MXPA00002642A - Laundry detergent compositions with cellulosic based polymers to provide appearance and integrity benefits to fabrics laundered therewith - Google Patents

Abstract

Compositions and methods which utilize certain cellulosic based polymer or oligomer materials as fabric treatment agents that can impart fabric appearance and integrity benefits to fabrics and textiles laundered in washing solutions which contain such materials. Specifically, the cellulosic based polymers or oligomers are of general formula (I), wherein each R is selected from the group consisting of R2, Rc, and (a);each R2 is independently selected from the group consisting of H and C1-C4alkyl;each Rc is (b);each Z is independently selected from the group consisting of M, R2, Rc and RH;and each RH is independently selected from the group consisiting of C5-C20alkyl, C5-C7cycloalkyl, C7-C20alkylaryl, C7-C20 arylalkyl, substituted alkyl, hydroxyalkyl, C1-C20alkoxy-2-hydroxyalkyl, C7-C20alkylaryloxy-2-hydroxyalkyl, (R4)2N-alkyl, (R4)2N-2-hydroxyalkyl, (R4)3N-alkyl, (R4)3N-2-hydroxyalkyl, C6-C12aryloxy-2-hydroxyalkyl, (c), (d) and (e). The Degree of Substitution for group RH in these cellulosic based polymers or oligomers is between about 0.001 and 0.1, and the Degree of Substitution for group Rc wherein Z is H or M in these cellulosic based polymers or oligomers is between about 0.2 and 2.0.

Description

DETERGENT COMPOSITIONS FOR LAUNDRY WITH CELLULOSE BASED POLYMERS TO PROVIDE BENEFITS OF APPEARANCE AND INTEGRITY TO WASHED FABRICS WITH THE SAME TECHNICAL FIELD The present invention relates to compositions, in liquid or granular form, for use in laundry applications, in which the compositions comprise certain polymer or oligomer materials that impart appearance and integrity benefits to fabrics and textiles washed in wash solutions. formed from said compositions.

BACKGROUND OF THE INVENTION Obviously, it is well known that alternating cycles of fabric and textile use and washing, such as garment articles and worn clothing, will inevitably adversely affect the appearance and integrity of used and washed fabric and textile articles. Fabrics and textiles simply wear out over time and with use. The laundry of fabrics and textiles is necessary to remove dirt and stains that accumulate in them and on them during ordinary use. However, the laundry operation itself, with several cycles, can accentuate and contribute to the deterioration of the integrity and appearance of said fabrics and textiles.

The deterioration of the integrity and appearance of the fabrics can manifest itself in several ways. The short fibers are discarded from the fabric / textile structures woven and knitted by the mechanical action of the laundry. Said discarded fibers can form lint, fluff or "pellets" that are visible on the surface of the fabrics and diminish the novel appearance of the fabric. In addition, repeated washing of fabrics and textiles, especially with laundry products containing bleach, can remove the colorant from fabrics and textiles and impart a faded, worn appearance, as a result of diminished color intensity, and in several cases , as a result of changes in shades or shades of color. Due to the above, there is clearly a need to identify materials that could be added to the laundry detergent products that would be associated with the fibers of fabrics and textiles washed using said detergent products and thus reducing or minimizing the tendency of the fabric / Washed textiles to deteriorate in appearance. Any such detergent product additive materials must, of course, be able to benefit the appearance and integrity of the fabric without unduly interfering with the ability of laundry detergents to perform their fabric cleaning function. The present invention is directed to the use of polymer or oligomer base materials in laundry applications that function in this desired manner.

BRIEF DESCRIPTION OF THE INVENTION The cellulose-based polymer or oligomer materials that are suitable for use in laundry operations and provide the desired appearance and integrity benefits to the fabric can be characterized by the following general formula: wherein each R is selected from the group consisting of R2, Rc, and wherein: each R2 is independently selected from the group consisting of H and CrC4 alkyl; OR - each Rc is (CH2) and - OOZ; wherein each Z is independently selected from the group consisting of M, R2, Rc, and RH; - each RH is independently selected from the group consisting of C5-C20 alkyl, C5-C7 cycloalkyl, C7-C2 alkylaryl, C7-C2 arylalkyl, substituted alkyl, hydroxyalkyl, C1-C20-alkoxy-2-hydroxyalkyl, alkylaryloxy of C7-C2o-2-hydroxyalkyl, (R4) 2N-alkyl, (R4) 2N-2-hydroxyalkyl, (R4) 3N-alkyl, (R4) 3N-2-hydroxyalkyl, C6-C2-2 aryloxy -hydroxyalkyl, - each R4 is independently selected from the group consisting of H, C? -C20 alkyl, C-C7 cycloalkyl, C7-C2 alkylaryl, C7-C20 arylalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, piperidinoalkyl, morpholinoalkyl, cycloalkylaminoalkyl and hydroxyalkyl; - each R5 is independently selected from the group consisting of H, C1-C20 alkyl, C5-C7 cycloalkyl, C7-C20 alkylaryl, C-C2 arylalkyl, substituted alkyl, hydroxyalkyl, (R4) 2N-alkyl, and ( R4) 3N-alkyl; wherein: M is an appropriate cation selected from the group consisting of Na, K, 1 / 2Ca, and 1 / 2Mg; each x is from 0 to 5; each y is from 1 to 5; and with the proviso that: - the Degree of Substitution for the RH group is between 0.001 and 0.1, more preferably between 0.005 and 0.05, and more preferably between 0.01 and 0.05; - the Degree of Substitution for the group Rc in which Z is H or M, is between 0.2 and 2.0, more preferably between 0.3 and 1.0, and more preferably between 0.4 and 0.7; - if any RH has a positive charge, it is balanced by a suitable anion; and - two R4's on the same nitrogen can together form a ring structure selected from the group consisting of piperidine and morpholine. The cellulose-based polymer or oligomer materials defined above can be used as a wash solution additive in either granular or liquid form. Alternatively, they can be mixed with granular detergents, dissolved in liquid detergent compositions or added to a fabric softening composition. The above description of uses for the cellulosic base fabric treatment materials defined herein is designed to be illustrative and other uses will be apparent to those skilled in the art and are designed to be within the scope of the present invention.

Laundry detergent compositions herein comprise from 1% to 80% by weight of a detersive surfactant, from 0.1% to 80% by weight of an organic or inorganic builder and from 0.1% to 5% by weight of the detergent compositions. cellulose-based fabric treatment materials of the present invention. The detersive surfactant and builders can be any of those useful in conventional laundry detergent products. Aqueous solutions of polymer materials or oligomer based on cellulose of the subject invention comprise from 0.1% to 80% by weight of materials fabric treatment based on cellulose dissolved in water and other ingredients such as stabilizers and pH adjusters. In its aspect of method, the present invention relates to the washing or treatment of fabrics and textiles in aqueous washing or treatment solutions formed from effective amounts of the detergent compositions described herein, or formed from individual components of said compositions. compositions Washing fabrics and textiles in said washing solutions, followed by rinsing and drying, imparts fabric appearance benefits to fabric and textile articles treated in this manner. Such benefits may include improved overall appearance, pellet / brittle reduction, anti-fading, improved abrasion resistance, and / or improved softness.

DETAILED DESCRIPTION OF THE INVENTION As noted, when the fabrics or textiles are washed in wash solutions comprising the cellulose-based polymer or oligomer materials of the present invention, the appearance and integrity of the fabric is improved. The cellulose-based fabric treatment materials can be added to washing solutions by incorporating them into a detergent composition, fabric softener or by adding them separately to the washing solution. The cellulosic-based fabric treatment materials are described herein primarily as liquid or granular detergent additives, however the present invention is not designed to be limited in that way. The cellulosic based fabric treatment materials, the detergent composition components, optional ingredients for said compositions and methods of using said compositions, are described in detail below. All percentages are by weight unless otherwise specified.

A) Cellulose-based Polymer or Oliqomer Materials The essential component of the compositions of the present invention comprises one or more cellulose-based polymers or oligomer. It has been found that such materials impart a number of appearance benefits to fabrics and textiles washed in aqueous solutions formed from detergent compositions containing such cellulose-based fabric treatment materials. Such fabric appearance benefits may include, for example, improved overall appearance of the washed fabrics, reduction of pellet and fluff formation, protection against color fading, improved resistance to abrasion, etc. The cellulosic based fabric treatment materials 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 detergent compositions in which said materials are incorporated. As will be apparent to those skilled in the art, an oligomer is a molecule consisting of only a few monomer units while the polymers consist of considerably more monomer units. For the present invention, the oligomers are defined as molecules having an average molecular weight below 1,000, and the polymers are molecules having an average molecular weight greater than 1,000. One type of suitable fabric treatment material of cellulose-based polymer or oligomer for use herein has an average molecular weight of 5,000 to 2,000,000, preferably 50,000 to 1,000,000. The cellulosic base fabric treatment component of the detergent compositions herein will generally comprise from 0.1% to 5% by weight of the detergent composition. More preferably, said cellulose-based fabric treatment materials will consist of 0.5% to 4% by weight of the detergent compositions, more preferably from 0.75% to 3%. However, as discussed above, when used as a solution additive for washing, that is, when the cellulosic based fabric treatment component is not incorporated in a detergent composition, the concentration of the cellulosic base component may consist of 0.1% to 80% by weight of the additive material. A suitable group of cellulose-based polymer or oligomer materials for use herein is characterized by the following formula: wherein each R is selected from the group consisting of R2, Rc, and wherein: - each R2 is independently selected from the group consisting of H and CrC4 alkyl; OR - each Rc is (CH2) and C OZ; In which each Z is independently selected from the group consisting of M, R2, Rc and RH; - each RH is independently selected from the group consisting of C5-C2o alkyl, C5-C7 cycloalkyl, C7-C2 alkylaryl > C7-C20 arylalkyl, substituted alkyl, hydroxyalkyl, C2-C20 alkoxy-2-hydroxyalkyl, C7-C20-2 alkylaryloxy-hydroxyalkyl, (R4) 2N-alkyl, (R4) 2N-2-hydroxyalkyl, (R4) ) 3N-alkyl, (R4) 3N-2-hydroxyalkyl, C6-C12-2-hydroxyalkyl aryloxy, - each R4 is independently selected from the group consisting of H, C1-C20 alkyl, C5-C7 cycloalkyl, C7-C2 alkylaryl, C7-C20 arylalkyl. aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, piperidinoalkyl, morpholinoalkyl, cycloalkylaminoalkyl and hydroxyalkyl; - each R5 is independently selected from the group consisting of H, C1-C20 alkyl, Cs-C7 cycloalkyl, C7-C20 alkylaryl, C7-C2 arylalkyl, substituted alkyl, hydroxyalkyl, (R4) 2N-alkyl, and ( R4) 3N-alkyl; in which: M is an appropriate cation selected from the group consisting of Na, K, 1 / 2Ca, and 1 / 2Mg; each x is from 0 to 5; each y is from 1 to 5; and with the proviso that: - the Degree of Substitution for the RH group is between 0.001 and 0.1, more preferably between 0.005 and 0.05, and more preferably between 0.01 and 0.05; - the Degree of Substitution for the group Rc in which Z is H or M, is between 0.2 and 2.0, more preferably between 0.3 and 1.0, and more preferably between 0.4 and 0.7; - if any RH has a positive charge, it is balanced by a suitable anion; and - two R4's on the same nitrogen can together form a ring structure selected from the group consisting of piperidine and morpholine. The "Substitution Degree" for the RH group, which is sometimes abbreviated herein as "DSR", means the number of moles of RH group components that are substituted per anhydrous glucose unit, which is a unit of Anhydrous glucose is a six-member ring as shown in the repeat unit of the previous general structure.

The "Substitution Degree" for group Rc, which is sometimes abbreviated here as "DSRC", means the number of moles of components of group Rc, in which Z is H or M, which are substituted per unit of anhydrous glucose, in which an anhydrous glucose unit is a six-membered ring as shown in the repeat unit of the above general structure. The requirement that Z be H or M is necessary to ensure that there is a sufficient number of carboxymethyl groups so that the resulting polymer is soluble. It is understood that in addition to the required number of components Rc in which Z is H or M, there may be, and more preferably are, additional Rc components in which Z is a group other than H or M. The production of materials in accordance with the present invention is further defined in the examples below.

B) Detersive Surfactant The detergent compositions herein comprise from 1% to 80% by weight of a detersive surfactant. Preferably, said compositions comprise from 5% to 50% by weight of surfactant. The detersive surfactants used may be of the anionic, nonionic, zwitterionic, ampholytic or cationic type or may comprise compatible mixtures of those types. The detergent surfactants useful herein are described in the U.S.A. 3,664,961, Norris, issued May 23, 1972, patent of E.U.A. 3,919,678, Laughiin et al, issued December 30, 1975, patent of E.U.A. 4,222,905, Cockrell, issued September 16, 1980, and in the patent of E.U.A. 4,239,659, Murphy, issued December 16, 1980. All of the mentioned patents are incorporated herein by reference. Of all the surfactants, anionic and nonionic are preferred. Useful anionic surfactants may be of several different types. For example, the water-soluble salts of the higher fatty acids, i.e., "soaps", are anionic surfactants useful in the compositions herein. This includes alkali metal soaps such as the sodium, potassium, ammonium, and alkylammonium salts of higher fatty acids containing from 8 to 24 carbon atoms, and preferably from 12 to 18 carbon atoms. Soaps can be made by direct saponification of fats and oils or by neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of the fatty acid mixtures derived from coconut oil and bait, that is, sodium or potassium soap from bait and coconut. Additional anionic surfactants without soap which are suitable for use herein include the water-soluble salts, preferably the alkali metal, and ammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing 10 to about 20 carbon atoms and a sulfonic acid ester or sulfuric acid group. (Included in the term "alkyl" is the alkyl portion of acyl groups). Examples of said group of synthetic surfactants are a) sodium, potassium and ammonium alkyl sulfates, especially those obtained by sulfation of higher alcohols (carbon atoms of CR-CIS) such as those produced by the reduction of oil glycerides. bait or coconut; b) the polyethoxylated alkyl sulfates of sodium, potassium and ammonium, particularly those in which the alkyl group contains from 10 to 22, preferably from 12 to 18 carbon atoms, and in which the polyethoxylate chain contains from 1 to 15, preferably from 1 to 6 ethoxylate portions; and c) sodium and potassium alkylbenzene sulphonates in which the alkyl group contains from 9 to 15 carbon atoms, in a straight chain or branched chain configuration, for example, those of the type described in US Pat. 2,220,099 and 2,477,383. Especially valuable are linear straight-chain alkylbenzenesulfonates in which the average number of carbon atoms in the alkyl group is 11 to 13, abbreviated as LAS of Cn-13. Preferred nonionic surfactants are those of the formula R? (OC2H4) nOH, wherein R1 is a C1-C16 alkyl group or a C8-C12 alkylphenyl group, and n is from 3 to about 80. Particularly preferred are the condensation products of alcohols of C-12-C15 with 5 to about 20 moles of ethylene oxide per mole of alcohol, for example, C12-C13 alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol.

Additional suitable nonionic surfactants include polyhydroxy fatty acid amides of the formula: wherein R is an alkyl or alkenyl of CQ.I7, RI is a methyl group and Z is glycityl derived from a reduced sugar or alkoxylated derivative thereof. Examples are N-methyl-N-1-deoxyglucitylcocoamide and N-methyl-N-1-deoxyglucityl-amide. The processes for making the polyhydroxy fatty acid amides are known and can be found in Wilson, U.S. Pat. 2,965,576 and Schwartz, patent of E.U.A. 2,703,798, the descriptions of which are incorporated herein by reference. Preferred surfactants for use in the detergent compositions described herein are amine-based surfactants of the general formula: wherein Ri is an alkyl group of C6-C? 2; n is from 2 to 4, X is a bridge formation group that is selected from NH, CONH, COO or O, or X may be absent; and R3 and R4 are individually selected from H, C C alkyl, or (CH2-CH2-0 (R5)) wherein R5 is H or methyl. Especially preferred are the amine based surfactants which include the following: R1 (CH2) 2 -NH.

R1- O- (CH2) 3- NH2 R1- C (O) - NH- (CH2) 3- N (CH3) 2 wherein Ri is an alkyl group of C6-C-i2 and Rs is H or CH3. Particularly preferred amines for use in the surfactants defined above include those selected from the group consisting of octylamine, hexylamine, decylamine, dodecylamine, bis (hydroxyethyl) amine of Cs-C-I2, bis (hydroxyisopropyl) amine of CB -C- | 2, C8-C-? 2 amido-propyldimethylamine, or mixtures thereof. In a highly preferred embodiment, the amine-based surfactant is described by the formula: R c C (0) -NH- (CH 2) 3-N (CH 3) 2 wherein R-α is C 8 -C 12 C alkyl) Detergency Meter The detergent compositions herein may also comprise from 0.1% to 80% by weight of a detergency builder. Preferably, said compositions in liquid form will comprise from 1% to 10% by weight of the builder component. Preferably, said compositions in granulated form will comprise from 1% to 50% by weight of the builder component. Builders are well known in the art and may comprise, for example, phosphate salts, as well as various non-phosphorus organic and inorganic builders. The water-soluble non-phosphorus organic builders useful herein include the various alkali metals, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxysulfonates. Examples of polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids and citric acid. Other polycarboxylates suitable for use herein are the polyacetalcarboxylates described in the U.S.A. 4,144,226, issued March 13, 1979 to Crutchfield et al, and patent of E.U.A. 4,246,495, issued March 27, 1979 to Crutchfield et al, which are incorporated herein by reference. Particularly preferred polycarboxylate builders are oxydisuccinates and ether carboxylate builder compositions comprising a combination of tartrate monosuccinate and tartrate disuccinate described in the U.S.A. 4,663,071, Bush et al, issued May 5, 1987, the disclosure of which is incorporated herein by reference. Examples of suitable non-phosphorous, inorganic detergency builders include silicates, aluminosilicates, borates and carbonates. Particularly preferred are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate and silicates having a weight ratio of SIO2 to alkali metal oxide of about 0.5 to 4.0., preferably from 1.0 to 2.4. Also preferred are aluminosilicates which include zeolites. Such materials and their use as detergency builders are more fully described in Corkill et al, U.S. Pat. No. 4,605,509, the disclosure of which is incorporated herein by reference. They are also described in the patent of E.U.A. No. 4,605,509 the crystalline layered silicates which are suitable for use in the detergent compositions of this invention.

D) Optional detergent ingredients In addition to the surfactants, builders, and cellulose-based polymer or oligomer materials described above, the detergent compositions of the present invention may also include any number of additional optional ingredients. These include conventional detergent composition components such as enzymes and enzyme stabilizing agents, foam impellers or suds suppressors, anti-rust and anti-corrosion agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, sources of alkalinity without builder, chelating agents, organic and inorganic fillers, solvents, hydrotropes, optical brighteners, dyes and perfumes. PH adjusting agents may be necessary in certain applications where the pH of the wash solution is greater than 10.0, since the fabric integrity benefits of the defined compositions begin to decrease at a higher pH. Therefore, if the wash solution is greater than 10.0 after the addition of the polymeric or cellulosic base oligomer materials of the present invention, a pH adjuster should be used to reduce the pH of the wash solution below the 10.0, preferably at a pH less than 9.5, and most preferably less than 7.5. Suitable pH adjusters will be known to those skilled in the art. A preferred optional ingredient for incorporation into the detergent compositions herein comprises a bleaching agent, for example, a peroxygen bleach. Said peroxygen bleaching agents may be of an organic or inorganic nature. Inorganic peroxygen bleaching agents are often used in combination with a bleach activator.

Useful organic peroxygen bleaching agents include perca rboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydecanedioic acid. Said bleaching agents are described in the patent of E.U.A. 4,483,781, issued to Hartman on November 20, 1984; European patent application EP-A-133,354 to Banks et al, published on February 20, 1985; and U.S. Patent 4,412,934, Chung et al., issued November 1, 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid (NAAPAA) as described in US Patent 4,634,551, issued 6 January 1987 to Burns et al. Inorganic peroxygen bleaching agents, generally in the form of particles, can also be used in the detergent compositions herein. In fact, inorganic bleaching agents are preferred. Such inorganic peroxygen compounds include perborate and alkali metal percarbonate materials. For example, sodium perborate (for example, mono- or tetrahydrate) can be used. Suitable inorganic bleaching agents may also include sodium or potassium carbonate peroxyhydrate bleaches and equivalent "percarbonate", sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide. Persulfate bleach can also be used (for example, OXONE, manufactured commercially by DuPont). Frequently, the inorganic peroxygen bleaches will be coated with silicate, borate, sulfate or water-soluble surfactants. For example, percarbonate coated particles are available from various commercial sources such as FMC, Solvay Interox, Tokai Denka and Degussa. Inorganic peroxygen bleaching agents, for example, perborates, percarbonates, etc., are preferably combined with bleach activators, which leads to in situ production in aqueous solution (i.e., during the use of the present compositions for laundry / bleaching fabrics) of the peroxide acid which corresponds to the bleach activator. Several non-limiting examples of activators are described in U.S. Patent No. 4,915,854, issued April 10, 1990 to Mao et al., And U.S. Patent 4,412,934 issued November 1, 1983 to Chung et al. The nonanoyloxybenzenesulfonate (NOBS) and tetraacetylethylenediamine (TAED) activators are typical and preferred. Mixtures thereof can also be used. See also U.S. Patent 4,634,551, to which reference is made above, for other typical bleaches and activators useful herein. Other useful bleach activators derived from amido are those of the formulas: R1N (R5) C (0) R2C (0) L or R1C (0) N (R5) R2C (0) L wherein R1 is an alkyl group which contains from 6 to 12 carbon atoms, R2 is an alkylene containing 1 to 6 carbon atoms, R5 is H or alkyl, aryl or alkaryl containing 1 to 10 carbon atoms, and L is any suitable residual group. A residual group is any group that moves from the bleach activator as a result of the nucleophilic attack in the bleach activator by the perhydrolysis anion. A preferred residual group is phenolsulfonate. Preferred examples of bleach activators of the above formulas include (6-octanamido-caproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzenesulfonate and mixtures thereof as described in US Pat. No. 4,634,551, to which reference is made previously. Another useful class of bleach activators comprises the benzoxazine type activators described by Hodge et al, in U.S. Patent 4,966,723, issued October 30, 1990, incorporated herein by reference. A highly preferred activator of the benzoxazine type is: Still another class and useful whitening activators include acyl lactam activators, especially acylcaprolactams and acylvalerolactams of the formulas: wherein R6 is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to about 12 carbon atoms. Highly preferred lactam activators include benzoylcaprolactam, octanoylcaprolactam, 3,5,5-trimethylhexanoylcaprolactam, nonanoylcaprolactam, decanoylcaprolactam, undecenoylcaprolactam, benzoylvalerolactam, octanoylvalerolactam, nonanoylvalerolactam, decanoylvalerolactam, undecenoylvalerolactam, 3,5,5-trimethylhexanoylvalerolactam and mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson on October 8, 1985, incorporated herein by reference, which discloses acylcaprolactams, including benzoylcaprolactam, adsorbed to sodium perborate. If used, the peroxygen bleaching agent will generally comprise from about 2% to 30% by weight of the detergent compositions herein. More preferably, the peroxygen bleaching agent will comprise from 2% to 20% by weight of the compositions. More preferably, the peroxygen bleaching agent will be present on the scale of about 3% to 15% by weight of the compositions herein. If used, the bleach activators may consist of 2% to 10% by weight of the detergent compositions herein. Frequently, the activators are used in such a way that the molar ratio of the bleaching agent to activator varies from 1: 1 to 10: 1, more preferably from 1.5: 1 to 5: 1. Another highly preferred optional ingredient in the detergent compositions herein is a detersive enzyme component. Although it is well known that some enzymes will degrade the peptide bonds of cellulosics, the cellulose-based polymer or oligomer materials of the present do not exhibit such degradation in the presence of enzymes. Enzymes can be included in the present detergent compositions for a variety of purposes, including the removal of protein-based substrates, carbohydrate-based, or triglyceride-based, for the prevention of migratory dye transfer in the laundry of fabrics, and for the restoration of the fabric. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof of any suitable origin, such as of 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 regard, bacterial or fungal enzymes, such as bacterial amylases and proteases and fungal cellulases, are preferred. "Detersive enzyme", as used herein, refers to any enzyme that has a beneficial cleaning effect, removal of stain or other in a detergent composition for laundry. Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases, amylases and peroxidases. Enzymes are normally incorporated in detergent compositions at levels sufficient to provide an "effective amount of cleaning". The term "effective cleaning amount" refers to any amount capable of producing a cleaning, stain removal, dirt removal, bleaching, deodorizing, or freshness enhancing effect on substrates such as fabrics. In practical terms for the current commercial preparations, typical amounts are up to 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the detergent composition. Established otherwise, 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 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. Suitable examples of proteases are the subtilisins that are obtained from particular strains of ß. subtilis and B. licheniformis. A suitable protease is obtained from a strain of Basillus, having maximum activity through the pH scale of 8-12, developed and sold as ESPERASE® by Novo Industries A / S of Denmark, hereinafter "Novo". The preparation of said enzyme and analogous enzymes is described in GB 1, 243,784 to Novo. Other suitable proteases include ALCALASE® and SAVINASE® from Novo and MAXATASE® FROM International Bio-Synthetics, Inc., The Netherlands; as well as protease A as described in EP 130,756 A, January 9, 1985 and protease B as described in EP 303,761 A, April 28, 1987 and EP 130,756 A, January 9, 1985. See also a pH protease high from Bacillus sp. NCIMB 40338 described in WO 9318140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 9203529 A to Novo. Other preferred proteases include those of WO 9510591 A to Procter & Gamble. When desired, a protease having reduced adsorption and increased hydrolysis is available as described in WO 9507791 to Procter & Gamble. A recombinant trypsin-like protease for detergents suitable herein is described in WO 9425583 to Novo. Cellulases useful herein include bacterial and fungal types, preferably having an optimum pH between 5 and 10. US Patent, 4,435,307, Barbesgoard et al, March 6, 1984, describes suitable fungal cellulases from the strain Humicola insolens or Humicola DSM 1800 or a cellulase 212 that produces fungi belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk, Dolabella Auricular Solander. Suitable cellulases are also described in 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. Lipase enzymes suitable for detergent use include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as described in GB 1, 372, 034. See also lipase in Japanese Patent Application 53,20487, open to the public, February 24, 1978. Said lipase is available from Amano Pharmaceutical Co. Ltd., under the trade name Lipasa P "Amano", or "Amano". P ". Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, for example Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., E.U.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. The LIPOLASE® enzyme derived from Humicola lanuginosa and commercially available from Novo, see also EP 341, 947, is a preferred lipase for use herein. The enzyme-containing compositions herein may optionally also comprise from 0.001% to 10%, preferably from 0.005% to 8%, more preferably from 0.01% to 6% by weight of an enzyme stabilizing system. The enzyme stabilizing system can be any stabilizing system that is compatible with the detersive enzyme. Such a system can be inherently provided by other formulation actives, or it can be added separately, for example, by the formulator or by an enzyme manufacturer ready for detergents. Said stabilization systems can, for example, comprise calcium, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, and mixtures thereof, and are designed to solve the different problems of stabilization depending on the type and form Physical detergent composition.

E) Preparation of the detergent composition The detergent compositions according to the present invention may be in liquid, paste or granular form. Said compositions can be prepared by combining the essential and optional components in the necessary concentrations in any suitable order and by any conventional means. Granulated compositions, for example, are generally manufactured by combining the ingredients of base granules, for example, surfactants, builders, water, etc., as a suspension, and spray drying the resulting suspension at a low residual moisture level. (5-12%). The remaining dry ingredients, for example, granules of the essential cellulose-based fabric treatment materials, can be mixed in the form of granulated powder with the spray-dried granules in a rotating mixing drum. The liquid ingredients, for example, solutions of the cellulosic base fabric treatment materials, enzymes, binders and perfumes, can be sprayed into the resulting granules to form the finished detergent composition. The granulated compositions according to the present invention can also be in "compact form", that is, they can have a relatively higher density than conventional granular detergents, ie, from 550 to 950 g / l. In such a 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 the alkaline earth metal salts of sulfates and chlorides, typically sodium sulfate; "Compact" detergents typically comprise no more than 10% filler salt. The liquid detergent compositions can be prepared by mixing the essential and optional ingredients in any desired order to provide compositions containing components in the necessary concentrations. The liquid compositions according to the present invention may also be in "compact form", in which case, the liquid detergent compositions according to the present invention will contain a lower amount of water, compared to conventional liquid detergents. The addition of the cellulose-based polymer or oligomer materials to the liquid detergent or other aqueous compositions of this invention can be achieved simply by mixing the desired cellulosic base treatment materials in the liquid solutions.

F) Fabric laundry method The present invention also provides a method for fabric laundry in a form that imparts the fabric appearance benefits provided by the cellulosic based polymer or oligomer materials used herein. Said method employs contacting said fabrics with an aqueous wash solution formed from an effective amount of the detergent compositions described above or formed from the individual components of said compositions. The contact of the fabrics with the washing solution will generally occur under agitating conditions, although the compositions of the present invention may also be used to form aqueous, non-agitated soaking solutions for fabric cleaning and treatment. As described above, it is preferred that the wash solution has a pH of less than 10.0, preferably having a pH of 9.5 and more preferably having a pH of 7.5. The agitation of preference is provided in a washing machine for good cleaning. Preferably washing is 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 500 to 7000 ppm, more preferably from 1000 to 3000 ppm.

G) Fabric Conditioning The cellulose-based polymer or oligomer materials described hereinabove as components of the laundry detergent compositions herein can also be used to treat and condition fabrics and textiles in the absence of the surfactant and enhancer components. detergency of the detergent composition embodiments of this invention. Thus, for example, a fabric conditioning composition comprising only the cellulosic-based fabric treatment materials themselves, or comprising an aqueous solution of the cellulosic-based fabric treatment materials, can be added during the rinsing cycle of a conventional domestic laundry operation in order to impart the desired appearance and integrity benefits of the fabric described above.

EXAMPLES The following examples illustrate the compositions and methods of the present invention, but does not necessarily mean that they limit or otherwise define the scope of the invention.

EXAMPLE I Preparation of granular detergent test composition Several heavy-duty granular detergent compositions containing various modified cellulosic polymers are prepared. These granular detergent compositions all have the following basic formula: TABLE A EXAMPLE II Preparation of Liquid Detergent Test Composition Several heavy duty liquid detergent compositions are prepared containing various modified cellulosic polymers. These liquid detergent compositions have all of the following basic formula: TABLE B EXAMPLE III Synthesis of modified CMC materials The carboxylation of cellulose to produce CMC is a process that is well known to those skilled in the art.

To produce the modified CMC materials of this invention, the material, or materials, to be replaced during the CMC-forming process is added. An example of such a procedure is given below. This same procedure can be used with the other substituent materials described herein by replacing the hexyl chloride with the material, or substituent materials, of interest, for example, cetyl chloride. The amount of material that must be added to the CMC formation process to achieve the desired degree of substitution will be readily calculated by those skilled in the art in light of the following examples.

Synthesis of CMC hexylether This example illustrates the preparation of a carboxymethylcellulose hydrophobically modified with carboxymethyl and is representative of the preparation of all ether cellulose derivatives of this invention. Cellulose (20 g), sodium hydroxide (10 g), water (30 g), and ethanol (150 g) are charged in a 500 ml glass reactor. The resulting alkali cellulose is stirred 45 minutes at 25 ° C. Then monochloroacetic acid (15 g) and hexyl chloride (1 g) are added and the temperature rises with time at 95 ° C and is maintained at 95 ° C for 150 minutes. The reaction is cooled to 70 ° C and then cooled to 25 ° C. The neutralization is achieved by the addition of a sufficient amount of nitric acid / acetic acid to achieve a slurry with pH between 8 and 9. The slurry is filtered to obtain a CMC hexel ether.

EXAMPLE IV Cellulosic polymers used in the test detergent compositions.

The representative modified cellulosic polymers used in the liquid and granular detergent compositions described in Examples I and II are characterized in Table C. The general polymer parameters are common to all polymers, while the specific chemical structure of the tested materials is listed under the specific polymer parameters.

TABLE C General polymer parameters TABLE D Parameters of specific polymers ID Polymer Type of modification *** Types of chemistry * A Hexyl CMC Hexyl Ether Chlorhexane added to the CMC formation process * B Decylone CMC decyl Chlorodecane added to the CMC formation process ** C C12 Alkoxy CMC Alkoxy Ether-Alkyl Ether C12-C13-2 C13-2 hydroxypropyl C12-C13 glycidyl hydroxypropyl added to the CMC formation process * D CMC of Hexadecyl Ether Chlorohexadecane Hexadecyl added to the CMC formation process * E Chloride Salt of Chloride of 2,3-Ether 3-3-trimethylammonium-2-epoxypropyltrimethylamine thymethylammonium-2-hydroxypropyl chloride added to the hydroxypropyl ether CMC CMC training * F [- (C (O) - Dimer of cetilceteho CH (C16H33) - added to C (0) CH2 (C16H33 procedure of )] CMC ester or CMC-1, 3- dioxo-2-hexadecyloctadecyl ester formation of CMC CMC = carboxymethylcellulose * Manufactured by Metsa Specialty Chemicals ** Manufactured by Akzo *** DSRH for those materials was on a scale of 0.001 to 0.1 EXAMPLE V General Appearance In a general appearance test, the fabrics are washed using several test compositions containing either no cellulose polymer (control) or one of the polymers defined in the tables C and D above. The fabrics are washed and after 10 cycles are graduated comparatively by three judges who evaluate the total appearance of the washed fabrics. It is the jury's decision that must be evaluated unless specific direction is given to evaluate an attribute such as color, pellet formation, blinding, etc. All tests are conducted under the same conditions which are carefully monitored. Examples of controlled conditions include: wash time, hardness and temperature of the wash water; agitation of the washing machine, rinsing time, temperature and hardness of the rinse water; dryer time and temperature; Fiber content of washing load and weight. In the total aspect test, the visual preference of the jury is expressed using the Scheff scale. This is: 0 = No difference 1 = I think this is better (not sure). 2 = I know that this one is a little better. 3 = I know that this one is much better. 4 = I know that this one is completely better.

For the Total Appearance test, the laundry conditions are as follows: Type of washing machine: Kenmore (64 liters) Washing time: 12 minutes Washing temperature: 32.2 ° C (90 ° F) Washing water hardness: 6 grains per 3,785 liters Washing machine agitation: normal Rinse time: 2 minutes Rinse temperature 15.6 ° C (60 ° F) Rinse water hardness: 6 grains per 3,785 liters Contents of wash load fabric: various garments and colored fabrics and white Washing load weight: 2.5 kg (5.5 Ibs) The results of the average total appearance test are shown in Table E.

TABLE E Total appearance test results EXAMPLE VI Pellet reduction In a pellet reduction test, the fabrics are washed using the different test compositions containing one of the cellulosic polymers defined in Example IV and compared to control fabrics washed in the same detergent compositions that do not contain cellulosic polymers. The washing conditions are kept constant and are the same as in Example V above. The fabrics washed in this way are then graded for pellet reduction using a computer-assisted pellet image analysis system that uses image analysis to measure the number of pellets on garments and fabrics tested. The Pellet reduction is calculated as: Pellet reduction (%) =. { [# pellets (control) - # pellets (polymers)] / # pellets (control)} x 100% The results of the average pellet reduction percentage test are shown in table F.

TABLE F Pellet-pellet reduction test results Composition ID Tested polymer Pellet / fluff granular test reduction% Control None 0 A Carboxymethylcellulose hexyl ether 38% D Carboxymethylcellulose hexadecyl ether 31% E 3-Trimethylammonium-27% ether chloride salt 2-hydroxypropyl carboxymethylcellulose F [(C (0) -CH (C16H33) -C (0) CH2 (C16H33)] 25% carboxymethylcellulose ester

Claims (10)

NOVELTY OF THE INVENTION CLAIMS

1. - A detergent composition characterized by: a) from 1% to 80% by weight of surfactants selected from the group consisting of nonionic, cationic, amphoteric, zwitterionic surfactants, or mixtures thereof, and b) from 1% to 5.0% by weight of a mixture of cellulose-based polymers or oligomers of the general formula: wherein each R is selected from the group consisting of R2, Rc, and wherein: each R2 is independently selected from the group consisting of H and C-? -C alkyl; OR each Rc is (CH2) and C OZ; wherein each Z is independently selected from the group consisting of M, R2, Rc, and RH; each RH is independently selected from the group consisting of C5-C20 alkyl, C5-C7 cycloalkyl, C7-C2 alkylaryl, C7-C2 arylalkyl, substituted alkyl, hydroxyalkyl, C1-C20 alkoxy-2-hydroxyalkyl, alkylaryloxy C7-C2o-2-hydroxyalkyl, (R4) 2N-alkyl, (R4) 2N-2-hydroxyalkyl, (R4) 3N-alkyl, (R) 3N-2-hydroxyalkyl, C6-C2-2 aryloxy hydroxyalkyl, - each R4 is independently selected from the group consisting of H, C1-C20 alkyl, C5-C7 cycloalkyl, C-C2o alkylaryl, C7-C20 arylalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, piperidinoalkyl, morpholinoalkyl, cycloalkylaminoalkyl and hydroxyalkyl; each R5 is independently selected from the group consisting of H, C1-C20 alkyl, C5-C7 cycloalkyl, C7-C2 alkylaryl, C7-C2 arylalkyl, substituted alkyl, hydroxyalkyl, (R4) 2N-alkyl, and (R4) 3 N-alkyl; wherein: M is an appropriate cation selected from the group consisting of Na, K, 1 / 2Ca, and 1 / 2Mg; each x is from 0 to 5; each y is from 1 to 5; and with the proviso that: -the Degree of Substitution for the RH group is between 0.001 and 0.1, more preferably between 0.005 and 0.05, and more preferably between 0.01 and 0.05; -the Degree of Substitution for the group Rc in which Z is H or M, is between 0.2 and 2.0, more preferably between 0.3 and 1.0, and more preferably between 0.4 and 0.7; - if any RH has a positive charge, it is balanced by a suitable anion; and - two R4's on the same nitrogen can together form a ring structure selected from the group consisting of piperidine and morpholine.

2. The detergent composition according to claim 1, further characterized in that RH is independently selected from the group consisting of: C5-C20 alkyl, C5-C7 cycloalkyl alkylaryl of C -C2o, arylalkyl of C7-C20, substituted alkyl , hydroxyalkyl, C1-C20 alkoxy-2-hydroxyalkyl, C7-C2o-2-hydroxyalkyl alkylaryloxy, (R4) 2N-alkyl, (R4) 2N-2-hydroxyalkyl, (R4) 3N-alkyl, (R4) 3N -2-hydroxyalkyl, C6-Ci2-2-hydroxyalkyl aryloxy.

3. The detergent composition according to claim 1, further characterized in that each R4 is independently selected from the group consisting of Or 11 R 1? 5 c- -C H CH. -OM;

4. - The detergent composition according to claim 1, further characterized in that the polymer or oligomer of cellulosic base has an average molecular weight of 5,000 to 2,000,000.

5. The detergent composition according to claim 1, further characterized in that the polymer or oligomer of cellulosic base has an average molecular weight of 10,000 to 1,000,000.

6. An additive composition for laundry characterized by: a) from 1% to 80% by weight of water; and b) from 0.1% to 80.0% by weight of cellulose-based polymers or oligomers of the general formula: wherein each R is selected from the group consisting of R2, Rc, and wherein: each R2 is independently selected from the group consisting of H and C-? -C4 alkyl; OR each Rc is (CH2) and C OZ; wherein each Z is independently selected from the group consisting of M, R2, Rc, and RH; - each RH is independently selected from the group consisting of C5-C2o alkyl, C5-C7 cycloalkyl, C7-C2 alkylaryl, C7-C2 arylalkyl, substituted alkyl, hydroxyalkyl, C1-C20 alkoxy-2-hydroxyalkyl, alkylaryloxy of C7-C2o-2-hydroxyalkyl, (R4) 2N-alkyl, (R4) 2N-2-hydroxyalkyl, (R4) 3N-alkyl, (R4) 3N-2-hydroxyalkyl, C6-Ci2-2-hydroxyalkyl aryloxy , - each R is independently selected from the group consisting of H, C 1 -C 20 alkyl, C 5 -C 7 cycloalkyl, C -C al alkylaryl, C 7 -C 2 arylalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, piperidinoalkyl, morpholinoalkyl, cycloalkylaminoalkyl and hydroxyalkyl; - each R5 is independently selected from the group consisting of H, C -? - C2o alkyl, Cs-C7 cycloalkyl, C-C2o alkylaryl, C7-C2 arylalkyl, substituted alkyl, hydroxyalkyl, (R ^ N-alkyl, and (R4) 3N-alkyl, wherein: M is a suitable cation selected from the group consisting of Na, K, 1 / 2Ca, and 1 / 2Mg, each x is from 0 to 5, each y is from 1 to 5. and with the proviso that: - the Degree of Substitution for the RH group is between 0.001 and 0.1, more preferably between 0.005 and 0.05, and more preferably between 0.01 and 0.05; -the Degree of Substitution for the Rc group in the which Z is H or M, is between 0.2 and 2.0, more preferably between 0.3 and 1.0, and more preferably between 0.4 and 0.

7, - if any RH has a positive charge, it is balanced by a suitable anion, and -two R4's about the same nitrogen can together form a ring structure selected from the group consisting of piperidine and morpholine 7.- The additive composition for laundry in accordance The composition according to claim 6 further characterized in that RH is independently selected from the group consisting of: C5-C2o alkyl, C5-C7 cycloalkyl, C7-C2 alkylaryl, C7-C20 arylalkyl, substituted alkyl, hydroxyalkyl, alkoxy-2- hydroxyalkyl of C1-C20, alkylaryloxy of C7-C20-2-hydroxyalkyl, (R4) 2N-alkyl, (R4) 2N-2-hydroxyalkyl, (R4) 3N-alkyl, (R4) 3N-2-hydroxyalkyl, C6-Ci2-2-hydroxyalkyl aryloxy.

8. The laundry additive composition according to claim 6 further characterized in that each R4 is independently selected from the group consisting of ;

9. - The laundry additive composition according to claim 6, further characterized in that the cellulose-based polymer or oligomer has an average molecular weight of 5,000 to 2,000,000.

10. The additive composition for laundry according to claim 6 further characterized in that the polymer or oligomer of cellulosic base has an average molecular weight of 10,000 to 1,000,000. SUMMARY OF THE INVENTION Compositions and methods using certain cellulose-based polymer or oligomer materials as fabric treatment agents that can impart appearance and integrity benefits to fabrics and textiles washed in wash solutions containing said materials; specifically, the cellulose-based polymers or oligomers are of the general formula I, in which each R is selected from the group consisting of R2, Rc and (a) each R2 is independently selected from the group consisting of H and C4 alkyl; each Rc is (b) each Z is independently selected from the group consisting of M, R2, Rc and RH; and each R is independently selected from the group consisting of C5-C20 alkyl, C5-C7 cycloalkyl, C-C20 alkylaryl, C7-C20 arylalkyl, substituted alkyl, hydroxyalkyl, CrC20-alkoxy-2-hydroxyalkyl, C7 alkylaryloxy. -C2o-2-hydroxyalkyl, (R4) 2N-alkyl, (R4) 2N-2-hydroxyalkyl, (R4) 3N-alkyl, (R4) 3N-2-hydroxyalkyl, C6-Ci2-2-hydroxyalkyl aryloxy, (c), (d) and (e) or II -c II- I 1 -C-H-? O -C-H. -c- -C H. -C H) M the degree of substitution for the RH group in those polymers or oligomers of cellulosic base is between 0.001 and 0.1, and the Degree of Substitution for the group Rc in which Z is H or M in those polymers or oligomers of cellulose base is between 0.2 and 2.0 P00 / 350F