CN1239503A - Method of washing fabrics using detergent compsn. comprising terpolymer - Google Patents

Abstract

The present invention is directed to a method of washing fabrics, comprising using a laundry detergent composition comprising a detersive surfactant and a terpolymer; wherein the terpolymer comprises at least a first monomeric unit comprising a weak acid function, a second monomeric unit comprising a strong acid function, and a third monomeric unit comprising a nonionic function.

Description

Method of laundering fabrics with detergent compositions containing terpolymers

Background

Detergent formulators are often faced with the task of designing products to remove a wide variety of soils and stains from fabrics. The soils and stains are generated by the use of the fabric prior to washing. However, many fabrics become soiled when laundered due to the laundering environment. For example, certain fabrics, especially white cotton fabrics, turn yellow after repeated washings. Therefore, detergent formulators are faced with the additional task of not only removing existing stains, but also preventing further contamination from the wash environment.

Based on the above, there isa need for a method of washing fabrics which inhibits yellowing due to repeated washing, thereby maintaining fabric whiteness.

Summary of The Invention

The present invention relates to a method of laundering fabrics comprising the use of a laundry detergent composition comprising a detergent surfactant and a terpolymer, wherein the terpolymer comprises at least one first monomer unit comprising a weak acid functional group, a second monomer unit comprising a strong acid functional group and a third monomer unit comprising a nonionic functional group.

The method meets the requirements of a method of washing fabrics to prevent yellowing and/or maintain fabric whiteness even after repeated washing.

These and other features, aspects, and advantages of the present invention will become apparent to those skilled in the art from a reading of the present disclosure and the appended claims.

Detailed Description

The following are definitions of terms used herein.

"alkyl" means a carbon-containing chain, preferably about C₁-about C₁₀More preferably about C₁-about C₆Still more preferably about C₁-about C₄(ii) a It may be linear, branched or cyclic, preferably linear or branched, more preferably linear; substituted (mono-or poly-) or unsubstituted; and saturated.

"aralkyl" means R '-R "-, where R' is aryl and R" is alkyl.

"aryl" refers to an aromatic group; substituted (mono-or poly-) or unsubstituted, preferably unsubstituted. Preferred aryl groups are phenyl, pyridyl, pyrimidyl and naphthyl; more preferably phenyl.

By "comprising" is meant that other steps and other components that do not affect the end result can be added. The term includes the terms "consisting of …" and "consisting essentially of …".

"cycloalkyl" refers to a cyclic alkyl group (i.e., having one or more closed rings).

"terpolymer" refers to a polymer formed from three or more monomers.

"HMI" refers to heavy metal ions, for purposes of discussion herein, including Fe⁺²、Fe⁺³、Mn⁺²、Mn⁺³、Mn⁺⁴、Cu⁺¹、Cu⁺²、Zn⁺²And Pb⁺²And their oxide and hydroxide salts.

"nonionic functional monomer" refers to a monomer unit that has no ionic charge when placed in an acidic, basic, or neutral solution.

"Strong acid functional monomer" refers to a monomer unit that contains one or more functional groups that completely dissociate in water. For example

"Weak acid functional monomer" refers to a monomeric unit that contains one or more functional groups that only partially dissociate in water. For example:

all percentages are by weight of the total composition, unless otherwise indicated.

All ratios are weight ratios unless otherwise indicated.

Unless otherwise indicated, all ppm (parts per million) refer to the amount in the final detergent composition.

All temperatures are in degrees Celsius (. degree. C.) unless otherwise noted.

The present invention relates to a method of laundering fabrics comprising the use of a detergent composition comprisinga detergent surfactant and a terpolymer, wherein the terpolymer comprises at least one first monomer unit comprising a weak acid functional group, a second monomer unit comprising a strong acid functional group and a third monomer unit comprising a nonionic functional group.

In investigating why certain fabrics lose whiteness (e.g., yellowing) after several washes, we believe, while not intending to be limited by theory, that we have identified the cause of the loss of whiteness and a method of addressing this previously unidentified cause. We have surprisingly found that fabrics exposed to wash or rinse water containing HMI have a significantly increased tendency to lose their whiteness and/or yellowing over time. Also, while not intending to be limited by theory, we believe that this is due to HMI sticking to the fabric. However, we have also found that yellowing typically occurs when HMI is present in the rinse water rather than the wash water. Thus, there is a need to identify substances that remain on fabrics (i.e., have fabric affinity, hereinafter "fabric substantivity") after the wash cycle, and thus, act during the rinse cycle. Unfortunately, many of the tested products did not have fabric substantivity and thus could not be applied to HMI during the rinse cycle. It is known that the pH during rinsing is generally lower compared to the washing process. While not intending to be bound by theory, it is believed that the decrease in pH changes and/or reduces fabric substantivity. We have found that the terpolymers used in the compositions of the invention have a surprising substantivity to fabrics during washing and rinsing despite a decrease in pH from wash to rinse. As a result, we have found that these terpolymers are surprisingly effective in maintaining whiteness and/or preventing yellowing of fabrics washed/rinsed in HMI-containing water.

The aspects and embodiments of the invention described herein have a number of surprising advantages, including maintaining whiteness and/or preventing fabric yellowing even after repeated washings. While not intending to be limited by theory, it is believed that the terpolymers used in the present invention sequester HMI in wash and/or rinse water. Chelation is achieved by binding of the polymer and/or chelating agent to HMI through ion-ion interactions, the complex formed remaining soluble in aqueous solution. We also believe that the terpolymer may be formed by reaction of a salt (e.g., Fe (OH)) in HMI₃) The HMI is "wrapped" around with the terpolymer to disperse the HMI, thereby preventing insoluble HMI salts from adhering to the fabric.

An additional effect of the composition used in the method of the present invention is to prevent the bleaching agent from being decomposed by HMI in the wash water. A common problem in bleach-containing detergent compositions is that the bleach is decomposed by the HMI in the wash and/or rinse water. Thus, chelating agents are added to the detergent composition containing the bleaching agent to prevent the bleaching agent from being decomposed by HMI. The use of terpolymers in the compositions of the present invention may additionally prevent or reduce bleach decomposition due to the chelating effect of the terpolymer, which may, therefore, reduce or eliminate the need to incorporate additional "bleach-protecting" chelants into the detergent composition.

Another possible effect of the process of the present invention is to prevent surface fouling caused by e.g. carbonates, silicates and/or orthophosphates typically present in detergent compositions. In hard water, this carbonate form, such as calcium carbonate, leaves the fabric with a hard or harsh feel when deposited on the fabric. The terpolymer used in the composition of the present invention can prevent the calcium carbonate from settling by dispersing the calcium carbonate.

Another possible effect for the process of the invention is improved physical properties. For example, if the detergent composition is in the form of a granular detergent, the terpolymer provides additional benefits where the composition has improved free-flowing properties. This free-flowing property in turn improves the processability during manufacture and packaging of the detergent composition. Previously known detergent compositions (i.e. products not containing the terpolymer of the invention) can become difficult during processing of the detergent particles, including agglomeration, caking or sticking, which can lead to process line plugging. However, the terpolymers used in the compositions of the present invention are in powder form and thus contribute to the free flow of the overall detergent composition in the process line by preventing or reducing agglomeration, caking or adhesion of the detergent particles.

The laundry detergent composition used in the process of the present invention may be in any suitable form, for example a high density liquid, light liquid or other pourable form, a granule, a laundry bar, a gel or a paste. The terpolymers of the present invention may be formulated into any detergent base chosen by the formulator.

The present invention is described in more detail below. Terpolymer and process for preparing the same

A terpolymer for use in detergent compositions contains a first monomer unit, a second monomer unit, and a third monomer unit. In addition to the three, other monomer units may optionally constitute the terpolymer, so long as these additional monomers do not significantly affect the whiteness maintenance and/or the prevention of yellowing properties imparted by the first, second, and third monomer units.

The detergent composition preferably contains at least about 0.2% terpolymer.

Theterpolymer preferably has a molecular weight of from about 500 to about 36000 daltons, more preferably from about 1000 to about 20000 daltons, still more preferably from about 3000 to about 6000 daltons.

The ratio of the first monomer unit to the second monomer unit to the third monomer unit in the terpolymer is preferably from about 3: 2: 1 to about 8: 6: 5, more preferably from about 4: 3 to about 8: 1, still more preferably from about 5: 3: 2 to about 6: 2.

Examples of terpolymers for use in the present invention and the synthesis of the terpolymers include those described in US4711725, issued 12, 8, 1987. a. First monomer unit

The first monomer unit contains a weak acid functional group. The first monomer unit preferably contains a carboxylic acid functional group. More preferably, the first monomer unit has the following structure:R¹is H or CH₃Preferably H. R²⁰Is H or C (O) -OX. X is independently H, a metal cation or N- (R)²)₄Wherein R is²Is H, C₁-C₄Hydroxyalkyl or mixtures thereof, preferably X is H or Na⁺More preferably, X is Na⁺。

More preferably, the first monomer unit has the following structure:R⁷independently is H or-COO^-Z⁺Preferably H. Z⁺Independently is H or Na, preferably Na (i.e. -COO)^-Na⁺). b. Second monomer unit

The second monomer unit contains a strong acid functional group. The second monomer unit preferably contains a sulfonic acid functional group. More preferably, the second monomer unit has the following structure:

R³is H or CH₃Preferably H. R⁴Is H or C₁-C₄Alkyl, preferably H or CH₃More preferably CH₃。R⁵Is C₁-C₈Alkyl or C₁-C₈Aralkyl, preferably C₁-C₄More preferably C₁Still more preferred are alkyl groups. Y is H, a metal cation or N- (R)²¹)₄Preferably X is H or Na⁺More preferably, X is Na⁺。R²¹Is H, C₁-C₄Hydroxyalkyl or mixtures thereof.

The second monomer unit preferably has the following structure:R⁸independently is H or-COOH^-Na⁺Preferably H. R⁹Is that

W⁺Independently H or Na, preferably Na. p is 1 to about 6, preferably about 1 to about 4, more preferably 1. R¹⁰Is H or C₁-C₄Alkyl, preferably H or CH₃More preferably CH₃. c. A third monomer unit

The third monomer unit contains a nonionic functional group. The third monomer unit is preferably a vinyl ester, vinyl acetate or substituted acrylamide, more preferably a methyl-substituted acrylamide:

the vinyl esters preferably have the following structure:R¹¹is H or CH₃Preferably H. R¹²Is C₁-C₆Alkyl radical, C₆-C₁₀Aryl radical, C₆-C₁₀Aralkyl orPreferably C₁-C₆Alkyl radical, C₆Aryl or

More preferably C₁-C₄An alkyl group. R¹³Is H or CH₃Preferably H. R¹⁴Is H or C₁-C₆Alkyl, preferably H. n is an integer from 1 to about 3, preferably 1.

Vinyl acetate preferably has the following structure:

the substituted acrylamide preferably has the following structure:

R¹⁵is H or CH₃Preferably H. R¹⁶And R¹⁷Independently is H, C₁-C₈Alkyl radical, C₆-C₈Cycloalkyl, benzyl or a group as defined above, such that R¹⁸And R¹⁹Not simultaneously H:

more preferably, the third monomer unit has the following structure:R¹¹independently of each other is H, -COO^-H⁺or-COO^-Na⁺Preferably H. R¹²Is thatq is independently 0 to 6, preferably about 0 to about 3, more preferably 1. R¹³And R¹⁴Independently is- (CH)₂)_mCH₃Or H. m is 0 to about 6, preferably about 0 to about 3, more preferably 0. Detergent surfactant

The detergent composition also contains a detergent surfactant. The detergent composition preferably contains at least about 0.01%, preferably at least about 0.1%, more preferably at least about 1%, still more preferably from about 1% to about 55% of a detergent surfactant.

Preferred detergent surfactants are cationic, anionic, nonionic, amphoteric, zwitterionic surfactants and mixtures thereof as further described below. Non-limiting examples of detergent surfactants useful in the detergent compositions of the present invention include conventional C₁₁-C₁₈Alkyl benzene sulfonates ("LAS") and primary, branched and random C₁₀-C₂₀Alkyl sulfate ('AS'), formula CH₃(CH₂)_x(CHOSO₃ ^-M⁺)CH₃And CH₃(CH₂)_y(CHOSO₃ ^-M⁺)CH₂CH₃C of (A)₁₀-C₁₈Secondary (2,3) alkyl sulfates wherein x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium,Unsaturated sulfates such as oleyl sulfate, C₁₀-C₁₈Alkyl alkoxy sulfates (' AE)_xS "; in particular EO1-7 ethoxy sulfate), C₁₀-C₁₈Alkylalkoxycarboxylates (in particular EO 1-5-ethoxycarboxylate)Acid salt), C₁₀-C₁₈Glyceryl ether, C₁₀-C₁₈Alkyl polyglycosides and their corresponding sulfated polyglycosides, and C₁₂-C₁₈α -sulfonated fatty acid esters if desired, conventional nonionic and amphoteric surfactants, such as C including the so-called narrow peak alkyl ethoxylates, may also be included in the overall composition₁₂-C₁₈Alkyl ethoxylates ("AE") and C₆-C₁₂Alkylphenol alkoxylates (in particular ethoxylates and mixed ethoxy/propoxylates), C₁₂-C₁₈Betaines and sulfobetaines, C₁₀-C₁₈Amine oxides, and the like. It is also possible to use C₁₀-C₁₈N-alkyl polyhydroxy fatty acid amides. Typical examples include C₁₂-C₁₈N-methylglucamide. See WO 9206154. Other sugar-derived surfactants include N-alkoxy polyhydroxy fatty acid amides, such as C₁₀-C₁₈N- (3-methoxypropyl) glucamide. N-propyl to N-hexyl C₁₂-C₁₈Glucamides are useful in low foam applications. Conventional C mayalso be used₁₀-C₂₀Soap. If high foam is desired, a branched chain C may be used₁₀-C₁₆Soap. Mixtures of anionic and nonionic surfactants are particularly useful. Other commonly used surfactants are listed in standard textbooks. Adjunct detergent composition Components

The detergent compositions of the present invention may optionally contain other known detergent ingredients including alkoxylated polycarboxylates, bleaching compounds, brighteners, chelants, clay soil removal/anti-redeposition agents, dye transfer inhibitors, enzymes, enzyme stabilizing systems, fabric softeners, polymeric soil release agents, polymeric dispersants, suds suppressors. The detergent composition may also contain other components including carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions. a. Alkoxylated polycarboxylates

Alkoxylated polycarboxylates, such as those prepared from polyacrylates, are suitable for use herein to provide additional grease removal properties. These substances are described on page 4 and below of WO91/08281 and PCT 90/01815. Chemically, these materials include polyacrylates having an ethoxy side chain for every 7-8 acrylate units. The side chain has the formula- (CH)₂CH₂O)_m(CH₂)_nCH₃Wherein m is 2 to 3 and n is 6 to 12. The side chains are attached to the polyacrylate "backbone" with ester linkages to provide a "comb" polymer type structure. The molecular weight can vary, but is generally in the range of from about 2000 to about 50000. The compositions of the present invention may contain from about 0.05% to about 10% of the alkoxylated polycarboxylate.b. Bleaching compounds-bleaches and bleach activators

The detergent compositions of the present invention may optionally contain a bleaching agent or a bleaching composition comprising a bleaching agent and one or more bleach activators. If present, especially for fabric laundering, the bleaching agent is generally present at levels of from about 1% to about 30%, more usually from about 5% to about 20% of the detergent composition. If present, the amount of bleach activator is typically from about 0.1% to about 60%, more typically from about 0.5% to about 40% of the bleaching composition comprising bleach and bleach activator.

The bleaching agent used in the present invention may be any bleaching agent useful for detergent compositions in fabric washing, hard surface cleaning or other known or to be known laundry applications. These include oxygen bleaches as well as other bleaching agents. Perborate bleaches such as sodium perborate (e.g., mono-or tetrahydrate) may be used in the present invention.

Another class of bleaching agents that may be used without limitation includes percarboxylic acid bleaching agents and salts thereof. Suitable examples of such bleaching agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid, and diperoxydodecanedioic acid. Such bleaches are disclosed in U.S. patent application 4483781 to Hartman, issued on 20.11.1984, european patent application 0133354 to Banks, published on 2.20.2.8978, U.S. patent application 740446,1985, issued on 3.6.1985, and US4412934 to Chung, et al, issued on 1.11.1983. Highly preferred bleaching agents also include 6-nonanamido-6-oxoperoxyhexanoic acid, which has been described in US4634551 to Burns et al, issued on 6.1.1987.

Peroxygen bleaches may also be used. Suitable peroxy bleach compounds include sodium carbonate peroxyhydrate and corresponding "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide. Persulfate bleach (e.g., OXONE, commercially produced by DuPont) may alsobe used.

Preferred percarbonate bleach compositions comprise dry particles having an average particle diameter in the range of from about 500 microns to about 1000 microns, wherein no more than about 10% of said particles are smaller than about 200 microns and no more than about 10% of said particles are larger than about 1250 microns. The percarbonate may optionally be coated with a silicate, borate or water soluble surfactant. Percarbonates are available from various commercial sources, such as FMC, Solvay, and Tokai Denka.

Mixtures of bleaching agents may also be used.

Peroxygen bleaches, perborates, percarbonates, and the like are preferably combined with bleach activators which form in situ aqueous peroxyacid solutions corresponding to the bleach activators (i.e., during the wash). Various non-limiting examples of activators are disclosed in US4915854 and US4412934 to Mao et al, issued 4, 10, 1990. Nonoyl Oxybenzenesulfonate (NOBS) and Tetraacetylethylenediamine (TAED) activators are typical, and mixtures thereof may also be used. Other typical bleaches and activators for use in the present invention are described in US 4634551.

Highly preferred amido-derived bleach activators are those having the formula:

R¹N(R⁵)C(O)R²c (O) L or R¹C(O)N(R⁵)R²C (O) L wherein R¹Is an alkyl group containing from about 6 to about 12 carbon atoms, R²Is an alkylene radical having from 1 to about 6 carbon atoms, R⁵Is H or an alkyl, aryl or alkyl radical containing from about 1 to about 10 carbon atomsAlkylaryl, and L is any suitable leaving group. A leaving group is any group displaced from the bleach activator upon nucleophilic attack of the bleach activator by the perhydrolytic anion. A preferred leaving group is phenylsulfonate.

Preferred examples of bleach activators having the above formula include (6-octanoylamino-hexanoyl) oxybenzene-sulfonate, (6-nonanoylamino hexanoyl) oxybenzene-sulfonate, (6-decanoylamino-hexanoyl) oxybenzene-sulfonate and mixtures thereof, as described in US 4634551.

Another class of bleach activators includes the benzoxazine-type activators disclosed in US4966723 to Hodge et al, issued 10.30.1990. Highly preferred benzoxazine type activators are:

another preferred bleach activator comprises acyl lactam activators, particularly acyl caprolactams and acyl valerolactams of the formula,

wherein R is⁶Is H or an alkyl, aryl, alkoxyaryl or alkylaryl group containing from 1 to about 12 carbon atoms. Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5, 5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5, 5-trimethylhexanoyl valerolactam and mixtures thereof. See also US4545784 to Sanderson, issued on 8.10.1985, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.

Other bleaching agents besides oxygen bleaching agents are also known in the art and may be used in the present invention. One non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as sulfonated zinc and/or aluminum phthalocyanines. See US4033718 to Holcombe et al, issued 7/5 in 1977. If used, detergent compositions typically contain from about 0.025% to about 1.25% by weight of such bleaching agents, especially sulfonated zinc phthalocyanines.

If desired, the bleaching compound may be catalyzed with a manganese compound. Such compounds are known in the art and include, for example, manganese-based catalysts as disclosed in US5246621, US5244594, US5194416, US5114606, and european patent applications nos. 549271a1, 549272a1, 544440a2 and 544490a 1. Preferred examples of such catalysts include Mn^IV ₂(u-O)₃(1,4, 7-trimethyl-1, 4, 7-triazacyclononane)₂(PF₆)₂、Mn^III ₂(u-O)₁(u-OAc)₂(1,4, 7-trimethyl-1, 4, 7-triazacyclononane)₂(ClO₄)₂、Mn^IV ₄(u-O)₆(1,4, 7-triazacyclononane)₄(ClO₄)₄、Mn^IIIMn^IV ₄(u-O)₁(u-OAc)₂(1,4, 7-trimethyl-1, 4, 7-triazacyclononane)₂(ClO₄)₃、Mn^IV(1,4, 7-trimethyl-1, 4, 7-triazacyclononane) - (OCH₃)₃(PF₆) And mixtures thereof. Other metal-based bleach catalysts include those disclosed in US4430243 and US 5114611. The use of magnesium and various complexing ligands to enhance bleaching performance is also reported in the following US4728455, 5284944, 5246612, 5256779, 5280117, 5274147, 5153161 and 5227084.

In practice, and not by way of limitation, the compositions and methods of the present invention can be modified to provide active bleach catalyst species in at least one part per million in the aqueous wash liquor, and preferably from about 0.1ppm to about 700ppm, more preferably from about 1ppm to about 500ppm, of catalyst species in the wash liquor. c. Whitening agent

Any fluorescent whitening agent or other whitening agent known in the art can generally be incorporated into the detergent compositions of the present invention at levels of from about 0.05% to about 1.2% by weight. Commercially available optical brighteners which may be used in the present invention may be classified into groups which include, but are not necessarily limited to, stilbene derivatives, pyrazolines, coumarins, carboxylic acids, methicenes, dibenzothiophene-5, 5-dioxides, pyrroles, derivatives of 5-and 6-membered heterocycles, and other heterochromes. Examples of these brighteners are disclosed in "production and use of fluorescent whitening agents", m.zahradnik, published by John Wiley&Sons, New York (1982).

Specific examples of optical brighteners used in the compositions of the present invention are the same as disclosed in US4790856 to Wixon, issued 12.13.1988. These brighteners include Verona's PHORWHITE brightener family. Other whitening agents disclosed in this reference include: tinopal UNPA, Tinopal CBS and Tinopal 5BM available from Ciba-Geigy; artic White CC and Artic WhitecWD available from Hilton-Davis, Italy; 2- (4-styrylphenyl) -2H-naphtho [1,2-d]triazole; 4, 4' -bis (1,2, 3-triazol-2-yl) stilbene; 4, 4' -bisstyrylbiphenyl and aminocoumarin. Specific examples of these whitening agents include: 4-methyl-7-diethylaminocoumarin; 1, 2-bis (benzimidazol-2-yl) ethylene; 1, 3-diphenylpyrazoline; 2, 5-bis (benzoxazol-2-yl) thiophene; 2-styryl-naphtho [1,2-d]oxazole and 2- (stilben-4-yl) -2H-naphtho [1,2-d]triazole. See also Hamilton, US3646015, issued 2, 29, 1972. Anionic brighteners are preferred for use in the present invention.

d. Builder

Detergent builders may optionally be included in the compositions to help control mineral hardness. Inorganic and organic builders can be used. Builders are commonly used in fabric washing compositions to aid in the removal of particulate soils.

The level of builder can vary widely depending on the end use of the composition and its desired physical form. If present, the compositions typically contain at least about 1% builder. Liquid formulations typically contain from about 5% to about 50%, more typically from about 5% to about 30%, by weight of detergent builder. Granular formulations typically contain from about 10% to about 80%, more typically from about 15% to about 50% by weight of detergent builder. However, this is not meant to exclude lower or higher levels of builder.

Inorganic or phosphorus-containing detergent builders include, but are not limited to, alkali metal, ammonium and alkanolammonium salts of polyphosphates (particularly tripolyphosphates, pyrophosphates, and glassy polymeric metaphosphates), phosphonates, phytates, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates, and aluminosilicates. However, non-phosphate builders are required in certain areas. Importantly, the compositions of the present invention surprisingly function well even in the presence of so-called "weak" builders (as compared to phosphates), such as citrate, or in so-called "under-building" conditions which may occur when zeolite or layered silicate builders are used.

Examples of silicate builders are alkali metal silicates, especially those of SiO₂∶Na₂Silicates and layered silicates with an O ratio of 1.6: 1 to 3.2: 1, such as the layered sodium silicate described in US4664839 to h.p. rieck, issued 5.12.1987. NaSKS-6 is a trademark of crystalline layered silicate supplied by Hoechst (both abbreviated herein as "SKS-6"). Unlike zeolite builders, the NaSKS-6 silicate builder is free of aluminum. NaSKS-6. delta. -Na with layered silicate₂SiO₅It may be prepared, for example, by the processes described in DE-A-3417649 and DE-A-3742043. SKS-6 is a highly preferred layered silicate for use in the present invention, but other such layered silicates, such as those having the general formula NaMSi, can also be used_xO_2x＋1·yH₂O, where M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0, other various layered silicates from Hoechst include NaSKS-5, NaSKS-7, and NaSKS-11 in α, β, and γ forms, respectively, as described above, δ -Na₂SiO₅(SKS-6 form) is most preferred for use in the present invention. Other silicates are also useful, such as magnesium silicate, which can be used as a crispening agent in granular formulations, as a stabilizer for oxygen bleaches, and as a component in foam control systems.

Examples of carbonate builders are the alkaline earth and alkali metal carbonates described in german patent application No2321001 published in 1973 at 11/15.

Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are very important in the recently marketed heavy-duty granular detergent compositions, and also as an important builder component in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula:

M_z(zAlO₂)_y]xH₂o wherein z and y are integers of at least 6, the molar ratio of z to y is from 1.0 to about 0.5, and x is an integer of from about 15 to 264.

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates may be crystalline or amorphous in structure, and may be naturally occurring aluminosilicates or synthetic. US3985669 to Krummel et al, issued 12/12 in 1976, describes a process for producing aluminosilicate ion exchange materials. Preferred synthetic crystalline aluminosilicate ion exchange materials for use in the present invention are available under the designations zeolite a, zeolite p (b), zeolite MAP and zeolite X. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:

Na₁₂[(AlO₂)₁₂(SiO₂)₁₂]xH₂o, wherein x is from about 20 to about 30, especially about 27. This material is known as zeolite a. Dehydrated zeolites (x ═ 0 to 10) can be used in the present invention. The particle size of the aluminosilicate is preferably from about 0.1 to 10 microns in diameter.

Organic detergent builders suitable for use in the present invention include, but are not limited to, various polycarboxylate compounds. "polycarboxylate" as used in the present invention refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylate groups. Polycarboxylate builders are typically added to the compositions in acidic form, but can also be added in the form of neutralizing salts. When used in the form of a salt, salts of alkali metals such as sodium, potassium and lithium, or alkanolammonium salts are preferred.

Polycarboxylate builders include a variety of useful classes of materials. One important class of polycarboxylate builders includes the ether polycarboxylate builders, including oxydisuccinates, see Berg, US3128287, issued 4-7, 1964, and Lamberti, et al, US3635830, issued 1-18, 1972. See also US4633071 to Bush et al, TMS/TDS builder issued 5/5 1987. Suitable ether polycarboxylates also include cyclic compounds, especially alicyclic compounds such as those described in US3923679, 3835163, 4158635, 4120874 and 4102903.

Other useful detergent builders include ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3, 5-trihydroxybenzene-2, 4, 6-trisulfonic acid; and carboxymethyl oxydisuccinic acid; various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid; and polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3, 5-tricarboxylic acid, carboxymethyl oxydisuccinic acid, and soluble salts thereof.

Citrate builders, such as citric acid and its soluble salts (especially the sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and biodegradability. Citrate salts may also be used in granular compositions, particularly in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also particularly useful in such compositions and mixtures.

3, 3-dicarboxy-4-oxa-1, 6-adipates and related compounds disclosed in US4566984 to Bush, published as monthly 28, 1986 are also suitable for use in the detergent compositions of the present invention. Useful succinic acid builders include C₅-C₂₀Alkyl and alkenyl succinic acids and salts thereof. A particularly preferred such compound is dodecenylsuccinic acid. Specific examples of succinate builders include: lauryl succinic acid, tetradecyl succinic acid, hexadecyl succinic acid, 2-dodecenyl succinic acid (preferred), 2-pentadecenyl succinic acid, etc. Lauryl succinate is preferred among others, and is described in European patent application 86200690.5/0200263 published on 5.11.1986.

Other suitable polycarboxylates are described in US4144226 to Crutchfield et al, issued on 3.13.1979 and in US3308067 to Diehl, issued on 3.7.1967. See also US3723322 to Diehl.

Fatty acids, e.g. C₁₂-C₁₈Monocarboxylic acids may also be added to the composition, either alone or in admixture with the aforementioned builders, especially citrate and/or succinate builders, to produce additional builder activity. This use of fatty acids can result in reduced foam, which the formulator should consider.

Where phosphorus-based builders can be used, and particularly in the formulation of blocks for use in hand washing processes, various alkali metal phosphates, such as the known sodium tripolyphosphates, pyrophosphates and orthophosphates, can be used. Phosphonate builders, such as ethane-1-hydroxy-1, 1-diphosphonate and other known phosphonates may also be used (see, for example, US3159581, 3213030, 3422021, 3400148 and 3422137). e. Chelating agents

The detergent compositions of the present invention may also optionally contain one or more iron and/or manganese chelating agents. Such chelating agents may be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof, as hereinafter defined. While not wishing to be bound by theory, it is believed that the effectiveness of these materials is due in part to their removal of iron and manganese ions from the wash liquor through the formation of soluble chelates.

Aminocarboxylates useful as selective chelating agents include ethylenediaminetetraacetate, N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, triethylenetetramine hexaacetate, diethylenetriaminepentaacetate, and ethanoldiglycine, alkali metal, ammonium, and substituted ammonium salts thereof, and mixtures thereof.

Amino phosphonates are also suitable for use as chelating agents in the compositions of the present invention when at least low levels of total phosphorus are permitted in detergent compositions and include ethylenediamine tetra (methylene phosphonate), DEQUEST. These amino phosphonates preferably do not contain alkyl or alkenyl groups of more than about 6 carbon atoms.

Polyfunctionally substituted aromatic chelating agents are also suitable for use in the compositions of the present invention. See Connor et al, US3812044, issued 5, 21, 1974. Preferred compounds of this type in the acid state are dihydroxydisulfobenzenes, such as 1, 2-dihydroxy-3, 5-disulfobenzene.

The preferred biodegradable chelating agents for use in the present invention are ethylenediamine disuccinate ("EDDS"), particularly the [ S, S]isomers as described in US4704233 to Hartman and Perkins, issued 11, 3, 1987.

The compositions of the present invention may also contain a water-soluble methylglycine diacetic acid (MGDA) salt (or acid form) as a chelating agent or as a co-builder used with, for example, water-insoluble builders such as zeolites, layered silicates and the like.

If used, these chelants typically comprise from about 0.1% to about 15% by weight of the detergent compositions herein. More preferably, these chelating agents, if used, comprise from about 0.1% to about 3.0% by weight of the composition. f. Clay soil removal/anti-redeposition agent

The compositions of the present invention may also optionally contain water-soluble ethoxylated amines having clay soil removal and anti-redeposition properties. Granular detergent compositions containing these compounds typically contain from about 0.01% to about 10.0% by weight of a water-soluble ethoxylated amine; liquid detergent compositions typically contain from about 0.01% to about 5%.

The most preferred soil removal and anti-redeposition agent is ethoxylated tetraethylenepentamine. Examples of ethoxylated amines are described in US4597898 to VanderMeer, issued on 7/1 1986. Another preferred class of clay soil removal/anti-redeposition agents are the cationic compounds disclosed in european patent application 111965 to Oh and Gosselink, published on 27.6.4. Other clay soil removal/anti-redeposition agents that may be used include ethoxylated amine polymers disclosed in european patent application 111984 to Gosselink, published on 27.6.4; zwitterionic polymers disclosed in European patent application 112592 to Gosselin, published on 4.7.4.1984; and Connor, US4548744 issued on 10/22 of 1985. Other clay soil removal/anti-redeposition agents known in the art may also be used in the compositions of the present invention. Another preferred class of antiredeposition agents includes carboxymethyl cellulose (CMC) materials. Such materials are well known in the art. g. Dye transfer inhibitors

The compositions of the present invention may also contain one or more substances effective in inhibiting the transfer of dyes from one fabric to another during the laundering process. Typical dye transfer inhibiting agents of this type include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanines, peroxidases and mixtures thereof. If used, these inhibitors comprise from about 0.01% to about 10%, preferably from about 0.01% to about 5%, more preferably from about 0.05% to about 2%, by weight of the composition.

More specifically, polyamine N-oxide polymers suitable for use in the present invention comprise units having the formula: R-A_x-P; wherein P is a polymerizable unit that can be attached to an N-O group or an N-O group forms part of a polymerizable unit or an N-O group can be attached to both units; a is one of the following structures: -nc (O) -, -c (O) O-, -S-, -O-, -N ═ O; x is 0 or 1; and R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group or any combination thereof to which the nitrogen of the N-O group may be attached or which the N-O group is part of. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.

The N-O group can be represented by the following general structure:

wherein R is¹、R²、R³Is an aliphatic, aromatic, heterocyclic or alicyclic group or a combination thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group may be attached to or form part of any of the groups described above. The amine oxide units of the polyamine N-oxide have a pKa of<10, preferably a pKa of<7, more preferably a pKa of<6.

Any polymer backbone can be used as long as the amine oxide polymer formed is water soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyethylenes, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide. Amine N-oxide polymers typically have an amine to amine N-oxide ratio of 10: 1 to 1: 1000000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by suitable copolymerization or a suitable degree of N-oxidation. Polyamine oxides can be obtained in almost any degree of polymerization. The average molecular weight is generally 500-1000000; more preferably 1000-; most preferably 5000-. A preferred class of substances may be referred to as "PVNO".

The most preferred polyamine N-oxide useful as a dye transfer inhibiting polymer in the detergent compositions of the present invention is poly (4-vinylpyridine-N-oxide) having an average molecular weight of about 50000 and an amine to amine N-oxide ratio of about 1: 4.

Polymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as "PVPVI") are also suitable for use in the present invention. The average molecular weight of PVPVPVI is preferably 5000-. (the average molecular weight range is determined by light scattering methods, e.g.Barth et al, chemical analysis, Vol 113, "modern methods of Polymer characterization"). The PVPVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone of from 1: 1 to 0.2: 1, more preferably from 0.8: 1 to 0.3: 1, most preferably from 0.6: 1 to 0.4: 1. These copolymers may be linear or branched.

Polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 5000 to about 400000, preferably from about 5000 to about 200000, more preferably from about 5000 to about 50000, may also be used as a dye transfer inhibitor in the present invention. PVP is known to those skilled in the art of detergents, see for example EP-A-262897 and EP-A-256696. Compositions containing PVP dye transfer inhibitors may also contain polyethylene glycol ("PEG") having an average molecular weight of from about 500 to about 100000, preferably from about 1000 to about 10000. The ratio of PEG to PVP in the wash solution is preferably provided in ppm in a range of from about 2: 1 to about 50: 1, more preferably from about 3: 1 to about 10: 1. h. Enzyme

Enzymes may be included in the detergent compositions of the present invention for a variety of purposes including the removal of protein, carbohydrate or triglyceride based soils from, for example, a substrate, in order to prevent transfer of fugitive dyes during fabric washing, and for rejuvenation of fabrics. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof, of any suitable origin, e.g., plant, animal, bacterial, fungal, and yeast origin. Their preferred choice is influenced by factors such as pH-activity and/or stability optima, thermal stability and stability towards active detergents, builders, etc. In this regard, bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.

As used herein, "detersive enzyme" refers to any enzyme that has a washing, detersive or other benefit in a laundry, hard-surface cleaning or personal care detergent composition. Preferred washing enzymes are hydrolases such as proteases, amylases and lipases. Preferred enzymes for laundry purposes are, but not limited to, proteases, cellulases, lipases and peroxidases. Highly preferred for automatic dishwashing are amylases and/or proteases, including the currently available varieties and the improved varieties, but for the improved varieties it has a certain sensitivity to bleach deactivation despite the fact that the improvements are constantly being made more and more compatible with bleaches.

Enzymes are typically added to detergent or detergent additive compositions at levels sufficient to provide a "cleaning effective amount". The term "cleaning effective amount" refers to any amount that produces a cleaning, stain removing, soil removing, whitening, deodorizing or freshness enhancing effect on a substrate such as fabric, dishware, etc. Typical amounts of active enzyme per gram of detergent composition are up to about 5mg, more typically 0.01mg to 3mg, by weight for the actual formulations commercially available today. In other words, the compositions of the present invention typically comprise from 0.001% to 5%, preferably from 0.01% to 1% by weight of a commercially available enzyme preparation. The amount of protease enzyme in such commercially available enzyme preparations should generally be sufficient to produce an activity of 0.005-0.1Anson Units (AU) per gram of composition. For certain detergents, for example in automatic dishwashing, it may be desirable to increase the active enzyme content of commercial formulations to reduce the total amount of non-catalytically active material, thereby improving spotting/filming or other end results. Higher active levels are also desirable in highly concentrated detergent formulations.

Suitable examples of proteases are subtilisins from particular strains of Bacillus subtilis and Bacillus licheniformis.A suitable protease is obtained from a Bacillus strain developed by Novo Industries A/S, Denmark and sold as ESPERASE, hereinafter referred to as "Novo", which has maximal activity over the entire pH range of 8-12. The preparation of this and similar enzymes is described in British patent 1243784 to Novo. Other suitable proteases include ALCALASE-and SAVINASE-from Novo and MAXATASE-from International Bio-Synthetic, Inc, the Netherlands; and protease A disclosed in EP130756A on 9 th 1985, and protease B disclosed in EP303761A on 28 th 1987 and EP130756A on 9 th 1985. See also the high pH protease from Bacillus NCIMB40338 described in WO9318140A to Novo. WO9203529A to Novo describes enzyme-containing detergents comprising a protease, one or more other enzymes and a reversible protease inhibitor. Other preferred proteases include the enzymes of WO9510591 of Procter&Gamble. Proteases with reduced adsorption and increased hydrolysis are obtained if desired, as described in WO9507791 to Procter&Gamble. WO9425583 to Novo describes a recombinant trypsin-like protease suitable for use in the detergents of the invention.

In more detail, particularly preferred proteases referred to as "protease D" are carbonyl hydrolase variants having an amino acid sequence not found in nature, as described in the patent applications A.Baeck et al, US serial No. 08/322676, entitled "cleaning compositions containing proteases", and Ghosh et al, US serial No. 08/322677, entitled "bleaching compositions containing proteases", filed on 10/13, 1994, obtained from a precursor carbonyl hydrolase by substitution of the amino acid residue corresponding to position +76 in the aforementioned carbonyl hydrolase with a different amino acid, which preferably in combination with the substitution corresponds to a residue selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +206, and +76, depending on the numbering of Bacillus amyloliquefaciens subtilisin One or more amino acid residues at position +210, +216, +217, +218, +222, +260, +265, and/or + 274.

Amylases suitable for use in the present invention, particularly amylases suitable for, but not limited to, automatic dishwashing purposes include, for example, the α -amylase described in British patent 1296839 to Novo, the International Bio-Synthesis, Inc. of the family rapdase, and the Novo of the family Novo is particularly useful as enzyme engineering for improved stability, e.g., oxidative stability, is known, see, for example, J.biologicalcchem.Vol.260, No. 11, 1985, on day 11, page 6518. 6521. certain preferred embodiments of the compositions of the present invention may use amylases having improved stability in detergents, e.g., automatic dishwashing type detergents, particularly improved stability, e.g., starch enzymes having "increased stability" as measured against the commercially available starch peroxidase strain, preferably starch peroxidase 35598, which is obtained from the parent Bacillus amylovorax strain of the family Noncorum strain, which is described herein as a starch peroxidase, particularly preferred for the family amyloperoxidase, the family amylase strain of the family amylovorax-starch peroxidase, the family Novo-amylase, the family Patch strain of the invention, the invention is described herein, the invention is particularly preferably the invention, the invention may be used for which is described by the invention, or the invention, the invention may be carried out of the invention, the invention may be carried out of the use of a strain, the invention is described in which is described, the invention is particularly the invention, the enzyme stability of the invention, the invention is described in which is particularly the invention, the use of the invention, the invention is described in which is particularly the use of the invention, the enzyme stability of the invention is described in the invention, the enzyme stability of the invention is described in Novozyphne, the invention is described in Novo-starch-2, the invention is described in Novo-2, the invention is the invention, the invention is the invention is the invention is the invention is the invention is the.

Other amylases include those described in WO95/26397 and in the co-pending application PCT/DK96/00056 to Novo Nordisk. Specific amylases suitable for use in the detergent compositions of the invention include-amylases: characterized by an-amylase having a specific activity at least 25% higher than that of Termamyl in the temperature range 25 ℃ to 55 ℃ and at a pH of 8 to 10, said activity being determined by the Phadebas-amylase activity test (which is described on pages 9 to 10 of WO/95/26397). Also included are amylases at least 80% homologous to the amino acid sequences shown in SEQ ID sequences in the references. These enzymes are preferably incorporated into laundry detergent compositions at levels of from 0.00018% to 0.060% pure enzyme by weight of the total composition, more preferably from 0.00024% to 0.048% pure enzyme by weight of the total composition.

Cellulases for use in the present invention include those of the bacterial and fungal type, preferably having an optimum pH of from 5 to 9.5. Barbesgord et al, in US4435307 at 3/6.1984, disclose suitable fungal cellulases from Humicola insolens or Humicola strain DSM1800 or a cellulase 212 producing fungus belonging to the genus Aeromonas, as well as cellulases extracted from the liver pancreas of the marine mollusk Dolabella Auricula Solander. Suitable cellulases are also disclosed in GB-A-2075028, GB-A-2095275 and DE-OS-2247832. CAREZYME _ and CELLUZYME _ (Novo) are particularly useful. See also WO9117243 to Novo.

Suitable lipases for use in detergents include those produced by a microorganism of the genus Pseudomonas, such as Pseudomonas stutzeri ATCC19.154 as disclosed in GB 1372034. See also lipase in japanese patent application 53,20487 published on 24.2.1978. Such lipases are available from Amano Pharmaceutical Co.Ltd, Nagoya, Japan, under the trade name Lipase P "Amano" or "Amano-P". Other suitable commercial lipases include Amano-CES, a lipase from Chromobacterium viscosum, such as Chromobacterium viscosum var. lipolyticum NRRLB3673 from Toyo Jozo Co., of Tagata, Japan; chromobacter viscosum lipases from U.S. Biochemical Corp. and Disoynth Co. of the Netherlands; and lipase from Pseudomonas gladioli. The LIPOLASE enzyme derived from Humicola lanugmosa and commercially available from Novo (see also EP341947) is a preferred lipase for use in the present invention. Lipase and amylase variants stable to peroxidases are described in WO9414951A to Novo. See also WO9205249 and RD 94359044.

Despite the large number of publications on lipases, lipases which have hitherto only been derived from Humicola lanuginosa and which are produced in Aspergillus oryzae as host have found widespread use as additives for textile washing products. It is available under the trade name Lipolase from Novo Nordisk as described above^TMThus obtaining the product. To optimize the detergency performance of lipases, Novo Nordisk prepared various variants. Such as WThe D96L variant of the native Humicola lanuginosa lipase, described in O92/05249, showed a 4.4-fold increase in lard stain removal efficiency over the wild-type lipase (enzymes compared in an amount ranging from 0.075 to 2.5mg protein per liter). Research Disclosure No. 35944(Novo Nordisk) published on 3/10 of 1994 discloses that lipase variant (D96L) can be added in an amount corresponding to 0.001-100mg (5-500000LU/l) per liter of wash liquor. The present invention provides in the manner disclosed herein that the use of low levels of the D96L variant in detergent compositions containing AQA surfactants provides improved whiteness maintenance benefits on fabrics, especially where D96L is used at levels of from about 50LU to about 8500LU per liter of wash solution.

Cutinases suitable for use in the present invention are described in WO8809367A to Genencor.

Peroxidases may be used in conjunction with oxygen sources such as percarbonate, perborate, hydrogen peroxide and the like, for "solution bleaching", or to prevent transfer of dyes or pigments removed from a substrate to other substrates present in a wash liquor during a wash process. Known peroxidases include horseradish peroxidase, ligninase, haloperoxidase such as chloro-or bromo-peroxidase. Detergent compositions containing peroxidase are disclosed in WO89099813A to Novo and WO8909813A to Novo at 10/19/1989.

WO9307263A and WO9307260A to Genencor International, WO8908694A to Novo, and US3553139 to McCarty et al, issued on 5.1.1971, also disclose a range of enzyme starting materials and methods for their incorporation into synthetic detergent compositions. Further enzymes are disclosed in US4101457 by Place et al, 7/18, 1978 and US4507219 by Hughes, 26/3, 1985. US4261868 to Hora et al, 4.14.1981, discloses enzyme raw materials for liquid wash formulations, and methods for their incorporation into such formulations. Enzymes used in detergents can be stabilized in various ways. Enzyme stabilization techniques are disclosed and exemplified in US3600319 by Gedge et al, 8/17 1971 and in EP199405 and EP200586 by Venegas, 10/29 1986. Enzyme stabilizing systems are also described, for example, in US 3519570. WO9401532A to Novo describes Bacillus AC13 capable of giving proteases, xylanases and cellulases. i. Enzyme stabilizing system

Including, but not limited to, the enzyme-containing liquid compositions of the present invention may optionally contain from about 0.001% to about 10%, preferably from about 0.005% to about 8%, and most preferably from about 0.01% to about 6% by weight of an enzyme stabilizing system. The enzyme stabilizing system may be any stabilizing system compatible with the detergent enzyme. Such systems may themselves be provided by other formulation actives or added separately, for example by the formulator or by the manufacturer of the detergent ready-to-use enzyme. Such stabilizing systems may, for example, include calcium ions, boric acid, propylene glycol, short chain carboxylic acids, boric acid, and mixtures thereof, and are designed to address different stabilization issues depending on the type and physical form of the detergent composition.

One method of stabilization is to use a water-soluble source of calcium and/or magnesium ions in the final composition that provides the enzyme with its ions. Calcium ions are generally more effective than magnesium ions and therefore it is preferred if only one cation is used. Typical detergent compositions, especially liquids, contain from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 8 to about 12, millimoles of calcium ion per liter of finished detergent composition, although variations are possible depending on factors including the diversity, type and level of enzyme added. Preferably, water-soluble calcium or magnesium salts are used, including, for example, calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide, and calcium acetate; more generally, calcium sulfate or the corresponding magnesium salt of the listed calcium salts can be used. It may of course be useful to further increase the calcium and/or magnesium content, for example to increase the degreasing action of certain classes of surfactants.

Another stabilization method is the use of borate-type substances. See Severson, US 4537706. Borate stabilizers may be used at levels up to 10% or more of the composition, but more generally levels of boric acid or other borate compounds such as borax or orthoborate suitable for use in liquid detergents are up to about 3% by weight. Substituted boric acids such as phenylboronic acid, butylboronic acid, p-bromophenylboronic acid and the like may be used in place of boric acid and, despite the use of such substituted boron derivatives, it is possible to reduce the total boron content of the detergent composition.

The stabilizing system of certain cleaning compositions, such as automatic dishwashing compositions, may further comprise from 0 to about 10%, preferably from about 0.01% to about 6%, by weight, of a chlorine bleach scavenger, the addition of which prevents chlorine bleach species present in many water supplies from attacking the enzyme and reducing its activity, especially under alkaline conditions. Although the chlorine content of water can be very low, typically between about 0.5ppm and 1.75ppm, the available chlorine in the total water contacted with the enzyme can be substantial, for example, during the washing of dishes or fabrics; therefore, in the case of using chlorine, the stability of the enzyme may be problematic. Since perborate or percarbonate, which are capable of reacting with chlorine bleach species, are present in certain present compositions in amounts that are metered separately from the stabilizing system, in general, the use of other anti-chlorine stabilizers may not be necessary, although their use may increase effectiveness. Suitable chlorine scavenger anions are widely known and readily available and, if used, may be salts of sulfites, bisulfites, thiosulfites, thiosulfates, iodides, and the like, containing ammonium cations. Additionally, antioxidants such as carbamates, ascorbic acid and the like, organic amines such as ethylenediaminetetraacetic acid (EDTA) or alkali metal salts thereof, Monoethanolamine (MEA) and mixtures thereof may be used. In addition, special enzyme inhibition systems can be added, so thatthe different enzymes have the greatest compatibility. Other conventional scavengers such as bisulfates, nitrates, chlorides, sources of hydrogen peroxide such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate, as well as phosphates, condensed phosphates, acetates, benzoates, citrates, formates, lactates, malates, tartrates, salicylates, and the like, and mixtures thereof, may be used if desired. In general, since the ingredients listed separately (e.g., hydrogen peroxide sources) may function as chlorine scavengers upon being deemed to function well, there is no absolute requirement to add a separate chlorine scavenger unless a compound that exerts that function to the desired extent is not present in the enzyme-containing embodiments of the present invention, even if that is the case, the scavenger is added for optimum effectiveness. Also, the formulator may employ the ordinary skill of a chemist in an attempt to prevent the use of any enzyme scavengers or stabilizers which are not substantially compatible with the other active ingredients (if used) when formulated. For the use of ammonium salts, such salts can simply be pre-mixed with the detergent composition, but tend to absorb water and/or release ammonia during storage. It is therefore desirable to protect this material, if present, within the particles, as described in US4652392 to Baginski et al. j. Fabric softener

Various fabric softeners which go through the washing cycle, particularly the fine grain smectite clay of Storm and U.S. Pat. No. 4,115,647 to Nirschl, issued on 12/13 of 1977, and other softener clays known in the art, can optionally be used in the compositions of the present invention at a level of from about 0.5% to about 10% by weight, so that fabric softening is achieved while cleaning the fabrics. Clay softeners may be used with the disclosed amine and cationic softeners as disclosed in US4375416 by Crisp et al, 3/1 1983 and Harris et al, 4291071, issued 9/22 1981.k. Polymeric soil release agents

Known polymeric soil release agents, hereinafter "SRA" may optionally be used in the detergent compositions of the present invention. If used, the SRA will typically comprise from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight of the composition.

It is generally preferred that the SRA contain hydrophilic segments to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and that the SRA also contain hydrophobic moieties deposited on the hydrophobic fibers and adhering to the fibers throughout the wash and rinse cycles, thus immobilizing the hydrophilic moieties. This makes stains generated after SRA treatment easier to clean in the subsequent washing process.

SRAs may comprise various charged species, such as anionic or even cationic species (see US4956447 to Gosselink et al, 1990, 9, 11) as well as uncharged monomeric units, the structures of which may be linear, branched or even star-shaped. They may include end-capping groups which are particularly effective in controlling molecular weight or altering physical or surface-active properties. The structure and charge distribution can be varied for application to different fibre or textile types and different detergent or detergent additive products.

Preferred SRAs comprise oligomeric terephthalates, typically prepared by a process comprising at least one transesterification/oligomerization process, typically using a metal catalyst, such as titanium (IV) alkoxide. The esters can be prepared using additional monomers that can be added to the ester structure through one, two, three, four or more positions, without, of course, forming a tightly cross-linked overall structure.

Suitable SRAs include the sulfonated products of substantially linear ester oligomers consisting of an oligomeric ester backbone of terephthaloyl and oxyalkylene repeat units and allyl-derived sulfonated end groups covalently attached to the backbone, as described, for example, in US4968451 by 11.6.1990 j.j.scheibel and e.p.gosselink. The ester oligomer can be prepared by the following method: (a) ethoxylated allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate ("DMT") and 1, 2-propanediol ("PG") in a two-stage transesterification/oligomerization process; and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRAs include the non-ionically end-capped 1, 2-propanediol/polyoxyethylene terephthalate polyester of US4711730 of Gosselink et al, 12.8.1987, prepared, for example, by transesterification/oligomerization of poly (ethylene glycol) methyl ether, DMT, PG, and poly (ethylene glycol) ("PEG"). Other examples of SRAs include the partially and fully anionic-terminated oligomeric esters of US4721580 of Gosselink, 26.1.1988, such as oligomers derived from ethylene glycol ("EG"), PG, DMT, and sodium 3, 6-dioxa-8-hydroxyoctanesulfonate; non-ionic end-capped block polyester oligomers of Gosselink, 27/10/1987, prepared, for example, from DMT, methyl-capped PEG and EG and/or PG, or a mixture of DMT, EG and/or PG, Me-capped PEG and dimethyl 5-sulfonate isophthalate; and US4877896 of Maldonado, Gosselink et al, 31/10/1989, particularly sulfoaroyl-terminated terephthalate, which is a typical type of SRA used in laundry and fabric conditioning products, examples of which are ester compositions prepared from monosodium m-sulfobenzoate, PG and DMT, optionally but preferably also with added PEG, such as PEG 3400.

SRA also includes simple copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see US3959230 to Hays, 5/25 th 1976 and US3893929 to Basadur, 7/8 th 1975; cellulose derivatives such as METHOCEL, hydroxyether cellulose polymers available from Dow; c_1-4Alkyl celluloses and C₄Hydroxyalkyl cellulose; see Nicol et al, U.S. patent 4000093, 12, 28, 1976; and a methylcellulose ether having an average degree of substitution (methyl) per anhydroglucose unit of from about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoise measured as a 2% aqueous solution at 20 ℃. This material is available as METOLOSE SM100 and METOLOSE SM200, which are trade names for methyl cellulose ethers prepared by Shin-etsu Kagaku Kogyo KK.

Suitable SRA's characterized by a poly (vinyl ester) hydrophobic moiety include poly (vinyl esters) such as C_1-6Graft copolymers of vinyl esters, preferably poly (vinyl acetate) grafted onto a polyoxyalkylene backbone. See EP0219048 to Kud et al, published on 22.4.1987. Commercially available examples include SOKALAN SRA, such as SOKALAN HP-22, available from BASF (Germany). Other SRAs are polyesters with repeating units comprising 10-15% by weight of ethylene terephthalate and 80-90% by weight of polyoxyethylene terephthalate, obtained from polyoxyethylene glycol having an average molecular weight of 300-5000. Commercial examples include ZELCON5126, available from Dupont, and mileas et, available from ICI.

Another preferred class of SRA is that of empirical formula (CAP)₂(EG/PG)₅(T)₅(SIP)₁The oligomer of (a) which contains terephthaloyl (T), Sulfoisophthaloyl (SIP), ethyleneoxy and oxy-1, 2-propylene (EG/PG) units, which is preferably terminated by end groups (CAP), the end groups preferably being modified isethionates, for example, the oligomer contains one sulfoisophthaloyl unit, 5 terephthaloyl units, defined ratios of ethyleneoxy and oxy-1, 2-propyleneoxy units,preferably from about 0.5: 1 to about 10: 1, and two capping units derived from sodium 2- (2-hydroxyethoxy) -ethanesulfonate. The SRA preferably also contains from 0.5% to 20% by weight of oligomer of a crystallinity-reducing stabilizer, for example an anionic surfactant such as sodium linear dodecylbenzene sulphonate or a material selected from the group consisting of xylene-, cumene-and toluene-sulphonates or mixtures thereof, these stabilizers or modifiers being added to the synthesis vessel, all as disclosed in US5415807 to 5.16.1995 in Gosselink, Pan, Kellett and Hall. Suitable monomers for use in the above-described SRA include sodium 2- (2-hydroxyethoxy) -ethanesulfonate, DMT, dimethyl 5-sulfonate isophthalate, EG, and PG.

Another preferred class of SRA are oligomeric esters comprising: (1) a backbone comprising (a) at least one unit selected from the group consisting of dihydroxysulfonate, polyhydroxysulfonate, an at least trifunctional, and ester linkage formed thereby to produce a branched oligomeric backbone, and mixtures thereof; (b) at least one unit which is a terephthaloyl group; and (c) at least one unsulfonated unit which is a1, 2-alkyleneoxy moiety; and (2) one or more end-capping units selected from the group consisting of nonionic end-capping units, anionic end-capping units, e.g., alkoxylated, preferably ethoxylated isethionates, alkoxylated propanesulfonates, alkoxylated propane disulfonates, alkoxylated phenol sulfonates, sulfoaroyl derivatives, and mixtures thereof. Esters of the empirical formula are preferred:

{(CAP)_x(EG/PG)_y’(DEG)_y”(PEG)_y”’(T)_z(SIP)_z’(SEG)_q(B)_mwherein CAP, EG/PG, PEG, T and SIP are as defined above, (DEG) represents di (oxyethylene) oxy units, (SEG) represents units derived from glycerol sulfoethyl ether and related radical units, (B) represents branched units which are at least three functional groups such that the ester linkages formed result in a branched oligomeric backbone, x is from about 1 to about 12, y ' is from about 0.5 to about 25, y "is from 0 to about 12, y '" is from 0 to about 10, the total ofy "+ y '" is from about 0.5 to about 25, z is from about 1.5 to about 25, z ' is from 0 to about 12, the total of z + z ' is from about 1.5 to about 25, and q is from about 0.05 to about 12; m is from about 0.01 to about 10, and x, y ', y ", y '", z ', q, and m represent the average number of moles of the corresponding units per mole of the ester, the ester having a molecular weight of from about 500 to about 5000.

Preferred SEG and CAP monomers for the above esters include sodium 2- (2-, 3-dihydroxypropoxy) ethanesulfonate ("SEG"), sodium 2- {2- (2-hydroxyethoxy) ethoxy } ethanesulfonate ("SE 3"), andits homologs and mixtures thereof and ethoxylated and sulfonated allyl alcohol products. Preferred SRA esters of this type include the transesterification and oligomerization of sodium 2- {2- (2-hydroxyethoxy) ethoxy } ethanesulfonate and/or 2- [2- {2- (2-hydroxyethoxy) ethoxy } ethoxy]ethanesulfonate using a suitable Ti (IV) catalyst]The product of sodium ethanesulfonate, DMT, sodium 2- (2, 3-dihydroxypropoxy) ethanesulfonate, EG and PG, may be referred to as (CAP)₂(T)₅(EG/PG)_1.4(SEG)_2.5(B)_0.13Wherein CAP is (Na)⁺O₃S[CH₂-CH₂-CH₂O]₃₅) -, and B are units derived from glycerol, the EG/PG molar ratio being about 1.7: 1, as determined by conventional gas chromatography after complete hydrolysis.

Another class of SRA includes: (I) nonionic terephthalates are attached to polyester structures using diisocyanurate coupling agents, see U.S. Pat. No. 4,4201824 to Violland et al and U.S. Pat. No. 4,4240918 to Lagasse et al; and (II) SRAs with carboxylate end groups prepared by addition of trimellitic anhydride to known SRAs to convert the terminal hydroxyl groups to trimellitate esters. By appropriate selection of the catalyst, the trimellitic anhydride bonds to the ends of the polymer through the individual carboxylic acid ester of the trimellitic anhydride rather than opening the anhydride linkage. Either nonionic or anionic SRA's can be used as starting materials, provided they have hydroxyl end groups which can be esterified. See Tung et al, US 4525524. Other substances include: (III) SRA of an anionic terephthalate group of a urethane linking species, see U.S. Pat. No. 4,4201824 to Violland et al; (IV) poly (vinyl caprolactam) and related copolymers with monomers such as vinyl pyrrolidone and/or dimethylaminoethyl methacrylate, including nonionic and anionic polymers, see US4579681 to Ruppert et al; (V) graft copolymers prepared by grafting acrylic monomers on sulfonated polyesters, in addition to the SOKALAN type obtained from BASF. These SRAs certainly have a soil-release activity and an anti-redeposition activity similar to known cellulose ethers: see EP279134A, 1988 to Rhone-Poulenc Chemie. Yet another class of substances includes: (VI) grafts of vinyl monomers such as acrylic acid and vinyl acetate on proteins such as casein, see EP457205A (1991) by BASF; and (VII) polyester-polyamide SRAs prepared by condensing adipic acid, caprolactam and polyethylene glycol, particularly suitable for treating polyamide fabrics, see DE2335044(Unilever N.V.) (1974) to Bevan et al. Other useful SRAs are described in US4240918, 4787989 and 4525524. 1. Polymeric dispersants

Polymeric dispersants may be advantageously employed in the compositions of the present invention at levels of from about 0.1% to about 7% by weight, especially in the presence of zeolite and/or layered silicate builders. Suitable polymeric dispersants include polymeric polycarboxylates and polyethylene glycols, although other polymeric dispersants known in the art may also be used. While not wishing to be bound by theory, it is believed that the performance of the overall detergent builder is enhanced by crystal growth inhibition, peptization to remove particulate soils, and anti-redeposition when polymeric dispersants are used with other builders (including low molecular weight polycarboxylates).

Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in the acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. In the polymeric polycarboxylates of the present invention, the presence of monomeric moieties such as vinyl methyl ether, styrene, ethylene and the like which do not carry carboxylate groups is suitable so long as it does not exceed about 40% by weight.

Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic-based polymers useful in the present invention are water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form is preferably about 2000-10000, more preferably about 4000-7000, and most preferably about 4000-5000. Water-soluble salts of such acrylic acid polymers include, for example, alkali metal, ammonium and substituted ammonium salts. Such soluble polymers are known substances. For example, US3308067 to Diehl, issued 3, 7, 1967, discloses the use of such polyacrylates in detergent compositions.

Acrylic acid/maleic acid based copolymers may also be used as a preferred component of the dispersing/anti-redeposition agent. Such materials include water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form is preferably about 2000-100000, more preferably about 5000-75000, and most preferably about 7000-65000. The ratio of acrylate to maleate moieties in such copolymers is generally from about 30: 1 to about 1: 1, more preferably from about 10: 1 to 2: 1. Water-soluble salts of such acrylic acid/maleic acid copolymers may include, for example, alkali metal salts, ammonium salts and substituted ammonium salts. Such soluble acrylate/maleate copolymers are known and are described in European patent application 66915, 12/15/1982 and EP193360, 9/3/1986, and also describe polymers of this type which contain hydroxypropyl acrylates. Other useful dispersants include terpolymers of maleic/acrylic/vinyl alcohol. This material is also disclosed in EP193360 and includes, for example, an 45/45/10 terpolymer of acrylic acid/maleic acid/vinyl alcohol.

Another class of polymers that may be included are polyethylene glycols (PEG). PEG can exhibit dispersant properties as well as acting as a clay soil removal/anti-redeposition agent. Polyethylene glycols for this use generally have a molecular weight in the range of from about 500 to about 100000, preferably from about 1000 to about 50000, more preferably from about 1500 to about 10000.

Polyaspartate and polyglutamate dispersing agents may also be used, especially in combination with zeolite builders. The dispersant, for example a polyaspartate, preferably has a molecular weight (average) of about 10000. m. suds suppressor

Compounds for reducing or inhibiting foam formation may be incorporated in the compositions of the present invention. The suppression of suds is particularly important in the case of the so-called "high-intensity washing method" described in US4489455 and 4489574 and in the case of the front-loading euro-washer.

Various materials may be used as suds suppressors, which are well known to those skilled in the art. See, for example, Kirk Othmer encyclopedia of chemical technology, 3 rd edition, volume 7, page 430-447 (John Wiley&Sons, Inc., 1979). One particularly important class of suds suppressors comprises monocarboxylic fatty acids and soluble salts thereof. See US2954347 to Wayne st.john, issued 9, 27 of 1960. Monocarboxylic fatty acids and their salts useful as suds suppressors generally have hydrocarbyl chains containing from 10 to about 24 carbon atoms, preferably from 12 to 18 carbon atoms. Suitable salts include alkali metal salts, such as sodium, potassium and lithium salts; ammonium and alkanolammonium salts.

The detergent compositions of the present invention may also contain non-surfactant suds suppressors. Such suds suppressors include, for example: high molecular weight hydrocarbons, e.g. paraffins, fatty acid esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C₁₈-C₄₀Ketones (e.g., stearyl ketone), and the like. Other suds suppressors include N-alkylated aminotriazines, such as tri-to hexa-alkylmelamines or di-to tetra-alkyldiamine chlorotriazines, which are the products of cyanuric chloride with 2 or 3 moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphate salts, such as monostearyl alcohol phosphate esters and monostearyl dialkali metal (e.g., K, Na, and Li) phosphate salts and phosphate esters. Hydrocarbons such as paraffins and halogenated paraffins may be used in liquid form. The liquid hydrocarbon should be liquid at room temperature and atmospheric pressure and should have a pour point of from about-40 c to about 50 c, with a minimum boiling point of no less than about 110 c (atmospheric pressure). It is known to use waxy hydrocarbons, preferably having a melting point below about 100 ℃. Such hydrocarbons are a preferred class of suds suppressors for detergent compositions. Hydrocarbon suds suppressors are described, for example, in US4265779 to Gandolfb et al, issued 5.5.1981. Thus, the hydrocarbons include aliphatic, alicyclic, aromatic and heterocyclic saturated or unsaturated hydrocarbons containing from about 12 to about 70 carbon atoms. The term "paraffin" as used inthe discussion relating to suds suppressors includes mixtures of true paraffins and cyclic hydrocarbons.

Another preferred class of non-surfactant suds suppressors comprises silicone suds suppressors. Such materials include the use of silicone oils, such as polydimethylsiloxanes, dispersions or emulsions of silicone oils or resins, and mixtures of silicones with silica particles, where the silicone is chemisorbed or fused to the silica. Silicone suds suppressors are well known in the art, for example, as disclosed in US4265779 to Gandolfo et al, issued 5.5.1981, and European patent application 89307851.9 to Starch, M.S., published 2.7.1990.

Other silicone suds suppressors are disclosed in US3455839, which relates to compositions and methods for eliminating aqueous foam by incorporating a small amount of polydimethylsiloxane fluid into the composition.

Mixtures of polysiloxanes and silanized silicas are described, for example, in German patent application DOS 2124526. Silicone antifoam and foam control agents in granular detergent compositions are described in US3933672 to Bartolotta et al and US4652392 to Baginski et al, 3.24 1987.

Examples of silicone-based suds suppressors for use in the present invention are suds suppressing amounts of suds controlling agents consisting essentially of:

a polydimethylsiloxane fluid having a viscosity of from about 20cs to about 1500cs at 25 ℃;

(ii) about 5 to 50 parts by weight per 100 parts by weight of (i) of a silicone resin Consisting of (CH)₃)₃SiO_1/2Unit and SiO₂Unit is pressed (CH)₃)₃SiO_1/2Units and SiO₂A ratio of units of about 0.6: 1 to about 1.2: 1; and

(iii) from about 1 to about 20 parts by weight of solid silica gel per 100 parts of (i).

In the preferred silicone suds suppressors for use herein, the solvent for the continuous phase is comprised of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol. The primary silicone suds suppressor is branched/crosslinked and preferably non-linear.

To further illustrate this point, typical liquid laundry detergent compositions having controlled suds optionally contain from about 0.001% to about 1%, preferably from about 0.01% to about 0.7%, most preferably from about 0.05% to about 0.5% by weight of said silicone suds suppressor which comprises (1) a non-aqueous emulsion of a primary suds suppressor which is a mixture of (a) a silicone, (b) a resinous silicone or silicone resin-yielding silicone compound, (c) a finely divided filler, and (d) a catalyst which facilitates reaction of mixture components (a), (b) and (c) to form silanolates; (2) at least one nonionic silicone surfactant; and (3) a polyethylene glycol or a polyethylene-polypropylene glycol copolymer having a solubility in water of more than 2% by weight at room temperature; polypropylene glycol was not present. Similar amounts can be used in particulate compositions, gels, and the like. See also US4978471 to Starch, 1990, 12-18, and US4983316,1994 to Huber et al, 5288431 to US4639489 and 4749740 to Aizawa et al, 1991, 2-8, 1991, 2-22, column 1, line 46 to column 4, line 35.

The silicone suds suppressors of the present invention preferably comprise: polyethylene glycol and polyethylene/polypropylene glycol copolymers having an average molecular weight of less than about 1000, preferably about 100-800. The polyethylene glycol and polyethylene/polypropylene glycol copolymers of the present invention have a solubility in water at room temperature of greater than about 2% by weight, preferably greater than about 5% by weight.

Preferred solvents for the present invention are polyethylene glycol having an average molecular weight of less than about 1000, more preferably about 100-800, and most preferably 200-400, and copolymers of polyethylene glycol/polypropylene glycol, preferably PPG200/PEG 300. Polyethylene glycol: the weight ratio of the polyethylene glycol-polypropylene glycol copolymer is preferably from about 1: 1 to 1: 10, most preferably from 1: 3 to 1: 6.

Preferred silicone suds suppressors for use herein are free of polypropylene glycol, especially those having a molecular weight of 4000. It is also preferably free of block copolymers of ethylene oxide and propylene oxide, such as PLURONICL 101.

Other suds suppressors useful herein include secondary alcohols (e.g., 2-alkyl alkanols) and the likeMixtures of these alcohols with silicone oils, such as the silicones disclosed in us patents 4798679, 4075118 and EP 150872. The secondary alcohol comprises a compound having C₁-C₁₆C of the chain₆-C₁₆An alkyl alcohol. The preferred alcohol is 2-butyloctanol, which is available from Condea under the trademark ISOFOL 12. Mixtures of secondary alcohols are available from Enichem under the trademark isachem 123. Mixed suds suppressors typically comprise a mixture of alcohol and silicone in a weight ratio of from 1: 5 to 5: 1.

For any detergent composition used in an automatic washing machine, the foam formed should not spill out of the washing machine. When a suds suppressor is used, it is preferably present in a "suds suppressing amount". By "suds suppressing amount" is meant that the amount of suds controlling agent selected by the formulator of the composition is sufficient to control suds to provide a low sudsing laundry detergent which can be used in an automatic washing machine.

The compositions of the present invention typically contain from 0% to about 5% of suds suppressors. When monocarboxylic fatty acids and salts thereof are used as suds suppressors, they are generally used in amounts up to about 5% by weight of the detergent composition. Preferably, from about 0.5% to about 3% of the fatty monocarboxylate suds suppressor is used. The silicone suds suppressors are generally used in amounts up to about 2.0% by weight of the detergent composition, although higher levels may also be used. This upper limit is practical due to first consideration of the efficiency with which foam control is effective, keeping costs to a minimum and using lower amounts. Preferably, from about 0.01% to about 1% of a silicone suds suppressor is used, more preferably from about 0.25% to about 0.5%. These weight percent values used in the present invention include any silica that may be used with the polysiloxane and any auxiliary materials that may be used. The monostearyl phosphate suds suppressors are generally used in amounts of from about 0.1% to about 2% by weight of the composition. Typically, the amount is from about 0.01% to about 5.0%, although higher amounts of hydrocarbon suds suppressors can be used. Alcohol suds suppressors are generally used in amounts of 0.2% to 3% by weight of the final composition. n. other Components

The compositions of the present invention may also contain various other components useful in detergent compositions, including other active ingredients, carriers, hydrotropes, processing aids, dyesMaterials or pigments, solvents for liquid formulations, solid fillers for bulk compositions, and the like. If high foam is desired, it is possible to add, for example, C to the composition₁₀-C₁₆Alkanolamide suds boosters, typically at levels of 1% to 10%. C₁₀-C₁₄Monoethanol and diethanol amides are typical examples of such suds boosters. It is also advantageous to use such suds boosters with high sudsingadjunct surfactants such as the amine oxides, betaines and sultaines described above. Soluble magnesium salts such as magnesium chloride, magnesium sulfate and the like may also be added, typically at levels of 0.1% to 2%, to provide additional foam and enhanced grease removal properties, if desired.

The various detergent components used in the compositions of the present invention may also optionally be further stabilized by adsorbing the components onto a porous hydrophobic substrate, which is then coated with a hydrophobic coating agent. Preferably the detergent is mixed with the surfactant prior to adsorption into the porous matrix. In use, the detergent component is released from the substrate into an aqueous wash solution to achieve its intended cleaning efficacy.

To illustrate the technique in more detail, porous hydrophobic silica (trademark SIPERNATD10, DeGussa) was mixed with a solution containing 3% -5% C_13-15A proteolytic enzyme solution of a nonionic surfactant of ethoxylated alcohol (EO 7). The amount of enzyme/surfactant solution is typically 2.5 times the weight of the silica. The powder obtained is dispersed in the silicone oil with stirring (various silicone oils with a viscosity of 500-12500 can be used). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent base. By this means, components such as the above-mentioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, optical brighteners, fabric conditioners and hydrolyzable surfactants can be "protected" for use in detergents, including liquid laundry detergent compositions.

Liquid detergent compositions may contain water and other solvents as carriers. Low molecular weight primary or secondary alcohols, such as methanol, ethanol, propanol and isopropanol, are suitable. Monohydric alcohols are preferred for solubilizing surfactants, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxyl groups (e.g., 1, 3-propanediol, ethylene glycol, glycerol, and 1, 2-propanediol) can also be used. The compositions may contain from 5% to 90%, typically from 10% to 50%, of such carriers.

The detergent compositions of the present invention are preferably formulated such that when used during aqueous washing operations, the wash water has a pH of from about 6.5 to about 11, preferably from about 7.5 to 10.5. The liquid dishwashing product formulation preferably has a pH of from about 6.8 to about 9.0. The laundry product is typically at a pH of 9-11. Techniques for controlling the pH within the desired range of use include the use of buffers, bases, acids, and the like, and are known to those skilled in the art.

Examples

The following examples further describe and demonstrate preferred embodiments within the scope of the present invention. The examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, as many variations thereof are possible without departing from the spirit and scope of the invention.

Example 1

This example illustrates a granular detergent composition useful in the process of the present invention.

The components are calculated by the weight of the composition

NaCFAS(C₁₂-C₁₈) (coconut fatty alcohol sulfate) 21

A(C₁₂-C₁₄) E6.5 (alkyl ethoxylates) 4

STPP (sodium tripolyphosphate) 17.5

Sodium carbonate 20.0

Zeolite 8.0

Nonoylbenzenesulfonates 2.3

Sodium perborate 2.28

Zinc phthalocyanine sulfonate 0.3

ACUMER3100 (terpolymer) 2.25

Diethylene triamine penta phosphonic acid salt (sodium salt) 1

Protease (protease activity, 1.0AU/g) 0.25

Amylase (Amylase Activity, 60000AMU/g) 0.50

Lipase (lipase activity, 100000LU/g) 0.12

Cellulase (cellulase Activity, 5000CEVU/g) 0.15

Water (including water of hydration), sodium sulfate and other minor ingredients in balance

Example 2

This example illustrates a liquid detergent composition useful in the process of the present invention.

The components are calculated by the weight of the composition

NaC₂₅-AS 20.5

A(C_12-14)E3S 5.0

A(C_12-13)E6.5 4.5

C_12-14Fatty acid 5.0

Citric acid 3.0

Ethanol 5.5

Hexanediol 8.5

Boric acid 3.5

ACUMER5000 (terpolymer) 3.0

Protease (protease activity, 1.0AU/g) 1.5

Lipase (lipase activity, 100000LU/g) 0.2

Cellulase (cellulase Activity, 5000CEVU/g) 0.1

Fluorescent brightener 49(4, 4' -stilbenes) 0.1

Water (including water of hydration) and balanceof other minor ingredients

Example 3

This example illustrates a block detergent composition for use in the process of the present invention.

The components are calculated by the weight of the composition

％

NaLAS(C12-18) 22.5

NaAS 3

Sodium carbonate 3

Diethylene triamine penta phosphonic acid salt (sodium salt) 0.70

Polyethylene oxide (MW 600) 0.30

Bentonite 10

Sokolan CP-5 (acrylic acid maleic acid copolymer, MW 36000) 0.7

ACUMER5000 (terpolymer) 1.5

TSPP (trisodium tripolyphosphate) 5

STPP 5

Zeolite 1.25

Protease (protease activity, 1.0AU/g) 0.10

Amylase (Amylase Activity, 60000AMU/g) 0.75

Lipase (lipase activity, 100000LU/g) 0.1

Cellulase (cellulase Activity, 5000CEVU/g) 0.15

Water (including water of hydration), sodium sulfate and other minor ingredients in balance

Example 4

This example illustrates a method of machine washing fabrics using the composition of example 1.

White clothes are selected and washed separately from colored clothes. 40g of the composition of example 1 was placed in an automatic washing machine. Then,about 1.5Kg of white clothes in total weight was added to the washing machine. The washing machine was loaded with about 33 liters of water after running the washing machine. The washing machine was allowed to continue an automatic cycle of about 10 minutes of washing, followed by two intermittent rinses. The garments are then allowed to air dry, sun dry or machine dried. The washed clothes did not yellow and the white clothes maintained their whiteness.

Example 5

This example illustrates a method of hand washing fabric using the composition of example 1.

Approximately 10 liters of water was placed in the basin. 40g of the composition of example 1 was dissolved in water. The white clothes (about 1.5Kg) were washed separately from the colored clothes. The clothes are scrubbed by hands or scrubbed by a washboard. The garments are occasionally immersed in a wash solution during the scrubbing process. After all the clothes are washed, the washing solution is discarded and replaced with fresh clean water for rinsing. Rinsing is performed by manually twisting and scrubbing and wringing out the water of the clothes. The rinse water was replaced with fresh clean rinse water. Rinsing and displacement of rinse water is continued until the final rinse water is clean and free of visible and persistent foam. After rinsing, the garments are air dried, sun dried or machine dried. The washed clothes did not yellow and the white clothes maintained their whiteness.

Example 6

This example illustrates a method of laundering fabrics using the composition of example 2.

The white clothes were pre-rinsed in a basin containing about 20 liters of water to remove any particulate soil. The pre-rinse water was discarded and replaced with fresh clean water. The garments are laundered piece by applying the pieces directly to the fabric and then scrubbed by hand or using a scrubbing implement, such as a scrubbing board. When all the clothes are washed, the wash water is discarded and replaced with fresh clean water. The clothes were then rinsed batch-wise until no visible foam or the final rinse water was clear. After rinsing, the garments are air dried, sun dried or machine dried. The garment is then machine dried or air dried. The washed clothes did not yellow and the white clothes maintained their whiteness.

Example 7

This example illustrates a method of laundering fabrics using the composition of example 3.

White clothes are washed separately from colored clothes. Stains and soils that are localized are pretreated with a small amount of the composition of example 3. The clothes (about 1.5Kg) were then placed in an automatic washing machine. An additional 39.6g of the composition of example 3 was added to the clothes of the automatic washing machine. The washing machine was loaded with about 33 liters of water after running the washing machine. The washing machine was allowed to continue an automatic cycle of about 10 minutes of washing, followed by two 3 minutes rinses. After rinsing, the garments are air dried, sun dried or machine dried. The washed clothes did not yellow and the white clothes maintained their whiteness.

All publications, patent applications, and issued patents mentioned above are herein incorporated by reference in their entirety.

It is understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application and scope of the appended claims.

Claims (10)

1. A method of laundering fabrics which comprises the use of a laundry detergent composition comprising:

a) at least about 0.01% detergent surfactant; and

b) at least about 0.2% of a terpolymer, wherein the terpolymer comprises:

i) 30-80% of a first monomer unit containing a weak acid functional group;

ii) 20-60% of a second monomer unit comprising a strong acid functional group; and

iii) 10% to 50% of a third monomer unit comprising a non-ionic functional group.

2. The method of claim 1, wherein the first monomer unit contains a carboxylate functional group and the second monomer unit contains a sulfonate functional group.

3. The method of claim 2, wherein

a) The first monomer unit has the following structure:

wherein R is¹Is H or CH₃；R²⁰Is H or C (O) -OX; and X is independently H, a metal cation or N- (R)²)₄Wherein R is²Is H, C₁-C₄Hydroxyalkyl or mixtures thereof;

b) the second monomer unit has the following structure:

wherein R is³Is H or CH₃；R⁴Is H or C₁-C₄An alkyl group; and R⁵Is C₁-C₈Alkyl or C₁-C₈Aralkyl group; and Y is H, a metal cation or N- (R)²¹)₄Wherein R is²¹Is H, C₁-C₄Hydroxyalkyl or mixtures thereof; and

c) the third monomer unit is a vinyl ester, vinyl acetate, or substituted acrylamide.

4. The method of claim 3, wherein R²⁰Is H and the composition further comprises a builder.

5. The method of claim 4 wherein the composition comprises from 0.5% to 10% of the terpolymer.

6. The method of claim 5, wherein the terpolymer is formed from three different monomers.

7. The method of claim 6 wherein the composition comprises 1% to 5% of the terpolymer.

8. The method of claim 7, wherein the detergent surfactant is an anionic surfactant, a nonionic surfactant, a zwitterionic surfactant, an anionic surfactant, an amphoteric surfactant, or a mixture thereof.

9. A method of laundering fabrics which comprises the use of a laundry detergent composition comprising:

a) at least about 0.1% of a detergent surfactant, wherein the detergent surfactant is an anionic surfactant, a nonionic surfactant, a zwitterionic surfactant, an anionic surfactant, an amphoteric surfactant, or a mixture thereof;

b) from 0.5% to 10% of a terpolymer, wherein the terpolymer comprises:

i) 30-80% of a first monomer unit having the structure:

wherein R is⁷Independently is H or-COO^-Z⁺(ii) a Wherein Z⁺Independently is H or Na;

ii) 20-60% of a second monomer unit having the structure:

wherein R is⁸Independently is H or-COO^-W⁺(ii) a And R⁹Is that

Wherein p is 1 to 6; and R¹⁰Is CH₃(ii) a And wherein W⁺Is H or Na;

iii) 10-50% of a third monomer unit having the structure:

wherein R is¹¹Independently of each other is H, -COO^-H⁺or-COO^-Na⁺(ii) a And R¹²Is- (CH)₂)_qCH₃、

Wherein q is independently 0 to 6; r¹³And R¹⁴Independently is- (CH)₂)_mCH₃Wherein m is 0 to 6.

10. The method of claim 9 wherein the composition comprises from 1% to 5% of the terpolymer and further comprises a builder.