[go: up one dir, main page]

MXPA97009888A - Cleaning compositions comprising condroitin - Google Patents

Cleaning compositions comprising condroitin

Info

Publication number
MXPA97009888A
MXPA97009888A MXPA/A/1997/009888A MX9709888A MXPA97009888A MX PA97009888 A MXPA97009888 A MX PA97009888A MX 9709888 A MX9709888 A MX 9709888A MX PA97009888 A MXPA97009888 A MX PA97009888A
Authority
MX
Mexico
Prior art keywords
carbon atoms
alkyl
compositions
enzyme
acid
Prior art date
Application number
MXPA/A/1997/009888A
Other languages
Spanish (es)
Other versions
MX9709888A (en
Inventor
Deepali Massey Brooker Anju
Arthur Jacques Kamiel Thoen Christiaan
Martin Dodd Ian
Oubrahim Youssef
Original Assignee
The Procter&Ampgamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from EP95303937A external-priority patent/EP0747469A1/en
Application filed by The Procter&Ampgamble Company filed Critical The Procter&Ampgamble Company
Publication of MX9709888A publication Critical patent/MX9709888A/en
Publication of MXPA97009888A publication Critical patent/MXPA97009888A/en

Links

Abstract

This invention relates to cleaning compositions similar to laundry compositions containing a chondroitinase enzyme, more particularly, the invention relates to compact compositions of detergent, liquid and granular compositions, as well as containing said chondroitin enzyme

Description

CLEANSING COMPOSITIONS COMPRISING CONPROITINASE FIELD OF THE INVENTION The present invention relates to cleaning compositions, including laundry compositions, which contain a chondroitinase enzyme. More particularly, the invention relates to compact detergent compositions, granules and liquids which also have said enzyme in the composition.
BACKGROUND OF THE INVENTION The operation of a detergent product for use in a washing or cleaning method, such as a laundry washing method, is judged by several factors, including the ability to remove the dirt and the ability to prevent redeposition of the dirt, or of the products of decomposition of the mugres, on the articles that are being washed. Stains that comprise body blemishes, such as stains based on scaling of the skin and sebum, are often difficult to effectively remove from a dirty substrate. The substrates can be made of fabric, such as collars, sleeves, underwear, but also towels, sheets or clothing. Chondroitin sulfates B are common in the skin. They are proteoglycans, also called protein polysaccharides, with a total molecular weight of 2 x 10s to 2 x 106. They contain between 20 and 60 polysaccharide chains per molecule. It is known that chondroitinase enzymes have the ability to degrade complex polysaccharide chains present in chondroitin sulfates. Chondroitinases are used in the art in the pharmaceutical or medical field. The types of chondroitinase enzyme ABC, AC, B C, from Sigma, are commercially available. In the Japanese patent application J04330280 (Seikagaku) a dry and stabilized chondroitinase ABC enzyme is described, with good stability during storage, and suitable for use in medical injection. EP 576 294 (Seikagaku) describes a purified, crystallizable chondroitinase ABC, used in a composition, together with serum albumin and gelatin, to treat the displacement of intervertebral discs. When used as a drug, it seems that activity is difficult to lose. However, the benefits of using chondroitinase ABC, AC, B and / or C in cleaning compositions have not been previously recognized.
BRIEF DESCRIPTION OF THE INVENTION ' li (k's (hi? M * n ah to which the enzyme cn roitmasa may be a valuable source in 'cleansing' compositions, .f? opf? tm at a level of 0.0001% a 2% by weight of active enzyme, related to the deposition, the inclusion of said enzyme, benefits of the production of filings / dirt, the eli ination of the very o / spots is provided and, in particular, the action of the cus tom of the cuc i po / rnanenas and / or spots Base tallow ID 1 has now found, surprisingly, that the application of rondroitinase at the levels mentioned above, in the cleaning compositions, provides a significant potential increase in cleaning performance. It is an object of the present invention to provide Ib cleansing compositions containing the enzyme chondroitmase and, in particular, provide laundry detergent compositions containing the aforementioned enzyme, which provide increased removal of body filth, from the fabrics. 0 DETAILED DESCRIPTION OF THE INVENTION An essential component of the cleaning compositions of the invention is a chondroitinase enzyme. This enzyme is incorporated in the compositions according to Invention, at a level of 0.0001% to 2%, preferably of 0. 0005% to 1.0%, better still, from 0.001% to 0.2% of active enzyme, by weight of the composition. By "chondroitinase enzyme" is meant here any enzyme that degrades, for example, that hydrolyzes and / or modifies the complex polysaccharide chains that exist, for example, in chondroitin sulfates. Chondroitinases ABC, AC, B and C are also called chondroitins ABC, AC, B and C-liasas and are classified as EC 4.2.2.4, EC 4.2.2.5 and EC 4.2.2, respectively. Chondroitinase variants, either occurring in nature or formed by genetic engineering as part of the present invention, can be specifically designed with respect to reaching the optimum point in functional efficiency in the detergent compositions of this invention. For example, the variants can be designed in such a way that the compatibility of the enzyme with the components commonly present in such compositions is increased.
DETERGENT COMPONENTS The detergent compositions of the invention may also contain additional detergent components. The precise nature of these additional components and the levels of their incorporation will depend on the physical form of the composition and the nature of the cleaning operation for which it is to be used.
For example, one can formulate the compositions of the invention as detergent compositions for washing clothes by hand and machine, including additive compositions for washing clothes, and suitable compositions for use in the pretreatment of stained fabrics, as softener compositions fabric to be added in the rinse, and as compositions for use in domestic cleaning operations in general, of hard surfaces. When the fopnula as suitable for use in a method of machine washing compositions, the compositions of the invention preferably contain both a surfactant and a builder compound detergency and additionally one or more detergent components selected preferably polymeric compounds organic, bleaching agents, additional enzymes, foam suppressants, dispersants, slurry and anti-redeposition agents, and corrosion inhibitors. The laundry compositions may also contain softening agents, as additional detergent components. If necessary, the density of laundry detergent compositions herein ranges from 550 to 1000 g / liter, preferably from 600 to 950 g / liter of composition, measured at 20 ° C. The "compact" form of the compositions herein is best reflected by the density and, in terms of composition, by the amount of inorganic filler salt; the inorganic filler salts are conventional ingredients of the powder detergent compositions; in conventional detergent compositions, the filler salts are present in substantial amounts, typically from 17 to 35% by weight of the total composition. In compact compositions, the filler salt is present in amounts not exceeding 15% of the total composition, preferably not exceeding 10%, better still, not exceeding 5% by weight of the composition. The inorganic filler salts, as it is intended to be expressed in the compositions herein, are selected from the alkali metal and alkaline earth metal salts of sulfates and chlorides. A preferred filler salt is sodium sulfate.
THE SURGICAL SYSTEM The detergent compositions according to the present invention comprise a surfactant system in the "which may be selected surfactant of nonionic and / or anionic and / or cationic and / or ampholytic and / or ionic Zwitter and / or ipolar Typically the surfactant is present at a level of 0.1% to 60% by weight. Preferred levels of incorporation are 1% to 35% by weight of fabric softener compositions added in the wash and rinse, according to the invention. It is preferred to formulate the surfactant to be compatible with the enzyme components present in the composition. In liquid or gel compositions, the surfactant is most preferably formulated in such a way as to promote, or at least not degrade, the stability of any enzyme present in said compositions. Preferred non-alkylbenzene sulfonate surfactant systems, to be used according to the present invention, comprise as one surfactant one or more of the nonionic and / or anionic surfactants described herein. Suitable for use as the nonionic surfactant of the surfactant systems of the present invention are the condensates of alkylphenols with polyethylene, polypropylene and polybutylene oxides; the polyethylene oxide condensates being preferred. These compounds include the condensation products of alkylphenols having an alkyl group containing about 6 to 14 carbon atoms, preferably around 8 to 14 carbon atoms, either in straight chain or branched chain configuration, with the alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal to about 2 to 25 moles, better still, about 3 to 15 moles of ethylene oxide per mole of alkylphenol. Commercially available nonionic surfactants of this type include Igepal ™ CO-630, sold by GAF Corporation; and Triton * "X-45, X-114, X-100 and X-102, all sold by Rohm &Haas Company, these surfactants are known as alkylphenol alkoxylates (eg, alkylphenol ethoxylates). condensation of primary and secondary aliphatic alcohols with about 1 to 25 moles of ethylene oxide are suitable for use as the nonionic surfactant of the nonionic surfactant systems of the present invention The alkyl chain of the aliphatic alcohol can be straight or branched, primary or secondary, and usually contains about 8 to 22 carbon atoms.The condensation products of alcohols having an alkyl group containing about 8 to 20 carbon atoms, better still, of 10 to 18 carbon atoms, with about 2 to 10 moles of ethylene oxide per mole of alcohol, about 2 to 7 moles of ethylene oxide are present in the aforementioned condensation products, and very preferred ible, from 2 to 5 moles of ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this type include Tergitol ™ 15-S-9 (the linear alcohol condensation product of 11 to 15 carbon atoms with 9 moles of ethylene oxide); Tergitol MR 24-L-6 NMW (the condensation product of primary alcohol of 12 to 14 carbon atoms with 6 moles of ethylene oxide, with a narrow molecular weight distribution), both sold by Union Carbide Corporation; Neodol ™ 45-9 (the linear alcohol condensation product of 14 to 15 carbon atoms with 9 moles of ethylene oxide); NeodolMR 23-3 (the condensation product of linear alcohol of 12 to 13 carbon atoms with 3 moles of ethylene oxide), NeodolMR 45-7 (the condensation product of linear alcohol of 14 to 15 carbon atoms with 7 moles of ethylene oxide), NeodolMR 45-5 (the linear alcohol condensation product of 14 to 15 carbon atoms with 5 moles of ethylene oxide) sold by Shell Chemical Company, KyroMR EOB (the condensation product of alcohol 13). at 15 carbon atoms with 9 moles of ethylene oxide), sold by The Procter & Gamble Company and Genapol LA 050 (the condensation product of alcohol of 12 to 14 carbon atoms with 5 moles of ethylene oxide) sold by Hoechst. The preferred scale of hydrophilic / lipophilic balance (EHL) in these products is from 8 to 11 and, most preferred, from 8 to 10. Also useful as nonionic surfactants of the surfactant systems of the present invention are the alkylpolysaccharides described in US Pat. U.S. Patent 4,565,647, to Llenado, issued January 21, 1986, which has a hydrophobic group containing from 6 to 30 carbon atoms, approximately, preferably from 10 to 16 carbon atoms, approximately, and a polysaccharide, for example , a polyglycoside; a hydrophilic group containing about 1.3 to 10, preferably about 1.3 to 3, most preferably about 1.3 to 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms, for example, glucose, galactose and galactosyl moieties, can be substituted for the glucosyl moieties. (Optionally, the hydrophobic group is attached at positions 2, 3, 4, etc., thus giving a glucose or a galactose as opposed to a glucoside or a galactoside). The intersaccharide ligatures may be, for example, between position one of the additional saccharide units and positions 2, 3, 4 and / or or of the preceding saccharide units. The alkyl polyglycosides have the formula: R20 (Cn H2 n 0) t (gl? COSI l?)? wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein the alkyl groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3; x is from 0 to 10, with about 1.3 to 3 being preferred, better still, about 1.3 to 2.7; and t is from 0 to 10. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is first formed and then reacted with glucose or a glucose source to form the glucoside (linkage at position 1). The additional glycosyl units can then be added between their position 1 and position 2, 3, 4 and / or 6 of the preceding glycosyl units, preferably in the 2-position predominantly.
The condensation products of ethylene oxide with a hydrophobic base, formed by the condensation of propylene oxide with propylene glycol, are also suitable for use as the additional nonionic surfactant systems of the present invention. The hydrophobic portion of these compounds preferably has a molecular weight of about 1500 to 1800 and will exhibit insolubility in water. The addition of polyoxyethylene portions to that hydrophobic portion tends to increase the water solubility of the molecule in its entirety, and the liquid nature of the product is retained to the point where the polyoxyethylene content is about 50% of the total weight of the product. condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide. Examples of compounds of this type include some of the commercially available Pluronic ™ surfactants sold by BASF. Also suitable for use as the nonionic surfactant of the nonionic surfactant system of the present invention are the condensation products of ethylene oxide with the product which is the result of the reaction of propylene oxide and ethylene diamine. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and an excess of propylene oxide; and in general it has an approximate molecular weight of 2,500 to 3,000. This hydrophobic portion is condensed with ethylene oxide to the extent that the condensation product contains about 40% to 80% by weight of polyoxyethylene and has an approximate molecular weight of 5,000 to 11,000. Examples of this type of nonionic surfactant include some of the commercially available Tetronic ™ compounds sold by BASF. Preferred for use as nonionic surfactant of the surfactant systems of the present invention are the condensates of alkylphenols with polyethylene oxide; the condensation products of primary and secondary aliphatic alcohols with about 1 to 25 moles of ethylene oxide, alkylpolysaccharides, and mixtures thereof. Most preferred are the alkylphenol ethoxylates of 8 to 14 carbon atoms in the alkyl, having 3 to 15 ethoxy groups, and alcohol ethoxylates of 8 to 18 carbon atoms (preferably 10 carbon atoms on average). ) that have from 2 to 10 ethoxy groups, and their mixtures. The most preferred nonionic surfactants are the polyhydroxy fatty acid amide surfactants of the formula: R2 -C-N-Z p. where Ri is H or a hid rock rbi lo of 1 to 4 carbon atoms, 2-hyd roxyethyl, 2-hid roxip ropyl, and R2 is a hydrocarbon radical of 5 to 31 carbon atoms and Z is a hydroxyhydroxy polyhydric having a linear hydrocarbyl chain with at least 3 hydroxy groups directly connected to the chain , or an alkoxylated derivative thereof. Preferably R is a methyl, R is a straight alkyl or alkenyl chain of 11 to 15 carbon atoms, such as cocoalkyl, or mixtures thereof; and Z is derived from a reducing sugar, such as glucose, fructose, maltose, lactose, in a reductive amination reaction. When laundry detergents are included in these laundry detergent compositions, the nonionic surfactant systems of the present invention act to improve the oily / greasy stain removing properties of said laundry detergent compositions, over a wide range of laundry conditions. . Extremely preferred anionic surfactants include alkoxylated alkyl sulfate surfactants, and water soluble salts or acids having the formula: RO (A) mS? 3M; wherein R is an unsubstituted alkyl or hydroxyalkyl group of 10 to 24 carbon atoms, having an alkyl component of 10 to 24 carbon atoms, preferably an alkyl or hydroxyalkyl of 12 to 20 carbon atoms, better still, alkyl or hydroxyalkyl of 12 to 18 carbon atoms; A is an ethoxy or propoxy unit; m is greater than zero, typically between about 0.5 and about 6; better yet, between about 0.5 and about 3; and M is H or a cation which may be, for example, a metal cation (eg, sodium, potassium, lithium, calcium, magnesium, etc.), an ammonium or substituted ammonium cation. Ethoxylated alkyl sulfates, as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include: methyl-, dimethyl- and trimethylammonium cations; and quaternary ammonium cations, such as tetramethylammonium and dimethylpiperidinium cations; and the alkylamines derivatives, such as ethylane, diethylamine, triethylamine, mixtures thereof and the like. Exemplary surfactants are: polyethoxylate sulfate (1.0) of alkyl of 12 to 18 carbon atoms (C12-C18-E (10) M), polyethoxylate sulfate (2.25 of alkyl of 12 to 18 carbon atoms (C12 - C? AE (2.25) M), polyethoxylate sulfate (3.0) of alkyl of 12 to 18 carbon atoms (C12 -C? ßE (3.0) M) and polyethoxylate sulfate (4.0) of alkyl of 12 to 18 carbon atoms carbon (C12 -C s E (4.0) M), where M is conveniently selected from sodium and potassium The suitable anionic surfactants to be used are the surfactants of this alkyl r-sulfonate, which include the esters linear carboxylic acids of 8 to 20 carbon atoms (ie, fatty acids), which are sulfonated with gaseous SO3 according to The Journal of the American Oil Chemists Society, 52 (1975), pages 323-329. Suitable starting materials would include natural fatty substances that are derived from tallow, from palm oil, etc. The surfactant Preferred alkyl ester sulfonate active, especially for laundry applications, comprises the alkyl sulfonate ester surfactants of the structural formula: 0 R3 - CH - C 0R < S03M wherein R3 is a hydrocarbyl of 8 to 20 carbon atoms, preferably an alkyl or a combination thereof; R * is a hydrocarbyl of 1 to 6 carbon atoms, preferably an alkyl, or a combination thereof; and M is a cation that forms a water-soluble salt with the alkyl sulfonate ester. Suitable salt-forming cations include metals such as sodium, potassium and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine and triethanolamine. Preferably, R3 is alkyl of 10 to 16 carbon atoms and R? it's methyl, ethyl or isopropyl. Especially preferred are methyl ester sulfonates, wherein R 3 is alkyl of 10 to 16 carbon atoms. Other suitable anionic surfactants include the alkyl sulfate surfactants, which are salts or water soluble acids of the formula ROSO3M, wherein R is preferably a hydrocarbyl of 10 to 24 carbon atoms, preferably an alkyl or hydroxyalkyl it has an alkyl component of 10 to 20 carbon atoms, better still, an alkyl or hydroxyalkyl of 12 to 18 carbon atoms; and M is H or a cation, for example, an alkali metal cation (eg, sodium, potassium, lithium) or ammonium or substituted ammonium) (eg, methyl-, dimethyl- and trimethylammonium cations and quaternary ammonium cations, such as tetramethylammonium and "5 dimethylpiperidinium cations; and quaternary ammonium cations derived from alkylamipads, such as ethylamine, diethylamine, triethylamine and mixtures thereof, and the like." Typically, alkyl chains of 12 to 16 carbon atoms are preferred for lower wash temperatures ( for example, unless -10 around 50 ° C) and alkyl chains of 16 to 18 carbon atoms are preferred for higher wash temperatures (eg, more than about 50 ° C). Other anionic surfactants, useful for detersive purposes, may also be included in the laundry detergent compositions of the present invention. These include the salts (including, for example, the sodium, potassium, ammonium and substituted ammonium salts, such as mono-, di- and triethanolamine salts) of soap; the primary or secondary alcansulfonates from 8 to 22 carbon atoms, the olefin sulfonates of 8 to 24 carbon atoms; sulfonated polycarboxylic acids, prepared by sulfonation of the pyrolyzed product of alkaline-earth metal citrates, for example, such as those described in British Patent Specification No. 1,082,179; ether sulphates alkyl polyglycolics (containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, acyl glycerol fatty sulphonates, fatty oleyl glycerol sulphates, alkylphenol ether sulfates ethylene oxide; the paraffin sulfonates, the alkyl phosphates, the isethionates, such as the acyl isethionates; the N-acyltaurates, the succinates and alkyl sulfosuccinates; the monoesters of sulfosuccinates (especially saturated and unsaturated monoesters of 12 to 18 carbon atoms) and the diesters of sulfosuccinates (especially the saturated and unsaturated diesters of 6 to 12 carbon atoms), the acyl sarcosinates, the alkyl polysaccharide sulfates, such as the alkyl polyglucoside sulfates (the non-sulfate, non-ionic compounds, which are described below); the primary, branched alkyl sulfates, and alkyl polyethoxycarboxylates, such as those having the formula RO (CH2CH2?) k -CH2C00-M +, wherein R is an alkyl of 8 to 22 carbon atoms; k is an integer from 1 to 10 and M is a soluble salt forming cation. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin and the resin acids and hydrogenated resin acids present in, or derived from, second distillation oil. Other examples are described in Surface Active Agents and Detergents (volumes I and II by Schwartz, Perry and Berch). A variety of such surfactants is also generally described in the U.S. Pat. 3,929,678, issued December 30, 1975, Laughlin and co-inventors, in column 23, row 28, to column 29, row 23 (incorporated herein by reference.) When included herein, the laundry detergent compositions of the present invention typically comprise about 1% to 40%, preferably about 3% to 20% by weight of said anionic surfactants.The laundry detergent compositions of the present invention may also contain cationic, ampholytic, zwitterionic and cationic surfactants. semi-polar, as well as non-ionic and / or anionic surfactants, in addition to those already described herein.Cathonic detergent surfactants, suitable for use in the laundry detergent compositions of the present invention are those having a long chain hydrocarbyl group Examples of such cationic surfactants include ammonium surfactants, t such as the alkyltrimethylamide halides, and the surfactants having the formula: [R2 (0R3) and] _R * (0R3)? 2RsN + X- wherein R2 is an alkyl group or an alkylbenzyl group having about 8 to 18 carbon atoms in the alkyl chain; each R3 is selected from the group consisting of CH2CH2-, -CH2CH (CH3) ~, -CH2CH (CH20H) -, -CH2CH2CH2-, and SUS mixtures thereof; each R * is selected from the group consisting of alkyl of 1 to 4 carbon atoms, hydroxyalkyl of 1 to 4 carbon atoms, benzyl ring structures, formed by joining the two groups R *, -CH2CHOH-CH0HC0R6CH0HCH? H, in where R6 is any hexose or hexose polymer having a molecular weight of less than about 1,000, and hydrogen, when and is not 0; R5 is equal to R * or is an alkyl chain; wherein the total number of carbon atoms of R2 plus R * is no more than about 18; each "y" is around 0 to about 10 and the sum of the "y" values is from 0 to about 15; and X is any compatible anion. Preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present invention, they have the formula: R 1 R2 R 3 R * N + X "(i) wherein Ri is alkyl of 8 to 16 carbon atoms, each of R 2, R 3 and RA is independently alkyl of 1 to 4 carbon atoms, hydroxyalkyl of 1 to 4 carbon atoms carbon, benzyl and (Q2H4?)? H, where x has a value of 1 to 5 and X is an anion.Not more than one of R2, R3 or R4 must be benzyl The length of the alkyl chain, preferred, for Ri it is 12 to 15 carbon atoms, particularly when the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat, or synthetically derived from olefin accumulation or by synthesis of 0X0 alcohols.
The preferred groups for R2, R3 and R * are methyl and hydroxyethyl groups and the anion X of halide, methosulfate, acetate and phosphate ions can be selected. Examples of quaternary ammonium compounds suitable for use herein are: cocotrimethylammonium chloride or bromide, cocomethyldihydroxyethylammonium chloride or bromide, decyltriethylammonium chloride, decyl dimethylhydroxyethylammonium chloride or bromide, dimethyl chloride or bromide of 12-15 carbon atoms. carbon-hydroxyethylammonium, cocodimethylhydroxyethylammonium chloride or bromide, myristyltrimethylammonium ethylsulfate, lauryldimethylbenzylammonium chloride or bromide, lauryldimethyl (ethoxy) -ammonium chloride or bromide; Hill esters [compounds of the formula (i)]. Other cationic surfactants, useful herein, are also disclosed in U.S. Patent No. 4,228,044, Cambre, issued October 14, 1980, and in European patent application EP 000,224. When included herein, the laundry detergent compositions of the present invention typically comprise about 0.2% to 25%, preferably 1% to 8%, by weight of said cationic surfactants. The ampholytic surfactants are also suitable for use in the laundry detergent compositions of the present invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of secondary and tertiary, heterocyclic amines, wherein the aliphatic radical can be straight or branched chain. One of the aliphatic substituents contains at least about 8 carbon atoms, typically about 8 to 18 carbon atoms, and at least one contains an anionic water-solubilizing group, for example, carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 to Laughlin and co-inventors, issued December 30, 1975 in column 19, lines 18 to 35, for examples of ampholytic surfactants. When included herein, the laundry detergent compositions of the present invention typically comprise from 0.2% to 15%, preferably from 1% to 10%, by weight of said ampholytic surfactants. Zinc ionic surfactants are also suitable for use in the laundry detergent compositions. These surfactants can be broadly described as derivatives of secondary and tertiary amines, as derivatives of heterocyclic secondary and tertiary amines, or as derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S. Patent 3,929,678, Laughlin and co-inventors, issued December 30, 1975, in column 19, line 38 to column 22, line 48, for examples of Zwitter ionic surfactants. When included herein, the laundry detergent compositions of the present invention typically contain 0.2% to 15%, preferably about 1% to 10%, by weight of said Zwitter ionic surfactants. The non-ionic, semi-polar surfactants are a special category of nonionic surfactants including water-soluble amine oxides, containing an alkyl portion of about 10 to 18 carbon atoms and two portions selected from the group consisting of groups alkyl and hydroxyalkyl groups containing about 1 to 3 carbon atoms; water-soluble phosphine oxides containing an alkyl portion of about 10 to 18 carbon atoms and two portions selected from the group consisting of alkyl groups and hydroxyalkyl groups containing about 1 to 3 carbon atoms; and water-soluble sulfoxides, which contain an alkyl portion of about 10 to 18 carbon atoms and a portion selected from the group consisting of alkyl and hydroxyalkyl portions of about 1 to 3 carbon atoms. The non-ionic, semi-polar detergent surfactants include the amine oxide surfactants having the formula: wherein R3 is an alkyl, hydroxyalkyl or alkylphenyl group, or mixtures thereof, containing about 8 to 22 carbon atoms; R * is an alkylene or hydroxyalkylene group containing about 2 to 3 carbon atoms or mixtures thereof; x is from 0 to about 3; and each of R 5 is an alkyl or hydroxyalkyl group containing about 1 to 3 carbon atoms, or a polyethylene oxide group containing about 1 to 3 ethylene oxide groups. The R5 groups can be linked together, for example, by means of an oxygen or nitrogen atom, to form an annular structure. These amine oxide surfactants, in particular, include alkyldi ethylamine oxides, of 10 to 18 carbon atoms in the alkyl portion, and alkoxyethyldihydroxyethyl oxides of 8 to 12 carbon atoms in the alkoxy moiety. When included herein, the laundry detergent compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1% to 10% by weight of said non-ionic, semi-polar agents.
THE OPTIONAL DETERGENT INGREDIENTS The preferred detergent compositions of the present invention may additionally comprise an enzyme that provides cleansing performance and / or fabric care benefits. Said enzymes include selected enzymes of: cellulases, hemicellulases, peroxidases, proteases, glucoamylases, amylases, lipases, cutinases, pectinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tanases, pentosanas, malanases, beta-glucanases, arabinosidases or its mixtures A preferred combination is a cleaning composition having a combination of applicable conventional enzymes, such as protease, amylase, lipase, cutinase and / or cellulase, in conjunction with the chondroitinase enzyme, according to the invention. The cellulases usable in the present invention include bacterial or fungal cellulase. Preferably, they will have an optimum pH between 5 and 9.5. Suitable cellulases are described in U.S. Patent 4,435,307, Barbesgoard and co-inventors, which describes fungal cellulase produced from Hu icola insolens. Suitable cellulases are also described in GB-A-2,075,028; GB-A-2,095,275 and DE-0S-2,247,832. Examples of such cellulases are cellulases produced by a strain of Humicola insolens (Humicola grísea var. Thermoidea). in particular the DSM 1800 strain of Humicola. Other suitable cellulases are the cellulases originated from Humicola insolens that have approximate molecular weights of 50 KDa, an isoelectric point of 5.5 and containing 415 amino acids. Especially suitable cellulases are cellulases which have color care benefits. Examples of these cellulases are those described in European patent application No. 91202879.2, filed on November 6, 1991 (de Novo). The enzymes peroxidase are used in combination with oxygen sources, for example, percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "bleaching in solution", that is, to prevent the transfer of dyes or pigments separated from the substrates during washing operations, towards other substrates present in the washing solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase and haloperoxidase, such as chloro- and bro-peroperoxidase. Peroxidase-containing detergent compositions are described, for example, in the international application of TCP WO 89/099813 and in European patent application EP No. 91202882.6, filed on November 6, 1991. Said cellulases and / or peroxidases are usually incorporated in the detergent composition at levels of 0.0001% to 2% active enzyme by weight of the detergent composition.
Preferred protease enzymes, available commercially, include those sold under the trademarks Alcalase, Savinase, Primase, Durazym and Esperase, by Novo Nordisk A / S (Denmark); those sold under the Maxatase, Maxacal and Maxapem brands by Gist-Brocades; those sold by Genencor International; and those sold under the brand Opticlean and Optimase by Solvay Enzymes. It is also possible to include the proteases described in the pending US application, by the same successor, Serial No. 08 / 136,797, in the detergent composition of the invention. The protease enzyme can be incorporated in the compositions according to the invention at a level of 0.0001% to 2% active enzyme by weight of the composition. Other preferred enzymes that can be included in the detergent compositions of the present invention include the lipases. Lipase enzymes suitable for use in detergents include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19,154, which is described in British Patent 1,372,034. Suitable lipases include those that show a positive immunological cross-reaction with the lipase antibody, produced by the microorganism Pseudomonas fluorescens IAM 1057. This lipase can be obtained from Amano Pharmaceutical Co., Ltd., Nagoya, Japan, under the trademark Lipase P "Amano", hereinafter referred to as "Amano-P". Particularly suitable lipases are lipases such as Ml Lipase and Lipomax® (Gist-Brocades) and Lipolase® (Novo), which have been found to be very effective when used in combination with the compositions of the present invention. Also suitable are cutinases [EC 3.1.1.50] that can be considered as a special class of lipase, that is, lipases that do not require interfacial activation.
The addition of cutinases to detergent compositions has been described, for example, in W0-A-88/09367 (Genencor). The lipases and / or the cutinases are usually incorporated in the detergent composition, at levels of 0.0001% to 2% of active enzyme, by weight of the detergent composition. Amylases (alpha and / or beta) can be included to eliminate carbohydrate-based stains. Suitable amylases are Termamyl R (Novo Nordisk), Fungamyl and BANR (Novo Nordisk). The enzymes mentioned above can be of any suitable origin, such as of vegetable, animal, bacterial, fungal and yeast origin. Said enzymes are normally incorporated in the detergent composition at levels of 0.0001% to 2% of active enzyme, by weight of the detergent composition. Other suitable detergent ingredients that can be added are the enzyme oxidation scavengers, which are described in the pending European patent application, of the same successor, No. 92870018.6, filed on January 31, 1992. Examples of such scavengers of oxidation of enzyme are ethoxylated teraethylenepolyamines. Especially preferred detergent ingredients are combinations with technologies that also provide a color care benefit. The examples of these technologies are the metal catalysts for color maintenance. Said metallo catalysts are described in the pending European patent application, of the same successor, No. 92870181.2. Other optional detergent ingredients that may be included in the detergent compositions of the present invention include bleaching agents such as PB1, PB4 and percarbonate, with a particle size of 400 to 800 microns. These bleaching agent components can include one or more oxygenated bleaching agents and, depending on the bleaching agent selected, one or more bleach activators. When present, the bleaching compounds will typically be at approximate levels of 1% to 25%. In general, bleaching compounds are optional components in non-liquid formulations, for example, in granular detergents. The bleaching agent component, for use herein, can be any of the bleaching agents useful for detergent compositions including oxygenated bleach, as well as others known in the art. The bleaching agent suitable for the present invention may be an activated or non-activated bleaching agent. A category of oxygenated bleaching agent that can be used comprises percarboxylic acid bleaching agents and their salts. Suitable examples of this class of agents include: magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyrate and diperoxydecanedioic acid. These bleaching agents are described in U.S. Patent 4,483,781; in U.S. Patent Application No. 740,446, in European Patent Application 0,133,354 and in U.S. Patent 4,412,934. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycapic acid, which was described in U.S. Patent 4,634,551. Another category of bleaching agents that can be used comprises halogenated bleaching agents. Examples of hypohalogenite bleaching agents, for example, include: trichloroisocyanuric acid and the sodium and potassium dichloroisocyanurates, as well as the N-chloro- and N-bromo-alkanesulfonamides. Such materials are usually added to 0.5-10% by weight of the final product, preferably 1 to 5 percent by weight. The hydrogen peroxide releasing agents can be used in combination with bleach activators, such as tetracetylethylenediamine (TAED), nonanoyloxybenzenesulfonate (NOBS, described in US Patent 4,412,934), 3,5-trimethylhexanoyloxybenzenesulfonate (ISONOBS, described in US Pat. EP 120,591) or pentaacetylglucose (PAG), which are hydrolyzed to form a peracid as the active bleaching species, which leads to an improved bleaching effect. In addition, bleach activators of 8-carbon (6-octanamido-caproyl) oxybenzenesulfonate, (9-carbon-6-nonanamidocaproyl) oxybenzene sulfonate, and (6-decanamido-caproic) oxybenzenesulfonate are very suitable. carbon atoms, or their mixtures. Also suitable activators are acylated citrate esters, such as those described in the pending European patent application, by the same successor, No. 91870207.7. Useful bleaching agents, including peroxyacids and bleaching systems comprising bleach activators and peroxygen bleach compounds, for use in cleansing compositions, according to the invention, are described in the co-pending US patent application. , Serial No. 08 / 136,626. Hydrogen peroxide may also be present by adding an enzymatic system (i.e., an enzyme and a substrate therefor), which is capable of generating hydrogen peroxide at the beginning of, or during the washing and / or rinsing process. These enzyme systems are described in EP patent application No. 91202655.6, filed October 9, 1991. Bleaching agents are also known in the art. • 5 different from oxygenates, and can be used here. One type of non-oxygenated bleaching agent, of particular interest, includes photoactivated bleaching agents, such as sulfonated zinc and / or aluminum phthacianins. These materials can be deposited on the -10 substrate during the washing process. By irradiation with light, in the presence of oxygen, for example, by hanging the clothes to be dried in daylight, the sulfonated zinc phthalocyanine is activated and, consequently, the substrate is bleached. The preferred zinc phthalocyanine and a bleaching process photoactivated are described in U.S. Patent No. 4,033,718. Typically, the detergent compositions will contain about 0.025% to 1.25% by weight of sulfonated zinc phthalocyanine. The compositions according to the present The invention may further comprise a builder system. Any conventional improver system for use herein is suitable, which includes aluminosilicate materials, silicates, polycarboxylates and fatty acids; materials such as ethylenediamine tetraacetate, metal ion sequestrants, such as aminopolyphosphonates, in particular ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepentamethylenephosphonic acid. Although less preferred for obvious environmental reasons, phosphate builders can also be used here. Suitable builders can be inorganic ion exchange materials, commonly an inorganic hydrous aluminosilicate material, in particular a hydrated synthetic zeolite, such as hydrated zeolite A, X, B, HS or MAP. Another suitable inorganic builder material is a layered silicate, for example, SKS-6 (Hoechst). SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na SÍ2? S). Suitable polycarboxylates containing a carboxy group include: lactic acid, glycolic acid and its ether derivatives, which were described in Belgian patents No. 831,368, 821,369 and 821,370. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malparated malonic acid (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in the application German Patent No. 2,466,686 and 2,446,668, and US Patent No. 3,935,257, and the sulfinyl carboxylates described in Belgian Patent No. 840,623. The polycarboxylates containing three carboxy groups include, in particular, the water-soluble citrates, aconitrates and citraconates, as well as the succinate derivatives, such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, the lactoxysuccinates described in the Application No. 7205873 and oxypolycarboxylate materials, such as the 2-oxa-l, l, 3-propane tricarboxylates described in British Patent No. 1,387,447. Polycarboxylates containing four carboxy groups include the oxydisuccinates described in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and tetracarboxylates of 1, 1,2,3-propane. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives described in British Patent No. 1,398,421 and 1,398,422, and US Patent No. 3,936,448, and the sulfonated and pyrolyzed citrates, described in British Patent No. 1,082,179, while Polycarboxylates containing phosphono substituents are described in British Patent No. 1,439,000. The alicyclic and heterocyclic polycarboxylates include: cis, cis, cyclopentane cis-tetracarboxylates, cyclopentadienide pentacarboxylates, cis, cis, cis-2,4,4,5-tetrahydrofuran cis-tetracarboxylates, cis-dicarboxylates, 5-tetrahydrofuran, 2,2,5,5,5-tetrahydrofuran tetracarboxylates, 1,2,3,4,5,6-hexane hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include: mellitic acid, pyromellitic acid and the phthalic acid derivatives described in British Patent No. 1,425,343. Of the above, preferred polycarboxylates "5 are hydroxycarboxylates containing up to three carboxy groups per molecule, particularly citrates." Preferred builder systems, for use in the compositions herein, include a mixture of a builder. of aluminosilicate, -10 insoluble in water, such as zeolite A, or of a layered silicate (SKS-6) and a water soluble carboxylate chelating agent, such as citric acid.The chelator suitable to be included in the compositions detergents according to the invention is ethylenediamine-NN'-disuccinic acid (EDDS) or its alkali metal, alkaline earth metal, ammonium or substituted ammonium salts, or mixtures thereof. free acid and its sodium or magnesium salts Examples of those preferred sodium salts of EDDS include 20 Na + EDDS and Na + EDDS Examples of those preferred magnesium salts of EDDS ncluyen MgEDDS and Mg2EDDS. Magnesium salts are most preferred for inclusion in the compositions according to the invention. The preferred builders systems include a mixture of an insoluble water-insoluble aluminosilicate builder, such as zeolite A and a water-soluble carboxylate chelating agent, such as citric acid. Other detergency builder materials, which may be part of the builder system for use in granular compositions, include inorganic materials, such as carbonates, bicarbonates, alkali metal silicates and organic materials, such as organic phosphonates, aminopolyalkylene phosphonates and the aminopolicarbo ilatos. Other suitable water-soluble organic salts are homo- or copolymeric acids or their salts, wherein the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of this type are described in GB-A-1,596,756. Examples of these salts are the polyacrylates of molecular weight 2,000 to 5,000 and their copolymers with maleic anhydride; said copolymers have a molecular weight of 20,000 to 70,000, especially about 40,000. Builder salts are usually included in amounts of 10% to 80% by weight of the composition, preferably 20% to 70% and most usually 30% to 60% by weight. Another optional ingredient is a foam suppressant, exemplified by silicones and silica-silicone blends. Silicones can be represented in general by the alkylated polysiloxane materials, while silica is normally used in finely divided forms, exemplified by silica aerogels and silica xerogels and hydrophobic silicas of various types. These materials can be incorporated as particles, wherein the foam suppressor is advantageously advantageously incorporated in a water-soluble or water-soluble detergent-impermeable substantially non-surfactant carrier. Alternatively, the foam suppressant can be dissolved or dispersed in a liquid carrier and applied by spraying to one or more of the other components. A preferred silicone foam controlling agent is described in US Pat. No. 3,933,672, to Bartollota and co-inventors. Other particularly useful foam suppressors are the self-emulsifying silicone foam suppressors described in the German patent application DTOS 2 646 126, published on April 28, 1977. An example of said compound is DC-544, commercially available from Dow Corning, which is a siloxane-glycol copolymer. Especially preferred foam controlling agents are the foam suppressor system comprising a mixture of silicone oils and 2-alkylalkanols. Suitable 2-alkylalkanols are 2-butyloctanol, which can be obtained commercially under the brand name Isofol 12 R. Said foam suppressant system is described in the pending European patent application, of the same successor, No. 92870174.7, filed on November 10, 1992. Especially preferred silicone foam controlling agents are described in co-pending European Patent Application No. 92291649.8. Said compositions may comprise a silicone / silica mixture, in combination with non-porous smoked silica, such as Aerosil.RTM. The foam suppressors described above are normally employed at levels of 0.001% to 2% by weight of the composition, preferably from 0.01% to 1% by weight. Other components used in the detergent compositions may be employed; such as the soil suspending agents, the soil release agents, the optical brighteners, the abrasives, the bactericides, the oxidation inhibitors, the coloring agents and / or the encapsulated or unencapsulated perfumes. Particularly suitable encapsulating materials are water-soluble capsules consisting of a polysaccharide matrix and polyhydroxy compounds, such as those described in GB 1,464.616 Other suitable water-soluble encapsulating materials comprise the dextrins derived from non-gelatinized starch acid esters of the substituted dicarboxylic acids, such as those described in US 3,455,838. Preferably, such dextrins of acid-ester are prepared from starches such as corn starch, waxy sorghum, sago, tapioca and potato. Suitable examples of such encapsulated materials include N-Lok, manufactured by National Starch. The N-Lok encapsulating material consists of a modified corn starch and glucose. The starch is modified by adding monofunctional substituted groups, such as octenylsuccinic acid anhydride. Anti-redeposition and slime suspension agents, suitable herein, include cellulose derivatives, such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or copolymeric polycarboxylic acids or salts thereof. Polymers of this type include polyacrylates and copolymers of maleic anhydride-acrylic acid, previously mentioned as detergency builders, as well as copolymers of maleic anhydride with ethylene, methylvinyl ether or methacrylic acid, constituting maleic anhydride at least 20 per cent. one hundred mole of the copolymer. These materials are normally used at levels of 0.5% to 10% by weight; better still, from 0.75% to 8%, most preferably from 1% to 6% by weight of the composition. Preferred optical brighteners are anionic in nature; examples thereof are 4,4'-bis- (2-diethanolamino-4-aminyl-s-triazin-6-ylamino) stilbene-2: 2'-disulfonate, 4,4'-bis- (2- morpholino-4-anilino-s-triazin-6-ylamino-stilbene-2: 2'-disodium disulfonate, 4,4'-bis- (2,4-dianilino-s-triazin-6-ylamino) stilbene-2 Disodium 2'-disulfonate, 4 ', 4"-bis- (2,4-dianilino-s-triazin-6-ylamino) -stilben-2-sulfonate monosodium, 4,4'-bis- (2- amino-4- (N-methyl-N-2-hydroxyethylamino) -s-thiazin-6-ylamino) -stilben-2, 2'-disodium disulfonate, 4,4'-bis- (4-phenyl-2) , l, 3-triazol-2-yl) -ethenylben-2, 2'-disodium disulfonate; 4,4'-bis- (2-anilino-4- (1-methy1-2-hydroxyethylamino) -s-triazine -6-ylamino) -stilben-2, 2'-disodium disulfonate, 2- (stilbe-4".- [naphtho-1 ', 2': 4,5) -l, 2,3-triazole-2" Sodium sulphonate and 4,4'-bis- (2-sulfoestiyl) biphenyl Other useful polymeric materials are polyethylene glycols, particularly those having molecular weights of 1,000 to 10,000, better still, 2,000 to 8,000 and, still better , preferably around of 4,000. They are used at levels of 0.20% to 5%, better still, from 0.25% to 2.5% by weight. These polymers and the homopolymer or copolymeric polycarboxylate salts, mentioned above, are valuable for improving the maintenance of whiteness, the deposition of ash in the fabric and the cleaning performance on clay, proteinaceous and oxidizable mulgres, in the presence of metal impurities of transition. The soil loosening agents useful in the compositions of the present invention are conventionally copolymers or terpolymers of terephthalic acid with ethylene glycol and / or propylene glycol units in various arrangements. Examples of such polymers are described in published European Patent Applications No. 0 272 033. A particularly preferred polymer according to EP-A-0 272 033 has the formula: (CH3) ((PEG) 43) 0.75 ( P0H)? 25 [Tp?) 2.8 (T-PEG) 0.4_T (P0-H) 0.25 ((PEG) 43CH3) _. 75 where PEG is - (0C2hs) 0-, PO is (OC3H6O) and T is (pcOCßH? CO).
Modified polyesters of random copolymers of dimethyl terephthalate, dimethyl sulfoisophthalate, ethylene glycol and 1,2-propanediol are also very useful; the extreme groups consisting, primarily, of sulfobenzoate and, secondly, of ethylene glycol monoesters and / or -10 propane diol. The goal is to obtain a polymer capped at both ends with sulfobenzoate groups, "primarily", in the present context, most of said copolymers herein will be capped at the end with sulfobenzoate groups. However, some copolymers will be less which are fully crowned and, consequently, their end groups can consist of monoelether of ethylene glycol and / or propane-1, 2-diol; which consist, "in second place", of said species. The polyesters selected in the present contain about 46% by weight of dimethylterephthalic acid; about 16% by weight of propane-1, 2-diol; about 10% by weight of ethylene glycol; about 13% by weight of dimethylsulfobenzoic acid and about 15% by weight of sulfoisophthalic acid; and they have a molecular weight of about 3,000. The polyesters and their method of preparation are described in detail in EPA 311 342.
THE SOFTENER AGENTS Fabric softening agents may also be incorporated into laundry detergent compositions in accordance with the present invention. These agents can be of inorganic or organic type. The inorganic softening agents are exemplified by the smectite clays described in GB-A-1 400 898 and in US Pat. No. 5,019,292. Organic fabric softening agents include tertiary amines insoluble in water, such as those written in GB-Al 514 276 and EP-BO 011 340; and its combination with quaternary monoammonium salts of 12 to 14 carbon atoms is described in EP-B-0 026 527 and EP-B-0 026 528, and long chain di-amides, such as those described in EP-B- 0 242 919. Other useful organic ingredients of fabric softening systems include the high molecular weight polyethylene oxide materials, which are described in EP-A-0 299 575 and 0 313 146. The smectite clay levels are usually on the scale from 5% to 15%, better yet, from 8 to 12% by weight; the material being added as a dry mix component to the rest of the formulation. Organic fabric softening agents, such as water-insoluble tertiary amines or long double-chain amide materials, are incorporated at levels of 0.5% to 5% by weight, usually from 1% to 3% by weight, while High molecular weight polyethylene oxide materials and water soluble cationic materials are added at levels from 0.1% to 2%, usually from 0.15% to 1.5% by weight. These materials are usually added to the spray-dried portion of the composition; although, in some cases, it may be more convenient to add them as a particulate material, dry-blended, or spray them as a molten liquid over the other solid components of the composition.
THE INHIBITION OF DYE TRANSFER The present invention also relates to a process for inhibiting the transfer of dye from one fabric to another, from the suspended and suspended dyes that are encountered during fabric washing operations, involving colored fabrics.
P0LIMERIC0S INHIBITORS OF DYE TRANSFER The detergent compositions according to the present invention also comprise from 0.001% to 10%, preferably from 0.01% to 2%, better still, from 0.05% to 1% by weight of polymeric agents inhibitors of dye transfer. Such dye-inhibiting polymeric agents are normally incorporated in the detergent compositions in order to inhibit the transfer of dyes from the colored fabrics onto the fabrics washed therewith. These polymers have the ability to form complexes with, or adsorb the fugitive dyes removed by washing the dyed fabrics, before the dyes have an opportunity to be attached to other articles present in the wash. Polyamine N-oxide polymers are especially suitable for polymer trapping dye inhibitors.; the copolymers of N-vinylpirolidone and N-vinyl imidazole; the polymers of polyvinylpyrrolidone, polyvinyloxazolidones and polyvinylimidazoles, and mixtures thereof. The addition of such polymers also increases the functioning of the enzymes according to the invention. a) Polyamine N-oxide polymers The polyamine N-oxide polymers suitable for use herein contain units having the following structural formula: wherein: P is a polymerizable unit, to which the group R-N-O may be added or wherein the group R-N-0 forms part of the polymerizable unit, or a combination of both circumstances. 0 0 0 1 'I A is NC, CO, C, -O-, -S-, -N-; x is O or 1; R are aliphatic, aliphatic, ethoxylated, aromatic, heterocyclic or alicyclic groups, or any combination thereof, to which the nitrogen of the group N-0 may be attached or where the nitrogen of the group N-0 is part of those groups. The group N-0 can be represented by the following general structures: 0 0 (R1) X -N- (R2) y = N- (R1) X (R3) z where: Rl R2 and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic, or combinations thereof; x and / or "y" and / or z is 0 or 1; and wherein the nitrogen of the group N-0 may be attached to, or wherein the nitrogen of the group N-0 forms part of these groups. The group N-0 may be part of the polymerizable unit (P) or may be attached to the polymer backbone, or a combination of both. Suitable polyamine N-oxides, wherein the group N-0 forms part of the polymerizable unit comprise the polyamine N-oxides in which R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. A class of said polyamine N-oxides comprises the group of polyamine N-oxides in which the nitrogen of the group N-0 forms part of the group R. The preferred polyamine N-oxides are those in which R is a group heterocyclic, such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof. Another class of polyamine N-oxides comprises the group of polyamine N-oxides, wherein the nitrogen of the group N-0 is attached to the group R. Other suitable polyamine N-oxidee are the polyamine oxides to which it is attached the group N-0 to the polymerizable unit. The preferred class of these polyamine N-oxides are the polyamine N-oxides having the general formula (I) in which R is an aromatic, heterocyclic or alicyclic group, wherein the nitrogen of the functional group N-0 is part of said group R. Examples of these classes are the polyamine oxides wherein R is a heterocyclic compound, such as pyrridine, pyrrole, imidazole and its derivatives. Another preferred class of polyamine N-oxides are polyamine oxides having the general formula (I), wherein R are the aromatic, heterocyclic or alicyclic groups, in which the nitrogen of the functional N-0 group is attached to said R groups. Examples of those classes are the polyamine oxides in which the R groups can be aromatic, such as phenyl.
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 structures are: polyvinyls, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof. The amine N-oxide polymers of the present invention typically have a ratio of amine to amine N-oxide from 10: 1 to 1: 1,000,000. However, the amount of amine oxide groups present in the polyamine oxide polymer can vary by appropriate copolymerization or by the appropriate degree of N-oxidation. Preferably the ratio of amine to amine N-oxide is from 2: 3 to 1: 1,000,000. Better yet, from 1: 4 to 1: 1,000,000; very preferable, from 1: 7 to 1: 1,000,000. The polymers of the present invention actually comprise random or block copolymers, wherein one type of monomer is an amine N-oxide and the other type of monomer is or is not an amine N-oxide. The amine oxide unit of the polyamine N-oxides has a pKa < 10, preferably pKa < 7, better yet, pKa < 6. Polyamine oxides can be obtained in almost any degree of polymerization. The degree of polymerization is not critical, provided that the material has the water solubility and the desired dye suspending potency. Typically, the average molecular weight is in the range of 500 to 1,000,000, preferably 1,000 to 50,000, even better, 2,000 to 30,000, especially 3,000 to 20,000. b) Copolymers of N-vinylpirolidone and N-vinyl imidazole The polymers of N-vinylimidazole and N-vinylpirolidone used in the present invention have an average molecular weight scale of 5,000 to 1,000,000, preferably 20,000 to 200,000. The highly preferred polymers for use in the detergent compositions according to the present invention comprise a polymer selected from the copolymers of N-vinyl idazole and N-vinylpyrrolidone, wherein said polymer has an average molecular weight scale of from 6,000 to 50,000, even, from 8,000 to 30,000, very preferable, from 10,000 to 20,000. The average molecular weight scale was determined by light diffraction, as described by Barth H. G. and Mays, J. W. Chemical Analysis. Volume 113, Modern Methods of Polymer Characterization. The highly preferred N-vinylimidazole and N-vinylpirolidone copolymers have an average molecular weight scale of 5,000 to 50,000; better still, from 8,000 to 30,000, very preferable, from 10,000 to 20,000. The copolymers of N-vinylimidazole and N-vinylpirolidone characterized by having the aforementioned scale of average molecular weight, provide excellent dye transfer inhibiting properties, while not adversely affecting the cleaning performance of the detergent compositions formulated therewith. The copolymer of N-vinylimidazole and N-vinylpyrrolidone of the present invention has a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2, better yet, from 0.8 to 0.3, rnuy preferable, from 0.6 to 0.4. c) Polyvinyl pyrrolidone The detergent compositions of the present invention can also use polyvinyl pyrrolidone ("PVP") having an average molecular weight of about 2,500 to 400,000, preferably about 5,000 to 200,000, better still, about 5,000 to 50,000, and, what more it is preferred, from 5,000 to 15,000. Suitable polyvinyl pyrrolidones are available commercially from ISP Corporation, New York, NY and Montreal Canada, under the product names PP K15 (viscosity molecular weight, 10,000), PVP K-30 (average molecular weight of 40,000), PVP K -60 (average molecular weight 160,000), and PVP K-90 (average molecular weight of 360,000). Other suitable polyvinyl pyrrolidones which are commercially available from BASF Corporation include: Sokalan HP 165 and Sokalan HP 12; the polyvinylpyrrolidones known to those skilled in the detergent field (see, for example, EP-A-262,897 and EP-A-256,696).
The polyvinyloxazolidone The detergent compositions of the present invention can also use polyvinyloxazolidone as a polymeric dye transfer inhibiting agent.
Said polyvinyloxazolidones have an average molecular weight of approximately 2,500 to 400,000, preferably 5,000 to 200,000; better yet, around 5,000 to 50,000; and very preferable, around 5,000 to 15,000. e) The polyvinyl idazole The detergent compositions of the present invention can also use polyvinylimidazole as the dye transfer inhibiting polymeric agent. Said polyvinylimidazoles averaged about 2,500 to 400,000, preferably about 5,000 to 200,000, better yet, about 5,000 to 50,000 and, most preferred, about 5,000 to 15,000.
THE WASHING METHOD The process described herein comprises contacting fabrics with a washing solution, in the usual manner, and as exemplified below. The process of the invention is conveniently carried out in the course of the cleaning process. The cleaning method is carried out preferably at 5 * C at 95 ° C, especially between 10 ° C and 60 ° C. The pH of the treatment solution is preferably from 7 to 11, especially from 7.5 to 10.5. The following examples are intended to exemplify the compositions of the present invention; but they do not necessarily mean that they limit or otherwise define the scope of the invention. In detergent compositions, the abbreviated identifications of the components have the following meaning: linear alkylbenzene sulfonate of 12 carbon atoms in the alkyl. TAS XYAS sodium alkylsulfate C? -C C sodium esoalkyl sulfate? in the alkyl. SAS secondary alkyl sulfate (2,3) of 12 to 14 carbon atoms in the alkyl, in the form of the sodium salt. APG alkylpolyglycoside surfactant of the formula Ci2- (glycosyl), wherein x is 1.5. AEC alkyl ethoxycarboxylate surfactant of the formula Etoxy (2) carboxylate of 12 carbon atoms SS secondary soap surfactant of the formula 2-butyloctanoic acid. 25EY A predominantly linear primary alcohol, of 12 to 15 carbon atoms, condemned with an average of Y moles of ethylene oxide. 45EY, a predominantly linear primary alcohol, from 14 to carbon atom, condensed with an average of Y moles of ethylene oxide. XYEZS C ??-C ?? sodium alkyl sulphate, condensed with an average of Z moles of ethylene oxide per mole. Non-ionic Ethoxylated / propoxylated mixed alcohol of 13 to 15 carbon atoms, with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5, sold under the trademark Plurafax LF404 by BASF GmbH. CFAA N-methylglucamide of alkyl of 12 to 14 carbon atoms. TFAA N-methylglucamide of alkyl of 16 to 18 carbon atoms. Amorphous sodium silicate silicate (ratio Si2: a2? = 2.0) NaSKS-6 layered crystalline silicate of the formula _- Na2SY2? 5. Carbonate: anhydrous sodium carbonate. Phosphate: MA / AA sodium tripolyphosphate 1: 4 copolymer of aleico / acrylic acids, average molecular weight around 80,000. Polyacrylate: polyacrylate homopolymer with an average molecular weight of 8,000, sold under the brand name PA30 by BASF GmbH. Zeolite A: hydrated sodium aluminosilicate of the formula: Nai (AIO2SÍO2) i2 -27H20, having a primary particle size on the scale of 1 to 10 micrometers. Citrate: trisodium citrate dihydrate. Citric acid citric Perborate: anhydrous sodium perborate monohydrate bleach, empirical formula NaB? 2.H2? 2-PB4 anhydrous sodium perborate tetrahydrate. TAED tetraacetylethylene diamine Paraffin paraffin oil sold under the brand name Winog 70 by Wintershall. Chondroitinase: enzyme described in the present application. Protease: proteolytic enzyme sold under the trademark Savinase by Novo Nordisk A / S. Amylase amylolitic enzyme sold under the brand name Termamyl by Novo Nordisk A / S. Lipase lipolytic enzyme sold under the brand name Lipolase by Novo Nordisk A / S. Peroxidase: enzyme peroxidase. Cellulase: cellulose enzyme sold under the brand name Carezyme or Celluzy e by Novo Nordisk A / S. CMC sodium carboxymethylcellulose HEDP 1,1-hydroxydanediphosphonic acid. DETPMP Diethylenetriamine penta (ethylene phosphonic acid), sold by Moneanto under the brand name Dequeet 2060. PVP polyvinylpyrrolidone polymer EDDS isomer [S, S] of ethylenediamine-N, N'-disuccinic acid, in the form of its sodium salt. Foam suppressor: 25% paraffin wax, melting point: 50 ° C, 17% hydrophobic silica, 58% paraffin oil. Suppressor granulated foam: 12% silicone / silica, 18% stearyl alcohol, 70% starch in granulated form. SCS sodium cumensulfonate. Anhydrous sodium sulfate sulfate. HMWPEO high molecular weight polyethylene oxide. PGMS Polyglycerol monostearate having the Radiasurf 248 brand. TAE 25 ethoxylate (25) tallow alcohol.
CONDROITINASE ACTIVITY B One unit will form 1.0 micromole of unsaturated uronic acid from chondroitin sulfate B, per hour, at pH 7.5 at 25 ° C.
In the following examples all indicated enzyme levels are expressed as active enzyme%, by weight of the composition.
EXAMPLE 1 The cleaning compositions of fabric, granulates, according to the invention, were prepared in the following manner: I II III IV LAS 22.0 22.0 22.0 22.0 Phosphate 23.0 23.0 23.0 23.0 Carbonate 23.0 23.0 23.0 23.0 Silicate 14.0 14.0 14.0 14.0 Zeolite A 8.2 8.2 8.2 8.2 DETPMP 0.4 0.4 0.4 0.4 Sodium Sulfate 5.5 5.5 5.5 5.5 Protease 0.01 0.02 0.01 0.005 Chondroitinase 0.001 0.03 0.05 0.10 Lipase 0.005 0.01 - - Cellulase 0.001 - - 0.001 Amylase 0.01 - 0.01 - Water / minor ingredients up to 100% EXAMPLE 2 Granular fabric cleaning compositions according to the invention were prepared as follows: I II • III IV LAS 12.0 12.0 12.0 12.0 Zeolite A 26.0 26.0 26.0 26.0 SS 4.0 4.0 4.0 4.0 SAS 5.0 5.0 5.0 5.0 Citrate 5.0 5.0 5.0 5.0 Sodium Sulfate 17.0 17.0 17.0 28.0 Perborate 16.0 16.0 16.0 - TAED 5.0 5.0 5.0 - Chondroitinase 0.20 0.01 0.02 0.008 Protease 0.06 0.03 0.02 0.08 Lipase 0.005 0.01 - - Cellulase 0.001 - - 0.001 Amylase 0.01 - 0.01 - Water / minor ingredients 100% EXAMPLE 3 Fabric cleaning compositions, granulated, according to the invention, which are especially useful in the washing of colored fabrics, were prepared as follows: LAS 11.4 10.7 - TAS 1.8 2.4 -TFAA - - 4.0 45AS 3.0 3.1 10.0 45E7 4.0 4.0 - 25E3S - - 3.0 25E5 - - 8.0 Citrate 14.0 15.0 7.0 Carbonate - - 10 Citric acid 3.0 2.5 3.0 Zeolite A 32.5 32.1 25.0 Na-SKS-6 - - 9.0 DETPMP 1.0 0.2 0.8 Chondroitinase 0.01 0.05 0.02 Protease 0.02 0.02 0.01 Lipase 0.03 0.04 0.005 Amylase 0.03 0.03 0.005 Pectinase 0.01 - 0.01 Cellulase 0.005 - 0.001 Silicate 2.0 2.5 - Sulphate 3.5 5.2 3.0 PV 0.3 0.5 _ N-oxide of poly (4-vinyl-0.2 pi ridine) / copolymer of vinylimidazole and vinyl-pi rrolidone.
Perborate 0.5 1.0 Peroxidase 0.01 0.01 Phenol sulfonate 0.1 0.2 water / ingredients menoree up to 100% - EXAMPLE 4 Granulated compositions for cleaning fabrics, according to the invention, were prepared as follows: -10 LAS 6.5 8.0 Sulfate 15.0 18.0 Zeolite A 26.0 22.0 Sodium nitrilotriacetate 5 .0 5.0 15 PVP 0 .5 0. 7 TAED 3. 0 3.0 Boric acid 4 .0 - Perborate 0. 5 1. 0 Phenol sulfonate 0. 1 0. 2 20 Protease 0.06 0.02 Chondroitin 0.01 0.02 Silicate 5.0 5.0 Carbonate 15.0 15.0 Peroxidase 0.1 0.1 25 Lipase 0.01 - Amylase 0.01 0.01 Pectinase 0.02 Cellulase 0.005 0.002 Water / minor ingredients up to 100% EXAMPLE 5 A granular and compact fabric cleaning composition according to the invention was prepared in the following manner: 45AS 8.0 25E3S 2.0 25E5 3.0 25E3 3.0 TFAA 2.5 Zeolite A 17.0 NaSKS-6 12.0 Citric acid 3.0 Carbonate 7.0 MA / AA 5.0 CMC 0.4 N-oxide of poly (4-vinylpyridine) / copolymer of vinylimidazole and vinyl-pi rrolidone 0.2 Chondroitinase 0.05 Protease 0.05 Lipase 0.005 Cellulase 0.001 Amylase 0.01 TAED 6.0 Percarbonate 22.0 EDDS 0.3 Granulated foam suppressor 3.5 Water / minor ingredients up to 100% EXAMPLE 6 Granular compositions were prepared for washing fabrics, according to the invention, which provide the ability to "softened during washing", as follows: 45AS - 10.0 LAS 7.6 - 68AS 1.3 - 45E7 4.0 - 25E3 - 5.0 Cocoalkyldimethylhydroxyethyl ammonium chloride 1.4 1.0 Citrate 5.0 3.0 Na-S S-6 - 11.0 Zeolite A 15.0 15.0 MA / AA 4.0 4.0 DETPMP 0.4 0.4 Perborate 15.0 - Percarbonate - 15.0 TAED 5.0 5.0 Smectite clay 10.0 10.0 HMWPEO - 0.1 Protease 0.02 0.01 Lipase 0.02 0.01 Amylase 0.03 0.005 Chondroitinase 0.03 0.005 Cellulase 0.02 0.001 Pectinase 0.01 0.02 Silicate 3.0 5.0 Carbonate 10.0 10.0 Granular foam suppressor 1.0 4.0 CMC 0.2 0.1 Water / minor ingredients up to 100%-- EXAMPLE 7 Liquid, heavy-duty fabric cleaning compositions were prepared for use in the pre-treatment of soiled fabrics, and for use in a machine-washing method, according to the invention, as follows: I II III IV V 24AS 20.0 20.0 20.0 20.0 20.0 SS 5.0 5.0 5.0 5.0 5.0 Citrate 1.0 1.0 1.0 1.0 1.0 12E3 13.0 13.0 13.0 13.0 13.0 Monoethanolamine 2.5 2.5 2.5 2.5 2.5 Chondroitinase 0.02 0.01 0.05 0.001 0.003 Protease 0.005 0.03 0.02 0.04 0.01 Lipase 0.002 0.01 0.02 - 0.004 Amylase 0.005 0.005 - - 0.004 Cellulase 0.04 - 0.01 - - Pectinase 0.02 0.02 - - - Water / propylene glycol / ethanol (100: 1: 1) EXAMPLE 8 , Liquid, fabric cleaning compositions heavy duty, according to the invention as follows was prepared: - 1 II III IV LAS acid form - 25.0 alkenylsuccinic -acetic 12-14 carbon atoms 10.0 3.0 8.0 citric -acid ! 10.0 15.0 2.0 2.0 25AS acid form 8.0 8.0 - 15.0 25AE2S acid form - 3.0 - 4.0 25AE7 8.0 6.0 25AE3 8.0 CFAA - - - 6.0 DETPMP 0.2 to 1 0.0 1.0 fatty acid - _ - 10.0 Oleic acid 1 8-1 0 4 0 4 0 -ethanol 6. 0 2.0 2.0 2.0 6.0 10.0 propanediol chondroitinase 0.05 0.01 0.02 0.005 0.02 0.02 Protease 0.02 0.01 Amylase .005 .01 .005 .01 .005 cellulase - - 0.02 pectinase _ - - chloride cocoalquildime-tilhidroxietila onium smectite clay 3.0 5.0 PVP 1.0 2.0 perborate 1.0 phenol sulphonate 0.01 NaOH up to pH 7.5 - water / minor ingredients --hasta 100% - - EXAMPLE 9 The following fabric softening composition was prepared, to be added in the rinse, in accordance with the invention (parts by weight): Active ingredient softener 24.5 PGMS 2.0 TAE 25 1.5 Chondroitinase 0.001 Cellulase 0.001 HCl 0.12 Antifoam agent 0.019 Blue color 80 ppm CaCl2 0.35 Perfume 0.90 EXAMPLE 10 A. Model tests were carried out in beaker for chondroitinase B (dermatan-sulphatase). It expresses the activities against the dermatan sulphate substrates model. Since these enzymes are biological enzymes, the activities are specified at pH 7. The activity of chondroitinase B at 25 ° C is specified. 0.25 g of heavily stained necks was exposed to 1 unit of enzyme. It was tested at pH 7 (TRIS regulator) and at pH 10.5 (bicarbonate / carbonate regulator) and at room temperature (20 ° C) and at 37 ° C for enzymes. Samples of neck fabric were also washed in deionized water. The cloth samples were left in solution for an hour, with delicate agitation, and allowed to air dry.
Enzyme Activity: Definition of unit (Sigma) of chondroitinase B: One unit will form 1.0 micromole of unsaturated uronic acid from chondroitin sulfate B, per hour, at pH 7.5, at 25 ° C.
B. Immersion tests were also carried out on unwashed neck swabs, at pH conditions of granular detergents and regular liquids, respectively, at 20 ° C and 37 ° C. It has also been discovered that increasing the temperature from 20 ° C to 37 ° C gives improved benefits. At pH 10.5 and 37 ° C, chondroitinase gives improved stain removal benefits, with respect to alkaline pH alone.
EXAMPLE 11 Performance data using chondroitinase, against the reference.
Body grime With chondroitinase, against: chondroitinase none UPS Preference Pillows +0.2 55: 45 Collars +0.3 58: 42 Socks + 0.7s 63 s 37 The level of enzyme used is 10 units / liter. • 5 THE TEST METHOD Chondroitinase enzyme was added in 1 liter of water, adjusted to pH 10.4. Soiled garments were soaked in this enzyme solution for 40 minutes. Then he dried and washed the stained items in Ariel Futur < R > (from P &G), without chondroitinase. The reference is a soak in solution without any enzyme (pH 10.4), followed by a wash with Ariel Futur < > (of 15 P &G) under the same conditions as for the test samples. The concentration of Ariel Futur < R) in the wash is 75 g / 12 L and the washing was carried out at 40'C, in tap water, with a Miele washer and using a short cycle.

Claims (6)

NOVELTY OF THE INVENTION CLAIMS
1. - Cleaning composition characterized in that it comprises a chondroitinase enzyme.
2. Cleaning composition according to claim 1, further characterized in that the enzyme is present at a level of 0.0001% to 2% of active enzyme, by weight of the composition.
3. Cleaning composition according to claims 1 or 2, characterized in that the composition is a detergent composition.
4. Cleaning composition according to claim 3, further characterized in that the detergent composition comprises one or more components selected from nonionic, anionic, cationic, Zwitter ionic, ampholytic or amphoteric surfactants; bleaching agents, additional enzymes, suds suppressants, dispersants, grime suspending agents and an i-redeposition of dirt, smectite clays, detergency builders and the like.
5. Cleaning composition according to claim 3 or 4, further characterized in that the detergent composition is a granular detergent composition containing not more than 15% in weight of inorganic filler salt.
6. - Cleaning composition according to claim 3, further characterized in that the detergent composition is a heavy duty liquid composition.
MXPA/A/1997/009888A 1995-06-08 1997-12-08 Cleaning compositions comprising condroitin MXPA97009888A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP95303937A EP0747469A1 (en) 1995-06-08 1995-06-08 Cleaning compositions comprising chondroitinase
EP95303937 1995-06-08
PCT/US1996/007820 WO1996041861A1 (en) 1995-06-08 1996-05-28 Cleaning compositions comprising chondroitinase

Publications (2)

Publication Number Publication Date
MX9709888A MX9709888A (en) 1998-03-29
MXPA97009888A true MXPA97009888A (en) 1998-10-15

Family

ID=

Similar Documents

Publication Publication Date Title
EP0791046B1 (en) Detergent compositions containing lipase and protease
US6030933A (en) Detergent compositions comprising immobilized enzymes
US6147045A (en) Detergent compositions comprising specific amylase and a specific surfactant system
US5786316A (en) Cleaning compositions comprising xylanases
US5837010A (en) Detergent compositions containing a lipase variant at low levels
JP2000505502A (en) Detergent compositions comprising improved amylase
JPH10508057A (en) Cleaning composition containing xylanase
MXPA97003153A (en) Cleaning compositions that understand xilana
JP2002504936A (en) Enzyme detergent composition
JPH11502256A (en) Detergent composition containing immobilized enzyme
WO1997031999A1 (en) Cleaning compositions comprising endo-dextranase
WO1997036977A1 (en) Detergent compositions comprising specific amylase and alkyl poly glucoside surfactants
MXPA98000749A (en) Detergent compositions that comprise a specific amylase and a prote
US5965507A (en) Cleaning compositions comprising chondroitinase
JPH11511780A (en) Detergent composition comprising specific lipolytic enzyme and coal soap dispersant
MXPA98000750A (en) Detergent compositions that comprise a specific amylase and a system of tensioactive agent specific
JPH11505562A (en) Cleaning composition containing keratanase
JPH11511778A (en) Detergent composition comprising lipolytic enzyme
MXPA97009888A (en) Cleaning compositions comprising condroitin
JPH11507692A (en) Cleaning composition containing chondroitinase
JPH11501979A (en) Detergent composition containing hyaluronidase
JP2001519832A (en) Detergent composition containing specific amylase and linear alkylbenzene sulfonate surfactant
MXPA98009637A (en) Compositions that comprise specific lipolytic enzyme and alkilglucos surgical agent
MXPA98009591A (en) Detergent compositions that include amylasses, more enhanced, cellulose and surgical agent cation
MXPA98000747A (en) Detergent compositions comprising a specific amylase and an alkylbencensulphonate surgical agent lin