MXPA97006917A - Detergent composition that comprises ether of non-ionic polysaccharide and anionic surgical agent is not of ja - Google Patents

Abstract

Detergent compositions comprising non-ionic polysaccharide and an anionic surfactant other than soap, ether and nonionic surfactant other than soap, ether and surfactant being in close physical proximity to the detergent composition are disclosed.

Description

COMPOSITION DETERGENT COMPRISING NON-IONIC PQLISACARIDE ETHER AND ANIONICQ SURGICAL AGENT THAT IS NOT 3ABON FIELD OF THE INVENTION The present invention relates to detergent compositions that provide dirt release performance.

BACKGROUND OF THE INVENTION During the fabric washing operation, it is highly desirable to provide dirt release properties to the fabrics, particularly man-made fabrics produced from synthetic fibers. Due to the hydrophobic nature of fabrics composed of partially or completely synthetic fibers, the removal of dirt and grease stains from them is particularly difficult. In order to face this problem, dirt-releasing polymers can be incorporated in the detergent composition. During washing, soil release agents are adsorbed onto the surface of the fabric, thus inducing greater hydrophobic character to the surface of the fabric. Once the fabric is treated with a soil release agent, the ease of removal of dirt and grease stains from the surface of the fabric is considerably improved.

The main types of soil release agents incorporated in detergent compositions, which provide benefits to primarily hydrophobic synthetic fabrics include synthetic soil release agents, preferably ethers based on terephthalate and polysaccharide. The polysaccharide ether can be conventionally characterized by one or more of molecular weight, degree of polymerization (gp) and degree of substitution (gs). Polysaccharide ethers such as or cellulose ethers have been described, for example, in GB 1 534 641 which discloses nonionic surfactant detergent compositions comprising cellulose ether soil release agents such as the alkyl and hydroxyalkyl cellulose ethers. Numerous descriptions of detergent compositions comprising cellulose ethers and optionally anionic surfactants exist in the prior art. For example, EPO 320296 relates to fabric softening additives for detergent compositions that soften natural fibers without creating redeposition problem on synthetic materials. An intimate mixture of cellulose ethers (gs = 0.5 3%, up to 3, gp = 50-1200) and fabric softeners at a ratio of 1: 1 to 0.06: 1 is described. The fabric softener can be an alkaline metal soap. EPO 213730 relates to detergent compositions for fabric treatment that soften natural fibers without creating redeposition problems. The compositions comprise 0. 5-3% nonionic cellulose ethers (HLB 3.1-4.3, gs = 0.5 - 3%, up to 3, gp = 50-1200), anionic detergent that is not soap (2-50%) and an agent fabric softener. The composition is prepared by dry mixing, coagglomeration or spray drying. EPO 213729 discloses detergent compositions comprising soap, nonionic surfactants and cellulose ether showing improved solubility at low temperature and low level of soil redeposition. Anionic surfactants are disclosed as optional surfactants. EPO 256696 describes a detergent composition for improved soil suspension comprising anionic surfactants (5-90%), vinylpyrrolidone polymer and nonionic cellulose ether. E.U.A. 4 100 094 discloses a detergent composition containing novel cellulose ethers having a molecular weight of 3000 to 10,000 and a g of 1.8-2.7 as soil release agents. Organic surfactants (5-60%) including anionic surfactants are disclosed. The compositions are formulated by dry mixing or spray drying. E.U.A. No. 136 038 discloses detergent compositions comprising 0.1-3% cellulose ether and 5-50% C12-C12 alkylbenzene sulphate, preferably having a ratio of 1: 5 to 1:50. The granulated compositions are prepared by combining all the components except the cellulose ether in an aqueous suspension of detergency and spray drying. The cellulose ether is added dry to the mixture. However, it has been observed that the dirt release performance of the fabrics attributable to the incorporation of the nonionic polysaccharide ether in a detergent composition can be significantly reduced due to the dispersion problems of the polysaccharide ether in the wash liquor. As a consequence of the tendency of the polysaccharide ethers to be added to the wash solution, their diffusion speed is reduced in the vicinity of the fabric and subsequently the maximum adsorption on the fabric is not achieved. The problem is exacerbated under adverse wash conditions. In particular, the use of short machine program cycles or high temperature cycles and the presence of heavily soiled fabrics covers the performance of the polysaccharide. In addition, the development of high density detergent formulations has also served to amplify these problems. Accordingly, there is a need to provide a detergent composition comprising a nonionic polysaccharide ether that reduces the tendency of the polysaccharide to be added while still providing acceptable soil release performance. * It has now surprisingly been found that this problem can be addressed by the use of a detergent composition comprising? N polysaccharide ether not ion in combination with an anionic surfactant in close physical proximity within said detergent composition. None of the prior art documents identified before faces the problem of cellulose Reter dispersion during washing. Furthermore, the prior art identified does not recognize that these problems can be faced by the user of polysaccharide ethers in combination with an anionic surfactant in close proximity within a detergent composition.

BRIEF DESCRIPTION OF THE INVENTION The present invention relates to a detergent composition comprising a non-ionic polysaccharide ether and an anionic non-soap surfactant, wherein said polysaccharide ether and anionic surfactant are in close proximity within the detergent composition. All weights, ratios and percentages are given as percent by weight of the total composition unless otherwise indicated.

DETAILED DESCRIPTION OF THE INVENTION According to the present invention, the detergent composition comprises as essential components a non-ionic polysaccharide ether and an anionic non-soap surfactant. It has been found that the soil release performance of a non-ionic polysaccharide ether can be improved by its use in combination with said surfactant in close physical proximity within said detergent composition. In addition, the ability of the nonionic polysaccharide ether to be dispersed in the wash solution can be improved by the close physical proximity of an anionic surfactant.

Close physical proximity In accordance with the present invention, the anionic surfactant and the nonionic polysaccharide ether are in close physical proximity within said detergent composition. Close physical proximity, as used herein, comprises particulate materials, granular materials, flakes, noodles and etruded materials containing said anionic surfactant and said nonionic polysaccharide ether. In a preferred embodiment of the present invention said surfactant and said ether are intimately mixed within said composition such that they are adjacent to said particulate materials, granulated materials, flakes, noodles and stripped materials. In another embodiment of the present invention the polysaccharide ether and said anionic surfactant are present in the same particulate materials, granulated materials, flakes, noodles and structured materials, but they are not adjacent and are separated by one or more optional additional components of the particulate materials, granulated materials, flakes, noodles and stripped materials, for example by means of at least one layer.

Non-ionic polysaccharide ethers According to the present invention, an essential component of the detergent composition is a non-ionic polysaccharide ether. Chemically, polysaccharides are composed of pentoses or hexoses. The polysaccharide esters suitable for use herein are selected from cellulose ethers, starch ethers, dextran ethers and mixtures thereof. Preferably said nonionic polysaccharide ether is a cellulose ether. Cellulose ethers are generally obtained from plant tissues and fibers, including cotton and wood pulp. The hydroxyl group of the anhydroglucose unit of the cellulose can be reacted with several reagents thus replacing the hydrogen of the hydroxyl group with other chemical groups. Various alkylating agents and hydroxyalkylating agents can be reacted with cellulose ethers to produce alkyl-, hydroxyalkyl- or alkylhydroxyalkylcellulose ethers or mixtures thereof. Most preferred for use in the present invention are C1-C4 alkyl cellulose ether or a hydroxyalkyl cellulose ether of C1-C4 or an alkylhydroxyalkylcellulose ether of Ci-C4 or mixtures thereof. Preferably, the polysaccharides of the present invention have a degree of substitution of 0.5 to 2.8, preferably 1 to 2.5, most preferably 1.5 to 2 inclusive. Suitable cellulose ethers include methyl ether and ethyl cellulose, hydroxypropyl ether, hydroxybutyl and hydroxyethyl methyl cellulose, hydroxypropyl and hydroxyethyl cellulose ether, hydroxybutyl ethyl cellulose ether, ethyl hydroxyethyl cellulose ether, hydroxyethyl cellulose ether, ethylhydroxyethylcarboxymethylcellulose and carboxymethylhydroxyethylcellulose. Most preferably said polyaccharide is a methyl cellulose ether commercially available as Methocel (Dow Chemicals), methylhydroxyethylcellulose ether and mixtures thereof. In accordance with the present invention, said polysaccharide ether preferably has a molecular weight of 10,000 to 200,000, most preferably 30,000 to 150,000. The weight average weight is obtained by normal analytical methods as described in polymer manuals. A preferred method is light scattering from polymer solutions as originally defined by Debye. The compositions of the present invention cooperate from 0.01% to 10%, preferably from 0.01% to 3%, most preferably from 0.1% to 2% of said nonionic polysaccharide ethers.

Nonionic Anionic Surfactants In accordance with the present invention, the other essential component of the intimate mixture is an anionic non-soap surfactant. Anionic surfactants useful herein include C10-C20 primary, branched-chain, and random alkylsulfates ("OS"), C14-Ciß secondary alkyls (2,3) of the formula CH3 (CH2) x (CHOSO3-M +) CH3 and CH3 (CH2) and (CH0S03 ~ M +) CH2CH3 where xy (y +1) are integers of at least 7, preferably at least about 9, and M is a cation of solubilization in water, especially sodium, unsaturated sulfates such as oleyl? lphate, the alkylalkoxysulfates of Cio-Ciß ("AE? S", especially ethoxysulfates EO 1-7), alkylalkyl carboxylates of Cio-Ciß (especially the ethoxycarboxylates EO 1-5) ), the alkyl polyglycosides of Cio-Ciß and the aliphatic fatty acid esters of C12-C18. In accordance with the present invention, the alkoxylated alkyl or hydroxyalkylsulfates for use herein are of the formula R0 (A) «S03M, wherein R is an unsubstituted C11-C24 alkyl or hydroxyalkyl component, preferably an alkyl or hydroxyalkyl component ? C12-C20, most preferably? C12-C18 alkyl or hydroxyalkyl component, A is an ethoxyproxy group, is from 1 to 15, most preferably from 1 to 10, and M is H or a cation that can be selected of metal cations such as sodium, potassium, lithium, calcium, magnesium, ammonium or substituted ammonium. Specific examples of substituted ammonium cations include methyl-, dimethyl-, tri-ethyl-a-onium and quaternary ammonium cations such as tetramethylammonium, dirnethylpiperidium and cations derived from alkanolamine, e.g. onoethanolarnin, diethanolamide and triethanolamine and mixtures thereof. Exemplary surfactants are C12-Cetyl polyethoxylated alkyl sulfate (2.25), polyethoxylated C12-C18 alkyl sulfate (3), polyethoxylated C? «-C? Al polyol ethoxylate (0.6) and polyethoxylated C12-C18 alkyl sulfate (4), where M is selected from sodium or potassium. Especially preferred is C14-C15 alkyl sulfate which has been ethoxylated with an average of 0.5 to 4 moles of ethylene oxide per molecule. Other suitable anionic surfactants for use herein include salts (eg, alkali metal and ammonium salts) of linear alkylsulfonates of Cn-C24, preferably C12-C20, particularly linear alkylbenzenesulfonates, primary or secondary alkanols, alkenesulphonates such as α-olefins, lyphonates, ether sulfonates, sulfonated polycarboxylic acids, oxyalcansulphates (fatty acid isethionates), alkyl sarcosinates, acylaminoalcansulphonates (taurides), alkylglycerolsulphonates, fatty acyl glycerol sulfonates, oleylglycerolsulfonates and mixtures thereof. In accordance with the present invention, the compositions comprise from 1% to 80%, preferably from 2% to 50%, rn? And preferably still from 5% to 40% of an anionic surfactant which is not soap. In accordance with the present invention, the anionic surfactant and the particulate nonionic polysaccharide may comprise a number of additional components commonly employed in the formulation of mixed particles. Suitable components include absorbent builders such as zeolites, chelators, structuring materials such as copolymers based on acrylic-maleic acid and inorganic fillers such as sulfates and carbonates. A complete description of said components is given in the following description of detergent composition in the present.

Detergent Composition In accordance with the present invention, the detergent composition may comprise a number of optional ingredients commonly employed for detergent applications such as surfactants, builders, chelators, polymers, antiredeposition agents and the like.

Optional surfactants If desired, conventional amphoteric and nonionic surfactants such as C12-Ciß alkylethoxylates ("AE") including the so-called peak alkyl ethoxylates. narrow and the C6-C12 alkyl phenolalkylates (especially ethoxylates and ethoxy / mixed propoxy), C12-C18 betaines and sulfobetaines ("sultaines"), C14-C14 amine oxides, and the like, can also be included in the compositions global The N-alkyl polyhydroxolic acid amides of Cio-Ciß can also be used. Typical examples include C12-C18 N-ethylglucamines. See UO 9,206,154. Other sugar-derivatized surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as N- (3-rnetoxipropiDglucamine of Cι-Ciß- The N-propyl to C 12 -C 18 N-hexylglucans can be used for low spurnation. Conventional C10-C20 soaps can also be used.If high foaming is desired, branched chain Cio-Ciß soaps can be used In addition to being in close proximity to the non-ionic polysaccharide ether, anionic surfactants can be present in the detergent composition as a component of the surfactant system.

Cationic Surfactant The cationic detersive surfactants suitable for use herein are those which have a long chain hydrocarbyl group. Examples of such cationic surfactants include ammonium surfactants such as alkyl ethylammonium halides and surfactants having the formula: [R2 (0R3) and 3CR4 (OR3) and] R5N + X- wherein R2 is an alkyl or alkylbenzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R3 is selected from the group consisting of CH2CH2-, -CH2CH (CH3) -, ~ CH2CH (CH20H) -, -CH2CH2CH2-, and mixtures thereof; each of R * is selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl ring structures formed by the joining of two groups *, -CH2CHOH-CHOHCOR6CHOHCH2OH wherein R * is any hexose or hexose polymer which has a molecular weight lower than about 1000 and hydrogen when and is not 0; RS is the same as * o is an alkyl chain where the total number of carbon atoms of R2 plus R5 is not greater than 18; each y is from about 0 to about 10 and the sum of the y values is from 0 to about 15; and X is any compatible anion. Preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition and have the formula: R 1 R2 3 * N + X- wherein Ri is a C 1 -Cis alkyl, each of R 2, R 3 and J , is independently C1-C4 alkyl, Ci-C4 hydroxyalkyl, benzyl and (C2r 0) HH where x has a value of 1 to 5 and x is an anion. No more than one of R2, R3 and R4 must be benzyl. The preferred alkyl chain length for Ri is C 12 -C 15 in particular wherein the alkyl group is a mixture of chain lengths derived from coconut fat or from palm seed or synthetically derived by olefin accumulation or synthesis of 0X0 alcohols. The preferred groups for R2, R3 and R "are methyl and hydroxyethyl groups and the anion X can be selected from halide, methosulfate, acetate and phosphate ions. Examples of quaternary ammonium compounds suitable for use herein are: chloride or coconut-tri-ethylammonium bromide; cobalt or bromide-ethyldihydroxyethylammonium bromide; decyltrimethylammonium chloride; decildi ethylhydroxyethylammonium chloride or bromide; chloride or bromide of di-ethylhydroxyethylammonium of C12-C15; coconut or dimethylhydroxyethylarnonium bromide or chloride; iristyltrimethylammonium methylsulfate; chloride or bromide of the? rildi ethyl-benzylamine; lauryldimethyl-ethoxy chloride or bromide) * ammonium and choline esters.

Detergency builders Builders may optionally be included in the compositions herein to help control the hardness of minerals. Inorganic and organic builders can be used. Builders are typically used in fabric washing compositions to help remove particulate soils. The level of builder can vary widely depending on the final use of the composition and its desired physical form. When they are present, the compositions typically they will comprise at least about 1% builder. Liquid formulations typically comprise from about 5% to about 50%, very typically from about 5% to about 30%, by weight builder. Granulated formulations typically comprise from about 10% to about 80%, very typically from about 15% to about 50% by weight of the builder. However, lower or higher detergency builder levels are not excluded. Detergency builders for inorganic or P-containing detergents include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the glassy polymeric tripolyphosphate, pyrophosphate and metaphosphate), phosphonates, phytic acid , silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates and aluminosilicates (see, for example, US Patents 3,159,581, 3,213,030, 3,422,021, 3,400,148 and 3,422,137). However, non-phosphate builders are not required in some locations. Importantly, the compositions herein work surprisingly well even in the presence of so-called "weak" detergents (as compared to phosphates) such as citrate, or in the so-called "s? B detergency" situation. What can happen with the zeolite or layered silicate builders. Examples of silicate builders are alkali metal silicates, particularly those having a ratio of SiO 2: N 2? in the scale from 1.6: 1 to 3.2: 1 and layered silicates, such as the layered sodium silicates described in US Pat. No. 4,664,839, issued May 12, 1987 to H. P. Riec. NaSKS-6 is the trade name for a crystalline layered silicate sold by Hoechst (commonly abbreviated as "SKS-6"). Unlike zeolite builders, the NaSKS-6 silicate detergent builder does not contain aluminum. NaSKS-6 has the morphological form of delta-Na2Si0s of stratified silicate. It can be prepared by methods such as those described in German Application DE-A-3,417,649 and DE-A-3, 742, 043. SKS-6 is a highly preferred layered silicate for use herein, but other layered silicates , such as those that have the general formula NaMSi ?? 2n +? and H 2 O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 may be used herein. Some other stratified silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11 as the alpha, beta and gamma forms. As indicated above, the delta-Na2 SiOs (NaSKS-6) form is most preferred for use herein. Other silicates can also be used such as for example magnesium silicate, which can serve as a tightening agent in granulated formulations, as a stabilizing agent for oxygen bleaches, and as a component of foam control systems. Examples of carbonate builders are the alkaline earth metal and alkaline carbonates as described in German Patent Application No. 2,321,001 published November 15, 1973. The aluminoeilicate detergent builders are useful in the present invention. Alkalosilicate builders are of great importance in the majority of heavy duty granulated commercially charged detergent compositions, and can also be an important detergency builder ingredient in liquid detergent formulations. Alu inosilicate builders include those that have the empirical formula: MzC (Si02) * (ZA102) and lxH20 where w, z and y are integers of at least 6, the molar ratio of zay is on the scale of about 1.0 at about 0.5, and x is an integer from about 15 to about 264. Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be of crystalline or amorphous structure and can be aluminosilicates that occur naturally or synthetically derived. A method for producing aluminosilicate ion exchange materials is described in US Patent 3,985,669, Krum et al. Issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the ion exchange material of crystalline aluminosilicate has the formula: Nai2p 102 l2 (S.ÍO2) 12] xH2? wherein x is from about 20 to about 30, especially from 27. The material is known as Zeolite A. Dehydrated zeolites (x = 0-10) can also be used herein. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter. Organic builders suitable for the purposes of the present invention include, but are not limited to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate builders can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When used in the form of salt, Alkali metals such as sodium, potassium and lithium, or alkanola onium salts are preferred. Included among the polycarboxylate builders are a variety of useful material categories. An important category of polycarboxylate builders comprises the ether polycarboxylates, including oxydisuccinate, as described in Berg, U.S. Pat. 3,128,287, issued April 7, 1964, and Lamberti et al., Patent of E.U.A. 3,635,830, issued January 18, 1972. See also detergent builders of "TMS / TDS" of the U.S. Patent. 4,663,071, issued to Bush et al. On May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in US Patent 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903. Other useful builders include ether hydroxypolycarboxylates, maleic anhydride copolymers with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid, and carboxymethyloxy-scyclic acid, the various metallic salts of alkali, ammonium and substituted ammonium of polyacetic acids such as ethylenediamine tetraacetic acid and nitriloacetic acid, as well as polycarboxylates such as methyl acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, acid carboxymethyloxysuccinic, and salts soluble of them. Citrate builders, eg, citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations because of their availability from renewable resources and their biodegradability. The citrates can also be used in granular compositions, especially in combination with zeolite builders and / or layered silicate. Oxydisuccinates are also especially useful in said compositions and combinations. Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-l, 6-hexanedioates and the related compounds described in the US patent. No. 4,566,984, Bush, issued January 28, 1986. Useful scyclic acid builders include alkyl and alkenyl succinic acids of Cs-C20 and salts of the same. A particularly preferred compound of this type is dodecenylsilycinic acid. Specific examples of succinate builders include: lauryl? Ccinate, myristyl? Ccinate, palmityl succinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate and the like. Larylsuccinates are the preferred detergency builders in this group, and are described in the European patent application 86200690. 5 / 0,200,263, published on November 5, 1986. Other suitable polycarboxylates are described in the patents of E.U.A. 4,144,226, Crutchfiel et al., Issued March 13, 1979 and in the U.S. patent. 3,308,067, Diehl, issued March 7, 1967. See also Patent of U.S.A.

Diehl, 3,723,322. The fatty acids, e.g., C12-C18 monocarboxylic acids, may also be incorporated into the compositions by themselves, or in combination with the aforementioned builders, especially citrate and / or succinate builders, to provide additional detergency builder activity. Said use of fatty acids will generally result in decreased foaming, which would be considered by the fornulator.

Chelating Agents The detergent compositions of the present invention may also optionally contain one or more iron and manganese chelating agents as an additive builder material. Such chelating agents can be selected from the group consisting of incarboxylates, aminophosphonates, polyfunctionally substituted aromatic q-elastinating agents and mixtures thereof, all as defined below. Without intending to be limited to theory, it is believed that the benefit of these materials is due in part to their exceptional ability to 7 remove iron and manganese ions from washing solutions by chelation of soluble chelates. The incarboxylates useful as chelating agents include ethylenediaminetetraacetates, N-hydroxyethylenediaminetriacetates, nitriloacetates, ethylene-diarninotetratripionates, triethylenetetraminehexaacetates, ethylene-triaminopentaacetate and ethanoldiglicines, alkali metal salts, ammonium and substituted ammonium thereof and mixtures thereof. Aminophosphonates are also suitable for use as chelating agents in the compositions of the invention when at least two levels of total phosphorus are allowed in detergent compositions, and include intetraqui ethylene (methylenephosphonates) as DEQUEST. It is preferred that these aminophosphonates do not contain alkyl or alkenyl groups with more than six carbon atoms. Poly-substituted aromatic chelating agents are also useful in the compositions herein. See patent of E.U.A. 3,812,044, issued May 21, 1974 to Connor and others. Preferred compounds of this type in acid form are the dihydroxydisulfobenzenes, such as 1,2-dihydroxy-3,5-dis? Lfobenzene. A preferred biodegradable chelator for use herein is ethylenediaminedis ccinate ("EDDS"), especially the ES, SU isomer described in the U.S. Pat. 4,704,233, on November 3 to Hart an and Perkins.

If used, these chelating agents will generally comprise from about 0.1% to about 10% by weight of said compositions.

Polymeric dirt release agent Any polymeric soil release agent known to those skilled in the art can optionally be employed in the compositions and methods of this invention. Polymeric soil release agents are characterized by having both hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments, to be deposited on hydrophobic fibers and to remain adhered thereto until the washing cycles are completed and rinse and serve as an anchor for the hydrophilic segments. This allows stains that appear after treatment with the soil release agent to be cleaned more easily in subsequent washing procedures. The polymeric soil release agents useful herein especially include those soil release agents having: (a) one or more nonionic hydrophilic components which consist essentially of (i) polyoxyethylene segments with a degree of polymerization of minus 2, or (ii) oxypropylene or polyoxypropylene segments with a polymerization degree of 2 to 10, wherein said hydrophilic segment does not comprise any unit of oxypropylene unless it is linked to adjacent portions at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene units and from 1 to about 30 oxypropylene units wherein said mixture contains a sufficient amount of oxyethylene units in such a way that the hydrophilic component has hydrophilic character sufficiently large to increase the hydrophilic character of the surfaces of conventional synthetic polyester fabrics on the deposit of the soil release agent on said surface, said hydrillic segments preferably comprising at least about 25% oxyethylene units and most preferably, especially for the components having about 20 to 30 oxypropylene units, at least 50% oxyethylene units; or (b) one or more hydrophobic components comprising (i) segments of C3 oxyalkylene terephthalate, wherein, if said hydrophobic component also comprises oxyethylene terephthalate, the ratio of oxyethylene terephthalate: C3 oxyalkylene terephthalate units is about 2: 1 or less, (ii) C4 -Ce alq? ile segments? C--Cβ oxyalkylene, or mixtures thereof, (iii) polyvinyl ester segments, preferably polyvinyl acetate, having a degree of polymerization of at least 2. Typically the polyoxyethylene segments of (a) (i) have a degree of polymerization from about 200, although higher levels can be used, preferably from 3 to about 150, most preferably from 6 to about 100. The oxyalkylene segments of Suitable hydrophobic agents include, but are not limited to, blocked ends of polymeric soil release agents such as M03SÍCH2) nOCH2CH2? -, where M is sodium and n is an integer of 4-6, such as is described in US Pat. 4,721,580 issued on January 26, 1988 to Gosselink. The polymeric soil release agents useful in the present invention also include cellulose derivatives such as hydroxyether cellulose polymers, copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene terephthalate oxide terephthalate? polypropylene terephthalate oxide and the like. Dirt releasing agents characterized by hydrophobic poly (vinyl ester) segments include poly (vinyl ester) graft copolymers, V.gr., Ci-Cß vinyl esters preferably poly (vinylacetate) grafted to metal oxide base structures. polyalkylene, such as polyethylene oxide base structures. See European Patent Application 0 219 048 published April 22, 1987 by K? D, and others. Commercially available soil release agents include Sokalan, V.gr., SOKALAN HP-22 material type, available from BASF (Germany). , r \ type of preferred soil release agent is a copolymer that has random blocks of terephthalate ethylene and polyethylene terephthalate oxide (PEO). The molecular weight of this polymeric soil release agent is in the range of about 25,000 to about 55,000. See U.S. Pat. 3,959,230 to Hays issued May 25, 1976 and the Patent of E.U.A. 3,893,929 to Basadur issued July 8, 1975. Another preferred polymeric soil release agent is a polyester with repeating units of ethylene terephthalate units containing 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyethylene glycol of average molecular weight of 300-5,000. Examples of this polymer include the commercially available material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See also the U.S. Patent. 4,702,857 issued on October 27, 1987 to Gosselink. Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer consisting of an oligomeric ester base structure of terephthaloyl and oxyalkylenoxy repeating units and terminal portions covalently attached to the base structure. These soil release agents are described extensively in the U.S. Patent. 4,968,451 issued November 6, 1990 to 3.3. Scheibel and E.P. Gosselink. Other suitable polymeric soil release agents include the terephthalate polyesters of the Patent of E.U.A. 4,711,730 issued December 8, 1987 to Gosselink et al., The oligomeric esters blocked at their anion ends from the U.S. Patent. 4,721,580 issued on January 26, 1988 to Gosselink, and the block oligomeric polyester compounds of the U.S. Patent. 4,702,857 issued on October 27, 1987 to Goeselink. Polymeric soil release agents also include the soil release agents of US Pat. 4,877,896 issued on October 31, 1989 to Maldonado et al., Which describes the anionic compounds, especially s-lfoarolyl, esters of terephthalate blocked at their ends. If used, soil release agents generally comprise from about 0.01% to about 10.0% by weight of the detergent compositions herein, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3.0. %. Another preferred soil release agent is an oligomer with repeated units of terephthaloyl, sulisotrephthaloyl, oxyethyleneoxy and oxy-l, 2-propylene. The repeating units form the base structure of the oligomer and are preferably terminated with blocking ends of the modified isothioate. A particularly preferred soiling agent of this type comprises approximately one sulfoisophthaloyl unit, 5 terphthaloyl units, oxyethyleneoxy units and oxy-1, 2-propyleneoxy units in one ratio of about 1.7 to about 1.8, and two units of sodium 2- (2-hydroxyethoxy) -etansul-fonate blocking ends, said soil release agent comprises from about 0.5% to about 20%, by weight of the oligomer , of a crystalline reduction stabilizer, preferably selected from the group consisting of ilensul fonate, curneneulonate, toluenesulfonate and mixtures thereof. As a practical matter, and not for the purpose of limitation, the co-location and procedures herein can be used to provide the order of at least one part per ten million of the active bleach catalyst species in the aqueous wash solution, and preferably provide from about 0.1 ppm to about 700 ppm, most preferably from about 1 ppm to about 500 ppm, of the catalyst species in the wash solution.

Bleaching Compounds-Bleaching Agents and Bleach Activators The detergent compositions herein may contain bleaching agents or bleaching compositions containing bleaching agent and one or more bleach activators. When the bleaching compounds are present, they will typically be at levels of about 1% to about 40%, very typically about 5% at about 30%, of the detergent composition, especially for fabric washing. If present, the amount of bleach activators will typically be from about 0.1% to about 60%, very typically from about 0.5% to 40% of the bleaching composition comprising a bleaching agent plus bleach activator. The bleaching agents used herein may be any of the bleaching agents useful for co-locating detergents in textile cleaning, hard surface cleaning or other cleaning purposes that are now known or will be known. These include oxygen bleaches as well as other bleaching agents. Preferred peroxygen bleaching agents are preferably used in the compositions. Suitable bleach peroxygen compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach can also be used (for example, OXONE, manufactured commercially by DuPont). A preferred percarbonate bleach comprises dry particles having an average particle size in the range of about 500 microns to about 1000 microns, no more than about 10% by weight of said particles being less than about 200 microns and Not Greater than about 10% by weight of said particles being less than about 1250 micrometers. Optionally, the percarbonate can be coated with water soluble, borate or silicate surfactants. Preferred coatings are based on carbonate / sulfate mixtures. Percarborate is available from several commercial sources such as FMC, Solvay and Tokai Denka. Another category of bleaching agents, which can be used without restriction, surrounds the bleaching agents of percarboxylic acid and salts of the latter. Suitable examples of this class of agents include magnesium onoperoxyphthalate hexahydrate, the magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydecanedioic acid. Said bleaching agents are described in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent Application 340,446, Burns et al., Filed on June 13, 1985, European Patent Application 0,133,354, Banks and others, published on February 20, 1985, and U.S. Patent 4,412,934, Ch? ng et al., issued November 1, 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in the North American patent 4,634,551, issued on January 6, 1987 to Burns et al. Mixtures of bleaching agents can also be used. Peroxygen bleaching agents, perborates (eg, mono- or tetrahydrate), percarbonates, etc., preferably combined with bleach activators, which lead to in situ production in the aqueous solution (ie, during the washing process) of the peroxyacid corresponding to the bleach activator. Various non-limiting examples of activators are described in the U.S. Patent. 4,915,854 issued April 10, 1990 to Mao et al., And in the U.S. Patent. 4,412,934. Typical activators of nonanoyloxy-benzenesulfonate (NOBS) and tetraacetylethylamine (TAED) and mixtures of the same can also be used. See also E.U.A. 4,634,551 for other typical bleaches and activators useful herein. The highly preferred amido-bleach activators are those of the formulas: R1N (R5) C) 0) R2C (0) L or R1C (0) N (RS) R2C (0) L wherein R * is an alkyl group which contains from about 6 to about 12 carbon atoms, R 2 is an alkylene containing from 1 to about 6 carbon atoms, R * is H or alkyl, aryl or alkaryl which contains from about 10 carbon atoms and L is any suitable residual group. A residual group is any group that is displaced from the bleach activator as a consequence of a nucleophilic attack on the bleach activator by the perhydroxylic anion. A preferred residual group is phenolsulfonate. Preferred examples of bleach activators of the above formulas include (6-octanamido-caproxydoxybenzene) Sulfonate, (6-nonanamidocaproyl) oxybenzenes? lonate and mixtures thereof as described in the patent of E.U.A. 4,634,551 which is incorporated herein by reference. Another class of bleach activators includes activators of the benzoxazine type described by Hodge et al. In the U.S. Patent. 4,966,723 issued October 30, 1990, which is incorporated herein by reference. A highly preferred bleach activator of the benzoxazine type is: Yet another class of preferred bleach activators includes acyl-lactam activators, especially acylcaprolactams and acylvalerolactams of the formulas: wherein Rβ is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to about 12 carbon atoms. Highly preferred lactase activators include benzoylcaprolactam, octanoylcaprolactam, 3,5,5-trimethyl-hexanoylcaprolactam, nonanoylcaprolactam a, decanoylcapro-lactam, undecenoylcaprolactam, benzoylvalerolactam, octanoylvalerolactan, decanoylvalerolactam a, undecenoylvalerolectan, nonanoylvalerolactane, 3,5,5-trimethylhexanoylvalerolactam and mixtures of same. See also the U.S. Patent. No. 4,545,784 issued to Sanderson on October 8, 1985, incorporated herein by reference, which discloses acylcaprolactants, edited in sodium perborate. Other preferred activators are cationic bleach activators. Bleaching agents other than oxygen bleaching agents are also known in the art and can be used herein. One type of oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as sulfonated and / or aluminum zinc phthalocyanines. See United States Patent 4,033,718, issued May 5, 1977 to Holcombe et al. If used, the detergent compositions will typically have from 0.025% to 1.25%, by weight, of said bleaches, especially phthalocyanine zinc sulphonate. If desired, the bleaching compounds can be catalyzed by means of a manganese compound. Such compounds are well known in the art and include, for example, the manganese-based catalysts described in US Patent 5,246,621, US Patent 5,244,594; U.S. Patent 5,194,416; Patent North American 5,114,606; and European Patent Application Publication Nos. 549,271A1, 549,272A1, 544,44002, and 544,490A1. Preferred examples of these catalysts include Mniv2 (u-0) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (PFß) 2, Mn? U2 (u-0)? (u-0Ac) 2 (1,4,7-trimethyl-1, 7-triazacyclononane) 2 (CI0 «2; Mn? V «(u-0) 6 (1, 4,7-triazacyclononane)« (CIO * U; niumniv ,; - (u-0) 1 (u-0Ac) 2- (1, 4,7-trimethyl) -l, 4,7-triazacyclononane) 2 (CIO *) 3, - nIV4 (1, 4,7-trimethyl-1, 4,7-triazacyclononane) (OCH 3) 3 (PFß), and mixtures of the other. Metal-based bleach catalysts include those described in US Patent 4,430,243 and US Patent 5,114,611 The use of manganese with various complex ligands to improve bleaching is also recorded in the following United States Patents: 4,728,455, 5,284,944, 5,246,612, 5,256,779; 5,280,117; 5,274,147; 5,153,161; 5,227,084.

Polymeric dispersing agents Polymeric dispersing agents can be advantageously used at levels of from about 0.1% to about 7%, by weight, in the compositions herein, especially in the presence of zeolite and / or layered silicate builders. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art may also be used. It is believed, although not intended to be limited by theory, that polymeric dispersing agents they increase the performance of the overall detergency builder, when used in combination with other builders (including lower molecular weight polycarboxylates) by inhibition of crystal growth, peptization of particulate and anti-redeposition. Polymeric polycarboxylate elastomers can be prepared by pollinating or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated nonomeric acids which can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, rneeaconic acid, citraconic acid, methylene allyl. The presence of the polymeric polycarboxylates in the present or polymeric segments, which do not contain carboxylate radicals such as vinyl ethyl ether, styrene, ethylene, etc., is suitable provided that said segments do not constitute more than about 40% by weight. weight. Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Said acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form perferrably ranges from about 2,000 to 10,000, most preferably from about 4,000 to 7,000, and preferably from about 4,000 to 5,000. The salts Water-soluble polymers of said acrylic acid polymers may include, for example, the alkali metal, ammonium and substituted ammonium salts. Sol? Blee polymers of this type are known materials. The use of polyacrylates of this type in detergent compositions has been described, for example, in Diehl, U.S. Pat. 3,308,067, issued March 7, 1967. Copolymers based on acrylic / aleic acid may also be used as a preferred component of the dispersing / anti-redeposition agent. Such materials include the water soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of said copolymers in the acid form preferably ranges from about 2,000 to 100,000, and preferably from about 5,000 to 90,000 and most preferably from about 7,000 to 80,000. The ratio of acrylate segments to those of maleate in said copolymers generally ranges from about 30: 1 to about 1: 1, most preferably from about 70:30 to 30:70. The water soluble salts of said acrylic acid / maleic acid copolymers may include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate / maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published on December 15, 1982, as well as in EP 193,360, published September 3, 1986, which also describes said polymers comprising hydroxypropylacrylate. Other dispersing agents include the terpolymers of rnaleic / acrylic / vinyl alcohol or vinyl acetate. Such materials are described in EP 193,360, including, for example, the acrylic / maleic / vinyl alcohol terpolymer 45/45/10. Another polymeric material that can be included is polyethylene glycol (PEG). PEG can exhibit dispersing agent performance and can act as an anti-redeposition agent for clay soiling. The typical molecular weight scales for these purposes vary from about 500 to about 100, 000, most preferably from about 1,000 to about 50,000 and even more preferably from about 1,500 to about 10,000. The polyaspartate and polyglutamate dispersing agents can also be used, especially in conjunction with zeolite builders. Dispersing agents such as those of preferable polyaspartate have a molecular weight (avg.) Of about 10,000.

Clay soil remover / anti-redeposition agents The compositions of the present invention may also optionally contain clay soil remover and anti-redeposition agents. The granular detergent compositions containing these compounds typically contain from about 0.01% to about . 0% by weight say agents, liquid detergent co-polls typically contain about 0.01% at about 5%. The preferred soil replenishing and anti-redeposition agent is ethoxylated tetraethylenepentamine. Example ethoxylated amines are more fully described in the U.S. Patent. 4,597,898, VanderMeer, issued July 1, 1986. Another group of clay dirt remover / anti-redeposition agents are the cationic compounds described in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984. Other clay soil remover / anti-redeposition agents that may be used include the ethoxylated amine polymers described in Europ Patent Application No. 111,984, Goeselink, published June 27, 1984; the zwitterionic polymers described in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides described in the U.S. Patent. No. 4,548,744, Connor, issued October 22, 1985. Other clay removers and / or anti-redeposition agents known in the art can be used in the compositions herein. Another type of preferred anti-redeposition agent includes the carboxylmethylcellulose (CMC) materials. These materials are well known in the art.

Dye transfer inhibiting agents The compositions of the present invention can also include one or more effective materials to inhibit the transfer of dyes from one fabric to another during the cleaning process. Typically, said dye transfer inhibiting agents include polyvinylpyrrolidone polymers, polyarynin N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylnitridazole, manganese phthalocyanine, peroxidases and mixtures thereof. If used, these agents typically comprise from 0.01% to about 10% by weight of the composition, preferably from 0.01% to about 5%, and preferably from 0.05% to approximately 2%. Very specifically, the preferred polyamine N-oxide polymers for use in the preend contain units having the following structural formula: R ~ A "-P; wherein P is a polyrneable unit to which a N-O group can be attached or the N-O group can form part of the polymerizable unit or the N-O group can be attached to both units; A is one of the following structures: -NC (O) -, -C (0) 0 ~, -S-, -0-, -N =; x is 0 or 1; and R is aliphatic, aliphatic, ethoxylated, aromatic, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group can be attached or the N-O group is part of these groups. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, .imidazole, pyrroline, piperidine and derivatives thereof. The N-O group can be represented by the following general structures: 0 0 wherein Ri, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group can be attached or forms part of any of the aforementioned groups. The amine oxide unit of the polyamine N-oxides has a pKa < 10, preferably pKa < 7, very preferably still pKa < 6. Any polymer base structure can be used as long as the amine oxide polymer formed is soluble in water and has dye transfer inhibiting properties. Examples of suitable polymeric base structures are polyvinyl, polyalkylene, polyesters, polyethers, polyamide, polyrides, polyacrylates and mixtures of metals. These polymers include random or block copolymers wherein a monomer type is an amine N-oxide and the other type of monomer is an N-oxide. The amine N-oxide polymers typically have an amine to amine N-oxide ratio of 10: 1 to 1: 1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation. The polyamine oxides are 4. 1 can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; u and preferred 1,000 to 500,000; even more preferred 5,000 to 100,000. This preferred class of materials can be referred to as "PVNO". The most preferred polyamine N-oxide useful in the detergent compositions herein is the poly (4-vinyl? Iridine N-oxide) which has an average molecular weight of about 50,000 and an amine ratio. to amine N-oxide of about 1: 4. Polymer copolymers of N-vinylporrolidone and N-vinylimidazole (also known as "PVPVI") are also preferred for use herein. Preferably, the PVPVI has an average molecular weight in the range of 5,000 to 1,000,000, most preferably 5,000 to 200,000 and most preferably even 10,000 to 20,000. (The average molecular weight scale is determined by light scattering as described in Barth, and other Chemical Analysis, Vol. 113. "Modern Methods of Polymer Characterization", the descriptions of which are incorporated herein by reference). PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1: 1 to 0.2: 1, most preferably from 0.8: 1 to 0.3: 1, most preferably from 0.6: 1 to 0.4: 1. These copolymers can be either linear or branched. It has also been observed that the additional benefits of dye transfer inhibition are provided by compositions comprising ether of non-ionic polysaccharide and dye transfer inhibitors such as PVNO and PVPVI as illustrated in Example 1, Formulation B, C and D. It is believed that a synergistic effect due to the combination of polysaccharides and dye transfer inhibitors provides the performance benefits of maintaining unexpected whiteness to fabrics that have been subjected to repeated washing. The compositions of the present invention may also employ a polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, and most preferably still from about 5,000 to about 50,000. . PVP's are known to those skilled in the field of detergents; see, for example, EP-A-262,897 and EP-A-256,696, incorporated herein by reference. The PVP-containing compositions may also contain polyethylene glycol ("PEG") which has an average molecular weight of from about 500 to about 100,000, preferably from about 1,000 to about 10,000. Preferably, the ratio of PEG to PVP on a ppm basis based on wash solution is from about 2: 1 to about 50: 1, and most preferably from about 3: 1 to about 10: 1. The detergent compositions herein may also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide an inhibitory action of dye transfer. If used, the compositions herein will preferably comprise from about 0.01% to 1% by weight of said optical brighteners. The hydrophilic optical brighteners useful in the present invention are those having the structural formula: wherein Ri is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R 2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-rnetilarnino, morphino, chloro and amino; and M is a salt-forming cation such as sodium or potassium. When in the above formula, Ri is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is acid 4,4 ', bis [(4-anilino-6- (N-2 ~ bis-hydroxyethyl) -s-triazin-2-iDaminol-2, 2'-stybendisulphonic and disodium salt This particular brightener species is marketed under the trade name Tinopal-UNPA-GX by Ciba-Geigy Corporation. UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions of the present invention.

When in the above formula R1 is anilino, R2 is N-2-hydroxyethyl-N-2-rnetilarnino and M is a cation such as sodium, the brightener is the disodium salt of 4,4'-bis [4- anilino-6- (N-2-hydroxyethyl-N-ritylamino) -s-triazin-2-yl) amino] -2,2'-eethylbenedisulfonic acid. This particular brightener species is combed under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation. When in the above formula R1 is anilino, R2 is oryphine and M is a cation such as sodium, the brightener is the sodium salt of 4,4'-bisC (4-anilino-6-morphino-3-triazin-2) -yl) amino] 2,2'-stilbenedisulfonic acid. This particular brightener species is sold com merily under the trade name Tinopal AMS-GX by Ciba-Geigy Corporation. The specific optical brightener species selected for use in the present invention provide effective specilizing dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents described above. The combination of said selected polymeric materials (e.g., PVNO and / or PVPVI) with said selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and / or Tinopal AMS-GX) provides inhibition of Dye transfer significantly better in aqueous wash solutions than any of those two components of detergent composition when used alone. Without being limited to theory, it is believed that said brighteners work in this way because they have high affinity for fabrics in the washing solution and therefore they deposit relatively quickly on these fabrics. The degree to which the brighteners are deposited on the fabrics in the washing solution can be defined by a parameter called "exhaustion coefficient". The depletion coefficient is generally co or the ratio of a) the polishing material deposited on the cloth to b) the initial rinse aid concentration in the wash liquor. Brighteners with relatively high depletion coefficients are most suitable for inhibiting dye transfer in the context of the present invention. Of course, it will be appreciated that other types of conventional optical brighteners may optionally be present in the compositions of the present to provide conventional "brightness" benefits to the fabrics, rather than a true dye transfer inhibiting effect. Said use is conventional and well known for detergent formulations. According to the present invention, the detergent composition can comprise any other ingredients commonly employed in conventional detergent compositions such as soaps, foam suppressors, dye transfer inhibitors, perfumes, softeners, brighteners, enzymes and enzyme stabilizers.

FORM OF COMPOSITIONS The compositions of the present invention can be used in laundry detergent compositions, compositions for fabric treatment and fabric softening compositions as well as hard surface cleaners. The compositions can be formulated as conventional granules, sticks, pastes or powders. The detergent compositions are manufactured in the conventional manner, for example in the case of powder detergent compositions, methods of asperion drying, aspersion mixing or algomeration can be used. Preferably, the detergent compositions granulated according to the present invention have a density of 400 g / 1 to 1200 g / 1, preferably from 500 g / 1 to 1000 g / 1, most preferably from 600 g / 1 to 1000 g / 1 . The average particle size of the components according to the invention should preferably be such that no more than 5% of the particles are greater than 1.7 mm in diameter and no more than 5% are less than 0.15 m in diameter. The intimate mixture of polysaccharide ether and the anionic surfactant of the present invention are present at least 10 ppm in the aqueous wash solution having a pH of 7 to 11, preferably 9 to 10.5.

Washing Method The present invention also relates to a method of fabric washing comprising contacting said sweat fabric with an aqueous washing solution containing conventional detersive ingredients described herein in addition to the intimate particulate mixture of nonionic polysaccharide ether and ammonium surfactant of the present invention. Polyester and polyester-cotton blends are used in a preferred method.

Process According to the present invention the intimate mixture of nonionic surfactant and nonionic polysaccharide ether can be prepared by agglomeration and spray drying techniques. Accordingly, the steps of the agglomeration process of the present invention comprise: 1. Mixing an optional premix of chelating agent surfactant and polymer. 2. Dry (optional). 3. Transfer to a high density mixer preferably by means of a twin screw extruder. 4. Agglomerate surfactant paste with an affective amount of powder comprising non-ionic polysaccharide ether. It will be understood that any convenient order of the process steps listed above may be contemplated. It may also be possible and even advantageous to bring out two or more of the above operations in a single piece of processing equipment. Each of these operations will now be described in more detail.

Preparation of a paste premix The surfactant paste premix can be prepared by any method that is known to one skilled in the art. Particularly useful methods include sulfating and / or sulfonation or other reactions to make the desired anionic surfactants, v. gr. in falling film sulfonation reactors, digestion tanks, esterification reactors, etc. It is particularly convenient to neutralize the acid precursors of anionic surfactants in a loop of continuous neutralization. In said piece of equipment the acid precursor is formed in a loop together with a neutralizing agent such as aqueous sodium hydroxide. The components are intimately mixed to promote neutralization and deepuée are fed through a heat exchanger to cool. A portion of the neutralized surfactant is removed from the loop, while the remainder is fed back to the injection point of the acid and alkali and passes around the loop again. In the present invention, the surfactant paste is then mixed with the optional chelating agent and a solution of a polymer or copolymer. This is It can be achieved in a convenient piece of mixing equipment, and can be carried out by any order of addition of the separated and premixed components.

Drying the pulp (in line) It is preferred that the moisture in the aqueous surfactant paste be as low as possible, while maintaining the flowability of the pulp, since the low humidity leads to a higher concentration of the surfactant of the pulp. finished particle. Preferably, the paste after the secund contains between 5 and 40% water, most preferably between 15 and 35% water and most preferably between 15% and 25% water. A highly attractive mode of operation for reducing pulp moisture is the installation, in-line, of an atmospheric dryer or an instant evaporator under vacuum, or a scraped surface heat exchanger or a rubbed film evaporator.

Double screw extruder The extrusion uses the functions of pumping and mixing the viscous paste of surfactant on a continuous basis. A basic extruder consists of a cylinder with a smooth internal cylindrical surface. Mounted inside the cylinder is an extruder screw. There is an entrance gate for the highly active paste which, when the screw is rotated, causes the pulp to move along the length of the cylinder. The detailed design of the extruder allows several extrusions to be carried out. First, additional gates in the cylinder can allow ingredient ponies, including chemical structuring agents, to be added directly to the cylinder. Second, a vacuum pump and a seal around the screw shaft allow a vacuum to be produced that lowers the moisture level. Third, heating or cooling means can be installed on the cylinder wall to control the temperature. Fourth, the careful design of the extruder screw promotes the mixing of the pulp either with itself or with other additives. A preferred extruder is the double screw extruder. This type of extruder has two screws mounted in parallel inside the same cylinder, which are made to rotate either in the same direction (co-orientation) or in opposite directions (counter-rotation) the co-rotating twin screw extrusion is the most preferred piece of equipment for use in this invention. An extruder is particularly useful in this invention because the paste can be effectively cooled by adding liquid nitrogen or solid carbon dioxide in the cylinder (this can be surprisingly considered, because normally an extruder heats its contents as a result of the input of mechanical energy to the resulting viscous shear forces) and at the same time pumping the pulp more and more viscous (colder) to the outside of the extruder and to the mixer / agglomerator where the granulation takes place. The twin screw extruders suitable for use in the present invention include those supplied by: APV Baker, (CP series); Uemer and Pfleiderer, (continuous series); üenger, (TF series); Leistritz, (series ZSE); and Buse, (LR series). The extruder - allows the paste to be conditioned by moisture and temperature reduction. Moisture can be removed under vacuum, preferably between 0 rn Hg (nanometic) and -55 mmHg (anometric), (0 - 7.3 kPa below atmospheric pressure). The temperature can be reduced - by the addition of solid carbon dioxide or liquid nitrogen directly to the extrusion cylinder. However, this is not the preferred mode of operation of the present invention.

Mixing dispersion and granulation of fine powders Any apparatus, plant or unit suitable for the processing of surfactants can be used to carry out the process according to the invention. Any number of mixers / binders can be used for mixing / agglomeration. A preferred embodiment, the method of the invention is carried out continuously. Especially preferred are mixers of the F? KaeR FS-G series manufactured by Fukae Powtech Kogyo Co., 3ap; East Apparatus ee essentially in the form of a bowl-shaped container accessible through an upper inlet, provided near its base with an agitator having a substantially vertical axis, and a cutter located on the side wall. The agitator - and the cutter can be operated independently of one another and at separately variable speeds. This container can be equipped with a cooling jacket or if necessary a cryogenic unit. other similar mixers which are suitable for use in the process of the invention include Diosna R V series ex Dierks a Sóhne, Germany; and Pharma Matrix® ex TK Fielder Ltd., England. Other mixers that are believed to be suitable for use in the process of the invention are the Fuji series "VG-C Fuji Sangyo Co., 3apón and Roto" ex Zanchetta a Co srl, Italy. Other preferred suitable equipment may include EirichP, RV series, manufactured by Gustau Eirich Hardheirn, Germany, LódigeR, FM series for intermittent mixing, Baud KM series for continuous mixing / agglomeration, manufactured by Lodige Manchinenbau GmbH, Paderborn Germany; DraisP T160 series, manufactured by Drais Ueke GmbH, Mannheim Germany and Uinkworth "RT 25 series, manufactured by Uinkworth Machinery Ltd, Berkshire, England The Littleford mixer model # FM-130-D-12, with internal shredder blades and processor of Cuisinart Food Processor, model # DCX-Plus, with blades (19.7) c are two examples of suitable mixers. Any other mixer capable of mixing by dispersion and granulation of fine powders can be used and has a residence time of the order of 0.1 to 10 minutes. The "turbine-type" impeller mixer having several blades on an axis of rotation is preferred. The invention can be put into practice as an intermittent or a continuous process. The paste can be introduced into the mixer at an initial temperature between its softening point (generally in the range of 40-60 ° C) and its point of degradation depending on the chemical nature of the paste, e.g., alkyl paste sulfate tends to degrade above 75-85 ° C). The high temperatures reduce the viscosity by simplifying the pumping of the pulp but result in lower active agglomerates. The introduction of the paste to the mixer can be done in many ways, from simple emptying to pumping at high pressure through small holes in the end of the tube, before the entrance to the mixer. Although all these forms are viable for manufacturing agglomerates with good physical properties, it has been found that in a preferred embodiment of the present invention the extrusion of the paste results in a better distribution in the mixer which improves the performance of particles with the desired size. The use of high pressure pumps before entering the mixer results in increased activity in the agglomerates final. By combining both effects, and introducing the paste through the holes (extrusion) sufficiently small to allow the desired flow rate but to maintain the pumping pressure at a maximum feasible in the system, highly advantageous results are achieved. It is within the scope of the present invention that the resulting detergent granules can be dried, cooled and / or sprinkled with a suitable surface coating agent.

Spray drying procedure In accordance with the present invention, the intimate mixture of anionic surfactant and nonionic polysaccharide ether can be prepared by methods of asperion drying known in the art. Using said procedure, a mixture of zeolite A, anionic teneioactive agent, chelator and nonionic polysaccharide ether is mixed in a vessel with stirring. Water is added together with optional viscosity modifying agents. The pH is adjusted so that it is greater than 10 and additional water is added to provide the mixture with the desired flow characteristics. The mixture is stirred for 1 hour. The mixture is then transferred to the top of the spray-drying tower unit. The inlet temperature and the resonance time are varied to produce the desired particle size and the desired moisture content. The resulting spray-dried powder is collected at the base of the tower.

Abbreviations used in the examples In the detergent compositions, the abbreviated identifications of the components have the following meanings: XYAS: C Al-C sodium alkyl sulfate ?? 25EY: A predominantly linear primary alcohol of C12-15 condensed with an average of Y moles of ethylene oxide. XYEZ: A linear primary alcohol predominantly of Ci? -Cy condensed with an average of Z oxide ethylene oxide. XYEZS: Sodium alkylsulfate of C ?? -C? condemned with an average of 20 moles of ethylene oxide per milliliter. TFAA Alkylated N-methylglycide of Ciß-iß Silicate Amorphous sodium silicate (ratio Si2: Na2 = 2.0) NaSKS-6: Crystalline layered silicate of formula 6Na2SÍ2? S - Carbonate: Anhydrous sodium carbonate. MA / AA: Rnaleic acid / acrylic copolymer 30:70, average molecular weight of approximately 70,000.

Zeolite A: Sodium aluminosilicate hydrated formula Nai2 (AIO2S.ÍO2) i2.27H2O having a primary particle size on the scale of 1 to .1.0 micras. Citrate: Trisodium citrate dihydrate. Peberbonate Anhydrous sodium percarbonate bleach coated with a sodium silicate coating (ratio of 2: 1 of Si2: Na2) to a weight ratio of percarbonate to sodium silicate of 39: 1. CMC Carboxymethyl cellulose of eodium DETPMP Diethylenetriaminepentamet acid . Polyphosphonic, marketed by Monsanto under the trade name Dequest 2060 PVNO Polyvinylpyridine N-oxide polymer of 10,000 molecular weight. Calcium Montmorillonite clay ex. Colin Stewart eenectite Minche Ltd. Foam suppressor 12% silicone / silica suppressor, 18% alcohol stearyl foams, 70% granular granulated starch LAS: C12 linear sodium alkoxybenzene sulfonate TAS Seboalquils? Sodium fato SAS: Secondary alkylsulfate (2,3) of C12-C14 in the form of the sodium salt Secondary soap surfactant agent of the formula 2-b-tyloctanoic acid Phosphate Trí olifosfa or sodium TAED Tetraacetiletilen iarnina PVP Polyvinylpyrrolidone polymer HMUPEO high molecular weight polyethylene oxide MC Methylcellulose ether with molecular weight of 110000 to 130000, available from Shin Etsu Chemicals under the tradename Metolose MHEC Tylose MH3000, available from Hoechst TAE 25 Ethoxylated Tallow Alcohol (25) PEO Polyethylene Oxide Sulfate Sodium Sulfate HEDP 1, 1-Hydroxyethane Phosphonic Acid EDDS Ethylene Disodium Inodisuccinate TS, s] DHAC C12 / C16 Dinethyl Hydroxyethylammonium Chloride E3EMPL0S In accordance with the present invention, the detergent composition can be manufactured using any of the methods known in the art such as spray drying, agglomeration, extrusion or pelletization. The particles 1 and 12 can be manufactured according to the following procedure. Similarly, particles 11-12 and 25-28 can also be manufactured using a method similar where the chelator is omitted. This example describes the procedure in intermittent mode in a laboratory-scale high shear mixer (food processor manufactured by Braun ([tradename]). Three hundred grams of powders including non-ionic polysaccharide ethers are first added to the mixer. In this particular case a 2: 1 ratio of zeolite A to finely divided light density sodium carbonate is used.The surfactant is an aqueous slurry.

C45AS / AE3S (80:20) with a detergent activity of 78% and a water content of 16%. In this example, the paste is premixed in a batch mixer with a 40% solution of the maleic acid and acrylic acid copolymer, sodium salt and 20% solution of the sodium salt of ethylene dianino-N, N- acid discinct The weight ratio of the paste: polymer: agent q-elater- was 1: 0.64: 0.09. The mixture is then dried at the original paste moisture of 16%. The paste mixture is placed in an oven at 60 ° C until the thermal equilibrium is reached. The mixer is then started and the paste is added at a rate of 500 g / min until the start of agglomeration and granulation formation. The extreme point is sharp and easily recognized. It is characterized by an increased potency attracted by the mixing and a change in the contents of the mixer from a mixture of finely divided powders and distributed surfactant paste, to agglomerates that They contain powders and pasta that have a particle size between 400-600 microns. The activity of the agglomerates formed is 51%. The particles 13-24 are prepared according to the spray-drying process described above.

Reference particle and particles 1 and 2 E3EMPL0 1 The following detergent compositions for laundry A, B, C, and D were prepared. Formulations ee and example represent embodiments of the invention.

A material removal test was carried out using a hot spot machine, short cycle, 40 ° C, water from the city of Newcastle with hardness of 12dH, single dose (75g). The fabrics were first treated with each of the formulations A, B, and C, using the conditions previously described. The blends of spots were evenly spread on the fabrics with a brush and left to dry on the bed overnight. The fabrics were then washed with the respective formulation again. Differences in the performance of removal of oily dirt were recorded in units of punctuation performed by the panel (psu), the poeitivas having a better performance than the reference product. The following rating scale was used (psu rating): 0 = 1 = I think this is better 2 = I know this is a little better 3 = This is much better 4 = This is still much better. The qualification was carried out under light conditions controlled by expert qualifiers. The number of replicas used in this test was six. 'S' denotes that the difference observed is statistically significant at a confidence level of 95%. The significant degree of differences between the formulations was obtained using a two-way ANOVA computation. Thus, the differences between the formulations and the differences between replicates were calculated separately using the corresponding variances and the difference was analyzed using the test of F.

Chicken *: sauce of chicken pan. Pizza **: cover for pizza. Indian sauce ***: tikka aseala sauce from india. Tuna salea ****: tuna eel with mayonnaise. The results indicate that an improvement in stain removal was obtained using Formulation C having an embodiment of the present invention as compared to Formulation B wherein the polysaccharide is not in close physical proximity to the anionic surfactant. 53 Examples of particles 3-10 for granular detergent compositions based on a tower process: Particles 9-12: Particles 13-18 produced using a tower process Blown dust particle 19-24 for use in high density granular compositions Agglomerated particles 25-28 Example 2: Granulated detergent compositions Example 3: Granulated detergent formulations E3EMPL0 4 Example 5 Compound E and F represent smoothing through the washing type compositions Example 6 Compositions E and F represent smoothing through the washing formation fifteen twenty ?F;

Claims (17)

NOVELTY OF THE INVENTION CLAIMS

1. A detergent composition comprising an ether-non-ionic polysaccharide and an anionic non-soap surfactant, wherein said polysaccharide ether and said anionic surfactant are in close physical proximity within said detergent composition.

2. A detergent composition according to claim 1, further characterized in that said nonionic polysaccharide ether and said anionic surfactant are in close physical proximity within a particulate material, granular material, flakes, noodles or extruded product.

3. A detergent composition according to any of claims 1 or 2, further characterized in that said polysaccharide ether and said anionic surfactant are intimately mixed within said composition.

4. A detergent composition according to claim 2, further characterized in that said polyaccharide ether and said nonionic surfactant are separated from each other.

5. A detergent composition according to claim 1, further characterized in that the ratio of said anionic surfactant which is not soap to said Non-ionic polysaccharide ether is from 1000: 1 to 1: 1.

6. A granular detergent composition according to claim 1, which has a volumetric density of 400 g / 1 to 1200 g / 1.

7. A granular detergent composition according to claim 1, having a bulk density of 500 g / 1 to 1000 g / 1.

8. A detergent composition according to claim 1, further characterized in that said nonionic polysaccharide ether is a cellulose ether,? N starch ether, a dextran ether or mixtures thereof.

9. A detergent composition according to claim 8, further characterized in that said polysaccharide is a cellulose ether selected from ethers of non-ionic polysaccharide of Ci-alkyl, hydroxyalkyl Ci-C, C 1 -C 4 alkylhydroxyalkyl, and mixtures thereof.

10. A detergent composition according to claim 8, further characterized in that said nonionic polysaccharide ether is a methylcellulose ether, a methylhydroxyethyl cellulose ether or mixtures thereof.

11. A detergent composition according to claim 8, further characterized in that it comprises from 0.01% to 10% of said nonionic polysaccharide ether.

12. A detergent composition according to claim 1, further characterized in that said anionic non-soap surfactant is selected from alkylsulfonate, alkylsulfate, alkylsarcosinates, alkoxylated alkylsulfates, alkylalkoxycarboxylates, sulphated alkylpolyplascosides, alkyl esters of alpha-ethoxylated fatty acids and mixtures thereof.

13. A detergent composition according to claim 12, further characterized in that said anionic surfactant is a water-soluble salt of a Cß-Ciß alkyl sulfate. A detergent composition according to any of claims 12 or 13 , which comprises 5% to 40% of said anionic surfactant. 15. A detergent composition according to claim 2, further characterized in that said particulate materials further comprise auxiliary detergent selected from zeolite builders, chelators, carbonates, polycarboxylates and mixtures of the moons. 16. A detergent composition according to claim 1, further characterized in that it comprises detergent auxiliaries selected from nonionic surfactants, detergency builders, chelators, bleaches and mixtures thereof. 17. A fabric treatment method comprising contacting said fabric with an aqueous solution comprising at least 10 ppm of a detergent composition according to claim 1.