CA2276188C - Laundry detergent compositions with cellulosic polymers - Google Patents

Abstract

Disclosed are detergent compositions and methods which utilize certain modified cellulose ethers as fabric treatment agents that can impart fabric appearance and integrity benefits to fabrics and textiles laundered in washing solutions which contain such agents. Such modified cellulose ether fabric treatment agents are those having selected types and amounts of anhydroglucose ring substituents in order to render them nonionic, cationic or anionic in nature.

Description

LAUNDRY DETERGENT COMPOSITIONS WITH CELLULOSIC POLYMERS
TO PROVIDE APPEARANCE AND INTEGRITY BENEFITS TO FABRICS
LAUNDERED THEREWITH
TECHNICAL FIELD
The present invention relates to heavy duty laundry detergent compositions, in either liquid or granular fonm, which contain certain types of modified cellulose ether materials to impart appearance and integrity benefits to fabrics and textiles laundered in washing solutions formed from such compositions.
BACKGROUND OF THE INVENTION
It is, of course, well known that alternating cycles of using and laundering fabrics and textiles, such as articles of worn clothing and apparel, will inevitably adversely affect the appearance and integrity of the fabric and textile items so used and laundered. Fabrics and textiles simply wear out over time and with use.
Laundering of fabrics and textiles is necessary to remove soils and stains which accumulate therein and thereon during ordinary use. However, the laundering operation itself, over many cycles, can accentuate and contribute to the deterioration of the integrity and the appearance of such fabrics and textiles.
. Deterioration of fabric integrity and appearance can manifest itself in several ways. Short fibers are dislodged from woven and knit fabric/textile structures by the mechanical action of laundering. These dislodged fibers may form Lint, fiizz or "pills"
which are visible on the surface of fabrics and diminish the appearance of newness of the fabric. Further, repeated laundering of fabrics and textiles, especially with bleach-containing laundry products, can remove dye from fabrics and textiles and impart a faded, worn out appearance as a result of diminished coloc intensity, and in many cases, as a result of changes in hues or shades of color.
Given the foregoing, there is clearly an ongoing need to identify materials which could be added to laundry detergent products that would associate themselves with the fibers of the fabrics and textiles laundered using such detergent products and thereby reduce or minimize the tendency of the laundered fabricltextiles to deteriorate in appearance. Any such detergent product additive material should, of course, be able to benefit fabric appearance and integrity without unduly interfering with the ability of the laundry detergent to perform its fabric cleaning function. The present invention is directed to detergent compositions containing certain types of cellulosic materials that perform in this desired manner.
SUMMARY OF TAE INVENTION
The laundry detergent compositions herein comprise from about 1% to 80% by weight of a detersive surfactant, from about 1% to 80% by weight of an organic oc inorganic detergency builder and from about 0.1% to 8% by weight of certain types of modified cellulose ether fabric treatment agents. The detersive surfactant and detergency builder materials can be any of those useful in conventional laundry detergent products. The modified cellulose ether materials are those which have a molecular weight of from about 10,000 to 2,000,000 and are wmprised of repeating substituted anhydroglucose units corresponding to the general Structural Formulas Nos. I, II and III set forth hereinafter in the "Detailed Description of the Invention"
section. (In the Structural Formulas hereinafter set forth, substituents are shown in specific positions on the anhydroglucose rings which repeat to form the substituted cellulose ether polymers. It should be understood that this is for illustration purposes only and that such substituents may be found on any of the carbon atoms of the anhydroglucose rings.) One useful type of ~ cxllulose ethers comprises hydrophobicallyr~wdified, nonionic materials with anhydroglucose ring alkyl substitution ranging from about 0.1% to 5% by weight of the cellulose ether. Ring substituents are alkoxylated in amounts ranging from about 1 to 20 moles.
A second useful type of cellulose ether comprises cationic cellulose ether materials which may have anhydrogiucosa ring alkyl substitution ranging from about 0.1% to 5% by weight of the cellulose ether. Anhydroglucose ring substituents contain from about 1 to 20 moles of alkoxylation and from about 0.005 to 0.5 moles of quaternary ammonium moieties.
A third type of cellulose ether comprises anionic cellulose ether materials which may have anhydroglucose ring alkyl substitution ranging from about 0.1 % to 5 % by weight of the cellulose ether. The anhydroglucose rings in such anionic materials also have a degree of carboxymethyl substitution ranging from about 0.05 to 2.5. Combinations of the nonionic, cationic and anionic modified cellulose ethers can also be employed.
In one particular embodiment there is provided a built, heavy duty laundry detergent composition in liquid or granular form which imparts fabric appearance benefits selected from pilUfuzz reduction, antifading, improved abrasion resistance and enhanced softness to fabrics and textiles laundered in aqueous washing solutions formed therefrom, which composition is characterized by: A) from 1% to 80% by weight of a detersive surfactant; B) from 1 % to 80 % by weight of an organic or inorganic detergency builder; C) from 0.1 % to 8 % by weight of a modified cellulose ether fabric treatment agent selected from: hydrophobically-modified, nonionic cellulose ethers which have a molecular weight of from 10,000 to 2,000,000 and which have repeating substituted anhydroglucose units corresponding to the general formula:
R
c wherein:
R is independently selected from the group consisting of H and Cg-CZa alkyl with alkyl substitution of the anhydroglucose rings ranging in an amount of from 0.1 % to 5 % by weight of the cellulose ether material;
RI is H or methyl; and x ranges from 1 to 20.

3a In its method aspect, ttar invention rotates to the ~aung or tresang of fabrics and textiles in aqueous washing or treating solutions ~t~mal from effective amounts of the detergent compositions described heron, or formed from the individual components of such compositions. Laundering of fltbrics and textiles in such washing solutions, followed by rinsing and drying, imparts fabric appearance benefits to the fabric and textile articles so ueated. gush be~refits can include improved overall appearance, pilUfuzz n~uction, antifading, in~rovad abrasion resistance, and/or enhanced softness.
SLED DESCRIPTION OF THE INY~~ON
As noted, the laundry detergent compositions of the present imrention essentially oontsin v~e s~rrfacxsnt, daagmt builder and certain nrodiged cellulose ether fabric treatment agents which serve to enhance fabric appearance and integrity upon use of the detergent aompoaitions to launder fabrics and textiles. Each of these ~smttial detergent composition components, as well as optional units for such compositions and metlada of using such compositions, are described in ddail as follows: All peroeatages and ratios given are by weight unless other speed.
A) The det~rt compositions hendn eaaentia~lly comprise R~om about 1% t0 80%
by weight of a detersive surfactant. Prefeeabiy such ~mpos~ons comprise fl~om about 5'X. to 50yG by w~aig~ of this Wit. Det~v~e surd 'ut>bmed can be of the anionic, noniotric, zvvitterionic, smpholytic or cationic type or can comprise oompstible mixtures of these types. Detergent sur~tsnts uaegrl ha~in are descn'bed in U.S. Patent 3,664,961, Norria, issued May 23, 1972, U.S. Pstent 3,919,678, Laughlin et al., iaa~red December 30, 1975, U.S. Patent 4,222,905, Cockrell, issued September 16, 1980, and in U.S. Patent 4,239,659, Murphy, issued December 16, 1980. Of all the surfactants, anionics and nonionics are preferred.
Useful anionic surfactants can themselves be of several different types. For example, water-soluble salts of the higher fatty acids, i.e., "soaps", are useful anionic surfactants in the compositions herein. This includes alkali metal soaps such as the sodium, potassium, ammonium, and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms. Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
Additional non-soap anionic surfactants which are suitable for use herein include the water-soluble salts, preferably the alkali metal, and ammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl" is the alkyl portion of aryl groups.) Examples of this group of synthetic surfactants are a) the sodium, potassium and ammonium alkyl sulfates, especially those obtained by sulfating the higher alcohols (Cg-C 1 g carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; b) the sodium, potassium and ammonium alkyl polyethoxylate sulfates, particularly those in which the alkyl group contains from 10 to 22, preferably from 12 to 18 carbon stoma, and wherein the poiyethoxylate chain contains from 1 to 15, preferably 1 to 6 ethoxylate moieties; and c) the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the _ type described in U.S. Patents 2,220,099 and 2,477,383. Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as C 11-13 ~~
Preferred nonionic surfactants are those of the formula R1(OC2H4)nUH, wherein Rl is a C l p-C 1 b ~ Si'~P or a Cg-C 12 alkyl phenyl group, and n is from 3 to about 80. Particularly preferred are condensation products of C ~ 2-C 15 alcohols with from about 5 to about 20 motes of ethylene oxide per mole of alcohol, e.g., C 12'C 13 ~oohol °°~ensed with about 6.5 moles of ethylene oxide per mole of alcohol.

Additional suitable nonionic surfactants include polyhydroxy fatty acid amides of the formula:
O R~
R-~-N-Z
wherein R is a Cg-17 alkyl or alkenyl, R1 is a methyl group and Z is glycityl derived from a reduced sugar or alkoxylated derivative thereof. Examples are N-methyl N-1-deoxyglucityl cocoamide and N-methyl N-1-deoxyglucityl oleamide. Processes for making polyhydroxy fatty acid amides are known and can be found in Wilson, U.S.
Patent 2,965,576 and Schwartz, U.S. Patent 2,703,798 .
B) eraent Builder The detergent compositions herein also essentially comprise from about 0.1%
to 80% by weight of a detergent builder. Preferably such compositions in liquid form will comprise from about 1 °l° to I O% by weight of the builder component.
Preferably such compositions in granular form will comprise from about 1°/. to 50%
by weight of the builder component. Detergent builders are well known in the art and can comprise, for example, phosphate salts as well as various organic and inorganic nonphosphorus builders.
Water-soluble, nonphosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy sulfonates. Examples of polyacetate and polycarboxyiste builders are the sodium, potassium, lithium, ammonium and substituted ammonium saps of ethylene diamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid. Other suitable polycarboxylates for use herein are the polyacetal carboxylates descnbed in U.S. Patent 4,144,226, issued March 13, 1979 to Crutchfield et al, and U.S.
Patent 4,246,495, issued March 27, 1979 to Crutchfield et al.
Particularly preferred polycarboxylate builders are the oxydisuccinates and the ether carboxylate builder compositions comprising a combination of tartrate monosuccinate and tartrate disuccinate described in U.S.
Patent 4,663,071, Bush et al., issued May 5, 1987.
Examples of suitable nonphosphorus, inorganic builders include the silicates, aluminosilicates, borates and carbonates. Particularly preferred are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetrabotate decahydrate, and silicates having a weight ratio of Si02 to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to . about 2.4. Also preferred ace aluminosilicates including zeolites. Such materials and their use as detergent builders are more fully discussed in Corkill et al, U.S. Patent No. 4,605,509. Also, crystalline layered silicates such as those discussed in Corkill et al, U.S.
Patent No. 4,605,509, are suitable for use in the detergent compositions of this invention.
C) Modified Cellulosic Polymers The thi;d essential component of the detergent compositions herein comprises one or more modified cellulosic polymers. Such materials have been found to impart .
a number of appearance benefits to fabrics and textiles laundered in aqueous washing solutions formed from detergent compositions which contain such modified cellulosic materials. Such fabric appearance benefits can include, for example, improved overall appearance of the laundered fab~cs, reduction of the formation of pills and fuzz, protection against ~ color fading, improved abrasion resistance, etc.
The modified cellulosic polymers used in the compositions and methods herein can provide such fabric appearance benefits with acceptably little or no loss in cleaning performance provided by the laundry detergent compositions into which such materials are incorporated.
The modified cellulosic polymers useful herein may be of the nonionic, cationic or anionic types, or the modified cellulosic polymeric component of the compositions herein may comprise combinations of these cellulosic polymer types. The modified cetlulosic polymer component of the compositions herein will generally comprise from about 0.1% to 8% by the weight of the composition. More preferably, such modified cellulosic materials will comprise from about 0.5% to 4% by weight of the compositionsy most preferably from about 1% to 3%.
One suitable type of modified cellulosic polymer for use herein comprises hydrophobicaUy-modified, nonionic cellulose ethers having a molecular weight of from about 10,000 to 2,000,000, preferably from about 50,000 to 1,000,000.
'The hydrophobically-modified nonionic materials have repeating, substituted anhydroglucose units which correspond to the genera! Structural Formula No. I
as follows:

-R
x ,_ Structural Formula No. I
In Structural Formula No. I, R is a combination of H and Cg-C24 alkyl, preferably Cg - C 16 alkyl. Alkyl substitution on the anhydrogluwse rings of the polymer ranges from about 0.1% to 5% by weight, more preferably from about 0.2%
to 2% by weight, of the polymu material. Also, in Structural Formula No. I, R1 is H
or methyl, and x ranges from about 1 to 20, prefetably from about 1 to 10.
The hydrophobically-modified nonionic cellulose ethers of Structural Formula No. I include those which ate commercially available and also include materials which can be prepared by conventional chemical modification of commercially available materials. Commercially available Mcellulose ethers of the Structural Formula No. I
type include Polysurf 67, Natrosol Plus 430 and Natrosol Plus 330, all marketed by Hercules, Inc.
Another suitable type of modified celluiosic polymer for use herein comprises certain cationic cellulose ethers, which may or may not be hydrophobically~modified, having a molecular weight of from about 10,000 to 2,000,000, more preferably from about 10,000 to 1,000,000. These cationic materials have repeating substituted anhydroglucose units which correspond to the general Structural Formula No. II
as follows:

~+
N-R4]y ~
RS

Structure! Formula No. II
In Structural Formula No. II, R is H or Cg-C24 alkyl, preferably Cg - C16 alkyl. Alkyl substitution on the anhydroglucose rings of the polymer ranges from about 0.1 % to 5% by weight, more preferably from about 0.2% to 2% by weight, of the polymeric material. Also, in Structural Formula No. II, R2 is CH2CHOHCH2 or Cg-C24 alkyl, preferably Cg - C 16 alkyl. R3, R4 and RS are each independently methyl, ethyl or phenyl. R6 is H or methyl. Further, in Structural Formula No.
II, x ranges from about 1 to 20, preferably from about 1 to 10; and y ranges from about 0.005 to 0.5, preferably from about 0.005 to 0.1; and Z is Ci- or Br-.
The cationic cellulose ethers of Structural Formula No. II likewise include those which are commercially available and further include materials which can be prepared by corrventional chemical modification of commercially available materials.
Commercially available cellulose ethers of the Structural Fo~rmuls No. II type include the JR 30M, JR 400, JR 125, LR 400 and LK 400 UCARlr polymers, all marketed by Union Carbide Corporation.
A third type of suitable modified cellulose polymers for use herein comprises certain anionic cellulose ethers, which also may or may not be hydrophobically modified, having a molecular weight of from about 10,000 to 2,000,000, more preferably from about 50,000 to 1,000,000. These anionic materials have repeating substituted anhydroglucose units which correspond to general Structural Formula No. III as follows:
CHiOR RO
OR
RO
'J
R HiOR
In Stnrctural Formula No. III, R is a combination of H and a) CH2COOA and, optionally, b) C2-C24~ Prefe~ly C2 - C 16, alkyl, ~"'ith A being Na or K.
Alkyl substitution on the anhydroglucose rings of the polymer ranges from about 0.1%
to 5% by weight, more preferably from about 0.2% to 2% by weight, of the polymer material. The anionic cellulose ethers also have a degree of carboxymethyl substitution which ranges from about 0.05 to 2.5, more preferably from about 0.1 to 1Ø
The anionic cellulose ethers of Structural Formula No. III also include those materials which are commercially available and further include those which can be ' prepared by conventional chemical modification of commercially available materials.
Commercially available cellulose ethers of the Structural Formula No. III
include CMC 7H, CMC 99-7M and CMC 99-7L, all marketed by Hercules, Inc. and CMC
D72, CMC D65 and CMC DHT, all marketed by Penn Carbose.
The commercially available cellulose ether materials useful herein are themselves derived from suitable natural sources of cellulose. Such sources include, for example, cotton linters and other vegetable tissues. The modified cellulose ethers used in this invention are generally all water-soluble materials. They can therefore be utilized for detergent composition preparation in the form of aqueous solutions of the such cellulosic polymers if desired.
D) Optional Detergent In redients In addition to the essential surfactants, builders and modified cellose ethers hereinbefore described, the detergent composition of the present invention can also include any number of additional optional ingredients. These include conventional detergent composition components such as bleaches and bleach activators, enzymes and enzyme stabilizing agents, suds boosters or suds suppressers, anti-tarnish and anticorrosion agents, soil suspending agents, soil release agents, germicides, pH
adjusting agents, non-builder alkalinity sources, chelating agents, organic and inorganic fillers, solvents, hydrotropes, optical brighteners, dyes and perfumes.
A preferred optional ingredients for incorporation into the detergent compositions herein comprises a bleaching agent, e.g., a peroxygen bleach.
Such peroxygen bleaching agents may be organic or inorganic in nature. Inorganic peroxygen bleaching agents are frequently utilized in combination with a bleach activator.
' Useful organic peroxygen bleaching agents include percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium ' monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.
Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, Issued November 20, 1984; European Patent Application EP-A-133,354, Banks et al., Published lU
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 (NAPAA) .as described in U.S. Patent 4,634,551, Issued January 6, i 98? to Burns et al.
Inocganic peroxygen bleaching agents may also be used, generally in particulate form, in the detergent compositions herein. Inorganic bleaching agents are in fact preferred. Such inorganic peroxygen compounds include alkali metal perborate and percarbonate materials. For example, sodium perborate (e.g. mono- or tetra-hydrate) can be used. Suitable inorganic bleaching agents can also include sodium or potassium carbonate peroxyl~ydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.
Persulfate bleach (e.g., OXONE,T manufactured commercially by DuPont) can also be used.
Frequently inorganic peroxygen bleaches will be coated with silicate, borate, sulfate or water-soluble surfactants. For example, coated percarbanate particles are available from various commercial sources such as FMC, Solvay Interox, Tokai Denka and Degussa.
Inorganic peroxygen bleaching agents, e.g., the perborates, the percarbonates, etc., are preferably combined with bleach activators, which lead to the irr situ production in aqueous solution ~.e., during use of the compositions herein for fabric laundering~bleacwng) of the peroxy acrid corresponding to the bleach activator.
Various non-limiting examples of activators are disclosed in U.S. Patent 4,915,854, Issued April 10, 1990 to Mao d al.; and U.S. Patent 4,412,934 Issued November 1, 1983 to Chung et al. The nonanoyloxybenzene sulfonate (HOBS) and tetraacetyl ethylene diamine (TAED) activators arc typical and preferred. ores thereof can also be usexl: See also the hereinbefore referenced U.S. 4,634,551 for other typical bleaches and activators useful herein.
Other useful amido-derived bleach activators are those of the formulae:
R 11V(R5~(O)R2C(O)L or R i C(O)N(RS)R2C(O)L.
wherein Rl is an alkyl group containing from about 6 to about 12 carbon atoms, is an aikylene containing from I to about 6 carbon atoms, RS is H or alkyl, aryl, or alkaryl cornaining from about 1 to about l0 carbon atoms, and L is any suitable leaving group. A (caving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion. A preferred leaving group is phenol sulfonate.

Preferred examples of bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamido-caproyl~xybenzenesulfonate and mixtures thereof as described in U.S. Patent 4,634,551.
Another class of useful bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al. in U.S. Pat~t 4,966, 723, Issued October 30, 1994. A highly preferred activator of the benzoxazin-type is:
O
'O
I
yC
N
Still another class of useful bleach activators includes the acyt lactam activators, especially aryl caprolactams and aryl valerolactams of the formulae:
O O
O C--CHZ-CHZ O ~--CHZ-CHH2 R -C-N . ~ ~ -C N
~CH2--CH2~ ~CHZ---CHz 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 bennoyl caprolactam, octanoyl caprolactarn, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolaetam, undecenoyl caprolactam, benzoyl valerolactam, oetanoyl vaterolactam, nonanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactant, 3,5,5-trimethylhexanayl valerolactam and mixtures thereof. .
See also U.S. Patent 4,545,784, Issued to Sanderson, October 8, 1985, which discloses acyl caprolactams, including benzoyl eaprolactam, adsorbed into sodium perborate.
If utilized, peroxygen bleaching agent will generally comprise from about 2%
to 30% by weight of the detergent compositions herein. More preferably, peroxygen bleaching agent will comprise from about 2% to 20'/e by weight of the compositions.
Most preferably, pemxygen bleaching agent will be present to the axtent of from about 3°I° to 15% by weight of the compositions herein. If utilized, bleach activators can comprise from about 2% to 10% by weight of the detergent compositions herein.

Frequently, activators are employed such that the molar ratio of bleaching agent to activator ranges from about 1;1 to 10:1, more preferably from about 1.5:1 to 5:1.
Another highly preferred optional ingredient in the detergent compositions herein is a detersive enzymes component. Enzymes can be included in the present detergent compositions for a variety of purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains from substrates, for the prevention of refugee dye transfer in fabric laundering, and for fabric restoration.
Suitable enzymes include proteases, amylases, lipases, ceIlulases, peroxidases, and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Preferred selections are influenced by factors such as pH-activity andlor stability optima, thermostability, and stability to active detergents, builders and the like. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
"Detersive enzyme", as used herein, means any enzyme having a cleaning, stain removing or otherwise beneficial effect in a laundry detergent composition.
Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases, amylases and peroxidases.
Enzymes are normally incorporated into detergent compositions at levels sufficient to provide a "cleaning-effective amount". The term "cleaning-effective amount" refers to any amount capable of producing a cleaning, stain removal, soil removal, whitening, deodorizing, or freshness improving effect on substrates such as fabrics. In practical terms for current commercial preparations, typical amounts are up to about 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the detergent composition. Stated otherwise, the compositions herein will typically comprise from 0.001% to 5%, preferably 0.01%-1% by weight of a commercial enzyme preparation. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (ALn of activity per gram of composition. Higher active levels may be desirable in highly concentrated detergent formulations.
Suitable examples of proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. lichen formis. One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH
range of 8-12, developed and sold as ESPERASE~ by Novo Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 to Novo. Other suitable proteases include ALCALASE~
and SAVINASE~ from Novo and MA,XATASE~ from International Bio-l3 Synthetics, Inc., The Netherlands; as weU as Protease A as disclosed in EP
130,756 A, January 9, 1985 and Protease B as disclosed in EP 303,761 A, April 28, 1987 and EP 130,756 A, January 9, .1985. See also a high pH protease from Bacillus sp.
NCI1VIB 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 professes include those of WO 9510591 A to Procter & Gamble . When desired, a protease having decreased 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 usable herein include both bacteria! and fungal types, preferably having a pH optimum between 5 and 10. U.S: 4,435,307, Barbesgoard et al, March 6, 1984, discloses suitable fungal ceilulases from Humicola irrsolens or Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromorras, and cellulase extracted from the hepatopancreas of a marine mollusk, Dotabella Auricula Solur~der. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CARFZYME~ and CELLUZYME~ (Novo) are especially useful. See also WO 9117243 to Novo.
Suitable lipase enzymes for detergent usage include those producad by microorganisms of the Pseudomoras group, such as Pseudomonas srrrtzeri ATCC
19.154, as disclosed in GB 1,372,034. See also lipases in Japanese Patent Application 53/20487, laid open Feb. 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade mark Lipase P "Amano,"
or "Arnano-P." Other suitable commercial lipsses include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscasum ~: lipolyticum NRRLB
3673 from Toyo Jozo Co., Tagata, Japan; Chromobckter viscasum lipases from U.S.
BiocJr~ical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pser~domo~ros gladioli. LIPOLASE~ enzyme derived from Humicala larrugiaasa and commercially available from Novo, see also EP 341,947, is a preferred lipase for use herein.
The enzyme-containing compositions herein rnay optionally also comprise from about 0.001 % to about 10'/0, preferably from about 0.005% to about 8%, most preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing system. The enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme. Such a system may be inherently provided by other formulation actives, or be added separately, e.g., by the formulator or by a manufacturer of detergent-ready enzymes. Such stabilizing systems can, for example, comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, and mixtures thereof, and are designed to address different stabilization problems depending on the type and physical form of the detergent composition.
E) Detergent Composition PreQaration The detergent compositions according to the present invention can be in liquid, paste or granular forms. Such compositions can be prepared by combining the essential and optional components in the requisite concentrations in any suitable order and by any conventional means.
Granular compositions, for example, are generally made by combining base granule ingredients (e.g. surfactants, builders, water, etc.) as a slurry, and spray drying the resulting slurry to a low level of residual moisture (5-12%). The remaining dry ingredients can be admixed in granular powder form with the spray dried granules in a rotary mixing drum and the liquid ingredients (e.g.
organic solutions of the essential cellulosic polymers, enzymes, binders and perfumes) can be sprayed onto the resulting ganules to form the finished detergent composition.
Granular compositions according to the present invention can also be in "compact form", i.e. they may have a relatively higher density than conventional granular detergents, i.e. from 550 to 950 g/1. In such case, the granular detergent compositions according to the present invention will contain a lower amount of "inorganic filler salt", compared to conventional granular detergents; typical filler salts are alkaline earth metal salts of sulphates and chlorides, typically sodium sulphate; "compact" detergents typically comprise not more than 10% filler salt.
Liquid detergent compositions can be prepared by admixing the essential and optional ingredients thereof in any desired order to provide compositions containing components in the requisite concentrations. Liquid compositions according to the present invention can also be in "compact form", in such case, the liquid detergent compositions according to the present invention will contain a lower amount of water, compared to conventional liquid detergents.
Addition of the cellulose ether component to liquid detergent compositions of this invention may be accomplished by simply mixing into the liquid dertergent aqueous solutions of the desired cellulose ethers. Cellulose ethers can alter the viscosity or other rheologica) characteristics of liquid detergent products.
It may therefore be necessary to compensate for any rheological changes in the liquid detergent product brought about by cellulose ether addition by altering the type and amount of hydrotropes and/or solvents that are used.
F) Fabric Laundering Method The present invention also provides a method for laundering fabrics in a manner which imparts fabric appearance benefits provided by the cellulosic polymers used herein. Such a method employs contacting these fabrics with an aqueous washing solution foamed from an effective amount of the detergent compositions hereinbefore described or formed from the individual components of such compositions.
Contacting of fabrics with washing solution will generally occur under conditions of agitation although the compositions of the present invention may also be used to form aqueous unagitated soaking solutions for fabric cleaning and treatment.
Agitation is preferably provided in a washing machine for good cleaning.
Washing is preferably followed by drying the wet fabric in a conventional clothes dryer. An effective amount of the liquid or granular detergent composition in the aqueous wash solution in the washing machine is preferably from about 500 to about 7000 ppm, more preferably from about 1000 to about 3000 ppm.
G) Fabric Conditio Ana The modified cellulose ethers hereinbefore described as components of the laundry detergent compositions herein may also be used to treat and condition fabrics and textiles in the absence of the surfactant and builder components of the detergent composition embodiments of this invention. Thus, for example, a fabric conditioning composition comprising only the modified cellulose ethers themselves, or comprising an aqueous solution of the modified cellulose ethers, may be added during the rinse cycle of a conventional home laundering operation in order to impart the desired fabric appearance and integrity benefits hereinbefore described.
EXAMPLES
The following examples illustrate the compositions and methods of the present invention, but are not necessarily meant to limit or otherwise define the scope of the invention.

EXAMPLE I
Liauid Detergent Test Composition Preparation Several heavy duty liquid detergent compositions are prepared containing various modified ceDulosic polymers. Such liquid detergent compositions all have the following basic formula:
Table A
Component Wt. /u C 12-15 ~kYl ether {2.5) sulfate 3 g C 12 glucose amide ~ 6. 86 Citric Acid 4.75 C12-14 Fatty Acid 2.00 Enzymes 1.02 MEA 1.0 Propanediol 0.36 Borax 6.58 Dispersant 1.48 Na Toluene Sulfonate 6.25 Modified Celluiosic Polymer (if present) 2.0 Dye, Perfume, Brighteners, Preservatives, B lanc Suds Suppressor, Other Minors, Water 100%

EXAMPLE II
Granular Detergent Test Composition Preparation Several heavy duty granular detergent compositions are prepared containing various modified cellulosic polymers. Such granular detergent compositions all have the following basic formula:
Table B
Component Wt.

C 12 Linear alkyl benzene sulfonate 9.31 C 14- I 5 alkyl ether (0.3 5 EO) sulfate I 2.

Zeolite Builder 27.79 Sodium Carbonate 27.31 PEG 4000 1.60 Dispersant 2.26 C12-I3 ~~ohol Ethoxylate (9 EO) 1.5 Sodium Perborate 1.03 Soil Release Polymer 0.41 Enzymes 0.59 Modified Cellulosic Polymer (if present) 2.5 Perfume, Brightener, Suds Suppressor, Other Bal Minors, Moisture, nc Sulfate 100%
EXAMPLE IlI
Cellulosic Polymers Used in Test 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 various substituents listed are those from Structural Formulas Nos. I, Ii and III
described hereinbefore.

T le C
Cellulosic Polymers Used in Test Deter ent Compositions Polymer m Polymer DescriptionA B ~ D

Polymer TradenamePolysurf LK-400 CMC Modified LK-400 (D72) Polymer ManufacturerHercules Union CarbidePenn Union Carbide Carbose Polymer Type Nonionic Cationic AnionicCationic Molecular Weight700-750M -..400I~I ~30pM ,"400M

Structure No. I II ~ III II
' R Cetyl H CH2C00 H

(C 16) A

Amount of Ring Alkyl Substitution 0.4%' 0 0 0 0.6%

Degree of Ring Carboxymethyl - ' 0.5 -Substitution R1 H _ _ R2 - -CH2CH(OH)CH2-- -CH2CH(OH)CH2-R3 _ -CH3 - -CH3 R4 _ -CH3 _ -CH3 RS _ -CH3 _ -CH3 R6 - H _ H

Y - --0.1 - -0.006 Z _ Cl- , C1_ A - - Na -Test compositions prepared as described in Examples I and II are evaluated for the effects that the various cellulosic polymers of Example III provide when samples of fabrics or garments are washed using the test compositions as described, all under identical conditions. A control sample with no polymer is usually compared to one composition with a test polymer to be evaluated. Testing conditions are also carefully monitored. Examples of controlled conditions include: wash time, wash water temperature and hardness; washer agitation; rinse time, rinse water temperature and hardness; dryer time and temperature; wash load fiber content and weight.
EXAMPLE IV
Overall t~ppearance In an Overall Appearance test, fabrics are washed using various test compositions containing either no cellulosic polymers or one of the Example III cellulosic polymers. The fabrics so washed after ten cycles are then comparatively graded by three judges who evaluate the overall appearance of the washed fabrics. It is the decision of the judge as to what is to be evaluated unless specific direction is given to evaluate one attribute such as color, pilling, fuu, etc.
In the Overall Appearance test, the visual preference of the judge is expressed using the Scheff scale.
That is: 0 ø No difference 1 = I think this one is better (unsure).
2 = I know this one is a little better.
3 = I know this one is a lot better.
4 = I know this one is a whole lot better.
For the Overall Appearsnce test, laundering conditions are as follows:
Washer Type: Katcnofe ( 17 gallons) Wash Time: 12 min Wash Tempecatura: 90°F (32.2°C) Wash Water Hardness: 6 grains per gallon Washer Agitation: normal Rinse Time: 2 min Rinse Tanperatura: 60°F ( 15.6°C) Rinse Water Hardness: 6 grains per gallon I Wash Load Fabric Content: various colored and white garments and fabrics Wash Load Weight: 5.5 Ibs (2.5 kg) The average overall appearance test results are shown in Tables D and E.

Table D
Overall Appearance Test Results Liauid Test Composition ID Poivmer Tested Overall Appearance Grade Control None A Polysurf 67 1.5 1.8 C CMC (D72) 1.0 Modified LK-400 1.2 Ta le E
Overall Appearance Test Results Granular Test CompositionPolymer Tested Overall A

ppearance Grade Control None 0 A Polysurf 6? 1.4 LK-400 1.0 C CMC (D72) 1.0 D Modified LK-400 1.1 EXAMPLE V
Pill Reduction In a Pill Reduction test, fabrics are washed using the various test compositions containing either no cellulosic polymers or one of the Example III cellulosic polymers. The fabrics so washed are then graded for Pill Reduction using a computer-assisted pilling image analysis system which employs image analysis to measure the number of pills on tested garments and fabrics. Pill reduction is calculated as:
Pill reduction(%) _ { [# pills (control) - # pills (polymers)] / # pills (control) } z 1fl0%

For the Pill Reduction test, laundering conditions are the same as used for the Overall Appearance test described hereinbefore in ExampleIV.
The average % Pill Reduction test results are shown in Tables F and G.
Ta I F
Pill Reduction Test Results i uids Liauid Test Composition ID Polymer Tested PilUFuzz Reduction ((%1 Control None 0 A Polysurf 67 2 i .5 LK-400 42.4 C CMC(D72) 26.8 Modified LK-400 25.9 Table G
Pill Reduction Test Results Granular Granular Test Composition Polymer Tested Pill/Fuzz Reduction (%1 ID
Control None A Polysurf 67 33.3 LK-400 51.6 C CMC{D72) 7.6 Modified LK-400 16.6 EXAMPLE VI
Color Protection In a Color Protection test, fabrics are washed using various test compositions containing either no cellulosic polymers or one of the Example III cellulosic polymers. The fabrics so washed are then tested with a Hunter colorimeter in order to determine a Delta E* value for each fabric tested. Delta E* is defined as the color difference (reflectance intensity, hue shift, etc.) between washed fabrics and unwashed fabrics.
For the Color Protection test, laundering conditions are the same as used for the Overall Appearance test described hereinbefore in Example IV.
The extent of Color Protection provided is based on percent of Delta E*
difference compared to an unwashed sample. Color protection is calculated as:
~/° Color Protection = { [dE*(control) - dE*(polymers)] / dE*(control) } a 100%
The average color protection test results are shown in Tables H and I.
Table H
Color Protection Test Results - Liquids Liquid Test Composition ID Polymer Tested Color Protection (%) Control None p A Polysurf 67 24.2 LK-400 36.5 C CMC (D72) 26.6 D Modified LK-400 27.2 Ta 1 I

Col9r Protection Test~.~ular Resulrs Granular Test Comp sition Polymer TestedColor Protection (%1 m Control None 0 Polysurf 67 33.9 LK-400 39.2 C CMC (D72) 15.5 Modified LK-400 24.7

Claims (5)

Claims:

1. A built, heavy duty laundry detergent composition in liquid or granular form which imparts fabric appearance benefits selected from pill/fuzz reduction, antifading, improved abrasion resistance and enhanced softness to fabrics and textiles laundered in aqueous washing solutions formed therefrom, which composition is characterized by:
A) from 1% to 80% by weight of a detersive surfactant;
B) from 1% to 80% by weight of an organic or inorganic detergency builder;
C) from 0.1% to 8% by weight of a modified cellulose ether fabric treatment agent selected from:
hydrophobically-modified, nonionic cellulose ethers which have a molecular weight of from 10,000 to 2,000,000 and which have repeating substituted anhydroglucose units corresponding to the general formula:
wherein:
R is independently selected from the group consisting of H and C8-C24 alkyl with alkyl substitution of the anhydroglucose rings ranging in an amount of from 0.1% to 5% by weight of the cellulose ether material;
R1 is H or methyl; and x ranges from 1 to 20.

2. A composition according to Claim 1 wherein A) the composition comprises of from 5% to 50% by weight of the detersive surfactant selected from anionic and nonionic surfactant materials B) the composition comprises from 10% to 50% by weight of the detergency builder selected from carboxylates, silicates, aluminosilicates, carbonates, borates and combinations thereof; and C) the composition comprises from 0.5% to 4% by weight of modified cellulose ether fabric treatment agent having a molecular weight ranging from 10,000 to 1,000,000.

3. A composition according to Claim 2 wherein the modified cellulose ether fabric treatment agent is a hydrophobically-modifed, nonionic material corresponding to Structural Formula No. 1 wherein a) R is independently selected from the group consisting of H and C8 to C16 alkyl;
b) R substitution of the anhydroglucose rings ranges from 0.2% to 2% by weight of the cellulose other;
c) R1 is H; and d) x ranges from 1 to 10.

4. A composition according to Claim 1 in liquid form which is characterized by:

a) from 5% to 50% by weight of a detersive surfactant selected from i) sodium, potassium and ammonium alkylsulfates wherein the alkyl group contains from 8 to 18 carbon atoms;
ii) sodium, potassium and ammonium alkylpolyethoxylate sulfates wherein the alkyl group contains from 10 to 22 carbon atoms and the polyethoxylate chain contains from 1 to 15 ethylene oxide moieties;
iii) polyhydroxy fatty acid amides of the formula wherein R is a C9-17 alkyl or alkenyl and Z is glycityl derived from a reduced sugar or alkoxylated derivatives thereof;
iv) alcohol ethoxylates of the formula R1 (OC2H4)n OH wherein R1 is a C10-C16 alkyl group or a C8-C12 alkyl phenyl group and n is from 3 to 80; and v) combinations of these surfactants; and b) from 1% to 10% by weight of a detergent builder component selected from carboxylate and polycarboxylate builders.

5. A composition according to Claim 1 in granular form which is characterized by:
a) from 5% to 50% by weight of a detersive surfactant selected from i) sodium and potassium alkylpolyethoxylate sulfates wherein the alkyl group contains from 10 to 22 carbon atoms and the polyethoxylate chain contains from 1 to 15 ethylene oxide moieties;
ii) sodium and potassium C9 to C15 alkyl benzene sulfonates;
iii) sodium and potassium C8 to C18 alkyl sulfates;
iv) polyhydroxy fatty acid amides of the formula wherein R is a C9-17 alkyl or alkenyl and Z is glycityl derived from a reduced sugar or alkoxylated derivatives thereof; and v) combinations of these surfactants; and b) from 1% to 50% by weight of a detergent builder selected from sodium carbonate, silicates, crystalline layered silicates, aluminosilicates, oxydisuccinates and citrates.