CN1239503A - Method for washing fabrics using a detergent composition containing a 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 for washing fabrics using a detergent composition containing a terpolymer

Background of the Invention

Detergent formulators are often faced with the task of designing products to remove various soils and stains from fabrics. The soils and stains are created by using the fabric prior to laundering. However, many fabrics become soiled during laundering due to the laundering environment. For example, certain fabrics, especially white cotton, turn yellow after repeated washing. Therefore, the detergent formulator is 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 is a need for a method of washing fabrics that suppresses yellowing due to repeated washing, thereby maintaining fabric whiteness.

Summary of 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 comprising at least one first monomer unit comprising a weak acid functionality, a first monomer unit comprising a strong acid functionality The second monomer unit and the third monomer unit containing non-ionic functional groups.

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

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

Detailed description of the invention

The following are definitions of terms used herein.

"Alkyl" means a carbon-containing chain, preferably about C ₁ to about C ₁₀ , more preferably about C ₁ to about C ₆ , still more preferably about C ₁ to about C ₄ ; it may be straight, 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" means an aromatic group; substituted (mono- or poly-) or unsubstituted, preferably unsubstituted. Preferred aryl groups are phenyl, pyridyl, pyrimidinyl and naphthyl; more preferred is phenyl.

"Containing" means that other steps and other components that do not affect the end result may be added. This term includes the terms "consisting of" and "consisting essentially of".

"Cycloalkyl" means a cyclic alkyl group (ie, having one or more closed rings).

"Terpolymer" means a polymer formed from three or more monomers.

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

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

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

"Weakly acid functional monomer" means a monomeric unit which contains one or more functional groups which only partially dissociate in water. For example:

          

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

All ratios are by weight unless otherwise indicated.

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

All temperatures are in degrees Celsius (° C.) unless otherwise indicated.

The present invention relates to a method of laundering fabrics comprising the use of a detergent composition comprising a detergent surfactant and a terpolymer comprising at least one first monomeric unit comprising weak acid functionality, comprising A second monomeric unit having a strong acid functional group and a third monomeric unit containing a nonionic functional group.

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

The aspects and embodiments of the invention described herein have a number of surprising advantages, including maintaining whiteness and/or preventing yellowing of fabrics even after repeated laundering. While not intending to be bound by theory, it is believed that the terpolymers used in the present invention sequester HMI in the wash and/or rinse water. Chelation is achieved by polymers and/or chelating agents binding the HMI through ion-ion interactions, and the complexes formed remain soluble in aqueous solutions. We also believe that the terpolymer disperses the HMI by "wrapping" the HMI salt (eg Fe(OH) ₃ ) around it with the terpolymer, thereby preventing undissolved HMI salt from adhering to the fabric.

An additional effect of the composition used in the method of the invention is to prevent the breakdown of the bleach by the HMI in the wash water. A common problem in detergent compositions containing bleach is that the bleach is broken down by HMI in the wash and/or rinse water. Chelating agents are therefore added to detergent compositions containing bleach to prevent the decomposition of the bleach by the HMI. The use of terpolymers in the compositions of the present invention additionally prevents or reduces bleach decomposition due to the sequestering effect of the terpolymers, thus reducing or eliminating the need for additional "bleaching" in detergent compositions. Chelating agent for agent protection.

Another possible effect of the method according to the invention is the prevention of fouling of surfaces caused by, for example, carbonates, silicates and/or orthophosphates normally present in detergent compositions. In hard water, such carbonate forms, such as calcium carbonate, can leave a stiff or rough feel to the fabric when deposited on the fabric. The terpolymer used in the composition of the present invention prevents calcium carbonate deposition by dispersing the calcium carbonate.

Another possible effect for the method of the invention is improved physical properties. For example, if the detergent composition is in the form of a granular detergent, the terpolymer provides an added benefit, wherein 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 that do not contain the terpolymer of the present invention) experience difficulties during the processing of detergent granules, including agglomeration, caking or sticking, which can lead to clogging of processing lines . However, the terpolymer used in the compositions of the present invention is in powder form, thus assisting the free flow of the overall detergent composition in processing lines by preventing or reducing agglomeration, clumping or sticking of detergent particles.

Laundry detergent compositions for use in the methods of the present invention may be in any suitable form, such as dense liquids, light liquids or other pourable forms, granules, laundry bars, gels or pastes. The terpolymers of the present invention can be formulated into any detergent base of the formulator's choice.

The present invention is described in more detail below. Terpolymer

Terpolymers useful in detergent compositions contain a first monomeric unit, a second monomeric unit and a third monomeric unit. In addition to these three, other monomeric units may optionally constitute the terpolymer, as long as these additional monomers do not significantly affect the whiteness maintenance imparted by the first, second and third monomeric units and/or prevent Yellowing properties are sufficient.

Detergent compositions preferably contain at least about 0.2% terpolymer.

The terpolymer preferably has a molecular weight of from about 500 to about 36,000 Daltons, more preferably from about 1,000 to about 20,000 Daltons, still more preferably from about 3,000 to about 6,000 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 4:3:3 to about 8:1:1, still more preferably from about 5:3:2 to about 6:2:2.

Examples of terpolymers useful in the present invention and the synthesis of such terpolymers include those described in US4711725, issued December 8,1987. a. The first monomer unit

The first monomer unit contains weak acid functionality. The first monomeric unit preferably contains carboxylic acid functional groups. The first monomer unit more preferably has the following structure: R ¹ is H or CH ₃ , preferably H. R ²⁰ is H or C(O)-OX. X is independently H, a metal cation or N-(R ² ) ₄ , wherein R ² is H, C ₁ -C ₄ hydroxyalkyl or a mixture thereof, preferably X is H or Na ⁺ , more preferably X is Na ⁺ .

The first monomer unit more preferably has the following structure: R ⁷ is independently H or -COO ^- Z ⁺ , preferably H. Z ⁺ is independently H or Na, preferably Na (ie -COO ^- Na ⁺ ). b. Second monomer unit

R³是H或CH₃，优选H。R⁴是H或C₁-C₄烷基，优选H或CH₃，更优选CH₃。R⁵是C₁-C₈烷基或C₁-C₈芳烷基，优选C₁-C₄，更优选C₁，仍更优选烷基。Y是H、金属阳离子或N-(R²¹)₄，优选X是H或Na⁺，更优选X是Na⁺。R²¹是H、C₁-C₄羟基烷基或它们的混合物。The second monomer unit contains strong acid functional groups. The second monomeric unit preferably contains sulfonic acid functional groups. The second monomer unit more preferably has the following structure:

^R3 is H or _CH3 , preferably H. R ⁴ is H or C ₁ -C ₄ alkyl, preferably H or CH ₃ , more preferably CH ₃ . R ⁵ is C ₁ -C ₈ alkyl or C ₁ -C ₈ aralkyl, preferably C ₁ -C ₄ , more preferably C ₁ , still more preferably alkyl. Y is H, a metal cation or N-(R ²¹ ) ₄ , preferably X is H or Na ⁺ , more preferably X is Na ⁺ . R ²¹ is H, C ₁ -C ₄ hydroxyalkyl, or a mixture thereof.

W⁺独立地是H或Na，优选Na。p是1-约6，优选约1-约4，更优选1。R¹⁰是H或C₁-C₄烷基，优选H或CH₃，更优选CH₃。c.第三单体单元The second monomer unit preferably has the following structure: R ⁸ is independently H or -COOH ^- Na ⁺ , preferably H. ^R9 is

W ⁺ is independently H or Na, preferably Na. p is 1 to about 6, preferably about 1 to about 4, more preferably 1. R ¹⁰ is H or C ₁ -C ₄ alkyl, preferably H or CH ₃ , more preferably CH ₃ . c. The third monomer unit

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

更优选C₁-C₄烷基。R¹³是H或CH₃，优选H。R¹⁴是H或C₁-C₆烷基，优选H。n是1-约3的整数，优选1。Vinyl esters preferably have the following structure: R ¹¹ is H or CH ₃ , preferably H. R ¹² is C ₁ -C ₆ alkyl, C ₆ -C ₁₀ aryl, C ₆ -C ₁₀ aralkyl or Preferably C ₁ -C ₆ alkyl, C ₆ aryl or

More preferred is C ₁ -C ₄ alkyl. R ¹³ is H or CH ₃ , preferably H. R ¹⁴ is H or C ₁ -C ₆ alkyl, preferably H. n is an integer from 1 to about 3, preferably 1.

取代的丙烯酰胺优选具有如下结构：

R¹⁵是H或CH₃，优选H。R¹⁶和R¹⁷独立地是H、C₁-C₈烷基、C₆-C₈环烷基、苄基或如上定义的如下基团，使得R¹⁸和R¹⁹不同时是H： Vinyl acetate preferably has the following structure:

The substituted acrylamide preferably has the following structure:

R ¹⁵ is H or CH ₃ , preferably H. R ¹⁶ and R ¹⁷ are independently H, C ₁ -C ₈ alkyl, C ₆ -C ₈ cycloalkyl, benzyl or the following groups as defined above, such that R ¹⁸ and R ¹⁹ are not H at the same time:

The third monomer unit more preferably has the following structure: R ¹¹ is independently H, -COO ^- H ⁺ or -COO ^- Na ⁺ , preferably H. R ¹² is q is independently 0-6, preferably about 0-about 3, more preferably 1. R ¹³ and R ¹⁴ are independently -(CH ₂ ) _m CH ₃ or H. m is from 0 to about 6, preferably from about 0 to about 3, more preferably 0. detergent surfactant

The detergent compositions also contain detersive surfactants. Detergent compositions preferably contain 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 detersive surfactant.

Preferred detersive 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 C ₁₁ -C ₁₈ alkylbenzene sulfonates ("LAS") and primary, branched and random C ₁₀ - C ₂₀ alkyl sulfate (“AS”), of the formula CH ₃ (CH ₂ ) _x (CHOSO ₃ ^- M ⁺ )CH ₃ and CH ₃ (CH ₂ ) _y (CHOSO ₃ ^- M ⁺ )CH ₂ CH ₃ C ₁₀ -C ₁₈ secondary (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, not Saturated sulfates such as oleyl sulfate, C ₁₀ -C ₁₈ alkyl alkoxy sulfate ("AE _x S"; especially EO1-7 ethoxy sulfate), C ₁₀ -C ₁₈ alkyl alkoxy Carboxylates (especially EO1-5 ethoxy carboxylates), C ₁₀ -C ₁₈ glyceryl ethers, C ₁₀ -C ₁₈ alkyl polyglycosides and their corresponding sulfated polyglycosides, and C ₁₂ -C ₁₈ alpha - Sulfonated fatty acid esters. Conventional nonionic and amphoteric surfactants such as C ₁₂ -C ₁₈ alkyl ethoxylates ("AE") including so-called narrow peak alkyl ethoxylates ("AE") and C ₆ -C ₁₂ alkylphenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxylates), C ₁₂ -C ₁₈ betaines and sultaines, C ₁₀ -C ₁₈ Amine oxide etc. C ₁₀ -C ₁₈ N-alkyl polyhydroxy fatty acid amides may also be used. Typical examples include C ₁₂ -C ₁₈ N-methyl glucamides. See WO9206154. Other sugar-derived surfactants include N-alkoxy polyhydroxy fatty acid amides such as C ₁₀ -C ₁₈ N-(3-methoxypropyl) glucamide. N-propyl to N-hexyl C ₁₂ -C ₁₈ glucamides can be used for low sudsing applications. Conventional _C10 - _C20 soaps may also be used. If high lather is desired, branched _C10 - _C16 soaps can be used. Mixtures of anionic and nonionic surfactants are particularly useful. Other conventionally used surfactants are listed in standard textbooks. Additional detergent composition components

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

Alkoxylated polycarboxylates, such as those prepared from polyacrylates, are suitable herein to provide additional degreasing performance. These substances are described on pages 4 et seq. of WO91/08281 and PCT90/01815. Chemically, these materials consist of polyacrylates with one ethoxy side chain per 7-8 acrylate units. The side chain has the formula -(CH ₂ CH ₂ O) _m (CH ₂ ) _n CH ₃ , where m is 2-3 and n is 6-12. The side chains are ester-linked to the polyacrylate "backbone" to provide a "comb" polymer type structure. Molecular weights can vary, but generally range from about 2,000 to about 50,000. The compositions of the present invention may contain from about 0.05% to about 10% of such alkoxylated polycarboxylates. b. Bleaching compounds - bleaching agents 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, bleaching agents will generally be present at levels from about 1% to about 30%, more usually from about 5% to about 20%, of the detergent compositions. Bleach activators, if present, will generally be present in amounts of from about 0.1% to about 60%, more typically from about 0.5% to about 40%, of the bleaching compositions containing the bleach and bleach activators.

The bleaching agent useful herein can be any bleaching agent useful for detergent compositions in fabric laundering, hard surface cleaning or other known or to be known laundering applications. These include oxygen bleaches as well as other bleaches. Perborate bleaches, such as sodium perborate (eg, mono- or tetra-hydrate), may be used in the present invention.

Another class of bleaches which may be used without limitation includes percarboxylic acid bleaches and salts thereof. Suitable examples of such bleaching agents include magnesium monoperoxyphthalate hexahydrate, magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid, and dodecane diperoxide. acid. US4483781 issued Nov. 20, 1984 to Hartman, U.S. Patent Application 740446 filed Jun. 3, 1985 by Burns et al., European Patent Application 0133354 published Feb. 20, 1985 to Banks et al., and Nov. 1983 Such bleaching agents are disclosed in US 4,412,934, Chung et al. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in US Patent 4,634,551, Burns et al., issued January 6,1987.

Peroxygen bleach can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate and the corresponding "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide. Persulfate bleaches (such as OXONE commercially available from DuPont) may also be used.

Preferred percarbonate bleaches include dry particles having an average particle diameter in the range of about 500 microns to about 1000 microns, wherein no more than about 10% of said particles are less than about 200 microns, and no more than about 10% of said particles are The particles are larger than about 1250 microns. The percarbonate can optionally be coated with silicates, borates or water soluble surfactants. Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.

A bleach mixture can also be used.

Peroxygen bleaches, perborates, percarbonates, etc. are preferably combined with a bleach activator which generates in situ (ie during the wash) an aqueous peroxyacid solution corresponding to the bleach activator. Various non-limiting examples of activators are disclosed in US4915854 and US4412934, Mao et al., issued April 10, 1990. Nonanoylbesylate (NOBS) and tetraacetylethylenediamine (TAED) activators are typical, and mixtures thereof may also be used. See US4634551 for other typical bleaches and activators useful herein.

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

R ¹ N(R ⁵ )C(O)R ² C(O)L or R ¹ C(O)N(R ⁵ )R ² C(O)L wherein R ¹ is a compound containing about 6 to about 12 carbon atoms R is an alkylene group ^{containing 1} to about 6 carbon atoms, R is H or an alkyl, aryl or alkaryl group containing about 1 to about 10 carbon atoms, and L is any suitable the leaving group. A leaving group is any group which is displaced from the bleach activator following nucleophilic attack on the bleach activator by the perhydrolysis anion. A preferred leaving group is phenylsulfonate.

Preferred examples of bleach activators having the above formula include (6-octanoylamino-caproyl)oxybenzenesulfonate, (6-nonanoylaminocaproyl)oxybenzenesulfonate, (6-decanoylamino-hexanoyl)oxybenzenesulfonate, Acyl)isobenzenesulfonates and mixtures thereof are described in US4634551.

Another class of bleach activators includes the benzoxazine-type activators disclosed in US Patent 4,966,723, Hodge et al., issued October 30,1990. Highly preferred benzoxazine type activators are:

其中R⁶为H或含有1-约12个碳原子的烷基、芳基、烷氧基芳基或烷芳基。高度优选的内酰胺活化剂包括苯甲酰基己内酰胺、辛酰基己内酰胺、3,5,5-三甲基己酰基己内酰胺、壬酰基己内酰胺、癸酰基己内酰胺、十一碳烯酰基己内酰胺、苯甲酰基戊内酰胺、辛酰基戊内酰胺、癸酰基戊内酰胺、十一碳烯酰基戊内酰胺、壬酰基戊内酰胺、3,5,5-三甲基己酰基戊内酰胺及其混合物。另外参见1985年10月8日颁布的Sanderson的US4545784，它披露了吸附到过硼酸钠中的包括苯甲酰基己内酰胺在内的酰基己内酰胺。Another preferred bleach activator includes acyl lactam activators, especially acyl caprolactams and acyl valerolactams having the formula,

wherein R is H or an ^alkyl , aryl, alkoxyaryl or alkaryl group containing 1 to about 12 carbon atoms. Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecylenoyl caprolactam, benzoyl valerolactam Amides, capryloyl valerolactam, decanoyl valerolactam, undecylenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also US Patent 4,545,784, Sanderson, issued October 8, 1985, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.

Bleaching agents other than oxygen bleaching agents are also known in the art and may be used in the present invention. One type of non-oxygen bleach of particular interest includes photoactivated bleaches such as sulfonated zinc and/or aluminum phthalocyanines. See US4033718, Holcombe et al., issued July 5,1977. If used, detergent compositions will generally contain from about 0.025% to about 1.25% by weight of such bleaching agents, especially sulfonated zinc phthalocyanines.

If desired, the bleaching compound can be catalyzed with a manganese compound. Such compounds are known in the art and include, for example, the manganese-based catalysts disclosed in US5246621, US5244594, US5194416, US5114606, and European Patent Application Nos. 549271A1, 549272A1, 544440A2 and 544490A1. Preferred examples of such catalysts include Mn ^IV ₂ (uO) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (PF ₆ ) ₂ , Mn ^III ₂ (uO ) ₁ (u-OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (ClO ₄ ) ₂ , Mn ^IV ₄ (uO) ₆ (1,4 ,7-triazacyclononane) ₄ (ClO ₄ ) ₄ , Mn ^III Mn ^IV ₄ (uO) ₁ (u-OAc) ₂ (1,4,7-trimethyl-1,4,7-tri Azacyclononane) ₂ (ClO ₄ ) ₃ , Mn ^IV (1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH ₃ ) ₃ (PF ₆ ) and its mixture. Other metal-based bleach catalysts include those disclosed in US4430243 and US5114611. The following US4728455, 5284944, 5246612, 5256779, 5280117, 5274147, 5153161 and 5227084 also report the use of magnesium and various complexing ligands to enhance bleach performance.

In practice, and without limitation, the compositions and methods of the present invention can be adjusted to provide at least one part per ten million active bleach catalyst material in the wash solution, and preferably about 0.1 ppm to From about 700 ppm, more preferably from about 1 ppm to about 500 ppm catalyst species. c. Whitening agent

Any optical brighteners or other brighteners known in the art can generally be incorporated at a level of from about 0.05% to about 1.2% by weight of the detergent compositions herein. Commercially available optical brighteners that can be used in the present invention can be divided into the following groups including, but not necessarily limited to, stilbene derivatives, pyrazolines, coumarins, carboxylic acids, methinecyanines, diphenyl Thiophene-5,5-dioxide, pyrrole, derivatives of 5- and 6-membered heterocycles, and other heterochromants. Examples of these brighteners are disclosed in "Production and Application of Optical Brighteners", M. Zahradnik, published by John Wiley & Sons, New York (1982).

Specific examples of optical brighteners useful in the compositions of the present invention are the same as disclosed in US Patent 4,790,856, Wixon, issued December 13,1988. These brighteners include Verona's PHORWHITE range of brighteners. Other brighteners disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM available from Ciba-Geigy; Artic White CC and Artic White CWD available from Hilton-Davis in Italy; 2-(4-Benzene Vinylphenyl)-2H-naphtho[1,2-d]triazole; 4,4′-bis(1,2,3-triazol-2-yl)stilbene; 4,4′-bisstyrene Biphenyls and aminocoumarins. Specific examples of these brighteners 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-(stilbene-4-yl)-2H-naphtho [1,2-d]triazole. See also US3646015, Hamilton, issued February 29,1972. Anionic brighteners are preferred for use herein.

d.Builder

Detergent builders can optionally be included in the compositions to help control mineral hardness. Inorganic and organic builders can be used. Typically builders are 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 will generally contain at least about 1% of builder. Liquid formulations generally contain from about 5% to about 50%, more typically from about 5% to about 30%, by weight, of detergent builder. Granular formulations generally 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 builders.

Inorganic or phosphorus-containing detergent builders include, but are not limited to, polyphosphates (particularly tripolyphosphates, pyrophosphates and glassy polymeric metaphosphates), phosphonates, phytic acid, silicates, Alkali metal, ammonium and alkanolammonium salts of carbonates (including bicarbonates and sesquicarbonates), sulfates and aluminosilicates. However, non-phosphate builders are required in some regions. Importantly, even in the presence of so-called "weak" builders (compared to phosphates) such as citrates, or when using zeolite or layered silicate builders, the The so-called "underbuilt" conditions also function surprisingly well.

Examples of silicate builders are alkali metal silicates, especially those with a SiO2: _Na2O ratio of _1.6 :1 to 3.2:1 and layered silicates as described in May 1987 Layered sodium silicates described in US 4,664,839, HP Rieck, issued 12th. NaSKS-6 is a trademark for a crystalline layered silicate supplied by Hoechst (all abbreviated herein as "SKS-6"). Unlike zeolite builders, NaSKS-6 silicate builders do not contain aluminum. NaSKS-6 has the delta-Na ₂ SiO ₅ morphology of phyllosilicates, which can be prepared, for example, by the methods described in DE-A-3417649 and DE-A-3742043. SKS-6 is a highly preferred phyllosilicate for use in the present invention, but other such phyllosilicates may also be used, such as those having the general formula _{NaMSixO2x +1.yH2O ,} Wherein M is sodium or hydrogen, x is a number of 1.9-4, preferably 2, and y is a number of 0-20, preferably 0. Various other phyllosilicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11 in the alpha, beta and gamma forms, respectively. As _noted above, delta- _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 crisping agent in granular formulations, as a stabilizer for oxygen bleaches, and as a component in suds control systems.

Examples of carbonate builders are the alkaline earth and alkali metal carbonates described in German Patent Application No. 2321001, published November 15,1973.

Aluminosilicate builders are useful herein. Aluminosilicate builders are of great importance in recently marketed heavy duty granular detergent compositions and can also be an important builder ingredient in liquid detergent formulations. Aluminosilicate builders include those materials having the empirical formula:

M _z (zAlO ₂ ) _y ] x H ₂ O wherein z and y are integers of at least 6, the molar ratio of z to y is in the range of 1.0 to about 0.5, and x is an integer of about 15-264.

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally occurring aluminosilicates or synthetic. US 3,985,669, Krummel et al., issued December 12, 1976, describes a process for the production of 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:

Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ]xH ₂ O, where x is about 20 to about 30, especially about 27. This material is known as Zeolite A. Dehydrated zeolites (x = 0-10) are useful in the present invention. The particle size of the aluminosilicate is preferably about 0.1-10 microns in diameter.

Organic detergent builders suitable for use herein include, but are not limited to, a wide variety of polycarboxylate compounds. "Polycarboxylate" as used herein refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylate groups. Polycarboxylate builders are generally incorporated into the compositions in acidic form, but may also be included in neutralized salt form. When used in salt form, alkali metals, such as sodium, potassium and lithium, or alkanolammonium salts are preferred.

Polycarboxylate builders include a wide variety of useful materials. An important class of polycarboxylate builders includes ether polycarboxylate builders, including oxydisuccinates, see US Pat. US3635830. See also "TMS/TDS" builders in US Patent 4,633,071, Bush et al., issued May 5,1987. Suitable ether polycarboxylates also include cyclic compounds, especially cycloaliphatic compounds, such as those described in US Pat.

Other useful detergent builders include ether hydroxy polycarboxylates, copolymers of maleic anhydride and ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid; and carboxymethyloxydisuccinic 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, oxygen Disuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxydisuccinic acid, and their soluble salts.

Citrate builders, such as citric acid and its soluble salts (especially the sodium salt), are particularly important polycarboxylates for heavy-duty liquid detergent formulations due to their renewable resource availability and biodegradability. salt builder. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also particularly useful in such compositions and mixtures.

The 3,3-dicarboxy-4-oxa-1,6-hexanedioates and related compounds disclosed in US Patent 4,566,984, Bush, issued January 28, 1986 are also suitable for use in the detergent compositions of the present invention. Useful succinic acid builders include _C5 - _C20 alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include: lauryl succinic acid, myristyl succinic acid, hexadecyl succinic acid, 2-dodecenyl succinic acid (preferred), 2-pentadecene base succinic acid etc. Lauryl succinate is preferred, and is described in European Patent Application 86200690.5/0200263, published November 5, 1986.

Other suitable polycarboxylates are described in US Pat. See also US3723322 to Diehl.

Fatty acids, such as C ₁₂ -C ₁₈ monocarboxylic acids, may also be added to the composition alone, or in combination with the aforementioned builders, especially citrate and/or succinate builders, to provide additional builder activity . This use of fatty acids can result in reduced foam, which should be taken into account by the formulator.

Where phosphorus-based builders can be used, and especially in the formulation of bars for use in handwashing processes, the various alkali metal phosphates such as the known sodium tripolyphosphate, sodium pyrophosphate and orthophosphate can be used. sodium phosphate. Phosphonate builders can also be used, such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see, eg, US Pat. e. Chelating agent

The detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents. Such chelating agents may be selected from amino carboxylates, amino phosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof, as defined below. While not wishing to be bound by theory, it is believed that these species are effective in part because they remove 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, Triethylenetetraaminehexaacetate, diethylenetriaminepentaacetate and ethanol diglycine, their alkali metal, ammonium and substituted ammonium salts, and mixtures thereof.

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

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

A preferred biodegradable chelating agent for use in the present invention is ethylenediamine disuccinate ("EDDS"), especially as described in US4704233, Hartman and Perkins, issued November 3, 1987 [S, S] isomer.

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

If utilized, these chelating agents will generally comprise from about 0.1% to about 15% by weight of the detergent compositions herein. Even more preferably, if employed, such chelating agents comprise from about 0.1% to about 3.0% by weight of the compositions. f. Clay Stain Removal/Anti-Redeposition Agent

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

The most preferred soil removal and antiredeposition agent is ethoxylated tetraethylenepentamine. Examples of ethoxylated amines are described in US Patent 4,597,898, VanderMeer, issued July 1,1986. Another preferred class of clay soil removal/antiredeposition agents are the cationic compounds disclosed in European Patent Application 111965, Oh and Gosselink, published June 27,1984. Other clay soil removal/anti-redeposition agents that may be used include the ethoxylated amine polymers disclosed in European Patent Application 111984, Gosselink, published June 27, 1984; Zwitterionic polymers disclosed in application 112592; and amine oxides disclosed in US Patent 4,548,744, Connor, issued October 22,1985. Other clay soil removal/anti-redeposition agents known in the art may also be used in the compositions of the present invention. Another class of preferred anti-redeposition agents includes carboxymethylcellulose (CMC) materials. These substances are well known in the art. g. Dye transfer inhibitors

The compositions of the present invention may also contain one or more materials effective to inhibit the transfer of dyes from one fabric to another during laundering. Typically such dye transfer inhibiting agents include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidase and their mixture. 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, the polyamine N-oxide polymers suitable for use in the present invention contain units having the formula: RA _x -P; where P is a polymerizable unit that can be attached to an NO group or the NO group forms a polymerizable Unit moieties or NO groups can be attached to both units; A is one of the following structures: -NC(O)-, -C(O)O-, -S-, -O-, -N=; 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 NO group may be attached or the NO group is part of such a group . Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.

其中R¹、R²、R³是脂族、芳族、杂环或脂环基团或它们的组合；x、y和z是0或1；和N-O基团的氮可连接于或形成上述任何基团的部分。聚胺N-氧化物的氧化胺单元的pKa＜10，优选pKa＜7，更优选pKa＜6。The NO group can be represented by the following general structure:

wherein R ¹ , R ² , R ³ are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the NO group may be attached to or form the above part of any group. The amine oxide units of the polyamine N-oxides have a pKa<10, preferably pKa<7, more preferably pKa<6.

Any polymer backbone can be used so 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 in which one monomer type is an amine N-oxide and the other monomer type is an N-oxide. Amine N-oxide polymers typically have a ratio of amine to amine N-oxide of 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by suitable copolymerization or a suitable degree of N-oxidation. Polyamine oxides are available in almost any degree of polymerization. The average molecular weight is usually 500-1,000,000; more preferably 1,000-500,000; most preferably 5,000-100,000. A preferred class of substances may be referred to as "PVNO".

The most preferred polyamine N-oxide for use as the dye transfer inhibiting polymer in the detergent compositions herein is poly(4-vinylpyridine-N-oxide), which has an average molecular weight of about 50,000, the amine The ratio to amine N-oxide is 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 PVPVI is preferably 5,000-1,000,000, more preferably 5,000-200,000, most preferably 10,000-20,000. (Average molecular weight ranges are determined by light scattering as described by Barth et al., in Chemical Analysis, Vol. 113, "Modern Methods for Characterization of Polymers"). The molar ratio of N-vinylimidazole to N-vinylpyrrolidone of the PVPVI copolymer is generally 1:1 to 0.2:1, more preferably 0.8:1 to 0.3:1, most preferably 0.6:1 to 0.4:1. These copolymers may be linear or branched.

Polyvinylpyrrolidones ("PVP") having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, are also useful herein as dye transfer inhibiting agents. PVP is known to those skilled in the detergent field, see for example EP-A-262897 and EP-A-256696. Compositions containing PVP dye transfer inhibiting agents may also contain polyethylene glycol ("PEG") having an average molecular weight of from about 500 to about 100,000, preferably from about 1,000 to about 10,000. The ratio of PEG to PVP in ppm is preferably provided in the wash solution from about 2:1 to about 50:1, more preferably from about 3:1 to about 10:1. h. Enzymes

Enzymes may be included in the detergent compositions of the present invention for a variety of purposes, including removal of protein-based, carbohydrate-based or triglyceride-based soils from e.g. Transfer, and restoration of fabrics. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases and mixtures thereof, of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Their preferred selection is influenced by factors such as pH-activity and/or stability optima, thermostability and stability to active detergents, builders and the like. In this respect, bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.

As used herein, "detersive enzyme" refers to any enzyme having a cleaning, stain removal or other benefit in a laundry, hard surface cleaning or personal care detergent composition. Preferred detergent 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 use in automatic dishwashing are amylases and/or proteases, both currently commercially available and improved, but for improved types, despite ongoing improvements to be more and more compatible with bleach, it Still have some bleach deactivation sensitivity.

Enzymes are typically incorporated into detergent or detergent additive compositions at levels sufficient to provide a "cleaning effective amount". The term "cleaning effective amount" refers to any amount capable of producing a cleaning, stain removing, soil removing, whitening, deodorizing or freshness enhancing effect on soiled substrates such as fabrics, dishware and the like. Typical amounts of active enzyme are up to about 5 mg by weight, more typically 0.01 mg to 3 mg, per gram of detergent composition for practical today's commercial formulations. In other words, the compositions of the invention generally comprise from 0.001% to 5%, preferably from 0.01% to 1% by weight of commercially available enzyme preparations. The amount of protease in such commercial enzyme preparations should generally be sufficient to produce 0.005-0.1 Anson Units (AU) of activity per gram of composition. For certain detergents, such as in automatic dishwashing, it may be desirable to increase the active enzyme content of commercial formulations in order to reduce the total amount of non-catalytically active species to improve spotting/filming or other end results. Higher active levels are also desirable in highly concentrated detergent formulations.

Suitable examples of proteases are subtilisins obtained from special strains of Bacillus subtilis and Bacillus licheniformis. A suitable protease is obtained from a Bacillus strain developed by Novo Industries A/S of Denmark and marketed as ESPERASE®, hereinafter "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 1,243,784 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, January 9, 1985, and Protease B disclosed in EP303761A and EP130756A of 9 January 1985. See also the high pH protease from Bacillus NCIMB40338 described in WO9318140A to Novo. Enzyme detergents comprising a protease, one or more other enzymes and a reversible protease inhibitor are described in WO9203529A to Novo. Other preferred proteases include those in WO9510591 to Procter & Gamble. If desired, proteases with reduced adsorption and increased hydrolysis are available as described in WO9507791 to Procter & Gamble. A recombinant trypsin-like protease suitable for use in the detergents of the present invention is described in WO9425583 to Novo.

In more detail, an especially preferred protease known as "Protease D" is a carbonyl hydrolase variant having an amino acid sequence not found in nature, as described in US Serial No. 08/322676, filed October 13, 1994. .Baeck et al., entitled "Protease-containing cleaning compositions" and Ghosh et al., US Serial No. 08/322677, entitled "Protease-containing bleaching compositions", by substituting different amino acids in The amino acid residue corresponding to position +76 in the above-mentioned carbonyl hydrolase is obtained from the precursor carbonyl hydrolase, which is preferably combined with a substitution corresponding to +99, +101, +103, + according to the numbering of Bacillus amyloliquefaciens subtilisin 104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, One or more amino acid residues at positions +217, +218, +222, +260, +265 and/or +274.

Amylases suitable for use in the present invention, especially those suitable for, but not limited to, automatic dishwashing purposes include, for example, the alpha-amylases described in British Patent No. 1,296,839 to Novo; RAPIDASE from International Bio-Synthetics, Inc. _ and TERMAMYL_ from Novo. FUNGAMYL_ from Novo is particularly useful. Enzyme engineering for improved stability, such as oxidative stability, is known. See, eg, J. Biological Chem. Vol. 260, No. 11, Jun. 11, 1985, pp. 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, especially improved TERMAMYL as used commercially relative to 1993_ref Oxidative stability of point assay. These preferred amylases of the present invention are characterized as "stability-increased" amylases characterized at least by the reaction of hydrogen peroxide/tetraacetyl Oxidative stability of ethylenediamine; as thermal stability at normal wash temperatures, such as about 60° C.; or as measurable improvement in alkali stability at a pH of about 8-11 (compared to the aforementioned reference point Amylase was measured). Stability can be measured using any of the assays disclosed in the art. See, eg, what is disclosed in WO9402597. Stability-enhanced amylases are available from Novo or from Genencor International. A highly preferred amylase of the present invention has in common that it is derived by site-directed mutagenesis from one or more Bacillus amylases, especially from Bacillus alpha-amylases, regardless of whether one, two or more Whether the amylase strain is an intermediate precursor. It is preferred to use amylases having increased oxidative stability relative to the reference amylases mentioned above, especially for use in bleaching detergent compositions according to the invention, more preferably oxygen bleaching detergent compositions as opposed to chlorine bleaching. Such preferred amylases include (a) amylases according to WO 9402597 to Novo, incorporated by reference above, on 3 February 1994, which may be further illustrated by mutants wherein alanine or threonine are used, Substitution of threonine at position 197 of the Bacillus licheniformis alpha-amylase known as TERMANYL, or variants at homologous positions of similar parent amylases such as Bacillus amyloliquefaciens, Bacillus subtilis or Bacillus stearothermophilus Methionine residues; (b) Genencor International, described in a paper entitled "Antioxidant α-amylases" presented by C. Mitchinson to the 207th Annual Meeting of the American Chemical Society, March 13-17, 1994 Increased stability of amylases. In it, it mentions that bleaches in automatic dishwashing detergents inactivate alpha-amylases, but Genencor has prepared amylases from Bacillus licheniformis NCIB8061 with improved oxidative stability. Methionine (Met) was identified as the most likely residue to be modified. Met was substituted one at a time at positions 8, 15, 197, 256, 304, 366 and 438, resulting in specific mutants, particularly important M197L and M197T, with the M197T variant being the most stably expressed variant. Stability is measured in CASCADE_ and SUNLIGHT_; (c) particularly preferred amylases for use in the present invention include amylase variants with additional modifications in previous generation parents as described in WO9510603A and available from assignee Novo Obtained as DURAMYL_. Other particularly preferred amylases with increased oxidative stability include those described in WO9418314 to Genencor International and WO9402597 to Novo. Any other amylase with increased oxidative stability may be used, for example derived by site-directed mutagenesis from known chimeric, hybrid or simple mutant parent forms of available amylases. Other preferred enzyme modifications can be made. See WO9509909 to Novo.

Other amylases include those described in WO95/26397 and co-pending application PCT/DK96/00056 at Novo Nordisk. Specific amylases suitable for use in the detergent compositions of the present invention include - Amylases characterized by having a specific activity at least 25% higher than Termamyl® in the temperature range of 25°C-55°C and at a pH of 8-10 Specific activity - Amylase, said activity being determined by the Phadebas -amylase activity test (the Phadebas -amylase activity test is described in WO/95/26397 pages 9-10). Also included are beta-amylases that are at least 80% homologous to the amino acid sequence shown in the SEQ ID sequence in the reference. 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 used in the present invention include bacterial and fungal types, preferably having an optimum pH of 5-9.5. Barbesgoard et al. disclosed in US4435307 March 6, 1984 suitable fungal cellulases from Humicola insolens or Humicola strain DSM1800 or cellulase 212-producing fungi belonging to the genus Aeromonas, and from Cellulase extracted from the hepatopancreas of the marine mollusk Dolabella Auricula Solander. GB-A-2075028, GB-A-2095275 and DE-OS-2247832 also disclose suitable cellulases. CAREZYME_ and CELLUZYME_ (Novo) are particularly useful. See also WO9117243 to Novo.

Lipases suitable for use in detergents include microorganisms of the genus Pseudomonas, such as the lipase produced by Pseudomonas stutzeri ATCC 19.154 as disclosed in GB1372034. See also lipases in Japanese Patent Application No. 53,20487, published February 24,1978. This lipase is available from Amano Pharmaceutical Co. Ltd. of Nagoya, Japan under the tradename Lipase P "Amano" or "Amano-P". Other suitable commercial lipases include Amano-CES from Chromobacter viscosum such as Chromobacter viscosum var. lipolyticum NRRL B3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum from U.S. Biochemical Corp., USA, and Disoynth Co., The Netherlands lipase; 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. Peroxidase-stable lipase and amylase variants are described in WO9414951A to Novo. See also WO9205249 and RD94359044.

Despite numerous publications on lipases, so far only lipases derived from Humicola lanuginosa and produced in Aspergillus oryzae as a host have been found to be widely used as additives to fabric washing products. It is available under the trade name Lipolase ^(TM) from Novo Nordisk as described above. To optimize the stain removal performance of lipase, Novo Nordisk has prepared various variants. As described in WO92/05249, the D96L variant of the native Humicola lanuginosa lipase was 4.4 times more efficient at removing lard stains than the wild-type lipase (enzymes compared in amounts ranging from 0.075-2.5 mg protein per liter). Research Disclosure No. 35944 (Novo Nordisk), published March 10, 1994, discloses that a lipase variant (D96L) may be added in an amount corresponding to 0.001-100 mg per liter of wash liquor (5-500000 LU/l). The present invention in the manner disclosed herein provides that the use of low levels of D96L variants in detergent compositions containing AQA surfactants provides improved whiteness retention on fabrics, especially at about 50 LU to about 8500 LU per liter of wash solution. The content of the case using D96L.

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

Peroxidases can be used in combination with oxygen sources such as percarbonate, perborate, hydrogen peroxide, etc. for "solution bleaching", or during washing, to prevent the transfer of dyes or pigments removed from the substrate onto other carriers present in the wash solution. Known peroxidases include horseradish peroxidase, ligninase, haloperoxidase such as chloro- or bromoperoxidase. Peroxidase-containing detergent compositions are disclosed in WO89099813A, Novo, October 19, 1989 and WO8909813A, Novo.

WO9307263A and WO9307260A to Genencor International, WO8908694A to Novo and US3553139 to McCarty et al. issued January 5, 1971 also disclose a range of enzyme raw materials and their incorporation into synthetic detergent compositions. Enzymes are further disclosed in US4101457, Place et al., July 18, 1978 and US4507219, Hughes, March 26, 1985. US Patent 4,261,868, Hora et al., April 14, 1981, discloses enzyme materials for use in liquid laundry formulations, and their incorporation into such formulations. Enzymes for use in detergents can be stabilized in a variety of ways. Enzyme stabilization techniques are disclosed and enumerated in US3600319, Gedge et al., August 17, 1971, and EP199405 and EP200586, Venegas, October 29, 1986. Enzyme stabilization systems are also described eg in US3519570. WO9401532A to Novo describes Bacillus AC13 capable of donating protease, xylanase and cellulase. i. Enzyme stabilization system

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

One method of stabilization is the use of water-soluble sources of calcium and/or magnesium ions in the final composition that provide the enzyme with its ions. Calcium ions are generally more effective than magnesium ions, so 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 final detergent composition, although according to Factors including the variety, type and amount of enzymes added are likely to vary. Water-soluble calcium or magnesium salts are preferably used, including, for example, calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide and calcium acetate; more generally, calcium sulfate or all The corresponding magnesium salts of the calcium salts are listed. It may of course be useful to further increase the calcium and/or magnesium content, for example to increase the degreasing effect of certain types of surfactants.

Another stabilization method is the use of borate species. See US4537706 to Severson. Borate stabilizers may be used at levels up to 10% or more of the composition, but boric acid or other borate compounds such as borax or orthoborate are more generally suitable for use in liquid detergents at levels up to about 3% by weight. Substituted boronic acids such as phenylboronic acid, butyric acid, p-bromophenylboronic acid, etc. can be used instead of boric acid, and despite the use of such substituted boron derivatives, it is still possible to reduce the total boron content of detergent compositions.

Stabilizing systems of certain detergent compositions, such as automatic dishwashing compositions, may further contain from 0 to about 10% by weight, preferably from about 0.01% to about 6%, of a chlorine bleach scavenger added to prevent the Chlorine bleach species in the supply attack enzymes and reduce their activity, especially under alkaline conditions. Although the chlorine content in water can be very little, generally about 0.5ppm-1.75ppm, for example, in the washing process of tableware or fabrics, the available chlorine in the total water contacted with enzymes will be quite large; therefore, when using chlorine In some cases, the stability of the enzyme is sometimes problematic. Since perborates or percarbonates capable of reacting with chlorine bleaching substances are present in some of the present compositions in amounts metered separately from the stabilizing system, the use of other anti-chlorine stabilizers may not generally be necessary , although their use may increase the effect. Suitable chlorine scavenger anions are widely known and readily available and, if used, may be salts of sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc. containing ammonium cations . Additionally, antioxidants such as carbamates, ascorbic acid, etc., organic amines such as ethylenediaminetetraacetic acid (EDTA) or its alkali metal salts, monoethanolamine (MEA) and mixtures thereof may be used. In addition, a special enzyme inhibition system can be added so that 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, can be used if desired , acetate, benzoate, citrate, formate, lactate, malate, tartrate, salicylate, etc., and mixtures thereof. In general, since ingredients listed separately on a basis of perceived superior function (such as a source of hydrogen peroxide) can function as a chlorine scavenger, there is no absolute requirement to add a separate chlorine scavenger unless that function is performed The compound is not present to the desired extent in the enzyme-containing embodiments of the invention, and even then the scavenger is added for optimum effect only. Also, the formulator can employ the ordinary skill of a chemist in order to avoid the use of any enzyme scavengers or stabilizers which are substantially incompatible when formulated with other active ingredients, if used. For the use of ammonium salts, such salts can simply be premixed with the detergent composition, but tend to absorb water and/or release ammonia during storage. Therefore, it is desirable to protect such material, if present, within the particles, as described in Baginski et al. US 4,652,392. j. Fabric softener

Various fabric softeners that have undergone a full laundering cycle, particularly the fine-grained smectite clays of US4062647, Storm and Nirschl, issued December 13, 1977, and other softener clays known in the art, can optionally be formulated as Amounts of from about 0.5% to about 10% by weight are used in the compositions of the present invention to achieve fabric softening while washing fabrics. Clay softeners may be used with the disclosed amine and cationic softeners, as disclosed in Crisp et al., US 4,375,416, Mar. 1, 1983, and Harris et al., US 4,291,071, Sept. 22, 1981. k. Polymeric detergent

Known polymeric soil release agents, hereinafter "SRA", can optionally be used in the detergent compositions of the present invention. If used, SRA will generally 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.

SRA generally preferably contains hydrophilic segments to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon. Part is fixed. This makes it easier to remove stains after SRA treatment in subsequent washes.

SRA can include various charged, for example anionic or even cationic species (see US4956447 issued September 11, 1990 to Gosselink et al.) as well as uncharged monomeric units, which can be linear, branched or chain in structure. Even star-shaped. They may include capping groups which are especially effective in controlling molecular weight or modifying physical or surface active properties. The structure and charge distribution can be changed for application to different fiber or textile types and different detergent or detergent additive products.

Preferred SRAs include oligomeric terephthalates, typically prepared by processes involving at least one transesterification/oligomerization process, typically using metal catalysts such as titanium(IV) alkoxides. The esters may be prepared using additional monomers capable of incorporating the ester structure through one, two, three, four or more positions without, of course, forming a tightly crosslinked overall structure.

Suitable SRAs include sulfonated products of substantially linear ester oligomers derived from an oligoester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl groups covalently attached to the backbone. End group composition, eg as described in US4968451, J.J. Scheibel and E.P. Gosselink, November 6, 1990. The ester oligomer can be prepared by: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate ("DMT") and 1,2- Propylene glycol ("PG") is reacted 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 terminated 1,2-propanediol/polyoxyethylene terephthalate polyesters of US4711730, Gosselink et al., December 8, 1987, for example from poly(ethylene glycol) methyl ether , DMT, PG, and poly(ethylene glycol) ("PEG") transesterification/oligomerization preparation. Other examples of SRAs include partially and fully anionically terminated oligoesters, such as those made from ethylene glycol ("EG"), PG, DMT, and 3,6-dioxa-8, US4721580, Gosselink, January 26, 1988. - oligomers derived from sodium hydroxyoctylsulfonate; Gosselink, Oct. 27, 1987, non-ionically terminated block polyester oligomers, for example by DMT, methyl-terminated PEG and EG and/or PG, or Preparation of a mixture of DMT, EG and/or PG, Me-terminated PEG and 5-sodium sulfonate dimethyl isophthalate; and the anions of US4877896, Maldonado, Gosselink et al., Oct. 31, 1989, especially sulfoaryl Acyl-terminated terephthalates, the latter being a typical type of SRA used in laundry and fabric conditioning products, examples of which are ester compositions prepared from m-sulfobenzoic acid monosodium salt, PG and DMT, optionally , but preferably also contain added PEG, such as PEG3400.

SRA also includes simple copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see May 25, 1976 US3959230 to Hays and US3893929 to Basadur, Jul. 8, 1975; Cellulose derivatives, such as METHOCEL from Dow, hydroxyether cellulose polymers; C _1-4 alkyl cellulose and C ₄ hydroxyalkyl cellulose ; see U.S. Patent 4,000,093, Nicol et al., December 28, 1976; and methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit of from about 1.6 to about 2.3, and at 20° C. at 2 The solution viscosity, measured as a % water solution, is from about 80 to about 120 centipoise. This material is available as METOLOSE SM100 and METOLOSE SM200, which are trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.

Suitable SRAs featuring poly(vinyl ester) hydrophobic segments include graft copolymers of poly(vinyl esters) such as C _1-6 vinyl esters, preferably poly(vinyl acetate) grafted onto a polyoxyalkylene backbone. ). See EP0219048, Kud et al., published April 22,1987. Commercially available examples include SOKALAN SRA, eg SOKALAN HP-22, available from BASF (Germany). Other SRAs are polyesters with repeating units containing 10-15% by weight ethylene terephthalate and 80-90% by weight polyoxyethylene terephthalate , which is obtained from polyoxyethylene glycol with an average molecular weight of 300-5000. Commercial examples include ZELCON5126 from Dupont and MILEASET from ICI.

Another preferred class of SRAs are oligomers of the empirical formula (CAP) ₂ (EG/PG) ₅ (T) ₅ (SIP) ₁ containing terephthaloyl (T), sulfoisophthaloyl Acyl (SIP), oxyethyleneoxy and oxy-1,2-propylene (EG/PG) units, which are preferably terminated by end groups (CAP), preferably modified isethionates , for example, oligomers containing one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a defined ratio, preferably about 0.5:1 to about 10:1, and two capping units derived from sodium 2-(2-hydroxyethoxy)-ethanesulfonate. The SRA preferably also contains 0.5% to 20% by weight of the oligomer of a crystallinity-reducing stabilizer, such as an anionic surfactant, such as linear sodium dodecylbenzenesulfonate or selected from xylene-, cumene- Alkene- and toluene-sulfonates or mixtures thereof, these stabilizers or modifiers are added to the synthesis vessel, all of which are disclosed in US5415807 issued May 16, 1995 to Gosselink, Pan, Kellett and Hall . Suitable monomers for use in the above SRAs include sodium 2-(2-hydroxyethoxy)-ethanesulfonate, DMT, sodium 5-sulfonate dimethylisophthalate, EG and PG.

Another preferred class of SRAs are oligomeric esters containing: (1) a backbone containing (a) at least one unit selected from the group consisting of dihydroxysulfonates, polyhydroxysulfonates, at least trifunctional groups such that Units and mixtures thereof; (b) at least one unit that is a terephthaloyl group; and (c) at least one unsulfonated unit that is 1 , a 2-oxyalkyleneoxy moiety; and (2) one or more capping units selected from nonionic capping units, anionic capping units, such as alkoxylated, preferably ethoxylated hydroxyethyl Sulfonates, alkoxylated propane sulfonates, alkoxylated propane disulfonates, alkoxylated phenol sulfonates, sulfoaroyl derivatives and mixtures thereof. Esters of the following empirical formula are preferred:

{(CAP) _x (EG/PG) _y' (DEG) _y” (PEG) _y”' (T) _z (SIP) _z' (SEG) _q (B) _m } where CAP, EG/PG, PEG, T and SIP are as defined above, (DEG) denotes di(oxyethylene)oxy units, (SEG) denotes units derived from glycerol sulfoethyl ether and related radical units, (B) denotes branched chain units, It is at least three functional so that the ester linkages formed create a branched oligomer 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 0 to about 10, y"+y"+y"' sums from about 0.5 to about 25, z is about 1.5 to about 25, z' is 0 to about 12, z+z' sums from about 1.5 to about 25, q is about 0.05 to about 12; m is from about 0.01 to about 10, and x, y', y", y"', z, z', q and m represent the average number of moles per mole of the corresponding unit of the ester having Molecular weight from about 500 to about 5000.

Preferred SEG and CAP monomers for the above esters include sodium 2-(2-,3-dihydroxypropoxy)ethanesulfonate (“SEG”), 2-{2-(2-hydroxyethoxy)ethoxy } Sodium ethanesulfonate ("SE3") and its homologues and mixtures thereof and products of ethoxylated and sulfonated allyl alcohols. Preferred SRA esters of this class include transesterification and oligomerization of sodium 2-{2-(2-hydroxyethoxy)ethoxy}ethanesulfonate and/or 2-[ Sodium 2-{2-(2-hydroxyethoxy)ethoxy}ethoxy]ethanesulfonate, DMT, sodium 2-(2,3-dihydroxypropoxy)ethanesulfonate, EG and PG The product, which can be called (CAP) ₂ (T) ₅ (EG/PG) _1.4 (SEG) _2.5 (B) _0.13 , where CAP is (Na ⁺ O ₃ S[CH ₂ -CH ₂ -CH ₂ O] ₃₅ ) -, and B are units derived from glycerol with an EG/PG molar ratio of about 1.7:1, as determined by conventional gas chromatography after complete hydrolysis.

Another class of SRAs includes: (I) attachment of nonionic terephthalate to polyester structures using diisocyanurate coupling agents, see US4201824 to Violland et al. and US4240918 to Lagasse et al; Carboxylate-terminated SRAs prepared by the addition of trimellitic anhydride to known SRAs to convert the terminal hydroxyl groups to trimellitate esters. By proper selection of the catalyst, the trimellitic anhydride bonds to the end of the polymer through the individual carboxylate ester of the trimellitic anhydride, rather than opening the anhydride bond. Both nonionic and anionic SRAs can be used as starting materials as long as they have hydroxyl end groups that can be esterified. See US4525524 by Tung et al. Other materials include: (III) anionic terephthalate-based SRAs of the urethane-linked species, see US4201824 to Violland et al; (IV) poly(vinylcaprolactam) and monomers such as vinylpyrrolidone and/or Related copolymers of dimethylaminoethyl methacrylate, including nonionic and anionic polymers, see US4579681 to Ruppert et al; Graft copolymers prepared from acrylic acid monomers. These SRAs certainly have soil release and antiredeposition activity similar to known cellulose ethers: see EP279134A, 1988, Rhone-Poulenc Chemie. Yet another class of materials includes: (VI) grafts of vinyl monomers such as acrylic acid and vinyl acetate on proteins, such as casein, see EP457205A (1991) of BASF; and (VII) grafts of adipic acid, caprolactam Polyester-polyamide SRA prepared with polyethylene glycol is especially suitable for processing polyamide fabrics, see DE2335044 (Unilever N.V.) (1974) of Bevan et al. Other useful SRAs are described in US4240918, 4787989 and 4525524. 1. Polymeric dispersant

Polymeric dispersants can advantageously be used at levels from about 0.1% to about 7% by weight in the compositions herein, especially when zeolite and/or layered silicate builders are present. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used. While not wishing to be bound by theory, it is believed that polymeric dispersants, when used together with other builders, including low molecular weight polycarboxylates, provide peptization of particulate soil and anti-renewal effects through crystal growth inhibition. Deposition can improve overall detergent builder performance.

The polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in the acid form. Unsaturated monomeric acids which 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 not bearing carboxylate groups such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that it does not exceed about 40% by weight %.

Especially suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-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 from about 2,000 to 10,000, more preferably from about 4,000 to 7,000, most preferably from about 4,000 to 5,000. 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, US Pat. No. 3,308,067 to Diehl, issued March 7, 1967, discloses the use of such polyacrylates in detergent compositions.

Acrylic/maleic acid based copolymers can also be used as a preferred component of the dispersing/anti-redeposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form is preferably from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000. The ratio of acrylate moieties 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, ammonium and substituted ammonium salts. Such soluble acrylate/maleate copolymers are known materials and are described in European Patent Application 66915, published December 15, 1982, and in EP193360, published September 3, 1986, which also describes Such polymers containing hydroxypropyl acrylate. Other useful dispersants include maleic acid/acrylic acid/vinyl alcohol terpolymers. Such materials are also disclosed in EP193360, which include for example a 45/45/10 terpolymer of acrylic acid/maleic acid/vinyl alcohol.

Another class of polymers that can be included is polyethylene glycol (PEG). PEGs can exhibit dispersant properties as well as clay soil removal/anti-redeposition agents. Polyethylene glycols for this use generally have a molecular weight in the range of from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000.

Polyaspartate and polyglutamate dispersants can also be used, especially in combination with zeolite builders. Dispersants, such as polyaspartate, preferably have a molecular weight (average) of about 10,000. m. Foam inhibitor

Compounds for reducing or inhibiting suds formation may be incorporated into the compositions of the present invention. Suds suppression is particularly important in the so-called "high strength wash process" described in US4489455 and 4489574 and in the case of front loading Euro washing machines.

Various substances can be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, eg, Kirk Othmer, Encyclopedia of Chemical Technology, 3rd Edition, Volume 7, pp. 430-447 (John Wiley & Sons, Inc., 1979). A particularly important class of suds suppressors includes monocarboxylic acid-based fatty acids and soluble salts thereof. See US2954347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids and salts thereof useful as suds suppressors generally have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include alkali metal salts such as sodium, potassium and lithium; 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, such as paraffin, fatty acid esters (such as fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C ₁₈ -C ₄₀ ketones (such as stearyl ketone), etc. . Other suds suppressors include N-alkylated aminotriazines, such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine chlorotriazines, which are cyanuric chloride with 2 or 3 molar Products of primary or secondary amines containing 1 to 24 carbon atoms, propylene oxide, and salts of monostearyl phosphates, such as monostearyl phosphate and monostearyl dialkali metals (such as K, Na , and Li) phosphates and phosphate esters. Hydrocarbons such as paraffins and halogenated paraffins can 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 not less than about 110°C (atmospheric pressure). It is known to use waxy hydrocarbons, preferably having a melting point below about 100°C. Such hydrocarbons are a preferred class of suds suppressors for detergent compositions. Hydrocarbon suds suppressors are described, for example, in US Patent 4,265,779, Gandolfb et al., issued May 5,1981. Thus, the hydrocarbon includes aliphatic, cycloaliphatic, aromatic and heterocyclic saturated or unsaturated hydrocarbons containing from about 12 to about 70 carbon atoms. The term "paraffin," as used in the discussion of suds suppressors, includes mixtures of true paraffins and cyclic hydrocarbons.

Another preferred class of non-surfactant suds suppressors includes silicone suds suppressors. Such materials include the use of silicone oils, such as polydimethylsiloxane, dispersions or emulsions of silicone oils or resins, and mixtures of silicone and silica particles, wherein the polysiloxane The siloxane is chemisorbed or fused onto the silica. Silicone suds suppressors are well known in the art and are disclosed, for example, in US 4,265,779, Gandolfo et al., issued May 5, 1981, and European Patent Application 8,9307,851.9, Starch, M.S., published February 7, 1990.

Other silicone suds suppressors are disclosed in US 3,455,839 which relates to compositions and methods for defoaming aqueous solutions by incorporating small amounts of polydimethylsiloxane fluids into the compositions.

Mixtures of polysiloxanes and silanized silicas are described, for example, in German patent application DOS2124526. Silicone antifoam and suds control agents in granular detergent compositions are described in US Patent 3,933,672 to Bartolotta et al. and US Patent 4,652,392, Baginski et al., issued March 24,1987.

An example of a silicone-based suds suppressor useful herein is a suds suppressing amount of a suds control agent consisting essentially of:

(i) a polydimethylsiloxane fluid having a viscosity of from about 20 cs to about 1500 cs at 25°C;

(ii) About 5 to 50 parts by weight per 100 parts by weight of (i) a silicone resin consisting of (CH ₃ ) ₃ SiO _1/2 units and SiO ₂ units in the form of (CH ₃ ) ₃ SiO Composition in a ratio of _1/2 units to _SiO2 units in a ratio 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) by weight.

In preferred silicone suds suppressors for use in the present invention, the solvent used for the continuous phase consists of certain polyethylene glycols or polyethylene glycol-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol . The primary polysiloxane suds suppressors are branched/crosslinked, preferably non-linear.

To further illustrate this point, a typical liquid laundry detergent composition having suds control optionally contains 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% of said silicone suds suppressor comprising (1) a non-aqueous emulsion of a primary suds suppressor which is (a) polysiloxane, (b) resinous silicone Oxane or polysiloxane compounds that yield polysiloxane resins, (c) finely divided fillers and (d) catalysts that cause the mixture components (a), (b) and (c) to react to form silanolates mixture; (2) at least one nonionic polysiloxane surfactant; and (3) polyethylene glycol or a copolymer of polyethylene glycol-polypropylene glycol having a solubility in water of more than 2% by weight at room temperature ; No polypropylene glycol in it. Similar amounts can be used in granular compositions, gels and the like. See also US4978471, Starch, issued December 18, 1990, and US4983316, Starch, issued January 8, 1991, 5288431, Huber et al., and US4639489 and 4749740, issued February 22, 1994, Huber et al. Column 4, line 46 to Column 4, line 35.

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

Preferred solvents of the present invention are polyethylene glycol with an average molecular weight of less than about 1000, more preferably about 100-800, most preferably 200-400, and polyethylene glycol/polypropylene glycol copolymers, preferably PPG200/PEG300. The weight ratio of polyethylene glycol:polyethylene glycol-polypropylene glycol copolymer is preferably about 1:1 to 1:10, most preferably 1:3 to 1:6.

Preferred silicone suds suppressors for use herein are free of polypropylene glycol, especially polypropylene glycol having a molecular weight of 4000. It is also preferably free of block copolymers of ethylene oxide and propylene oxide, such as PLURONICL101.

Other suds suppressors useful herein include secondary alcohols such as 2-alkyl alkanols and mixtures of these alcohols with silicone oils such as the silicones disclosed in US Patent Nos. 4,798,679, 4,075,118 and EP 150,872. Secondary alcohols include _C6 - _C16 alkyl alcohols having a _C1 - _C16 chain. A preferred alcohol is 2-butyloctanol, which is available from Condea under the trademark ISOFOL12. A mixture of secondary alcohols is available from Enichem under the trademark ISALCHEM123. Mixed suds suppressors generally contain a mixture of alcohol and polysiloxane in a weight ratio of 1:5 to 5:1.

As with any detergent composition for use in automatic washing machines, the suds formed should not overflow the washing machine. When a suds suppressor is used, it is preferably present in a "foam suppressing amount". By "suds suppressing amount" is meant the suds controlling amount selected by the formulator of the composition to control suds sufficiently to provide a low sudsing laundry detergent which can be used in automatic washing machines.

The compositions of the present invention generally contain from 0% to about 5% suds suppressor. When used as suds suppressors, monocarboxylic fatty acids and their salts are generally used at levels up to about 5% by weight of the detergent compositions. Preferably, from about 0.5% to about 3% fatty monocarboxylate suds suppressor is used. Silicone suds suppressors are generally used at levels up to about 2.0% by weight of the detergent composition, although higher levels can also be used. This upper limit is practical due to the primary considerations of keeping costs to a minimum and the effectiveness of lower levels for effective foam control. Preferably from about 0.01% to 1% silicone suds suppressor is used, more preferably from about 0.25% to 0.5%. These weight percent values used in the present invention include any silica that may be used with the polysiloxane as well as any auxiliary materials that may be used. Monostearyl phosphate suds suppressors are generally used at levels of from about 0.1% to about 2% by weight of the compositions. Hydrocarbon suds suppressors are typically used at levels of from about 0.01% to about 5.0%, although higher levels 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

Various other ingredients useful in detergent compositions may also be included in the compositions of the present invention, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, block Solid fillers for shaped compositions, etc. If high foam is required, a foam booster such as C ₁₀ -C ₁₆ alkanolamide can be added to the composition, generally at a content of 1%-10%. C ₁₀ -C ₁₄ monoethanols and diethanolamides are typical examples of this class of suds boosters. It is also advantageous to use such suds boosters with high sudsing co-surfactants such as the amine oxides, betaines and sultaines mentioned above. If desired, soluble magnesium salts such as magnesium chloride, magnesium sulfate, etc. may also be added, typically at levels of 0.1% to 2%, to provide additional foam and enhanced degreasing performance.

The various detergent ingredients used in the compositions of the present invention can optionally be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, which is then coated with a hydrophobic coating agent. change. Preferably the detergent component is mixed with the surfactant prior to adsorption into the porous matrix. In use, the detergent components are released from the substrate into the aqueous wash solution to accomplish their intended detergency.

To illustrate the technique in more detail, a proteolytic enzyme containing porous hydrophobic silica (trademark SIPERNATD10, DeGussa) with a nonionic surfactant containing 3%-5% _C13-15 ethoxylated alcohol (EO7) The solution is mixed. The amount of the enzyme/surfactant solution is typically 2.5 times the weight of silica. The resulting powder is dispersed in silicone oil (various silicone oils with a viscosity of 500-12500 can be used) under stirring. The resulting silicone oil dispersion is emulsified or incorporated into the final detergent base. In this way, components such as the aforementioned 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. For solubilizing surfactants, monohydric alcohols are preferred, but polyols, such as those containing 2 to about 6 carbon atoms and 2 to about 6 hydroxyl groups (e.g., 1,3-propanediol, ethylene glycol, glycol, glycerin and 1,2-propanediol). The compositions may contain from 5% to 90%, usually from 10% to 50%, of such carriers.

The detergent compositions of the present invention are preferably formulated so that when used during an aqueous laundering operation, the wash water has a pH of from about 6.5 to about 11, preferably from about 7.5 to 10.5. Liquid dishwashing product formulations preferably have a pH of from about 6.8 to about 9.0. Laundry products are typically pH 9-11. Techniques for controlling pH within the desired range for use include the use of buffers, bases, acids, etc., and are known to those skilled in the art.

Example

The following examples further describe and demonstrate preferred embodiments within the scope of the present invention. The examples are for illustration only and are not intended to be limiting of the invention since many changes may be made 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.

Components % by weight of composition

NaCFAS(C ₁₂ -C ₁₈ ) (coconut fatty alcohol sulfate) 21

A(C ₁₂ -C ₁₄ )E6.5(Alkyl ethoxylate) 4

STPP (sodium tripolyphosphate) 17.5

Sodium carbonate 20.0

Zeolite 8.0

Nonanoylbenzenesulfonate 2.3

Sodium perborate 2.28

Zinc Phthalocyanine Sulfonate 0.3

ACUMER3100 (terpolymer) 2.25

Diethylene triamine pentaphosphonate (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

Balance of water (including water of hydration), sodium sulfate and other minor components

Example 2

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

Components % by weight of composition

NaC ₂₅ -AS 20.5

A(C _12-14 )E3S 5.0

A(C _12-13 )E6.5 4.5

C _12-14 fatty acids 5.0

Citric acid 3.0

Ethanol 5.5

Hexylene glycol 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 whitening agent 49 (4,4'bistilbene) 0.1

Balance of water (including water of hydration) and other minor components

Example 3

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

Components By weight of composition

%

NaLAS(C12-18) 22.5

NaAS 3

Sodium Carbonate 3

Diethylene triamine pentaphosphonate (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 components Balance

Example 4

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

Wash whites separately from colored clothes. 40 g of the composition of Example 1 were placed in an automatic washing machine. Then add white clothes with a total weight of about 1.5Kg in the washing machine. After running the washing machine, the washing machine is filled with about 33 liters of water. Run the washer on an automatic cycle of about 10 minutes of washing, followed by two intermittent rinses. Then allow the garment to air dry, sun dry, or machine dry. Laundered clothes did not yellow and white clothes kept their whiteness.

Example 5

This example illustrates the use of the composition of Example 1 to handwash fabrics.

Put about 10 liters of water in the basin. 40 g of the composition of Example 1 were dissolved in water. Wash white clothes (about 1.5Kg) separately from colored clothes. Scrub the garment by hand or scrub it with a washboard. Dip the garment in the wash solution from time to time during scrubbing. After all laundry has been washed, discard the wash solution and replace with fresh clean water for rinsing. Rinse is performed by hand swirling and scrubbing and wringing out of the water of the garment. Replace the rinse water with fresh clean rinse water. Continue rinsing and replacing the rinse water until the final rinse water is clean and free of visible and persistent suds. After rinsing, air dry, line dry, or machine dry. Laundered clothes did not yellow and white clothes kept their whiteness.

Example 6

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

Pre-rinse white clothes in a basin of about 20 liters of water to remove any particulate soil. Discard the pre-rinse water and replace with fresh water. Wash garments piece by piece by applying the block directly to the fabric, then scrub by hand or using a scrubbing implement, such as a scouring pad. When all laundry has been washed, discard the wash water and replace with fresh clean water. Then rinse the clothes in batches until there is no visible suds or the final rinse water is clear. After rinsing, air dry, line dry, or machine dry. Then allow the clothes to machine dry or air dry. Laundered clothes did not yellow and white clothes kept their whiteness.

Example 7

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

Wash whites separately from colored clothes. Spotted area stains and soils were pretreated with a small amount of the composition of Example 3. Clothes (approximately 1.5 Kg) were then placed in an automatic washing machine. An additional 39.6 g of the composition of Example 3 was added to the clothes in the automatic washing machine. After running the washing machine, the washing machine is filled with about 33 liters of water. Run the washer on an automatic cycle of about 10 minutes of washing, followed by two 3-minute rinses. After rinsing, allow the garment to air dry, line dry, or machine dry. Laundered clothes did not yellow and white clothes kept their whiteness.

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

It can be understood that the examples and implementations described herein are for illustration only, and those skilled in the art can suggest various improvements or changes according to the present invention, which are included in the spirit and purview of the present application and the 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.