removed)
is a fatty acyl moiety. Suitable fatty acyl moieties for use in the softener actives of the present invention are derived from sources of triglycerides including tallow, vegetable oils and/or partially hydrogenated vegetable oils including inter aha canola oil, safflower oil, peanut oil, sunflower oil, com oil, soybean oil, tall oil, rice bran oil. Yet more preferred are the Diester Quaternary Ammonium Compounds (DEQA's) wherein the index m is equal to 2
The formulator, depending upon the desired physical and performance properties of the final fabric softener active, can choose any of the above mentioned sources of fatty acyl moieties, or alternatively, the formulator can mix sources of triglyceride to form a "customized blend" However, those skilled in the art of fats and oils recognize that the fatty acyl composition may vary, as in the case of vegetable oil, from crop to crop, or from variety of vegetable oil source to variety of vegetable oil source. DEQA's which are prepared using fatty acids derived from natural sources are preferred.
A preferred embodiment of the present invention provides softener actives comprising R' units which have at least about 3%, preferably at least about 5%, more preferably at least about 10%, most preferably at least about 15% C11-C22 alkenyl, including polyalkenyl (polyunsaturated) units inter alia oleic, hnoleic, linolemc.
For the purposes of the present invention the term "mixed chain fatty acyl units" is defined as "a mixture of fatty acyl units comprising alkyl and alkenyl chains having from 10 carbons to 22 carbon atoms including the carbonyl carbon atom, and in the case of alkenyl chains, from one to three double bonds, preferably all double bonds in the cis configuration". With regard to the R.I units of the present invention, it is preferred that at least a substantial percentage of the fatty acyl groups are unsaturated, e.g., from about 25%, preferably from about 50% to about 70%, preferably to about 65%. The total level of fabric softening active containing polyunsaturated fatty acyl groups can be from about 3%, preferably from about 5%, more preferably from about 10% to about 30%, preferably to about 25%, more preferably to about 18%. As stated herein above cis and trans isomers can be used, preferably with a as/trans ratio is of from l-i, prefeiably at least 3:1, and more preferably from about 4:1 to about 501, more preferably about 20 1, however, the minimum being 1 1
The level of unsaturation contained within the tallow, canola, or other fatty acyl unit chain can be measured by the Iodine Value (IV) of the corresponding fatty acid, which in the present case should preferably be in the range of from 5 to 100 with two categories of compounds being distinguished, having a IV below or above 25
Indeed, for compounds having the formula
(Formula Removed)
derived from tallow fatty acids, when the Iodine Value is from 5 to 25, preferably 15 to 20, it has been found that a cis/trans isomer weight ratio greater than about 30/70, preferably greater than about 50/50 and more preferably greater than about 70/30 provides optimal concentrabihty
For compounds of this type made from tallow fatty acids having a Iodine Value of above 25, the ratio of cis to trans isomers has been found to be less critical unless very high concentrations are needed A further preferred embodiment of the present invention comprises DEQA's wherein the average Iodine Value for R1 is approximately 45.
The R.1 units suitable for use in the isotropic liquids present invention can be further characterized in that the Iodine Value (IV) of the parent fatty acid, said IV is preferably from about 10, more preferably from about 50, most preferably from about 70, to a value of about 140, preferably to about 130, more preferably to about 115. However, formulators, depending upon which embodiment of the present invention they choose to execute, may wish to add an amount of fatty acyl units which have Iodine Values outside the range listed herein above. For example, "hardened stock" (IV less than or equal to about 10) may be combined with the source of fatty acid admixture to adjust the properties of the final softener active.
A prefered source of fatty acyl units, especially fatty acyl units having branching, for example, "Guerbet branching", methyl, ethyl, etc. units substituted along the primary alkyl chain, synthetic sources of fatty acyl units are also suitable. For example, the formulator may with to add one or more fatty acyl units having a methyl branch at a "non-naturally occunng" position, for example, at the third carbon of a C17 chain What is meant herein by the term "non-naturally occunng" is "acyl units whihc are not found m significant (greater than about 0.1%) quantities is common fats and oils which serve as feedstocks for the source of triglycerides described herein " If the desired branched chain fatty acyl unit is unavailable from readily available natural feedstocks, therefore, synthetic fatty acid can be suitably admixed with othei synthetic materials or with other natural triglyceride derived sources of acyl units
The following are examples of preferred softener actives according to the present invention.
N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride; N,N-di(canolyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;
N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate, N,N-di(canolyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate, N,N-di(tallowylamidoethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate, N,N-di(2-tallowyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride, N,N-di(2-canolyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chlonde, N,N-di(2-tallowyloxyethylcarbonyloxyethyl)-N,N-dimethyl ammon'ium chlonde. N,N-di(2-canolyloxyethylcarbonyloxyethyl)-N,N-dimethyl ammonium chlonde, N-(2-tallowoyloxy-2-ethyl)-N-(2-tallowyloxy-2 -oxo-ethyl)-N,N-dimethyl ammonium
chlonde; N-(2-canolyloxy-2-ethyl)-N-(2-canolyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium
chlonde, N,N,N-tn(tallowyl-oxy-ethyl)-N-methyl ammonium chlonde; N,N,N-tn(canolyl-oxy-ethyl)-N-methyl ammonium chlonde; N-(2-tallowyloxy-2-oxoethyl)-N-(tallowyl)-N,N-dimethyl ammonium chlonde; N-(2-canolyloxy-2-oxoethyl)-N-(canolyl)-N,N-dimethyl ammonium chlonde; l,2-ditallowyloxy-3-N,N,N-tnmethylammoniopropane chloride; and 1,2-dicanolyloxy-3-N,N,N-tnmethylammoniopropane chlonde; and mixtures of the above actives. Particularly preferred is N,N-di(tallowoyl-oxy-ethyl)-N,N-dimethyl ammonium chlonde, where the tallow chains are at least partially unsaturated and N,N-di(canoloyl-oxy-ethyl)-N,N-dimethyl ammonium chlonde, N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate; N,N-di(canolyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate, and mixtures thereof.
Additional fabric softening agents useful herein are descnbed in U.S. 5,643,865 Mermelstem et al., issued July 1, 1997, U.S 5,622,925 de Buzzaccanni et al., issued Apnl 22, 1997; U.S. 5,545,350 Baker et al., issued August 13, 1996; U.S. 5,474,690 Wahl et al, issued December 12, 1995; U.S. 5,417,868 Turner et al., issued January 27, 1994; U.S. 4,661,269 Tnnh et al., issued Apnl 28, 1987; U.S. 4,439,335 Burns, issued March 27, 1984; U.S. 4,401,578 Verbruggen, issued August 30, 1983; U.S. 4,308,151 Cambre, issued December 29, 1981, U.S 4,237,016 Rudkin et al., issued October 27, 1978; US 4,233,164 Davis, issued November 11, 1980; U.S. 4,045,361 Watt et al., issued August 30, 1977; U.S. 3,974,076 Wiersema et al, issued August 10, 1976; U.S. 3,886,075 Bernadmo, issued May 6, 1975; U.S. 3,861,870 Edwards et al, issued January 21 1975; and European Patent Application publication No. 472,178, by Yamamura et al., all of said documents being incorporated herein by reference.
EXAMPLES The following examples illustrate the compositions and methods of the present invention, but are not necessarily meant to limit or otherwise define the scope of the invention
EXAMPLE I Dye Maintenance Parameter 1 est To evaluate a dye maintenance polymer, prepare a 10 ppm solution of the dye maintenance polymer in water Add 800ml of this solution to a l000mL beaker Introduce 8 gm+/-50mg of CI 10 fabric (CI 10 is a poplin fabric dyed with Direct Black 112 and supplied by Empirical Manufacturing Company of Cincinnati, OH) swatch in the solution such that it is completely immersed m the liquid Agitate the solution gently with a magnetic stirrer for 120 minutes A portion of the dye from the fabric will slowly bleed into the water After 120 minutes, withdraw an aliquot of the liquor, place it in a 5 cm path length cell and measure its absorbance at wavelength of 600nm with a Hewlett Packard Model 8453 uv-vis spectrophotomer following the general instructions provided by the manufacturer for the use of this instrument This absorbance is called AbsPolymer.
Using the procedure outlined above, repeat the procedure with distilled water alone with no added dye maintenance polymer to obtain AbsWtler
The Dye Maintenance Parameter ("DMP") is defined as (AbSw„„ - AbsPolymtr)
EXAMPLE II Calculation of the Average Charge Per Molecule
While there are many ways to calculate the charge density of a polymeric matenal known to those skilled m the analytical arts, one such method is as follows. Specifically, the charge density for molecules with a known chemical structure, is determined by a standard acid-base titration or a potentiometnc titration to give charge to mass ratio Charge density can then be converted to an average charge per molecule by determining the average molecular weight of the matenal and simply dividing the charge density by the average molecular weight to determine the average number of positive charges per molecule
For low molecular weight matenals, molecular weight is determined standard techniques such as mass spectrosocpy For polymenc matenals, molecular weight is determined by gel permeation chromatography. These methods are descnbed in analytical text books such as "Instrumental Methods of Analysis" by Willard, Memtt, Dean, and Settle
EXAMPLE III TABLE III comprises numerous examples according to the present invention along with some compantive examples of matenal known to the art of laundry detergents The chemical structures shown in the examples below are idealized structures Side reactions expected to occur dunng the condensation are not shown
TABLE III
(Table Removed)
EXAMPLE IV Granular Detergent Test Composition Preparation Several heavy duty granular detergent compositions are prepared containing one or more dye maintenance polymer having a DMP according to this invention. These granular detergent compositions all have the following basic formula:
TABLE IV
(Table Removed)
EXAMPLE V Liquid Detergent Test Composition Preparation Several heavy duty liquid detergent compositions are prepared containing one or more dye maintenance polymer havmg a DMP according to this invention These liquid detergent compositions all have the following basic formula
TABLE V
(Table Removed)
EXAMPLE VI Granular Detergent Test Composition Preparation Several granular detergent compositions are prepared containing one or more dye maintenance polymer having a DMP according to this invention. Such granular detergent compositions all have the following basic formula
TABLE VI
(Table Removed)
EXAMPLE VII Fabnc Softener Test Composition Preparation Several fabnc softener compositions are prepared containing one or more dye maintenance polymer having a DMP according to this invention Such fabnc softener compositions can have any of the following basic formulae
TABLE VIIa
(Table Removed)
1 N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride (tallowyl having an I V of 50)
2 N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride (tallowyl having an I V of 18)
3 l,2-Ditallowyloxy-3-N,N,N-tnmethylammoniopropane chloride.
4 Ditallow dimethyl ammonium chloride

5. Methyl bis(tallow amidoethyl)-2-hydroxyethyl ammonium methyl sulfate
6. 1 -Tallowamidoethyl-2-imidazoline.

10. N,N,N' ,N'-terakis(2-hydroxypropyl)ethylenediamine.
11. Dimethyl terephthalate, 1,2-propylene glycol, methyl capped PEG polymer.
12. N,N'-bis(3-aminopropyl)-1,3-propylenediamine
TABLE Vllb
(Table Removed)
1 N,N-di(canoyloxyethyl)-N-2-hydroxyethyl-N-methyl ammonium methyl sulfate available from Witco
2 Monocanolyl tnmethyl ammonium chloride, available as Adogen 417® from Witco

6 N,N'-(3-ammopropyl)ethylenediamine
7 N,N'-(3-ammopropyl)butylenediamine
8 Tnpropylenetetraamme
9 Tnmethyl pentanediol available from Eastman Chemical.
10 1,4-cyclohexane dimethanol available from Eastman Chemical
11 Minors can include perfume, dye, acid, preservatives, etc
EXAMPLE Vni Aqueous Treatment Composition Preparation Several aqueous treatment compositions are prepared containing one or more dye maintenance polymer having a DMP according to this invention. Such treatment compositions can have any of the following basic formulae.
TABLE VIII
(Table Removed)
1. N,N-di-(canolyl-oxy-ethyl)-N-methy l-N-(2- hycIroxyethyl ammonn lm methy sulfate
2. Selected from REWIN SRF, REWIN SRF-O and REWIN DWR ex CHT-Beitlich GMBH
3 Polyalkyleneimine having a molecular weight of 1800 and an average ethoxylation per backbone nitrogen of approximately 4
4 Polyalkyleneimine having a molecular weight of 1800 and an average ethoxylation per backbone nitrogen of approximately 1
5 Polyalkyleneimine having a molecular weight of 1800 and an average ethoxylation per backoone nitrogen of approximately 7
6 Hydroxyethanediphosphonate (HEDP)
7 BAYHIBIT AM ex Baeyer
8 Suitable enzymes include cellulase, lipase, protease, peroxidase, and mixtures thereof
9 N,N' -bis(propyleneammo)-1,4-piperazme

We claim:
1. A biaxially oriented transparent holographic film comprising:
- an upper skin layer of high crystalline polypropylene of at least 60% crystallinity having 5 to 25% of the total film thickness:
- a core layer of polypropylene polymer sandwiched between the said upper and lower skin layers being more than 80% of the total film thickness;
- a lower skin layer of copolymers selected from propylene-ethylene random copolymers, propylene-α-olefin copolymers or ethylene-alpha olefin copolymer or an appropriate blend thereof having 5 to 25% of the total film thickness, wherein the said upper skin and lower skin layers contain antiblocking agents in 0.2 - 1.0% while the lower skin layer contains polar polymers as herein described in the range of 12-13% and additionally with silicone resins in the range of 0.25% to 1.25%.
2. A film as claimed in claim 1, wherein the thickness of upper skin layer is 5-12%
of the total thickness.
3. A film as claimed in claim 1. wherein the thickness of lower skin layer is 10-12.5% of the total thickness.
4. A film as claimed in claim 1, wherein thickness of said core layer is upto 90% of the total thickness.
5. A film as claimed in claim 1, wherein the said antiblocking agents are polymethylene methacrylate, Nylon, Polyisobutyl methacrylate, silica, silicates and/ or a mixture thereof.
6. A film as claimed in claim 1, wherein the said silicone resins are in the range of 0.5-1.0%.
7. A film as claimed in claim 1, wherein the said polar polymers are acrylic modified or maleic anhydride modified polypropylene.
8. A film as claimed in claim 1, wherein at least one skin layer is made of high crystalline polypropylene with a crystallinity of more than 65%.
9. A film as claimed in claim 1, wherein the isotactic index of said high crystalline polypropylene used is 90%, preferably more than 95%.
10. A process for manufacturing a biaxially oriented transparent holographic film as claimed in claim 1 comprising the steps of:

- providing a body of thermoplastic film;
- orienting the said film along a first axis by passing the film through a series of powered calender rollers which tension the film in the longitudinal direction;
- orienting the film along a second axis, normal to the first axis, by clamping the edges of the film in a tenter frame which tensions the film in the transverse direction;
- raising the temperature of the film to a desired annealing temperature above room temperature;
- continuing to maintain the film at a temperature above room temperature while embossing a diffraction pattern into a surface of the film, the film being continuously maintained at a temperature above room temperature and under tension along at least one of said first and second axes from the time the film temperature is raised to the desired annealing temperature until the diffraction pattern is embossed into the film;
- cooling the film to room temperature; and
- depositing a metallic layer as herein described over the diffraction pattern embossed into the surface of the film.
11. A biaxially oriented transparent holographic film substantially as herein before described with reference to the accompanying drawings.
12. A process for manufacturing a biaxially oriented transparent holographic film substantially as herein before described with reference to the accompanying drawings.

Documents:

in-pct-2001-255-del-abstract.pdf

in-pct-2001-255-del-claims.pdf

in-pct-2001-255-del-correspondence-others.pdf

in-pct-2001-255-del-correspondence-po.pdf

in-pct-2001-255-del-description (complete).pdf

in-pct-2001-255-del-form-1.pdf

in-pct-2001-255-del-form-19.pdf

in-pct-2001-255-del-form-2.pdf

in-pct-2001-255-del-form-26.pdf

in-pct-2001-255-del-form-3.pdf

in-pct-2001-255-del-form-5.pdf

in-pct-2001-255-del-pct-304.pdf

in-pct-2001-255-del-pct-409.pdf

in-pct-2001-255-del-pct-416.pdf

in-pct-2001-255-del-petition-137.pdf

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Patent Number

230834

Indian Patent Application Number

IN/PCT/2001/00255/DEL

PG Journal Number

13/2009

Publication Date

27-Mar-2009

Grant Date

28-Feb-2009

Date of Filing

29-Mar-2001

Name of Patentee

THE PROCTER & GAMBLE COMPANY

Applicant Address

ONE PROCTER & GAMBLE PLAZA, CINCINNATI, STATE OF OHIO 45202, U.S.A.

Inventors:

#	Inventor's Name	Inventor's Address
1	PANANDIKER, RAJAN KESHAV	6484 OREGON PASS, WEST CHESTER,OHIO, 45069, U.S.A.
2	LITTING JANET SUE	159 HIDDEN HILLS DRIVE, FAIRFIELD, OHIO, 45014, U.S.A.
3	GOSSELINK EUGENE PAUL	3754 SUSANNA DRIVE, CINCINNATI, OHIO, 45251, U.S.A.
4	RANDALL,SHERRI LYNN	5836 MINDY DRIVE, HAMILTON, OHIO, 45011, U.S.A.
5	BJORKOUST, DAVID WILLIAM	36 OLVER ROAD, WYOMING,OHI, 45215, U.S.A.

PCT International Classification Number

C11D 3/37

PCT International Application Number

PCT/US1999/22935

PCT International Filing date

1999-10-13

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	60/103978	1998-10-13	U.S.A.
2	60/126074	1999-03-25	U.S.A.
3	60/148053	1999-08-10	U.S.A.