DE69513967T2 - FIBER COMPOSITION WITH PROTEASE - Google Patents

Abstract

Bleaching and cleaning compositions comprising a bleaching compound, one or more bleach activators, and protease enzymes are provided. Thus, laundry detergent compositions which comprise protease, perborate or percarbonate and activators such as benzoyl caprolactam exhibit improved dingy clean-up performance.

Description

Technical area

The present invention relates to cleaning and bleaching compositions which use protease enzymes to enhance performance, particularly on soil stains and deposits. Bleaching, fabric detergent, dishwashing and disinfectant compositions are provided.

Background of the invention

It has been found that certain proportions of bleach activators and peroxide bleach compounds can be used with certain proportions of protease enzymes in bleach compositions to obtain surprisingly effective cleaning of soil deposits. The synergy of the bleach activators, peroxide bleach compound and the proteases which hydrolyze protein stains is greater than expected in this bleach composition, particularly in view of the fact that bleaches are known to oxidize enzymes. Without wishing to be bound by theory, it is believed that at these proportions there is synergy between the bleach activator/peroxide bleach compound and the protease such that the combined cleaning effect of the two is greater than the additive effect of each individually.

Accordingly, it is an object of the present invention to provide improved cleaning and bleaching compositions utilizing bleaching compounds and protease enzymes. Another object hereof is to provide a means for removing soil deposits and stains from fabrics utilizing the bleaching agent systems and protease enzymes of the present invention. These and other objects are achieved herein as will be apparent from the disclosures below.

Background of the field

The use of amido-derived bleach activators in laundry detergents is described in U.S. Patent 4,634,551. Lactam activators are described in co-pending applications Serial Nos. 08/064,624; 08/064,562; 08/196,322; and 08/082,270.

Protease enzymes are described in EP-90915958.4; US Patent No. 5,185,250; US Patent No. 5,204,015; copending application US Application No. 08/136,797; and copending application US Application No. 08/136,626.

Summary of the invention

The present invention encompasses bleach compositions which enable soil cleaning comprising protease enzymes, a bleach or bleach compound capable of achieving hydrogen peroxide in an aqueous liquor, and one or more specific bleach activators such that the combined performance of the bleach activator/bleach compound and the protease enzyme, as measured by the Hunter Whiteness Value, is more than additive.

Modified bacterial serine protease enzymes obtained from Bacillus subtilis, Bacillus lentus or Bacillus licheniformis are preferred. These enzymes comprise at least 0.001%, preferably 0.001 to 5%, of the detergent compositions.

Preferred bleaching agents are members selected from the group consisting of H₂O₂, perborate, percarbonate, persulfate and mixtures thereof. Particularly preferred bleaching agents include percarbonate or perborate bleaching agents or mixtures thereof. The bleach activators are selected from acyl lactam type activators.

Particularly preferred activators used in the present invention include benzoylcaprolactam, nonanoylcaprolactam, benzoylvalerolactam, nonanoylvalerolactam, 3,5,5-trimethylhexanoylcaprolactam, 3,5,5-trimethylhexanoylvalerolactam, octanoylcaprolactam, octanoylvalerolactam, decanoylcaprolactam, decanoylvalerolactam, undecenoylcaprolactam and undecenoylvalerolactam. Examples of particularly preferred substituted benzoyl lactams include methyl benzoyl caprolactam, methyl benzoyl valerolactam, ethyl benzoyl caprolactam, ethyl benzoyl valerolactam, propyl benzoyl caprolactam, propyl benzoyl valerolactam, isopropyl benzoyl caprolactam, isopropyl benzoyl valerolactam, butyl benzoyl caprolactam, butyl benzoyl valerolactam ylbenzoylcaprolactam, tert-butylbenzoylvalerolactam, pentylbenzoylcaprolactam, pentylbenzoylvalerolactam, hexylbenzoylcaprolactam, hexylbenzoylvalerolactam, ethoxybenzoylcaprolactam, ethoxybenzoylvalerolactam, propoxybenzoylcaprolactam, propoxybenzoylvalerolactam, isopropoxybenzoylcaprolactam, Isopropoxybenzoylvalerolactam, Butoxybenzoylcaprolactam, Butoxybenzoylvalerolactam, tert-Butoxybenzoylcaprolactam, tert-Butoxybenzoylvalerolactam, Pentoxybenzoylcaprolactam, Pentoxybenzoylvalerolactam, Hexoxybenzoylcaprolactam, Hexoxybenzoylvalerolactam, 2,4,6-Trichlorbenzoylcaprolactam, 2,4,6-Trichlorbenzoylvalerolactam, Pentafluorbenzoylcaprolactam, Pentafluorbenzoylvalerolactam, Dichlorbenzoylcaprolactam, Dimethoxybenzoylcaprolactam, 4-Chlorbenzoylcaprolactam, 2,4-Dichlorbenzoylcaprolactam, Terephthaloyldicaprolactam, Pentafluorbenzoylcaprolactam, Pentafluorbenzoylvalerolactam, Dichlorbenzoylvalerolactam, Dimethoxybenzoylvalerolactam, 4-chlorobenzoylvalerolactam, 2,4-dichlorobenzoylvalerolactam, terephthaloyldivalerolactam, 4-nitrobenzoylcaprolactam, 4-nitrobenzoylvalerolactam, dinitrobenzoylcaprolactam, dinitrobenzoylvalerolactam and mixtures thereof.

Particularly preferred bleach activators are selected from the group consisting of benzoylcaprolactam, benzoylvalerolactam, nonanoylcaprolactam, nonanoylvalerolactam, 4-nitrobenzoylcaprolactam, 4-nitrobenzoylvalerolactam, octanoylcaprolactam, octanoylvalerolactam, decanoylcaprolactam, decanoylvalerolactam, undecanoylcaprolactam, undecanoylvalerolactam, 3,5,5-trimethylhexanoylcaprolactam, 3,5,5-trimethylhexanoylvalerolactam, dinitrobenzoylcaprolactam, dinitrobenzoylvalerolactam, terephthaloyldicaprolactam, terephthaloyldivalerolactam and mixtures thereof.

Preferably, the molar ratio of hydrogen peroxide achieved by the peroxide-bleaching compound to bleach activator is greater than 1.0. More preferably, the molar ratio of hydrogen peroxide to bleach activator is at least 1.5.

The invention also encompasses detergent compositions, in particular laundry detergents, comprising other conventional surfactants and other detergent ingredients.

All percentages, ratios and proportions are by weight unless otherwise stated. All documents cited are incorporated herein by reference in relevant parts.

Detailed description of the invention

Without being bound by theory, it is believed that soil deposits and stains are the result of combinations of greasy soils and soil particles. Greasy soils include lipids, proteins and pigments deposited on fabrics by contact with human or animal skin. The majority of lipids are secreted as sebum from the hair follicle or sebaceous gland apparatus. Proteins and pigments from skin fragments are released by the breakdown of skin cells. Soil particles mostly include airborne particles and floor/soil dust. Sebum is believed to be the main soil found on laundry and its removal is important because unremoved grease acts as a matrix for holding soil particles. Furthermore, it is believed that compounds present in sebum oxidize and thus contribute to the yellowing of fabrics. Soil particles include topsoil and products generated during the incomplete combustion of petroleum products.

Dirt removal performance can be measured using Hunter Whiteness (W) values calculated using the following equation:

W = (7L² - 40Lb)/700

where L, a and b are determined from a tristimulus measurement reading and represent a three-axis countercolor scale system based on the theory that color is perceived by black-white (L) and yellow-blue (b) sensations. The higher the value of W, the better the whitening performance and soil removal. See Hunter R. S. and Harold R. W., The Measurement of Appearance, 2nd edition, John Wiley & Sons, New York, 1987, and ASTM Standards on Color and Appearance Measurement, 3rd edition, ASTM, Philadelphia, PA, 1991.

Compositions of the invention comprise protease enzyme and bleach activator/bleach compounds in proportions such that the Hunter Whiteness value for the composition is more than additive, i.e., W for the composition is greater than the sum of the W's for compositions without protease plus the W's for compositions without the bleach activator/bleach compound, as determined by a statistically significant series of tests.

Protease enzymes

Protease enzymes are usually present in such commercially available preparations in amounts sufficient to provide at least about 0.005 Anson Units (AU) of activity per gram of the composition. Therefore, these enzymes comprise at least 0.001%, preferably 0.001 to 5%, of the detergent compositions.

Suitable examples of proteases are the subtilisins obtained from certain strains of B. subtilis, B. lentus and B. licheniformis. Another suitable protease is a modified bacterial serine protease enzyme obtained from Bacillus subtilis or Bacillus licheniformis, with an activity maximum in the pH range of 8-12, developed and sold by Novo Industries A/S under the registered trademark ESPERASE. The preparation of this enzyme and analogous enzymes is described in Novo's British Patent Specification No. 1,243,784. Proteolytic enzymes suitable for removing protein stains that are commercially available include those sold under the trademarks ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics, Inc. (Netherlands). Other proteases include Protease A (see European Patent Application 130,756, published January 9, 1985) and Protease B (see European Patent Application 251,446, filed April 28, 1987, and European Patent Application 130,756, Bott et al., published January 9, 1985). Most preferred is the protease referred to herein as "Protease C" which is a variant of an alkaline serine protease from Bacillus, particularly Bacillus lentus, wherein arginine replaces lysine in position 27, tyrosine replaces valine in position 104, serine replaces asparagine in position 123 and alanine replaces threonine in position 274. Protease C is described in EP-451,244; US Patent No. 5,185,250; and US Patent No. 5,204,015. Also preferred are proteases described in copending application US Application No. 08/136,797 entitled "Protease-Containing Cleaning Compositions" and copending application US Application No. 08/136,626 entitled "Bleaching Compositions Comprising Protease Enzymes," which are incorporated herein by reference. Genetically modified variants, particularly of protease C, are also included herein.

Bleaching compounds

The present bleach compositions contain bleach mixtures containing a bleach and one or more bleach activators in an amount sufficient to provide bleaching of the stain or stains of interest. Bleach is usually present at levels of from 1 to 80%, typically 5 to 20%, of the detergent composition, especially for fabric cleaning. Bleach and soak compositions may comprise from 5 to 99% of the bleach. The amount of bleach activators is usually from 0.1 to 60%, typically 0.5 to 40%, of the bleach mixture comprising the bleach plus bleach activator.

The bleaching agents used herein may be any of the bleaching agents now known or become known useful for detergent compositions in fabric cleaning, hard surface cleaning or other cleaning purposes. These include oxygen bleaching agents as well as other bleaching agents. Perborate bleaching agents, e.g., sodium perborate (e.g., mono- or tetrahydrate), may be used herein.

Peroxide bleaching agents are preferably used in the compositions. Suitable peroxide bleaching compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) may also be used.

A preferred percarbonate bleach comprises anhydrous particles having an average particle size in the range of 500 to 1,000 microns, with no more than 10% by weight of the particles being smaller than 200 microns and no more than 10% by weight of the particles being larger than 1,250 microns. Optionally, the percarbonate may be coated with silicate, borate or water-soluble surfactants. Percarbonate is available from various commercial suppliers such as FMC, Solvay and Tokai Denka.

The compositions according to the invention may also comprise mixtures of bleach activators.

Peroxide bleaching agents, perborates, percarbonates, etc. are preferably combined with bleach activators, which in aqueous solution (i.e. during the washing process) cause the in situ generation of the peroxyacid corresponding to the bleach activator.

When the activators are used, optimum surface bleaching performance is obtained with wash solutions, the pH of such solution being between about 8.5 and 10.5, and preferably between 9.5 and 10.5, to promote the perhydrolysis reaction. Such pH can be obtained with materials generally known as buffering agents, which are optional components of the present bleaching systems.

A class of bleach activators includes the acyllactam activators, in particular acylcaprolactams and acylvalerolactams of the formulas:

wherein R6 is H, an alkyl, aryl, alkoxyaryl or alkaryl group having 1 to 12 carbon atoms, or a substituted phenyl group having 6 to 18 carbon atoms. See co-pending U.S. applications 08/064,562 and 08/082,270, which disclose substituted benzoyl lactams. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed on sodium perborate.

Various non-limiting examples of activators which the bleach compositions disclosed herein may also comprise include those disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al., and U.S. Patent 4,412,934. See also U.S. Patent 4,634,551 for other typical bleaches and activators useful herein.

Aid components

The present compositions may optionally include one or more other detergent adjuvant materials or other materials to assist or enhance cleaning performance, to treat the substrate to be cleaned, or to modify the aesthetics of the detergent composition (e.g., perfume, pigments, dyes, etc.). The following are illustrative examples of such adjuvant materials.

Detergent surfactants

Non-limiting examples of surfactants which are typically useful in the present detergent compositions at levels of from 1 to 55 wt.% include the conventional C11-C18 alkylbenzenesulfonates ("LAS") and C10-C20 primary, branched chain and random alkyl sulfates ("AS"); the C10-C18 (2,3) secondary alkyl sulfates of the formula CH3(CH2)x(CHOSO3-M+)CH3 and CH₃(CH₂)y(CHOSO₃⁻ M⁺)CH₂CH₃, wherein x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizable cation, especially sodium; unsaturated sulfates such as oleyl sulfate; the C₁₀-C₁₈ alkylalkoxysulfates ("AExS"; especially EO-1-7-ethoxysulfates); C₁₀-C₁₈ alkylalkoxycarboxylates (especially the EO-1-5-ethoxycarboxylates); the C₁₀-C₁₈ glycerol ethers; the C₁₀-C₁₈ alkyl polyglycosides and their corresponding sulfated polyglycosides; and the alpha-sulfonated C₁₂-C₁₈ fatty acid esters. Optionally, the conventional nonionic and amphoteric surfactants such as the C₁₂-C₁₈ alkyl ethoxylates ("AE") including the so-called alkyl ethoxylates with closely spaced performance maxima and C6-C12 alkylphenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy compounds); C12-C18 betaines and sulfobetaines ("sultaines"); C10-C18 amine oxides and the like may also be included in the overall compositions. The C10-C18 N-alkyl polyhydroxy fatty acid amides may also be used. Typical examples include the C12-C18 N-methylglucamides. See WO-9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides such as C10-C18-N-(3-methoxypropyl)glucamide. The N-propyl to N-hexyl C12-C18 glucamides can be used for low sudsing. Conventional C10-C20 soaps can also be used. If high sudsing is desired, the branched chain C10-C16 soaps can be used. Mixtures of anionic and nonionic surfactants are particularly useful. Other conventional useful surfactants are listed in standard texts.

Builders

Detergent builders may optionally be included in the present compositions to assist in mineral hardness control. Both inorganic and organic builders may be used. Builders are commonly used in fabric cleaning compositions to assist in the removal of soil particles.

The level of builder can vary widely depending on the intended use of the composition and its desired physical form. If present, the compositions typically comprise at least 1% builder. Liquid preparations typically comprise 5 to 50%, typically 5 to 30%, by weight of detergent builder. Granular preparations typically comprise 10 to 80%, typically 15 to 50%, by weight of detergent builder. However, lower or higher levels of builder are not excluded.

Inorganic or P-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates and glassy polymeric metaphosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates and aluminosilicates. However, in some areas nonphosphate builders are required. Importantly, the present compositions perform surprisingly well even in the presence of the so-called "weak" builders (compared to phosphates) such as citrate or in the so-called "under-adjusted" situation that can occur with zeolite or layered silicate builders.

Examples of silicate builders are the alkali metal silicates, particularly those having a SiO₂:Na₂O ratio in the range of 1.6:1 to 3.2:1, and layered silicates such as the sodium layered silicates described in U.S. Patent 4,664,839 issued May 12, 1987 to Rieck HP. NaSKS-6 is the trademark for a crystalline silicate sold by Hoechst. lines layered silicate (generally abbreviated herein as "SKS-6"). Unlike zeolite builders, the NaSKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta Na₂SiO₅ morphology form of a layered silicate. It can be prepared by processes such as those described in German DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a particularly preferred layered silicate for use in the present invention, however, other such layered silicates such as those of the general formula NaMSixO2x+1 x yH₂O, where M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0, may be used herein. Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11 in alpha, beta and gamma forms. As indicated above, delta Na₂SiO₅ (NaSKS-6 form) is particularly preferred for use in the present invention. Other silicates may also be useful, such as magnesium silicate, which may be used as a granulating agent in granular formulations, as a stabilizing agent for oxygen bleaches and as a component of foam control systems.

Examples of carbonate builders are the alkaline earth and alkali metal carbonates, as disclosed in German Patent Application No. 2,321,001, published on November 15, 1973.

Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most granular heavy-duty detergent compositions currently on the market and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those of the empirical formula:

[Mz(zAlO₂)y] x H₂O

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 0.5, and x is an integer of 15 to 264.

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates may be crystalline or amorphous in structure and may be derived from naturally occurring aluminosilicates or synthetically. A process for preparing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel et al., issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:

Na 12 [(AlO 2 ) 12 (SiO 2 ) 12 ] x H 2 O

where x is 20 to 30, especially 27. This material is known as zeolite A. Dehydrated zeolites (x = 0-10) can also be used here. Preferably the aluminosilicate has a particle size of about 0.1-10 µm in diameter.

Organic detergent builders suitable for use in the present invention include, but are not limited to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylate groups. The polycarboxylate builder can generally be added to the composition in the acid form, but also in the form of a neutralized salt. When used in the salt form, alkali metals such as sodium, potassium and lithium or alkanolammonium salts are preferred.

The polycarboxylate builders include a variety of categories of useful materials. One important category of polycarboxylate builders comprises the ether polycarboxylates including oxydisuccinate as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al., U.S. Patent 3,635,830, issued January 18, 1972. See also the "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al. on May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those disclosed in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.

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

Citrate builders, e.g. citric acid and soluble salts thereof (especially the sodium salt), are polycarboxylate builders which are of particular importance for liquid heavy-duty detergent preparations because of their availability from renewable sources and their biodegradability. Citrates can also be used in granular compositions, particularly in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also particularly useful in such compositions and combinations.

Also useful in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenyl succinic acid.

Specific examples of succinate builders include: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate, and the like. Lauryl succinates are the preferred builders of this group and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.

Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226, Crutchfield et al., issued March 13, 1979, and in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. See also Diehl, U.S. Patent 3,723,322.

Fatty acids, e.g. C₁₂-C₁₈ monocarboxylic acids, may be incorporated into the compositions alone or in combination with the above-mentioned builders, particularly the citrate and/or succinate builders, to provide additional builder activity. Such use of fatty acids generally results in a reduction in foaming, which should be taken into account by the manufacturer.

In situations where phosphate-based builders can be used, and particularly in the formulation of soap bars used for hand-washing processes, the various alkali metal phosphates, such as the well-known sodium tripolyphosphates, sodium pyrophosphates and sodium orthophosphates, can be used. Phosphonate builders, such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.

Enzymes

Optionally, enzymes may be included in the present preparations for a wide variety of fabric cleaning purposes, including, for example, for removing protein, carbohydrate or triglyceride stains or preventing volatile dye transfer and for fabric care. The enzymes to be incorporated include amylases, lipases, cellulases and peroxidases and mixtures thereof. Other types of enzymes may also be included. They may be of any suitable origin, such as plant, animal, bacterial, fungal and yeast. However, their choice will be determined by several factors such as pH activity and/or stability optima, thermostability, stability to detergent actives, builders, etc. In this regard, bacterial or fungal enzymes are preferred, such as bacterial amylases and fungal cellulases.

Enzymes are normally incorporated in amounts sufficient to provide up to about 5 mg by weight, usually about 0.01 mg to about 3 mg, of active enzyme per gram of composition. Unless otherwise specified, the present compositions usually comprise from 0.001 to 5% by weight, preferably from 0.01 to 1% by weight, of a commercially available enzyme preparation.

Amylases include, for example, α-amylases described in British Patent Specification No. 1,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc., and TERMAMYL, Novo Industries.

The cellulases useful in the present invention include both bacterial and fungal cellulases. Preferably, they have a pH optimum between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al., issued March 6, 1984, which describes a cellulase produced by Humicola insolens and the Humicola strain DSM1800-produced fungal cellulase or a cellulase 212-producing fungus belonging to the genus Aeromonas, and a cellulase extracted from the midgut gland of a marine mollusk (Dolabella auricula solander). Suitable cellulases are also disclosed in GB-A-2,075,028; GB-A-2,095,275 and DE-OS-2,247,832. CAREZYME (Novo) is particularly useful.

Suitable lipase enzymes for use in detergents include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent No. 1,372,034. See also the lipases in Japanese Patent Application 53,20487, which was opened for public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co., Ltd., Nagoya, Japan, under the trademark Lipase P "Amano", hereinafter referred to as "Amano P". Other commercially available lipases include Amano-CES, lipases from Chromobacter viscosum, e.g. Chromobacter viscosum Var. lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and also Chromobacter viscosum lipases from US-Biochemical Corp., USA, and Disoynth Co., Netherlands, and lipases from Pseudomonas gladioli. The LIPOLASE enzyme derived from Humicola lanuginosa and commercially available from Novo (see also EPO-341,947) is a preferred lipase for use in the invention.

Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "bleaching in solution", i.e. to prevent the transfer of dyes or pigments which are released from substrates during washing processes to other substrates in the washing solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase and haloperoxidase such as chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions are disclosed, for example, in International PCT Application WO-89/099813, published October 19, 1989, by Kirk O., assigned to Novo Industries A/S.

A wide range of enzyme materials and means for their incorporation into synthetic detergent compositions are also disclosed in U.S. Patent 3,553,139, issued January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. Patent 4,101,457, Place et al., issued July 18, 1978, and in U.S. Patent 4,507,219, Hughes, issued March 26, 1985. Enzyme materials useful for liquid detergent compositions and their incorporation into such compositions are disclosed in U.S. Patent 4,261,868, Hora et al., issued April 14, 1981. Enzymes for use in detergent compositions can be stabilized by various methods. Enzyme stabilization processes are disclosed and illustrated in U.S. Patent 3,600,319, issued August 17, 1971 to Gedge et al., and in European Patent Application Publication No. 0 199 405, Application No. 86200586.5, published October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. Patent 3,519,570.

Enzyme stabilizers

The enzymes used herein are stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to the enzymes. (Calcium ions are generally somewhat more effective than magnesium ions and are preferred here when only one type of cation is used). Additional stability can be provided by the presence of various other stabilizers disclosed in the art, particularly borate compounds: see Severson, US-4,537,706. Typical detergents, particularly liquids, comprise from 1 to 30, preferably from 2 to 20, more preferably from 5 to 15, and most preferably from 8 to 12 millimoles of calcium ions per liter of the finished composition. This may vary somewhat depending on the amount of enzyme present and its response to the calcium or magnesium ions. The proportion of calcium or magnesium ions should be chosen so that, after allowing complex formation with builders, fatty acids, etc. in the composition, there is always a minimum amount available to the enzyme. Any water-soluble calcium or magnesium salt may be used as a source of calcium or magnesium ions, including, but not limited to, calcium chloride, calcium sulfate, calcium malate, calcium maleate, calcium hydroxide, calcium formate, and calcium acetate and the corresponding magnesium salts. A small amount of calcium ions, generally about 0.05 to about 0.4 millimoles per liter, is also often present in the composition due to calcium in the enzyme slurry and formula water. In solid detergent compositions, the formulation may include a sufficient amount of a water-soluble calcium ion source to provide such amounts in the wash liquor. Alternatively, natural water hardness may be sufficient.

It should be understood that the above levels of calcium and/or magnesium ions are sufficient to provide enzyme stability. More calcium and/or magnesium ions may be added to the compositions to provide an additional level of grease removal performance. Accordingly, as a general recommendation, the present compositions typically comprise from 0.05% to 2% by weight of a water-soluble source of calcium and/or magnesium ions, or both. The amount may, of course, vary with the amount used in the composition and the type of enzyme used.

The present compositions may also optionally, but preferably, contain various additional stabilizers, particularly borate-type stabilizers. Typically, such stabilizers are used in the compositions at levels of from 0.25 to 10%, preferably from about 0.5 to about 5%, more preferably from 0.75 to 3%, based on the weight of boric acid or other borate compound capable of forming boric acid in the composition (calculated on a boric acid basis). Boric acid is preferred, although other compounds such as boric oxide, borax and other alkali metal borates (e.g., sodium ortho-, meta- and pyroborate and sodium pentaborate). Substituted boric acids (e.g. phenylboronic acid, butaneboronic acid and p-bromophenylboronic acid) can also be used instead of boric acid.

Polymeric dirt solvent

Any polymeric soil release agent known to those skilled in the art can optionally be used in the compositions and methods of the invention. Polymeric soil release agents are characterized by having both hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments whose purpose is to deposit on hydrophobic fibers and remain adhered to them until the completion of the wash and rinse cycles, thus serving as an anchor for the hydrophilic segments. This allows stains that appear after treatment with the soil release agent to be more easily removed in subsequent laundering processes.

The polymeric soil release agents useful herein include those soil release agents comprising: (a) one or more nonionic hydrophilic components consisting essentially of (i) polyoxyethylene segments having a degree of polymerization of at least 2; or (ii) oxypropylene or polyoxypropylene segments having a degree of polymerization of from 2 to 10, wherein the hydrophilic segment does not have an oxypropylene moiety unless it is attached at each end to adjacent groups by ether linkages; or (iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to about 30 oxypropylene units, the mixture containing a sufficient amount of oxyethylene units such that the hydrophilic component has a hydrophilicity great enough to increase the hydrophilicity of conventional polyester synthetic fiber surfaces upon deposition of the soil release agent on such surfaces, wherein the hydrophilic segments preferably comprise at least 25% oxyethylene units, and more preferably, particularly for those components having from 20 to 30 oxypropylene units, at least 50% oxyethylene units; or (b) one or more hydrophobic components comprising (i) C3 oxyalkylene terephthalate segments, wherein when the hydrophobic components also comprise oxyethylene terephthalate, the ratio of oxyethylene terephthalate units:C3 oxyalkylene terephthalate units is about 2:1 or less; (ii) C₄-C₆ alkylene or oxy-C₄-C₆ alkylene segments or mixtures thereof; (iii) poly(vinyl ester) segments, preferably poly(vinyl acetate), having a degree of polymerization of at least 2; or (iv) C₁-C₄ alkyl ether or C₄ hydroxyalkyl ether substituents or mixtures thereof, wherein the substituents are in the form of C₁-C₄ alkyl ether or C₄ hydroxyalkyl ether cellulose derivatives or mixtures thereof and such cellulose derivatives are amphiphilic, whereby they possess a sufficient proportion of C₁-C₄ alkyl ether and/or C₄ hydroxyalkyl ether units to deposit on conventional polyester synthetic fiber surfaces and to retain a sufficient proportion of hydroxyl groups, after adhering to such synthetic fiber surface to increase fiber surface hydrophilicity; or a combination of (a) and (b).

Typically, the polyoxyethylene segments of (a)(i) have a degree of polymerization of 200, although higher degrees can be used, preferably from 3 to 150, and more preferably from 6 to 100. Suitable hydrophobic oxy-C4-C6 alkylene segments include, but are not limited to, end caps of polymeric soil release agents such as MO3S(CH2)nOCH2CH2O-, where M is sodium and n is an integer from 4 to 6, as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink.

Polymeric soil release agents useful in the present invention also include cellulose derivatives such as hydroxyether cellulose polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are commercially available and include hydroxyethers of cellulose such as METHOCEL (Dow). Cellulosic soil release agents for use in the present invention also include those selected from the group consisting of C1-C4 alkyl and C4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol et al.

Soil release agents characterized by poly(vinyl ester) hydrophobic segments include graft copolymers of poly(vinyl ester), e.g. C1-C6 vinyl ester, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones. See European Patent Application 0 219 048, published April 22, 1987 by Kud et al. Commercially available soil release agents of this type include the SOKALAN type of material, e.g. SOKALAN HP-22, available from BASF (West Germany).

A preferred type of soil release agent is a random block copolymer of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight of this polymeric soil release agent is in the range of about 25,000 to about 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976, and U.S. Patent 3,893,929 to Basadur, issued July 8, 1975.

Another preferred polymeric soil release agent is a polyester having repeating units of ethylene terephthalate units containing 10 to 15 weight percent ethylene terephthalate units together with 90 to 80 weight percent polyoxyethylene terephthalate units derived from a polyoxyethylene glycol having an average molecular weight of 300 to 5,000. Examples of this polymer include the commercially available material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See also U.S. Patent 4,702,857, issued October 27 to Gosselink.

Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer consisting of an oligomeric ester backbone of repeating terephthaloyl and oxyalkyleneoxy units and covalently bonded end groups to the backbone. These soil release agents are described in detail in U.S. Patent 4,968,451, issued November 6, 1990 to Scheibel JJ and Gosselink EP. Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al.; the anionic end-capped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink; and the block polyester oligomer compounds of U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.

Preferred polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al., which discloses anionic, particularly sulfarolyl end-capped terephthalate esters.

If used, soil release agents generally comprise from 0.01 to 10.0% by weight of the detergent compositions herein, usually from 0.1 to 5% by weight, preferably from 0.2 to 3.0% by weight.

Another preferred soil release agent is an oligomer having repeating units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1,2-propylene units. The repeating units form the backbone of the oligomer and are preferably terminated with modified isethionate end caps. A particularly preferred soil release agent of this type comprises about one sulfoisophthaloyl unit, five terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of 1.7 to 1.8, and two end cap units of sodium 2-(2-hydroxyethoxy)ethanesulfonate. This soil release agent also comprises 0.5 to 20%, based on the weight of the oligomer, of a crystal formation reducing stabilizer, preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.

Chelating agents

The present detergent compositions may also optionally contain one or more iron and/or manganese chelating agents. Such chelating agents may be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents, and mixtures thereof, all as defined below. Without wishing to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by forming soluble chelates.

Aminocarboxylates useful as optional chelating agents include ethylenediaminetetraacetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediaminetetrapropionates, triethylenetetraaminehexaacetates, diethylenetriaminepentaacetates and ethanoldiglycines, alkali metal, ammonium and substituted ammonium salts thereof and mixtures thereof.

Aminophosphonates are also suitable for use as chelating agents in the compositions according to the invention if at least small amounts of total phosphorus allowed in detergent compositions and include ethylenediaminetetrakis(methylenephosphonates) such as DEQUEST. Preferably, these aminophosphonates do not contain alkyl or alkenyl groups having more than about 6 carbon atoms.

Polyfunctionally substituted aromatic chelating agents are also useful in the present compositions. See U.S. Patent 3,812,044, issued May 21, 1974 to Connor et al. Preferred compounds of this type in acid form 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"), particularly the [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.

If used, these chelating agents generally comprise from about 0.1 to about 10% by weight of the detergent compositions herein. More preferably, if used, the chelating agents comprise from about 0.1 to about 3.0% by weight of such compositions.

Clay dirt removing/anti-dirt deposition agent

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

The most preferred soil release and antisoil redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986. Another group of preferred clay soil removal/antisoil redeposition agents are the cationic compounds disclosed in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984. Other clay soil removal/antisoil redeposition agents which may be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22, 1985. Other clay soil removal/antisoil redeposition agents known in the art can also be used in the present compositions. Another type of preferred antisoil redeposition agent includes the carboxymethyl cellulose (CMC) materials. These materials are well known in the art.

Polymeric dispersants

Polymeric dispersants may advantageously be used at levels of from 0.1 to 7% by weight in the present compositions, particularly in the presence of zeolite and/or layered silicate builders. Suitable polymeric dispersants include polymeric polycarboxylates and polyethylene glycols, although others known in the art may also be used. Although not wishing to be bound by theory, polymeric dispersants are believed to enhance overall detergent builder performance when used in combination with other builders (including low molecular weight polycarboxylates) through crystal growth inhibition, soil particle dissolving peptization and antisoil redeposition.

Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their 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. The presence of monomeric segments in the present polymeric polycarboxylates which do not contain carboxylate groups, such as vinyl methyl ether, styrene, ethylene, etc., is suitably provided such that such segments do not constitute more than about 40% by weight.

Particularly suitable polymeric polycarboxylates may be derived from acrylic acid. Such acrylic acid-based polymers useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form preferably ranges from 2,000 to 10,000, more preferably from 4,000 to 7,000, and most preferably from 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers may include, for example, the alkali metal, ammonium, and substituted ammonium salts. Soluble polymers of this type are known materials. The use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent No. 3,308,067, issued March 7, 1967.

Acrylic acid/maleic acid based copolymers may also be used as a preferred component of the dispersant/antisoil 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 preferably ranges from 2,000 to 100,000, more preferably from 5,000 to 75,000, most preferably from 7,000 to 65,000. The ratio of acrylate to maleate segments in such copolymers generally ranges from 30:1 to 1:1, more preferably from 10:1 to 2:1. Water-soluble salts of such acrylic acid/maleic acid copolymers may include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known. Materials described in European Patent Application No. 66915, published December 15, 1982, and in EP-193,360, published September 3, 1986, which also describes such polymers comprising hydroxypropyl acrylate. Other useful dispersants include the maleic acid/acrylic acid/vinyl alcohol terpolymers. Such materials are also disclosed in EP-193,360, including, for example, the 45/45/10 terpolymer of maleic acid/acrylic acid/vinyl alcohol.

Another polymeric material that can be included is polyethylene glycol (PEG). PEG can exhibit dispersant performance as well as be effective as a clay soil removal/anti-soil redeposition agent. Typical molecular weight ranges for these purposes are from 500 to 100,000, preferably from 1,000 to 50,000, more preferably from 1,500 to 10,000.

Polyaspartate and polyglutamate dispersants may also be used, especially in conjunction with zeolite builders. Dispersants such as polyaspartate preferably have a molecular weight (average) of 10,000.

Brightener

Any optical brighteners or other brightening or bleaching agents known in the art may be incorporated into the present detergent compositions at levels of typically 0.05 to 1.2% by weight. Commercially available optical brighteners which may be useful in the present invention can be divided into subgroups which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methine cyanines, dibenzothiphene-5,5-dioxide, azoles, 5- and 6-membered ring heterocycles and other various agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", Zahradnik M., published by John Wiley & Sons, New York (1982).

Specific examples of optical brighteners useful in the present compositions are those identified in U.S. Patent 4,790,856, issued to Wixon on December 13, 1988. These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners disclosed in this reference include Tinopal UNPA, Tinopal CBS and Tinopal SBM, available from Ciba-Geigy; Artic White CC and Artic White CWD, available from Hilton-Davis, located in Italy; the 2-(4-styrylphenyl)-2H-naphthol[1,2-d]triazoles; 4,4'-bis-(1,2,3-triazol-2-yl)-stilbenes; 4,4'-bis-(styryl)-biphenyls; and the aminocoumarins. Specific examples of these brighteners include 4-methyl-7-diethyl-aminocoumarin, 1,2-bis-(venzimidazol-2-yl)-ethylene, 1,3-diphenylphrazoline; 2,5-bis-(benzoxazol-2-yl)-thiophene; 2-styrene naphth-[1,2-d]oxazole; and 2-(stilbene-4-yl)-2H-naphtho-[1,2]triazole. See also U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton. Anionic brighteners are preferred herein.

Foam inhibitors

Compounds for reducing or suppressing foaming can be incorporated into the compositions of the invention. Foam suppression can be of particular importance in the so-called "high concentration cleaning process" as described in US-4,489,455 and 4,489,574 and in European front-loading washing machines.

A wide variety of materials can be used as a foam inhibitor, and foam inhibitors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, 3rd Edition, Volume 7, 430-447 (John Wiley & Sons, Inc., 1979). One category of foam inhibitor of particular interest includes monocarboxylic fatty acids and soluble salts thereof. See U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids and salts thereof used as a foam inhibitor typically have hydrocarbyl chains containing from 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium and lithium salts, and ammonium and alkanolammonium salts.

The present detergent compositions may also contain non-surfactant foam inhibitors. These include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g. fatty acid triglycerides), fatty acid esters of monohydric alcohols, C18-C40 aliphatic ketones (e.g. stearone), etc. Other foam inhibitors include N-alkylated aminotriazines such as tri- to hexaalkylmelamines or di- to tetraalkyldiaminechlorotriazines which are produced as products of cyanuric chloride with two or three moles of a primary or secondary amine having 1 to 24 carbon atoms, propylene oxide and monostearyl phosphates such as monostearyl alcohol phosphate esters and monostearyl di-potassium metal (e.g. K, Na and Li) phosphates and phosphate esters. The hydrocarbons such as paraffin and haloparaffin can be used in liquid form. The liquid hydrocarbons are liquid at room temperature and atmospheric pressure and have a pour point in the range of about -40°C to about 50°C and a boiling point minimum of less than about 110°C (atmospheric pressure). The use of waxy hydrocarbons, preferably having a melting point below about 100°C, is also known. The hydrocarbons represent a preferred category of foam inhibitor for detergent compositions. Hydrocarbon foam inhibitors are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. Finally, the hydrocarbons include aliphatic, alicyclic, aromatic and heterocyclic, saturated or unsaturated hydrocarbons containing from about 12 to about 70 carbon atoms. The term "paraffin" as used in this foam inhibitor review is intended to include mixtures of pure paraffins and cyclic hydrocarbons.

Another preferred category of non-surfactant suds suppressors comprises silicone suds suppressors. This category includes the use of polyorganosiloxane oils such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles, wherein the polyorganosiloxane is chemically absorbed or fused to the silica. Silicone suds suppressors are well known in the art and are disclosed, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al., and in European Patent Application No. 89307851.9, published February 7, 1990, by Starch M. S.

Other silicone antifoams are disclosed in U.S. Patent 3,455,839, which relates to compositions and methods for defoaming aqueous solutions by incorporating small amounts of polydimethylsiloxane fluids.

Mixtures of silicone and silanized silica are described, for example, in German Patent Application DOS-2, 124,526. Silicone defoamers and foam control agents in granular detergent compositions are disclosed in US Patent 3,933,672, Bartolotta et al., and in US Patent 4,652,392, Baginski et al., issued March 24, 1987.

An exemplary silicone-based foam inhibitor for use in the present invention is a foam suppressing amount of a foam control agent consisting essentially of:

(i) a polydimethylsiloxane fluid having a viscosity of 20 to 1,500 cs at 25ºC;

(ii) 5 to 50 parts per 100 parts by weight of (i) of a siloxane resin consisting of (CH₃)₃SiO1/2 units and SiO₂ units in a ratio of (CH₃)₃SiO1/2 units to SiO₂ units of about 0.6:1 to about 1.2:1; and

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

In the preferred silicone foam inhibitors used herein, the solvent for a continuous phase is certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred) or polypropylene glycol. The primary silicone foam inhibitor is branched/crosslinked and preferably non-linear.

To further illustrate this point, conventional liquid controlled foam laundry detergent compositions optionally comprise from 0.001 to 1% by weight, preferably from 0.01 to 0.7% by weight, more preferably from 0.05 to 0.5% by weight of the silicone suds inhibitor comprising (1) a nonaqueous emulsion of a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-forming silicone compound, (c) a finely divided filler material, and (d) a catalyst to accelerate the reaction of the mixture components (a), (b) and (c) to form silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature temperature of greater than about 2% by weight; and without polypropylene glycol. Appropriate amounts can be used in granular compositions, gels, etc. See also U.S. Patents 4,978,471, Starch, issued December 18, 1990, and 4,983,316, Starch, issued January 8, 1991, 5,288,431, Huber et al., issued February 22, 1994, and U.S. Patents 4,639,489 and 4,749,740, Aizawa et al., column 1, line 46 through column 4, line 35.

The present silicone foam inhibitor preferably comprises polyethylene glycol and a copolymer of polyethylene glycol/polypropylene glycol, all having an average molecular weight of less than 1,000, preferably between 100 and 800. The polyethylene glycol and polyethylene/polypropylene copolymers here have a solubility in water at room temperature of greater than 2% by weight, preferably greater than 5% by weight.

The preferred solvent here is polyethylene glycol having an average molecular weight of less than 1,000, more preferably between 100 and 800, particularly preferably between 200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300. A weight ratio of polyethylene glycol: copolymer of polyethylene-polypropylene glycol of between 1:1 and 1:10, particularly preferably between 1:3 and 1:6, is preferred.

The preferred silicone foam inhibitors used here do not contain polypropylene glycol, especially at a molecular weight of 4,000. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, such as PLURONIC L 101.

Other foam inhibitors useful herein include the secondary alcohols (e.g., 2-alkylalkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in US 4,798,679, 4,075,118 and EP-150,872. The secondary alcohols include the C6-C16 alkyl alcohols having a C1-C16 chain. A preferred alcohol is 2-butyloctanol, which is available from Condea under the trademark ISOFOL 12. Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem. Mixed foam inhibitors typically comprise mixtures of alcohol + silicone in a weight ratio of 1:5 to 5:1.

All detergent compositions to be used in automatic laundry washing machines should not foam to an extent that the washing machine overflows. Foam inhibitors, if used, are preferably present in a "foam suppressing amount." The term "foam suppressing amount" means that the manufacturer of the composition can select an amount of this foam control agent that will sufficiently control foaming to provide a low foaming laundry detergent for use in automatic laundry washing machines.

The present compositions generally comprise 0 to 5% foam inhibitor. When monocarboxylic fatty acids and salts thereof are used as foam inhibitors are used, they are typically present in amounts of up to 5% by weight of the detergent composition. Preferably, 0.5 to 3% fatty monocarboxylate foam inhibitor is used. Silicone foam inhibitors are typically used in amounts of up to 2.0% by weight of the detergent composition, although higher amounts may be used. This upper limit is practical, primarily due to problems of keeping costs down and the effectiveness of lower amounts to effectively control foaming. Preferably, 0.01 to 1% silicone foam inhibitor is used, more preferably 0.25 to 0.5%. As used herein, these weight percentages include any silica which may be used in combination with the polyorganosiloxane, as well as any adjuvant materials which may be used. Monostearyl phosphate foam inhibitors are generally used in amounts ranging from 0.1 to 2% by weight of the composition. Hydrocarbon foam inhibitors are typically used in amounts ranging from 0.01 to 5.0%, although higher amounts may be used. The alcohol foam inhibitors are typically used at 0.2-3% by weight of the finished compositions.

Textile softeners

Various fabric softeners effective during the laundering process, particularly the ultrafine smectite clays of U.S. Patent 4,062,647, Storm and Nirschl, issued December 13, 1977, as well as other softening clays known in the art, can optionally be used, usually at levels of 0.5 to 10 weight percent, in the present compositions to provide fabric softening benefits simultaneously with fabric cleaning. Clay softeners can be used in combination with amine and cationic softeners, as disclosed, for example, in U.S. Patent 4,375,416, Crisp et al., March 1, 1983, and U.S. Patent 4,291,071, Harris et al., issued September 22, 1981.

Other ingredients

A wide variety of other ingredients useful in detergent compositions can be included in the present compositions including other actives, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid preparations, solid fillers for soap bar compositions, etc. If high lathering is desired, lather boosters such as the C₁₀-C₁₆ alkanolamides can be incorporated into the compositions, usually at levels of 1 to 10%. The C₁₀-C₁₄ monoethanol and diethanolamides illustrate a typical class of such lather boosters. The use of such lather boosters with high lathering auxiliary surfactants such as the amine oxides, betaines and sultaines listed above is also advantageous. Optionally, soluble magnesium salts such as MgCl₂, MgSO₄ and the like can be included at levels of Typically 0.1 to 2% is added to provide additional foam and increase grease removal performance.

Various detergent ingredients used in the present compositions can optionally be further stabilized by adsorbing the ingredients to a porous hydrophobic substrate and then coating the substrate with a hydrophobic coating. Preferably, the detergent ingredient is mixed with a surfactant before being adsorbed to the porous substrate. In use, the detergent ingredient is released from the substrate into the aqueous wash liquor where it exerts its desired cleaning action.

To illustrate this process in more detail, a porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) is mixed with a proteolytic enzyme solution containing 3 to 5% of a nonionic ethoxylated C13-15 alcohol (EO 7) surfactant. Typically, the enzyme/surfactant solution is 2.5 times the weight of the silica. The resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range 500-12,500 can be used). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent base. By this process, ingredients such as the above-mentioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescent substances, fabric care agents and hydrolysable 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, exemplified by methanol, ethanol, propanol and isopropanol, are suitable. Monohydric alcohols are preferred for solubilizing the surfactant, but polyols such as those having from 2 to 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerin and 1,2-propanediol) may also be used. The compositions may contain from 5 to 90%, usually from 10 to 50%, of such carriers.

The present detergent compositions are preferably formulated so that during use in aqueous cleaning processes the wash water has a pH between 6.5 and 11, preferably between 7.5 and 10.5. Liquid dishwashing detergent product formulations preferably have a pH between 6.8 and 9.0. Detergent products are typically pH 9-11. Methods for regulating pH at recommended use levels include the use of buffers, alkalis, acids, etc. and are well known to those skilled in the art.

Dye transfer inhibiting agents

The compositions of the invention may also include one or more materials effective in inhibiting the transfer of dyes from one fabric to another during the cleaning process. In general My understanding is that such dye transfer inhibiting agents include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. When used, these agents typically comprise from 0.01 to 10% by weight of the composition, preferably from 0.01 to 5% by weight, and more preferably from 0.05 to 2% by weight.

More specifically, the preferred polyamine N-oxide polymers for use in the present invention contain units of the following structural formula: R-Ax-P, wherein P is a polymerizable unit to which an N-O group may be attached, or the N-O group may be part of the polymerizable unit, or the N-O group may be attached to both units; A is one of the following structures: -NC(O)-, -C(O)O-, -S-, -O-, or -N=; x is 0 or 1; and R is aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic groups, or any combination thereof, to which the nitrogen atom of the N-O group may be attached or the N-O group is part of these groups. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine or derivatives thereof.

The NO group can be represented by the following general structures:

wherein R₁, R₂ and R₃ are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen atom of the N-O group may be bonded to or form part of any of the above-mentioned groups. The amine oxide moiety of the polyamine N-oxides has a pKa < 10, preferably a pKa < 7 and more preferably a 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 polymer backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates, and mixtures thereof. These polymers include random or block copolymers wherein one type of monomer is an amine N-oxide and the other type of monomer is an N-oxide. The amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of from 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation. The polyamine oxides can be obtained in virtually any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000, more preferably 1,000 to 500,000, and most preferably 5,000 to 100,000. This preferred class of materials may be referred to as "PVNO".

The most preferred polyamine N-oxide useful in the present detergent compositions is poly(4-vinylpyridine N-oxide) which has an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1:4.

Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (mentioned as a class as "PVPVI") are also preferred for use in the present invention. Preferably, the PVPVI has an average molecular weight range of 5,000 to 1,000,000, more preferably 5,000 to 200,000, and most preferably 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth et al., Chemical Analysis, Vol. 113, "Modern Methods of Polymer Characterization," the disclosures of which are incorporated by reference.) The PVPIV copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone of 1:1 to 0.2:1, more preferably 0.8:1 to 0.3:1, and most preferably 0.6:1 to 0.4:1. These copolymers can be either linear or branched.

The compositions of the present invention may also comprise a polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, and more preferably from about 5,000 to about 50,000. PVPs are known to those skilled in the detergent art; see, for example, EP-A-262,897 and EP-A-256,696, incorporated herein by reference. PVP-containing compositions 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. Preferably, the ratio of PEG to PVP on a ppm basis released into the wash solutions is about 2:1 to about 50:1, and more preferably about 3:1 to about 10:1.

The present detergent compositions may also optionally contain from 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibiting effect. If used, the present compositions preferably comprise from 0.01% to 1% by weight of such optical brighteners.

The hydrophilic optical brighteners useful in the invention are those of the structural formula:

wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chlorine and amino; and M is a salt forming cation such as sodium or potassium.

In the above formula, when R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, then the brightener is 4,4'-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazin-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener compound is sold commercially under the trademark Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tiriopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the present detergent compositions.

In the above formula, when R1 is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, then the brightener is 4,4'-bis[(4-anilino-6- (N-2-hydroxyethyl-N-methylamino)-s-triazin-2-yl)amino]-2,2'-stilbenedisulfonic acid, disodium salt. This particular brightener compound is sold commercially under the trademark Tinopal 5BM-GX by Ciba-Geigy Corporation.

In the above formula, when R1 is anilino, R2 is morphilino and M is a cation such as sodium, then the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazin-2-yl)-amino]-2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener compound is sold commercially under the trademark Tinopal AMS-GX by Ciba-Geigy Corporation.

The specific optical brightener compounds selected for use in the present invention provide particularly effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents described above. The combination of such selected polymeric materials (e.g., PVNO and/or PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX, and/or Tinopal AMS-GX) provides significantly better dye transfer inhibition in aqueous wash solutions than either of these two detergent composition components when used alone. Without wishing to be bound by theory, it is believed that such brighteners are effective in this manner because they have a high affinity for fabrics in the wash solution and therefore deposit relatively quickly on those fabrics. The extent to which the brighteners deposit on the fabrics in the wash solution can be defined by a parameter called the "approximation coefficient". The approximation coefficient is generally given as the ratio of a) the brightener material deposited on the fabric to b) the initial brightener concentration in the wash liquor. Brighteners with relatively high approximation coefficients are the most suitable in the context of the present invention for inhibiting dye transfer.

Of course, it will be appreciated that other conventional optical brightener compound types may optionally be used in the present compositions to provide conventional fabric "whitening" benefits rather than true dye transmission inhibiting effect. Such use is common and well known for detergent preparations.

Claims (5)

1. A bleaching composition which enables soil cleaning, comprising protease enzymes, a bleaching compound which is capable of producing hydrogen peroxide in an aqueous liquor, and one or more bleach activators selected from the group consisting of N-acyl lactam bleach activators of the formula: wherein n is 0 to 8, preferably 0 to 2, and R6 H is an alkyl, aryl, alkoxyaryl or alkaryl group having 1 to 12 or a substituted vinyl group having 6 to 18 carbon atoms, for the composition the combined performance of the bleach activator/bleach compound and the protease enzyme as measured by Hunter Whiteness Values is more than additive. 2. The composition of claim 1, wherein the protease enzyme is modified bacterial serine protease derived from Bacillus subtilis, Bacillus lentus or Bacillus licheniformis. 3. Bleaching composition according to claim 1, wherein the bleach compound is percarbonate or percarborate or mixtures thereof, and wherein the bleach activator is selected from the group consisting of benzoylcaprolactam, benzoylvalerolactam, nonanoylcaprolactam, nonanoylvalerolactam, 4-nitrobenzoylcaprolactam, 4-nitrobenzoylvaleroactam, octanoylcaprolactam, octanoylvalerolactam, decanoylcaprolatam, decanoylvalerolactam, undecanoylcaprolactam, undecanoylvalerolactam, 3,5,5-trimethylhexanoylcaprolactam, 3,5,5-trimethylhexanoylvalerolactam, dinitrobenzoylcaprolactam, dinitrobenzoylvalerolactam, terephthaloyldicaprolactam, terephthaloyldivalerolactam and Mixtures of these. 4. A laundry detergent composition comprising detergent surfactants, detergent ingredients and a bleaching composition according to claim 1. 5. A method for improving the soil cleaning performance of bleach compositions comprising a bleach compound capable of producing hydrogen peroxide in aqueous liquor and a bleach activator selected from the group consisting of N-acyl lactam bleach activators of the formula wherein n is 0 to 8, preferably 0 to 2, and R6 H is an alkyl, aryl, alkoxyaryl or alkaryl group having 1 to 12 or a substituted vinyl group having 6 to 18 carbon atoms, the improvement comprising adding thereto an effective amount of a protease enzyme such that the performance of the composition comprising the protease enzyme as measured by Hunter Whiteness Value is more than additive.