JPH06508394A - Laundry detergent containing polyhydroxy fatty acid amide and insoluble ethoxylated alcohol - Google Patents

Abstract

The present invention provides laundry detergent compositions comprising one or more water soluble anionic, cationic, ampholytic or zwitterionic detersive surfactants or mixtures thereof and a combination of (a) at least 1 % by weight of the composition of a polyhydroxy fatty acid amide having formula (I), wherein R1 is H, a C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2 hydroxy propyl, or mixtures thereof, R<2> is a C5-C31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyl groups directly connected to the chain, or an alkoxylated derivative thereof; and (b) at least 1 % by weight of the composition of a substantially water-insoluble ethoxylated C11-C15 primary aliphatic alcohol containing an average of no more than five ethylene oxide groups per mole and having an ethylene oxide content of less than 50 % by weight. Preferred water soluble surfactants are anionic surfactants and more preferred compositions are free of alkyl benzene sulfonate surfactants.

Description

[Detailed description of the invention] Laundry detergent containing polyhydroxy fatty acid amide and insoluble ethoxylated alcohol agent Technical field TECHNICAL FIELD This application relates to fabric cleaning compositions, and more particularly, to fabric cleaning compositions for cleaning grease and oil stains. The present invention relates to a fabric cleaning composition capable of providing removal.

The surfactant systems in commercially available fabric cleaning compositions remove various types of Designed to remove dirt. Most such systems contain more than one type of shade. Ionic surfactants and trace amounts of other surfactant types, e.g. non-ionic surfactants , characterized by amphoteric surfactants and cationic surfactants, especially with a predominant proportion of anionic surfactants. The combination of on-ion surfactants and small proportions of non-ionic surfactants is effective in removing particulate stains. and grease/oil removal properties. Ru. A detergent composition containing a surfactant system whose main component is a nonionic surfactant is Technically, for example, EP-A 0006268 and British Patent No. 2206 No. 601, but any commercial application is of a specialized nature. There was a tendency for these to have the following characteristics. It is based on anionic surfactants The composition provides acceptable cleaning power over a wide spectrum of soils. and exhibit greater compatibility with additives such as optical brighteners, fabric softening additives, etc. It is also less aggressive towards fabric dyes and washing machine parts.

Therefore, without sacrificing the removal of other soil types and without impacting the performance of other detergent ingredients. There remains a need for detergent compositions that exhibit improved grease/oil stain removal without impact. It exists.

The present invention comprises one or more polyhydroxy fatty acid amides and one or more additional nonionic A laundry detergent composition containing a nonionic surfactant system consisting of a surfactant and a surfactant is provided. Ru.

When incorporated into such laundry detergent compositions, these nonionic surfactant systems are , unexpectedly, this kind of resistance against grease and oil stains over a wide range of washing conditions The composition improves childhood.

Commonly Assigned Co-pending U.S. Patent Application No. 0715 filed September 28, 1990 No. 78760 discloses a polyhydroxy fatty acid amide consisting of a polyhydroxy fatty acid amide and one or more additional non- Discloses a non-ionic surfactant system consisting of a combination with an ionic surfactant. . Polyhydroxy fatty acid amide has the formula (In the formula, R is HSO1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydrocarbyl, roxypropyl, or a mixture thereof, and R2 is C-C hydrocarbyl. and Z is a linear chain having at least three hydroxyl groups directly linked to the chain. Polyhydroxyhydrocarbyl or its alkoxylation with a dolocarpyl chain derivative) has. The weight ratio of polyhydroxy fatty acid amide to additional nonionic surfactant is , about 1:5 to about 5=1. other nonionic surfactant types, For example, anionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, Active agents and semi-polar surfactants can be included as optional ingredients and are part of the surfactant system. Formulated detergent compositions are also disclosed.

Applicants have unexpectedly discovered that polyhydroxy fatty acid amides and water-insoluble ethoxylated non-ionic This general surfactant contains a combination of surfactants along with other water-soluble surfactants Detergent compositions formulated with non-ionic surfactant systems are effective for cleaning against other soil types. Found to provide unexpected oil/grease stain removal benefits without reduction in performance Ta.

Background technique Various polyhydroxy fatty acid amides have been described in the art. For example, N-a Syl-N-methylglucamide was prepared by J.W. Gutsupai, M.A., Marcus, E. Chin, and P. L. Finn, “Thermal analysis of some straight-chain carbohydrate amphiphiles. Tropic Liquid Crystals J, Liquid Crystals.

1988, Vol. 3, No. 11, pp. 1569-1581, and A. Mu. Ra-Farnara, ■.

Zabel, M., Stiffa, and R. Hilgenfeld, “Nonionic Detergents Molecular structure and crystal structure of nonanoyl-N-methylglucamide J J, Ch ets, Soc, Chew.

Comwun, 1986, pp. 1573-1574. . The use of N-alkyl polyhydroxyamide surfactants has recently been explored in biochemistry. As a result, it has become of practical interest, for example, in its use in dissociating biofilms. It's here. For example, in J.E., a journal article by Hildreth, “N. -D-glucose N-methyl-alkanamide compound, a new type of nonionic detergent ”, Blochem, J. (1982), Vol. 207, pp. 363-36 See page 6.

The use of N-acylated lucamines in detergent compositions has also been discussed. E,R , U.S. Patent No. 2,965.576, issued December 20, 1960 to Wilson. Specification and published on February 18, 1959, Thomas and Hedley end car. British Patent No. 809,060, assigned to Company Ltd. Amide surfactant (this is added as a low temperature foaming agent) (which may include tilglucamide). These compounds Examples include N-acyl groups of higher straight chain fatty acids having 10 to 14 carbon atoms. Ru. These compositions contain alkali metal phosphates, alkali metal silicates, sulfur Auxiliary substances such as ates, carbonates, etc. may also be included. Also, it is generally desirable Additional ingredients that impart desirable properties to the composition, such as fluorescent dyes, bleaching agents, fragrances, etc. It has been pointed out that it can be incorporated into compositions.

U.S. Patent No. 2,703,798 issued March 8, 1955 to A. M. Schwartz. The specification describes the condensation reaction product of N-alkylglucamine and aliphatic ester of fatty acid. The present invention relates to an aqueous detergent composition containing the composition. The product of this reaction is available without further purification. It is said that it can be used in aqueous detergent compositions. A.M. Schwartz 1955 As disclosed in U.S. Pat. No. 2,717,894, issued September 13, It is also known to produce sulfate esters of glycated glucamine.

PCT International Application No. 83 by J. Hildreth, published December 22, 1983 No. 104412 applies to cosmetics, medicines, shampoos, lotions, and eye ointments. as a surfactant, as a medical emulsifier and dispensing agent, and as a membrane, whole cell or has other uses in biochemistry for solubilizing tissue samples and producing liposomes. Polyhydroxyl aliphatic groups are said to be useful for a variety of purposes, including Contains an amphipathic compound. This disclosure includes the formula R'CON (R)CH 2R' and R' CON (R) R' (wherein R is hydrogen or an organic atomic group , R' is an aliphatic hydrocarbon group having at least 3 carbon atoms, and R' is an aldose (which is a residue of) is included.

European Patent No. 0285 of H. Kerkenberg et al. published on January 12, 1988 Specification No. 768 discloses that N-polyhydroxyalkyl fatty acid amide is used in an aqueous detergent system. Concerning use as a thickener. formula RC (0) N (X) In the RC formula, R1 is C-C1□ (preferably C-C> is alkyl, R2 is hydrogen, C-C (preferably 01-C6) alkyl or is alkylene oxide, and X is polyhydroquine alkyl having 4 to 7 carbon atoms. ), such as N-methyl coconut fatty acid glucamide. aqueous The surfactant system may contain other anionic surfactants, such as alkylaryl sulfonates. olefin sulfonates, sulfosuccinic acid half ester salts, and fatty alcohols. ether sulfonates, and nonionic surfactants such as fatty alcohols. polyglycol ether, alkylphenol polyglycol ether, fat Acid polyglycol ester, polypropylene oxide-polyethylene oxide blend It can contain polymers, etc., but the thickening properties of amides are lower than those containing paraffinsulfonate. It has been pointed out that it has particular use in liquid surfactant systems for a. paraffin Ruphonate/N-Methyl Coconut Fatty Acid Glucamide/Nonionic Surfactant Shan Pooh formulation is exemplified. In addition to thickening properties, N-polyhydroxyalkyl The fatty acid amides are said to have excellent skin tolerability properties.

No. 2,982,737 issued May 2, 1961 to Boettner et al. The specifications include urea, sodium lauryl sulfate anionic surfactant, and N-methyl- N-Sorbityllaurinamide and N-methyl-N-sorbityl myristamide A detergent solid containing an N-alkyl glucamide nonionic surfactant selected from Regarding shapes.

Other glucamide surfactants may be used, e.g. (In the formula, R is c-c alkyl, R2 is C10-C22 alkyl, , n is 3 or 4). selected from one or more surfactants and polymeric phosphates. Detergent compositions containing builder salts, sequestering agents and detergent alkalis DT No. 2゜226. of H, W, Esocart, etc. announced on December 20, 1973. No. 872. N-acylpolyhydroxyalkylamine is , trj is added as a suspending agent.

U.S. Patent No. 3,654,16 issued April 4, 1972 to H, W, Esocart et al. Specification No. 6 describes anionic surfactants, zwitterionic surfactants and nonionic surfactants. Formula R as at least one surfactant selected from the group and fabric softener , N (Z)C(0)R2 [wherein R is C1,o=022 alkyl, R 2 is C7~C2Ia] R and R2 have a total of 23 to 39 carbon atoms, and Z is -CH(CHOH) CH20H (where m is 3 or m is a polyhydroxyalkyl which can be 4) - A detergent composition containing an N-alkyl polyhydroxyalkyl compound.

No. 4,021,539 issued May 3, 1977 to H. Mellor et al. The calligraphy is the expression RN (R) CH (CHOH) R (wherein, R1 is Hll m2 lower alkyl, hydroxy lower alkyl, or aminoalkyl, as well as heterocycles is the formula aminoalkyl, and Ri;! Same as R, but both can be H Scratch, ]- R is CHOH or COOH) The present invention relates to skin treatment cosmetic compositions containing alkylamines.

French Patent No. 1,36 assigned to Commercial Trubenz Corporation Specification No. 0,018 (April 26, 1963) is based on the formula RC(0)N (R Engineering) G (wherein R is a carboxylic acid functionality having at least 7 carbon atoms) , R1 is hydrogen or a lower alkyl group, and G is a group having at least 5 carbon atoms. Formalde stabilized against polymerization by adding an amide of Concerning solutions of Hyde.

German Patent No. 1,261,861 (February 29, 1968, A. Hines ) is the expression N(R)(R)(R2) (wherein, R is a sugar residue of glucamine, and R is a C-C a R2 is a C1-C5 acyl group) as a wetting agent/dispersing agent. The present invention relates to glucamine derivatives that can be used for various purposes.

Announced on February 15, 1956 and transferred to Atlas Powder Company. British Patent No. 745,036 describes chemical intermediates, emulsifiers, wetting agents/dispersing agents, Heterocyclic amides, which are said to be useful as detergents, fabric softeners, etc. Regarding these carboxylic acid esters.

The compound is 2N(R)(R)C(0)R2 (wherein R is anhydrous hexaneben It is a residue of toll or its carboxylic acid ester, and R1 is a monovalent hydrocarbon group. (-C(0)R2 is an acyl group of a carboxylic acid having 2 to 25 carbon atoms) expressed.

U.S. Patent No. 3,312,627 issued April 4, 1967 to D. T. Hooker. The specification includes anionic detergents and alkaline builder substances which are substantially toothless and consist of Lithium soap of fatty acids, consisting of propylene oxide-ethylenediamine-ethylene Oxide condensate, propylene oxide-propylene glycol-ethylene oxy Contains a nonionic surfactant selected from polycondensates and polymerized ethylene glycols. and also has the formula RC(0)NR"(R2) (wherein RC(0) is about 10 to about 1 has 4 carbon atoms, and R and R2 are each H or c-c alkyl group. and the alkyl group has a total number of carbon atoms of 2 to about 7 and a substituent hydroxyl group. non-ionic foaming properties that can include polyhydroxyamides having a total number of 2 to about 6) A solid cosmetic bar also containing ingredients is disclosed. Substantially similar disclosures include D, T, Hooker, U.S. Pat. No. 3,312,626, issued April 4, 1967. be discovered.

The use of nonionic surfactants in detergent compositions is known in the art. two cars U.S. Pat. No. 3,654,166 issued on April 4, 1972 to Interface selected from ionic surfactants, zwitterionic surfactants and nonionic surfactants Activator and N-alkyl-N-acyl-N-polyhydroxyalkyl compound A detergent composition comprising:

Another disclosure of the use of nonionic surfactants in detergent compositions is that the average ethylene oxide 08-C15 substantially unbranched alcohol having oxide content of ~51% by weight The ethylene oxide adduct of British patent teaches that surfactants can serve as detergency improvers No. 1,241,754. Modifiers are surfactants vs. modifiers A weight ratio of 5:1 to 1:1 is used. However, the literature shows that water-insoluble poly Hydroxy fatty acid amide surfactants and certain water-insoluble ethoxylated nonionic surfactants According to the invention, automatic laundry A laundry detergent composition useful for cleaning fabrics in a machine, the composition comprising one or more water-soluble anionic detergent surfactants, cationic detergent surfactants, amphoteric detergent surfactants or zwitterionic detergent surfactants or mixtures thereof and optionally detersive detergents. (a) at least one compound of the composition); Amount% formula (wherein R1 is H, C-C hydrocarbyl, 2-hydroxyethyl, 2 -hydroxypropyl or mixtures thereof, and R2 is C-C hydrocarbyl. Z is a linear chain with at least three hydroxy groups directly attached to the chain. Polyhydroxyhydrocarbyl having a hydrocarbon chain or its alkoxylated derivative a polyhydroxy fatty acid amide having a conductor); and (b) a small amount of the composition. Contains at least 1% by weight of ethylene oxide groups, with an average of not more than 5 ethylene oxide groups per mole, and substantially water-insoluble ethoxylated material having an ethylene oxide content of less than 50% by weight A laundry detergent composition comprising a 11-C15 primary aliphatic alcohol provided.

Preferably, the composition is granular and contains 3-15% by weight of anionic surfactant. component (a) 1% to 10% and component (b) 1% to 10%, anionic surfactant The weight ratio of agent to total weight of component (a) and component (b) is from 1:3 to 3:1.

More preferably, the anionic surfactant comprises a major proportion of water-soluble CI4-C15 alkyl An average of 3 ethoxylates per mole of rusulfate and alkyl ethoxy sulfates Mixture with CI2-C15 alkyl ethoxy sulfate (small proportion) containing Consists of compounds.

BEST MODE FOR CARRYING OUT THE INVENTION The detergent composition of the present invention comprises three essential components: polyhydroxy fatty acid amide; Water-insoluble ethylene oxide adduct of C11-C15 aliphatic alcohol, and negative Ionic surfactants, cationic surfactants, amphoteric surfactants or zwitterionic surfactants water-soluble surfactants which may be

The polyhydroxy fatty acid amide surfactant component of the present invention has the structural formula: [Wherein, R1 is H, C-C hydrocarbyl, 2-hydroxyethyl, 2-hydro xypropyl, or mixtures thereof, preferably O1-C4 alkyl, more preferably Preferably C or C2 alkyl, most preferably 01 alkyl (i.e. methyl) R2 is C-c human Ocarbyl, preferably linear C11''C19 acarbyl; alkyl or alkenyl, more preferably straight chain C15-C19 alkyl or aryl alkenyl, most preferably straight chain C15-C17 alkyl or alkenyl, and is a mixture thereof; Z is at least three hydroxyl groups directly linked to the chain; polyhydroxyhydrocarbyl or polyhydroxyhydrocarbyl having a linear hydrocarpyl chain with an alkoxylated derivative thereof (preferably ethoxylated or propoxylated)] It consists of a compound of Z is preferably derived from a reducing sugar in a reductive amination reaction more preferably Z is glycityl. As a suitable reducing sugar are glucose, fructose, maltose, lactose, galactose, manganese and xylose. High dextrose corn as raw material syrup, high fructose corn syrup, and high maltose corn syrup can be used in the same way as the individual sugars mentioned above. These corn syrups are A mix of minutes may be prepared. Never try to exclude other suitable raw materials. You should understand that there is no such thing. Z is preferably -CH2-(CHOH)n- CH20H.

-CH(CH20H)-(CHOH)n-I CH20H.

-CH2(CHOH) 2(CHOR")(HCHOH)-CH20H (in the formula, n is an integer from 3 to 5, R' is H or a cyclic or aliphatic monosaccharide), and and their alkoxylated derivatives. n is 4 Glycythyl, especially -CH2-(CHOH)4-CH20H is most preferred.

In formula (1), R1 is, for example, N-methyl, N-ethyl, N-propyl, N-i sopropyl, N-butyl, N-2-hydroxyethyl, or N-2-hydroxy It can be cipropyl.

R2-Co-N< is, for example, cocoa amide, stearamide, oleamide, la Urinamide, myristamide, caprinamide, palmitamide, tallowamide It can be, for example, de.

Z is 1-deoxygludityl, 2-deoxyfructityl, 1-deoxymal Tityl, 1-deoxyglutyl, 1-deoxygalactityl, 1-deoxyglutyl Dityl, ]-deogymyl-)liothytyl, and the like.

The most preferred polyhydroxy fatty acid amide has the general formula (wherein R is C11=c 19 straight chain alkyl or alkenyl group) has.

Methods for making polyhydroxy fatty acid amides are known in the art. Generally, they are Alkylamines are reacted with reducing sugars in a reductive amination reaction to form the corresponding N-alkylamines. N-alkylpolyhydroxyamine and then N-alkylpolyhydroxyamine react with aliphatic esters or triglycerides in a condensation/amidation step to produce an N-alkyl-N-polyhydroxy fatty acid amide product. Therefore, it can be manufactured. The method for producing a composition containing polyhydroxy fatty acid amide is as follows: For example, 1959 by Thomas Headley & Company Ltd. British Patent No. 809,060, published February 18, 2008, to E. R. Wilson. U.S. Pat. No. 2,965,576, issued December 20, 1960; and Andrew M. Schwartz U.S. Patent Nos. 2 and 7, issued March 8, 1955. No. 03,798 and U.S. Patent issued December 25, 1934 to Bigot. No. 1.985.424, each of which is incorporated herein by reference. Disclosed.

If the glycityl component is derived from glucose and N-alkyl or N-hydroxya N-methyl, N-ethyl, N-propyl, N-butyl, N-hydro N-alkyl or N-hydroxy, which is loxethyl or N-hydroxypropyl Preferred method for producing droxyalkyl-N-deoxyglycityl fatty acid amide If so, the product contains N-alkyl- or N-hydroxyalkyl-glucamine. Trilithium phosphate, trisodium phosphate, tripotassium phosphate, tetrasodium birophosphate Lithium, pentapotassium tripolyphosphate, lithium hydroxide, sodium hydroxide, hydroxide potassium chloride, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate , disodium tartrate, dipotassium tartrate, potassium sodium tartrate, citric acid trisodium acid, tripotassium citrate, basic sodium silicate, basic silicic acid Potassium, basic sodium aluminosilicate, and basic potassium aluminosilicate fatty methyl in the presence of a catalyst selected from the group consisting of fatty acid esters selected from esters, fatty ethyl esters and fatty triglycerides; It is produced by reacting with stell. The amount of catalyst is preferably N-alkyl from about 0.5 mol % to about 5 mol % or N-hydroxyalkyl-glucamine on a mole basis. 0 mol%, more preferably about 2.0 mol% to about 10 mol%. The reaction is favorable Typically, the temperature is about 38°C to about 170°C for about 20 to about 90 minutes. Trigri When utilizing cerides in the reaction mixture as a source of fatty acid esters, the reaction is preferably < is about 1% to about 10% by weight of saturated fat, calculated on a weight% basis of the total reaction mixture. alcoholboriethoxylate-1, alkyl polyglycoside, linear glucamide interface Using a phase transfer agent selected from activators and mixtures thereof1. I will do it.

Preferably, the method is carried out as follows: (a) the fatty acid ester is heated to about 38°C to Preheat to about 170”C; (b) Fat heated with N-alkyl or N-hydroxyalkylglucamine Add the acid ester and mix to the extent necessary to prepare the two-phase liquid-liquid mixture 1-; (C) incorporating a catalyst into the reaction mixture; (d) Stir for a predetermined reaction time.

Also preferably, if the fatty acid ester is a triglyceride, about 2 ~20% by weight of linear N-alkyl/N-hydroxyalkyl produced - The N-linear glucosyl fatty acid amide product is added to the reaction mixture as a phase transfer agent. I can do it. This accelerates the reaction and thereby increases the reaction rate. detailed fruit The test method is given below in the experiment.

The polyhydroxy "fatty acid" amide materials used herein are also wholly or primarily natural. It has the advantage of being manufactured from naturally renewable, non-petrochemical feedstocks and being degradable. Provided to detergent formulators. Also, they exhibit low toxicity to aquatic organisms.

In one particularly preferred embodiment of the invention, the polyhydroxy fatty acid amide material is, R2 is c-c straight chain a15 1st chain Derived from tallow fat, which is a lukyl group. Polyhydroxy fatty acid of formula (1) Along with the amides, the methods used to produce them also typically consist of amounts of Also produces non-volatile by-products such as ester amides and cyclic polyhydroxy fatty acid amides. You should be aware that this will happen.

The amounts of these byproducts will vary depending on the specific reactants and process conditions. Dew. Preferably, the polyhydroxy fatty acid amide blended into the detergent composition herein is , the polyhydroxy fatty acid amide-containing composition added to the detergent is a cyclic polyhydroxy fatty acid. Provided in such a form that it contains less than about 10% fatty acid amides, preferably less than about 4%. There will be.

The preferred method described above produces rather small amounts of by-products, including such cyclic amide by-products. It is advantageous because it only produces things.

The polyhydroxy fatty acid amide component is present in an amount of at least 1% by weight of the composition, and more Preferably present in an amount of 1 to 10% by weight, most preferably in an amount of 2 to 6% by weight. .

The laundry detergent composition of the present invention includes, in addition to the polyhydroxy fatty acid amide component, Contains one or more of the nonionic surfactants described. Nonionic surfactants described here will hereinafter be referred to as "additional nonionic surfactant".

Nonionic compounds other than these additional nonionic surfactants are nonionic compounds of the present invention. It may optionally be included in the surfactant system. Any of these other nonionic compounds will hereinafter be referred to as "any non-ionic compound". Limit by theory Although it is not intended that any such nonionic compound be considered as a nonionic compound of the present invention, When included in surfactant systems, they offer the unexpected stain removal benefits described herein. It is considered that there is no benefit.

Additional nonionic surfactant Primary fused with an average of not more than 5 ethylene oxide groups per mole of alcohol 01□ to C15 aliphatic alcohols are additional nonionic fields useful in the compositions of the present invention. Constitutes a surfactant. Such alcohol ethoxylates are ethylene oxy It should have a carbon content of less than 50% by weight and should be water-insoluble.

Preferred aliphatic alcohol ethoxylates have an average of 3 ethoxylates per mole of alcohol. on average 12 to 15 carbon atoms in the alkyl chain, ethoxylated with ethoxy groups of is a linear or substantially linear aliphatic alcohol having a

The additional nonionic surfactant represents at least 1% by weight of the composition, preferably 1 to 1%. It is present in an amount of 0% by weight, more preferably 1-6% by weight.

The third essential component of the laundry detergent composition according to the present invention is an anionic surfactant, a cationic surfactant, and a cationic surfactant. One or more water-soluble surfactants selected from surfactants, amphoteric surfactants, and amphoteric surfactants It is a surfactant.

anionic surfactant In addition to the nonionic surfactant system of the present invention, the laundry detergent compositions of the present invention include: It can contain one or more anionic surfactants such as those listed above.

Alkyl ester sulfonate surfactant here Alkyl ester sulfonate As a surfactant, ``The Journal on the American Oil Chemistry'' Sutsu Society J, 52 (1975), pp.

C8-C2o carbo sulfonated with gaseous S O3 according to 323-329 linear esters of fatty acids (ie fatty acids). Suitable starting materials include: Natural fatty substances such as those derived from tallow, palm ura, etc. may be mentioned. .

Particularly preferred alkyl ester sulfonate surfactants for laundry applications have the structural formula (wherein R is 08-C2o hydrocarbyl, preferably alkyl, or and R4 is C'=C6 hydrocarbyl, preferably alkyl , or a combination thereof, where M is an alkyl ester sulfonate and a water-soluble Alkyl ester sulfonate surfactant (which is a cation that forms a salt) It will be.

Suitable salt-forming cations include metals such as sodium, potassium and phosphorus. thium, and substituted or unsubstituted ammonium cations, e.g. monoethanol ethanolamine, jetanolamine, and triethanolamine. good Preferably, R3 is C-C alkyl tote and R4 is methyl, ethyl or isopropyl. R3 is C-C alkyl Particularly preferred are methyl ester sulfonates.

Alkyl sulfate surfactant The alkyl sulfate surfactant herein has the formula RO803M [wherein R is preferably or C10-024 hydrocarbyl, preferably C1(1”20 alkyl moiety more preferably CI2-018 alkyl or hydroxyalkyl having alkyl or hydroxyalkyl, M is H or a cation, e.g. Potassium metal cations (e.g., sodium, potassium, lithium), or ammonia or substituted ammonium (e.g. methyl-, dimethyl-1 and trimene) tylammonium cations and quaternary ammonium cations, e.g. Methyl-ammonium and dimethylpiperidinium cations, and ethyla Derived from alkylamines such as amine, diethylamine, triethylamine, etc. (e.g., quaternary ammonium cations, and mixtures thereof) Or acid. Alkyl having 12 to 16 carbon atoms, more preferably 14 to 15 carbon atoms The alkyl alkoxylated sulfate surfactant herein has the formula RO (A) SO3M In the formula, R is an unsubstituted C having a C10-024 alkyl component l0 = 024 alkyl or hydroxyalkyl group, preferably 012-C2 o alkyl or hydroxyalkyl, more preferably 12 to 18 carbon atoms, especially It is an alkyl group having 12 to 15 carbon atoms, and A is an ethoxy or propoxy unit. m is greater than 0, typically about 0.5 to about 6, more preferably about 0.5 ~3, and M is H or, for example, a metal cation (e.g., sodium, carbonate). lithium, lithium, calcium, magnesium, etc.), ammonium or substituted A water-soluble salt or acid of a cation which can be an ammonium cation It is. Alkyl ethoxylated sulfates and alkyl propoxylated sulfates is intended here. A specific example of a substituted ammonium cation is methyl -, dimethyl-, trimethyl-ammonium cations and quaternary ammonium cations cations such as tetramethyl-ammonium and dimethylpiperidinium cations and alkylamines, such as ethylamine, diethylamine, and those derived from triethylamine, and mixtures thereof.

A preferred example of an alkyl alkoxylated sulfate surfactant is an alkyl ethyl sulfate surfactant. 012-C1 containing on average up to 3 ethoxy groups per mole of cisulfate 8 alkyl ethoxy sulfate.

Particularly preferred surfactants are 012-C15 alkyl polyethoxylates (3, 0) sulfate (CI2-C15E(3,0)M). Other exemplary surfactants As a sex agent, 012-018 alkyl polyethoxylate (1,0) sulfate (C-c E(1,0)M), C12-C18 alkyl polyethoxylate (2,25) sulfate (C-CE (2,25) M), C12-C1 8 alkyl polyethoxylate (3,0) sulfate (012~CE(3,0 ) M), and 012-018 alkyl polyethoxylate (4,0) sulfur ate (012~Cl8E(4,0)M) (where M is sodium and potassium (conveniently selected from the list).

Other anionic surfactants Other anionic surfactants useful for cleaning purposes may also be included in the laundry detergent compositions of the present invention. Wear. These include soap salts (e.g. sodium salts, potassium salts, ammonia salts, salts, and substituted ammonium salts, such as monoethanolamine salts, (including tanolamine salts and triethanolamine salts), 09-C20 linear Alkylbenzene sulfonate, 08-C22 primary or secondary alkanesul phonates, 08-C24 olefin sulphonates, e.g. British Patent No. 1,08 Thermal decomposition products of alkaline earth metal citrates as described in US Pat. No. 2,179 Sulfonated polycarboxylic acid produced by sulfonation of 08-C24 alkaline Kill polyglycerol ether sulfate (up to 10 moles of ethylene oxide) ), alkylglycerol sulfonates, fatty acylglycerol sulfones Fatty oleylglycerol sulfate, alkylphenol ethylene oxide Oxide ether sulfate, paraffin sulfonate, alkyl phosphate , isethionates, such as acyl isethionate, N-acyl taurate, acyl isethionate, Lukyrsufucinamate and sulfosuccinate, monoester of sulfosuccinate esters (especially saturated and unsaturated C12-C18 monoesters), sulfosuccine diesters (especially saturated and unsaturated 06-C12 diesters), acylsa lucosinates, sulfates of alkyl polysaccharides, e.g. alkyl polygelcones (non-ionic, non-sulfated compounds are listed below), branched primary alkyl rusulfate, and alkyl polyethoxy carboxylates, such as formula R O(CH2CH20), -CH3COOM (wherein R is 08-C22 alkyl , k is an integer from O to 10, and M is a soluble salt-forming cation) can be mentioned. Resin acids and hydrogenated resin acids, e.g. rosin, hydrogenated rosin , and resin acids and hydrogenated resins present in or derived from tall oil. Fatty acids are also suitable. Yet another example is “Surfactants and Detergents” (Schwartz) , Veri and Birch, Volumes 1 and 2). Various saws Surfactants such as Patent No. 3,929,678, column 23, line 58 to column 29, line 23 (here (incorporated as a reference).

Preferred anionic surfactant systems for use in the laundry detergent compositions of the present invention include alkyl Contains no benzene sulfonate. A highly preferred system has a major proportion of water-soluble C34 ~C15 alkyl sulfate and per mole of alkyl ethoxy sulfate C1° to C15 alkyl ethoxy sulfate containing an average of 3 ethoxy groups (small proportion). The laundry detergent compositions of the present invention typically include on surfactant] to about 20% by weight, preferably from about 3 to about 15% by weight, most preferably from about 3% to about 15% by weight. or 5 to 10% by weight.

Other surfactants The laundry detergent composition of the present invention includes a cationic surfactant, an amphoteric surfactant, a zwitterionic surfactant, and a zwitterionic surfactant. It may also contain polarity agents and semipolar surfactants.

Cationic detergent surfactants suitable for use in the laundry detergent compositions of the present invention include one It has a long chain hydrocarbyl group. Such cationic detergent surfactants Examples of agents include ammonium surfactants, such as alkyldimethylammonium surfactants. umhalogenide, and the formula [wherein R2 is about 8 to about 18 atoms in the alkyl chain] an alkyl or alkylbenzyl group having a carbon atom, each R being -CH2C H2-1-CH2CH(CH3)-1-CH2CH(CH20H)-1 selected from the group consisting of -CH2CH2CH2- and mixtures thereof; each R4 is C-C alkyl, C-C4 hydroxyalkyl, benzyl, bonding two R groups The ring structure formed by -CHCHOH-CHOHCOR6CHOH CHOH (wherein R6 is a hexose or a hexose having a molecular weight less than about 1000) hydrogen (when y is not 0); R5 is R 4 or is an alkyl chain, and the total number of carbon atoms in R2+R5 is about 18 or more. each y is from 0 to about 10, and the sum of the y values is from O to about 15; Examples include surfactants having an anion.

Other cationic surfactants useful here also include In U.S. Pat. No. 4,228,044 to Bure (incorporated herein by reference), Are listed.

When incorporated therein, the laundry detergent compositions of the present invention typically Contains from 0 to about 25% by weight, preferably from about 3 to about 15% by weight of ionic surfactant.

Amphoteric surfactants are also suitable for use in the laundry detergent compositions of the present invention. these The surfactants are secondary or Aliphatic derivatives of tertiary amines or aliphatic derivatives of heterocyclic secondary and tertiary amines It can be broadly described as a group derivative. one of the aliphatic substituents has at least 8 carbon atoms , typically having about 8 to about 18 carbon atoms and at least one anionic water Contains solubilizing groups such as carboxy, sulfonate, sulfate. bisexual world For examples of surfactants, see the US Pat. No. 3,929.678 specification, column 19, lines 18 to 35 (references here) (incorporated as).

When formulated therein, the laundry detergent compositions of the present invention typically contain such ambidextrous 0 to about 15% by weight, preferably about 1 to about 10% by weight of a surfactant.

Zwitterionic surfactants are also suitable for use in laundry detergent compositions. These surfactants The sexing agents include derivatives of secondary and tertiary amines, heterocyclic secondary and tertiary amines, derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium. It can be broadly described as a derivative of a phonium compound. For examples of zwitterionic surfactants, 1 U.S. Pat. No. 3,929.678 to Rollin et al., issued Dec. 30, 1975. See Column 19, Line 38 to Column 22, Line 48 of the specification (incorporated herein as a reference).

When incorporated therein, the laundry detergent compositions of the present invention typically contain such dual components. 0 to about 15% by weight, preferably about 1 to about 10% by weight of a surfactant.

Semipolar nonionic surfactants are a special category of nonionic surfactants, Examples include one alkyl moiety of about 10 to about 18 carbon atoms and one alkyl moiety of about 1 to about 18 carbon atoms. 2 moieties selected from the group consisting of about 3 alkyl groups and hydroxyalkyl groups a water-soluble amine oxide containing one alkyl moiety having about 10 to about 18 carbon atoms; and alkyl groups and hydroxyalkyl groups having about 1 to about 3 carbon atoms. a water-soluble phosphine oxyto containing two selected moieties; and from about 10 carbon atoms; one alkyl moiety of about 18 and alkyl and hydroxy of about 1 to about 3 carbon atoms; A water-soluble sulfoxide containing one moiety selected from the group consisting of alkyl moieties is Can be mentioned.

The semipolar nonionic detergent surfactant may be of the formula (wherein R3 has a carbon number of about 8 to about 22 an alkyl, hydroxyalkyl, or alkylphenyl group or a mixture thereof. compound; R4 is alkylene or hydroxyalkylene having about 2 to about 3 carbon atoms; or mixtures thereof; X is from 0 to about 3; each R5 has from about 1 to about 3 carbon atoms; 3 alkyl or hydroxyalkyl groups or about 1 to about 3 ethyleneoxy polyethylene oxide group containing a do group) Examples include amine oxide surfactants having the following. The R5 group may be, for example, oxygen or can be bonded to each other through nitrogen atoms to form a ring structure.

These amine oxide surfactants include, among others, CI Rho C18 alkyl dimethyl Thylamine oxide and 08-C12 alkoxyethyl dihydroxydiethyl amine Mine oxide is mentioned.

When formulated therein, the laundry detergent compositions of the present invention typically contain such semi- Contains from 0 to about 15% by weight, preferably from about 1 to about 10% by weight of a polar nonionic surfactant. nothing.

builder The laundry detergent compositions of the present invention can be used as an inorganic or organic detergent to aid in mineral hardness control. It can contain sex virgoo.

The amount of builder can vary widely depending on the end use and desired physical form of the composition. Ru. Liquid formulations typically contain at least about 1% by weight detersive builder, more typically typically about 5 to about 50% by weight, preferably about 5 to about 30% by weight. granular formulation typically contains at least about 1% by weight detergent builder, more typically from about 10% to 96% by weight, preferably about 15% to about 50% by weight. While doing so, more A smaller or larger amount of builders does not mean exclusion.

Inorganic detergent builders include, without limitation, polyphosphoric acid (tripolyphosphate). , pyrophosphate, and glassy polymer metaphosphate), phosphonic acid, phytic acid, silicic acid, carbonic acid (including bicarbonate and sesquicarbonate), Sulfuric acid and alkali metal salts, ammonium salts and alkanoyl aluminosilicates ammonium salts. Borate builders and detergent storage or cleaning Builders containing borate-forming substances that can form borates under conditions may also be used. However, it is not preferred under cleaning conditions below about 50°C, particularly below about 40°C. good Preferred builder systems also do not contain phosphates.

Examples of silicate builders are alkali metal silicates, especially SiO:Na 20 with a ratio of 1.6:1 to 3.2:1 and layered silicates, e.g. , a layered sodium silicate.

Preferred crystalline layered sodium silicate has the general formula % formula % (where M is sodium or hydrogen, X is a number from 1.9 to 4, and y is 0 =20). This kind of crystalline layered sodium silicate is EP- A No. 0164514 and their manufacturing method is disclosed in DE-A No. No. 341.7649 and DE-A No. 3742043 (see herein). (incorporated as a research document). For the purposes of the present invention, X in the general formula above is It has a value of 2.3 or 4, preferably 2. More preferably, M is Natori. and y is 0, and a preferred example of this formula is α-1β of Na2Si2O5. -1 Consists of γ- and δ-forms. These substances are derived from Hoechst AG FRG. Na5KS-5, Na5KS-7, Na5KS-11 and Na5KS-, respectively. Available as 6. The most preferred substance is δ-Na St ONa5KS-6 De 2 25ゝ Ru.

Other silicates, such as magnesium silicate (burr imparting agent in granular formulations) (can serve as an ingredient in anti-foam systems, as a stabilizer for oxygen bleaches) can also be useful.

Examples of carbonate builders are sodium carbonate and sodium sesquicarbonate. German Patent Application No. 2.321.001 published on November 15, 1973 Ultrafine carbonic acid as disclosed in No. If (the disclosure of which is incorporated herein by reference) Carbonates of alkaline earth metals and alkali metals, including mixtures with calcium It is.

Aluminosilicate builders are particularly useful in the present invention. aluminum non-licade Builder is a major component of most currently commercially available heavy-duty granular detergent compositions. It is of great importance that it can also be a significant builder ingredient in liquid detergent compositions. Ru. As an aluminosilicate builder, the experimental formula %formula%) (where M is sodium, potassium, ammonium or substituted ammonium) and 2 is about 0.5 to about 2: y is 1) This substance has Ca per gram of anhydrous aluminosilicate. C03 hardness has a magnesium ion exchange capacity of at least about 501 g equivalent.

Preferred aluminosilicates have the formula %formula% (wherein 2 and y are integers of at least 6, and the molar ratio of 2 to y is from 1.0 to about 0.5, and X is an integer from about 15 to about 264) It is a zeolite builder with

Aluminosilicate ion exchange materials are commercially available. these aluminum Nosilicates can be crystalline or amorphous in structure and are naturally occurring aluminum It can be a silicic acid or can be synthetically derived.

The method of manufacturing aluminosilicate ion exchange materials is described in the published October 12, 1976 No. 3,985,669 to Rumel et al. (incorporated herein by reference). ) is disclosed. Preferred synthetic crystalline aluminosilicate ions useful herein The exchange materials are named zeolite A1, zeolite P (B), and zeolite Available at X.

In particularly preferred embodiments, the crystalline aluminosilicate ion exchange material has the formula %formula% (wherein X is about 20 to about 30, especially about 27). This substance is zeo It is known as Light A.

Preferably, the aluminosilicate has a particle size of about O11-10μ in diameter.

Specific examples of polyphosphates are alkali metal tripolyphosphates, sodium, carbonate, Lithium and ammonium pyrophosphate, sodium, potassium and ammonium sodium pyrophosphate, sodium and potassium orthophosphate, degree of polymerization Sodium polymetaphosphate, which has a molecular weight of about 6 to about 21, and a salt of phytic acid.

An example of a phosphonate builder salt is ethane-1-hydroxy-1,1-diphosphone. Water-soluble salts of acids, especially sodium and potassium salts, methylene diphosphonic acid in water Soluble salts, such as trisodium and tripotassium salts and substituted methylene diphos Water-soluble salts of fonic acids, such as trisodium and tripotassium ethylidene, in Propylidenebenzylmethylidene and halomethylidene diphosphonate.

Phosphonate builder salts of the above type were described in Deal, December 1, 1964 and U.S. Pat. No. 3,159,581, issued October 19, 1965; No. 3,213,030, U.S. Patent No. 3 issued January 14, 1969 to Roy. , 422,021 and Finby September 3, 1968 and 196 U.S. Patent Nos. 3,400,148 and 3,42, issued January 14, 2009 No. 2,137 (the disclosure of which is incorporated herein by reference) .

Polycarboxylate builders generally can be added to the composition in acid form, but It can also be added in the form of salt. When used in salt form, sodium salt, potassium salt, Alkali metal salts such as tium salts, especially sodium salts, or ammonium salts and Bi-substituted ammonium salts (eg vulcanol ammonium salts) are preferred.

Polycarboxylate builders include various categories of useful materials.

One important category of polycarboxylate builders is the ether polycarboxylate builder. Includes boxylate. Numerous ether polymers used as detergent builders Boxylate is disclosed.

Examples of useful ether polycarboxylates include Berub U.S. Pat. No. 3,128,287 and issued January 18, 1972 No. 3,635,830 to Lamberch et al. cydisuccinate (both incorporated herein by reference) e Certain types of ether polycarboxylates useful as builders in the present invention include is the general formula % formula %)() (wherein A is H or OH; B is H or -0-CH(COOX)-CH 2(COOX) and X is H or a salt-forming cation) Examples include those having the following. For example, in the general formula above, both A and B are H. If present, the compound is oxydisuccinic acid and its water-soluble salts. A is OH , B is H, then the compound is tartrate monosuccinic acid (TMS) and It is its water-soluble salt. A is H, B is -0-CI (COOX')-CH2(CO OX), the compound is tartrate disuccinic acid (TDS) and its It is a water-soluble salt of Mixtures of these builders are particularly preferred for use here. Yes. Weight ratio of TMS to TDS: 97=3 to about 20:80 TMS and TD Particular preference is given to mixtures with S. These builders were published on May 5, 1987. No. 4,663,071 issued to Tsusch et al.

In addition, suitable ether polycarboxylates include cyclic compounds, especially alicyclic compounds. compounds, e.g., U.S. Pat. No. 3,923,679, No. 3,835,16 Specification No. 3, Specification No. 4,158,635, Specification No. 4,120,874 and and No. 4,102,903, all of which are incorporated herein by reference. Examples include those listed in (1).

Other useful detergency builders include the structure HO-[C(R)(COOM)-C( R)(COOR)-01°-H [wherein M is hydrogen or a cation (the resulting salt is water soluble), preferably an alkali metal, ammonium or substituted ammonium cation. and n is about 2 to about 15 (preferably n is about 2 to about 10, more preferably Preferably, n is about 2 to about 4), each R is the same or different, hydrogen, 01 to 4 atoms. 1 to 4 selected from alkyl or C-substituted alkyl (preferably R is hydrogen)] Examples include polycarboxylates.

Other ether polycarboxylates include maleic anhydride and ethylene or or copolymer with vinyl methyl ether, 1.3.5-)rihydroxybenzene -2゜4.6-trisulfonic acid and carboxymethyloxysuccinic acid are mentioned. It will be done.

As organic polycarboxylate builders, various alkali metal salts of polyacetic acid are used. , ammonium salts and substituted ammonium salts. Polyacetic acid builder salt Examples are the sodium salts of ethylenediaminetetraacetic acid and nitrilotriacetic acid, potassium ammonium salts, lithium salts, ammonium salts and substituted ammonium salts.

Also, mellitic acid, succinic acid, polymaleic acid, benzene-1,3,5-)lical Polymers such as bonic acid, benzenepentacarboxylic acid, and carboxymethyloxysuccinic acid Also included are recarboxylates and their soluble salts.

Citric acid-based builders, such as citric acid and its soluble salts, are - A polycarboxylate builder of particular importance in liquid detergent formulations. However, granular compositions can also be used. Suitable salts include metal salts, e.g. ammonium salts, lithium salts and potassium salts, and ammonium salts and substituted ammonium salts. Examples include nium salts.

Other carboxylate builders include Deal, published March 28, 1973; No. 3,723,322 (incorporated herein by reference) carboxylated carbohydrates.

Also, Bushu U.S. Pat. No. 4.566.984, issued January 28, 1986. 3,3-dicarboxy-4-oxy as disclosed in the specification (herein incorporated by reference) Sur-1,6-hexanedioate and related compounds can be used in laundry detergent compositions of the present invention. It is suitable for Useful succinic acid builders include 05-02o alkyl succinates. Acids and their salts are mentioned. A particularly preferred compound of this type is dodecenyl It is succinic acid. Alkyl succinic acids typically have the general formula %formula% is a derivative of succinic acid (wherein R is a hydrocarbon, e.g. C-C alkyl or alkenyl, preferably C12-C, or R is as described in said patent hydro 0 xyl, sulfo, sulfoxy or sulfone substituents).

Succinate builders are preferably sodium salts, potassium salts, ammonium salts, etc. It is used in the form of water-soluble salts, including ammonium salts and alkanol ammonium salts.

Specific examples of succinate builders include lauryl cono monophosphate and myris succinate. Chyl, balmityl succinate, 2-dodecenyl succinate (preferred), cono)lic acid Examples include 2-pentadecenyl. Lauryl succinate is the preferred of this group. European Patent Application No. 86200690 published on November 5, 1986 ．． 510.200.263.

Also, examples of useful builders include sodium and potassium carboxymers. Tyloxymalonate, carboxymethyloxysuccinate, Cl5-cyclohe Xanehexacarboxylate, eis-cyclobenkunetetracarboxylate, water soluble polyacrylates (those polyacrylates with a molecular weight greater than about 2.000) acrylates can also be effectively used as dispersants), and maleic anhydride and vinyl Mention may be made of salts of copolymers with methyl ether or ethylene.

Other suitable polycarboxylates include Krutschfi, published March 13, 1979. U.S. Pat. No. 4,144,226 to Old et al., incorporated herein by reference. ) is a polyacetal carboxylate disclosed in . These polyacetal lacquer Ruboxylates can be produced as follows. Glyoxylic acid ester and a polymerization initiator together under polymerization conditions. Next, the obtained polyacetal pigment By bonding carboxylic acid esters to chemically stable terminal groups, polyacetal carboxyl Stabilizes the sylate against rapid depolymerization in alkaline solutions and converts it to the corresponding salt. and add to the surfactant.

Polycarboquine rate builder is listed in the U.S. special edition of Deal, published March 7, 1967. Also disclosed in Patent No. 3,308.067 (incorporated herein as a reference) There is.

Such substances include maleic acid, itaconic acid, mesaconic acid, fumaric acid, Single polymers of aliphatic carboxylic acids such as conitic acid, citraconic acid, methylene malonic acid, etc. Water-soluble salts of polymers and copolymers are included.

Other organic builders known in the art can also be used. For example, long chain hydrocarbyl Monocarboxylic acids and their soluble salts are available. As these , substances commonly referred to as "soaps". C1o = C20 chain length is standard It is typically used. Hydrocarbyls can be saturated or unsaturated .

enzyme Detergent enzymes e.g. protein-based stains, carbohydrate-based Removal of stains or triglyceride-based stains and prevention of fugitive dye migration They can be incorporated into the laundry detergent compositions of the present invention for a variety of reasons, including detergent.

Enzymes that should be combined include protease, amylase, lipase, cellulase, and peroxidases, as well as mixtures thereof. They are squid of suitable origin, such as plant, animal, bacterial, fungal and yeast origin. Good too. However, their selection depends on several factors, such as po activity and / or stability optimum conditions, thermal stability, stability against active detergents, builders, etc. Therefore, it is controlled. In this respect, bacterial or fungal enzymes, such as bacterial amylases and and proteases, and fungal cellulases are preferred.

Suitable examples of proteases include Bacillus subtilis and Bacillus licheniformus (B, L It is a subtilisin obtained from a specific strain of B. lcheniforms. another Suitable proteases are those developed and registered by Novo Industries A/S. A pH of 8 to 12 sold under the trade name Esperase■ This enzyme is obtained from a strain of N. tyrus with maximum activity over the entire range. and similar enzyme preparations are described in Novo UK Patent No. 1,243,784. It is listed. Commercially available tanning agents suitable for removing protein-based residues The protein-degrading enzyme is produced by Novo Industries A/S (Denmark). The product names are Alcalase (ALCALASETM) and Sabinase (SAY I). Those sold at NASETM and International Biosciences Trade name: Maxator by Insetx Incorporated (Netherlands) Examples include those sold under MAXATASETM.

The enzymes herein referred to as protease A and protease B are particularly useful in liquid detergent compositions. I'm interested in the category of tanno-degrading enzymes because of things. Protease A and The manufacturing method is described in European Patent Application No. 13, No. 756, published on January 9, 1985. (incorporated here as a reference). Protease B is an amino Brothiase A has a leucine instead of tyrosine at position 217 in the acid sequence. are different proteolytic enzymes. Protease B was released on April 28, 1987. European Patent Application No. 87303761.8 (incorporated herein by reference) )It is described in. In addition, the manufacturing method for protease B was announced on January 9, 1985. European Patent Application No. 130,756 to Pot et al., incorporated herein by reference. (in Japanese).

Amylases include, for example, British Patent No. 1, previously incorporated herein by reference. , 296.839 (Novo). Examples include α-amylase obtained from special strains of bacteria.

Starch-degrading proteins include, for example, International Urn Biosin. Rapidase (RAPIDASETM) manufactured by Cetics Φ Innie Borated , and TERMAMYLTM manufactured by Novo Industries. Can be mentioned.

Cellulases that can be used in the present invention include bacterial cellulases and fungal cellulases. Both can be mentioned. Preferably they have a pH optimum of 5 to 9.5. Will. A suitable cellulase is Humicola insolens (Hulcola insolens). 3, 1984, which discloses a fungal cellulase produced from In5olens). U.S. Pat. No. 4,435.307 to Barbesgaard et al. (incorporated as a reference). Also suitable cellulases are Patent No. 2.075.028, British Patent No. 2.095.275 and and DE-O5 No. 2.247.832.

An example of such a cellulase is Humicola insolens. Humicola grisea var, t hervoldea), especially produced by Humicola strain DSM1800. The produced cellulase and the Bacillus N fungus or cellulase belonging to the genus Aeromonas. Cellulases produced by lulase 212-producing fungi, and marine molluscs [ Travelella auricula It is a cellulase extracted from the hepatopancreas of 5.

Lipase enzymes suitable for use in detergents include British Patent No. 1.372,034. Pseudomonas stuzeri (P. seudowonas 5 tutzerl) AT CC19,154 etc. Examples include those produced by microorganisms of the Pseudomonas group. suitable ripper The microorganism Pseudomonas fluorescens Antibody to lipase produced by S. fluorescens) IAM1057 Examples include those that show positive immunological cross-reactivity with This lipase and its purification method is described in Japanese Patent Application Laid-Open No. 53-20487 published on February 24, 1978. It is.

This lipase is commercially available from Amanor Pharmaceutical Co., Ltd. in Nagoya, Japan. Product Name: Lipase P [Amano (^■ano) Available at J (hereinafter referred to as "Amano P") ). Such lipases of the present invention are based on the well-known standards related to ophthalmology. Immunodiffusion method (Acta, Med, 5can, 133゜ pages 76-79 (1950)) should show positive immunological cross-reactivity with Amanor P antibodies. Ru. Methods for these lipases and their immunocross-reactivity with Amanor P No. 4,707,291 to Tom et al., issued November 17, 1987. It is described in the detailed book (incorporated here as a reference). A typical example of these is No-P lipase, lipase ex Pseudowonasf’raglFERM P1339 (available under the product name Amanor B), Lipase ex Pseudow onas n1troreducens var.

Ijpolytlcus F E RM P 1338 (Product name Amanor CE S), lipase ex Chrosobactervlscosum, For example, C hrosobactervlscosum var, Ilpolytlcum NRRL B 3673; U.S., Biochemical Corp. tion and further Chros from the Dutch Desoint Company. obacter vjscosus lipase, and lipase exPseudo Monas gladioli. A particularly preferred lipase is Novo Ind. Product name: Lipolase by Stoli A/S (Denmark) (Biotechnology News, March 7, 1988) 6) and together with other suitable lipases according to EPPO 2258068. It is stated in the Specific Book (Nobo) (incorporated here as a reference).

Peroxidase enzymes contain oxygen sources such as belcarbonate, belborate, Used in combination with versulfate, hydrogen peroxide, etc. They are used for "solution bleaching" i.e. dyes or pigments removed from the substrate during the cleaning operation are combined with other dyes or pigments in the cleaning solution. Used to prevent migration to the substrate. peroxidase enzyme technology For example, horseradish peroxidase, ligninase , and haloperoxidases, such as chloroperoxidase and bromo Examples include peroxidase. Peroxidase-containing detergent compositions include, for example: 0.00 of the transfer to Novo Industries A/S announced on October 19, 1989. car PCT International Application No. WO 891099813 (herein incorporated by reference) (incorporated).

A wide range of enzyme substances and methods of incorporation into synthetic detergent granules were also described by McCarty et al. U.S. Patent No. 3,553,139, issued January 5, 1971 (referenced herein) (incorporated as ). Enzymes are further described in the publication published on July 18, 1978. U.S. Patent No. 4,101°457 to Race et al. and March 26, 1985 Published by Hiko.

-U.S. Pat. No. 4,507,219, both herein incorporated by reference. Disclosed in (incorporated). Enzymatic materials useful in liquid detergent formulations and such treatments The method of compounding into square dishes is described in U.S. Patent No. 4.261 by Hora et al., issued on April 14, 1981. , No. 868 (incorporated herein by reference).

The enzyme usually contains up to about 5 mg of active enzyme per gram of composition, more typically about 0. ．． 05■ to about 3■.

In the case of granular detergents, the enzymes are preferably coated with enzyme-inert additives or Lyllation minimizes dust formation and improves storage stability of L1. this thing Techniques for achieving this are well known in the art. Liquid formulation “τ” is enzyme stable The system is preferably 1. Rike is used. Enzyme stabilization technology for aqueous detergent compositions is a technology It is well known. For example, one enzyme stabilization technique in aqueous solution is calcium acetate. MM calcium ion from sources such as calcium formate, calcium propionate, etc. Dye the use of dyes. Calcium iodine is a short chain carboxylate, preferably 1. <Hagi Can be used in combination with acid salts. For example, U.S. Patent No. Retton et al., issued March 9, 1982, 1L Specification No. 318,818 (incorporated here as a reference)? Light. Also, It has also been proposed to use polyols such as cerol and sorbitol.

Alkoxy-alcohols, dialkyl glycoethers, polyhydric alcohols and polyfunctional Aliphatic amines (e.g. jetanolamine, triethanolamine, diisopropylene) alkanolamines such as ropatoolamine), and boric acid or Alkali metal borates. Enzyme stabilization techniques were additionally described in Horn et al. U.S. Pat. No. 4,261.868, issued May 14, 1-971 to Gedge et al. No. 3,600,319, issued Aug. (incorporated as a bibliography) and Venegas' European patent published on October 29, 1986. Application Publication No. 0 199 405 Specification, Application No. 86200586.5 Specification as disclosed and illustrated in . Boric acid and non-borate stabilizers are preferred. Yes.

Enzyme stability systems are also described, for example, in U.S. Pat. No. 4,261°868, No. No. 600,319 and No. 3,519,570 .

Bleaching compounds - bleaching agents and bleach activators The laundry detergent composition of the present invention comprises a bleaching agent, or a bleaching agent and one or more bleach activators. It may contain a bleaching composition containing 1°. When included, the bleaching compound Typically, from about 1% to about 20% of such laundry detergent compositions, more typically It will account for about 1% to about 0%. Generally, bleaching compounds are used in non-liquid formulations, e.g. For example, it is an optional ingredient in granular detergents. The amount of bleach activator, if present, is typically Typically from about 0.0111% to about 60% of the bleaching composition, more typically from about 0.506% to about 60%. It would be about 40%.

The bleach used here is suitable for fabric cleaning, hard surface cleaning, or and of bleaching agents useful in detergent compositions for other cleaning purposes that are or become known. It can be either.

One category of bleaches that can be used is belucarboxylic acid bleaches and their salts. include. A suitable example of this type of bleach is Monoperoxyphthalate Magnesium. Siium hexahydrate, ■-Magnesium salt of chloroperbenzoic acid, 4-nonylamino- Mention may be made of 4-oxoperoxybutyric acid and diperoxide dodecanedioic acid.

Such bleaching agents are described in the No. 1-Tman US patent issued November 20, 1984. No. 4,483,781, filed June 3, 1985, U.S. Pat. Patent Application No. 740,446, published on February 20, 1985 by Nkusu et al. European Patent Application No. 0.133,354, January 1983] U.S. Pat. No. 4,412.934 to Jung et al. (incorporated as a research document). A highly preferred bleaching agent is No. 4, issued January 6, 1987, to Z. et al. 634, Specification No. 551 (incorporated herein as a reference) Also mentioned is xicabronic acid.

The laundry detergent compositions of the present invention generally contain a peroxygen bleach, usually an inorganic perhydrate. Bleach (usually in the form of sodium salts) will be included.

Suitable verhydrate bleaches include perborates, percarbonates, perphosphates, and persilicates. It can be any inorganic salt such as an acid salt, but it is usually an alkali metal, usually a sodium salt. perborate or percarbonate of um. Thorium perborate has the nominal formula Na Monohydrate of BO2H2O2 or tetrahydrate of Na B OHO’3 H20 It can be in the form of

The preferred perhydrate, sodium percarbonate, is 2Na Co 3H is an addition compound with a formula corresponding to 202 and is commercially available as a crystalline solid and 17. ing. Most commercially available substances are small amounts that are incorporated into detergent compositions during the manufacturing process. amounts of heavy metal ion sequestering agents, such as EDTA, 1-hydroxyethylidene-1, Examples include 1-diphosphonic acid (HEDP) or aminophosphonates.

Bel carbonate can be incorporated into detergent compositions without additional protection; A preferred formulation of the composition utilizes the material in coated form. Various coatings used However, 2 to 10% (usually 3 to 5%) of silica by weight of bell carbonate can be used. SiO:Na2O ratio 1.6:1 applied as an aqueous solution to give an amount of solids to 3.4:1, preferably 2.8:1, is the most economical. Ru. Magnesium silicate can also be included in the coating.

The peroxygen bleach is preferably combined with a bleach activator, which means that the bleach activator In situ generation (i.e. during the cleaning process) in aqueous solution of peroxyacids corresponding to bring.

A wide range of bleach activators can be used, examples include Subajini et al., U.S. Pat. No. 4,179,390. Disclosed in the specification. Preferred bleach activators include tetraacetylalkyl Diamines, especially tetraacetylethylenediamine (TAED) and tetra Cetylglycouril (TAGU) may be mentioned: (wherein R is an alkyl group having about 1 to about 18 carbon atoms, and a carbonyl carbon The longest linear alkyl chain extending from and including the carbonyl carbon is about 6 to about 10 carbon atoms, L is a leaving group, and the conjugate acid has a pKa of about 4 to about 13. do). These bleach activators are covered by a U.S. patent issued April 10, 1990 to Mao et al. No. 4,915°854 (incorporated herein by reference) and U.S. Pat. No. 4,412,934 (previously incorporated herein by reference). Ru.

Bleaching agents other than oxygen bleach are also known in the art and available herein. specific interest One type of non-oxygen bleach that is flavored is a light-activated bleach, such as a sulfonate bleach. zinc phthalocyanine and/or aluminum phthalocyanine. Ru. These substances can be deposited on the substrate during the cleaning process. dry in the sun Upon irradiation with light in the presence of oxygen, by hanging the cloth to The talocyanine is activated and the substrate is therefore bleached. preferred zinc phthalo Cyanine and photoactivated bleaching methods are described in Holcombe et al., published July 5, 1977. Described in National Patent No. 4,033,718 (incorporated herein as a reference) ing. Typically, the detergent composition will contain about 0.02 sulfonated zinc phthalocyanine. It will contain from 5 to about 1.25% by weight.

High content prevention stain agent Any high content preventive stain agent known to those skilled in the art can be used in the laundry detergent compositions of the present invention. . High polymer stain prevention agents are used to make the surface of hydrophobic fibers such as polyester and nylon hydrophilic. hydrophilic segments for adhesion onto hydrophobic fibers and for cleaning and rinsing. remains glued throughout the completion of the cell and thus serves as a pot for hydrophilic segments. characterized by having both a hydrophobic segment and a . This means that the stains that form after treatment with antifouling agents can be cleaned up more easily with subsequent cleaning methods. can be made possible.

As a polymeric antifouling agent, cellulose such as hydroxyether cellulose polymers are recommended. ethylene terephthalate or propylene terephthalate and polyester With tyrene oxide terephthalate or polypropylene oxide terephthalate copolymer blocks and the like.

Cellulose derivatives that function as antifouling agents are commercially available, such as Cellulose hydroxyl, such as Methocel® (Dow) -tel is mentioned.

Cellulose-based antifouling agents include methyl cellulose, ethyl cellulose, and hydroxyl cellulose. 01 to cypropyl methylcellulose, hydroxybutyl methylcellulose, etc. Also selected from the group consisting of C4 alkyl and C hydroxyalkylcellulose It can also be mentioned. Various cellulose derivatives useful as antifouling polymers are described by Nicol et al. No. 4,000,093 issued on December 28, 1976! F( (incorporated herein by reference).

Poly(vinyl ester) as an antifouling agent characterized by hydrophobic segments is a graft copolymerization of poly(vinyl ester), e.g. C-C vinyl ester. on a polyalkylene oxide backbone, preferably a polyethylene oxide backbone. Examples include poly(vinyl acetate) grafted to Such substances are technically European Patent Application No. 02 published on April 22, 1987 by Hood et al. It is described in the specification of No. 19048.

Suitable commercially available antifouling agents of this type include those of the Sokalan™ type. For example, Tsukaran TMHP-22 available from BASF (West Germany) can be lost.

One type of preferred antifouling agent is ethylene terephthalate and polyethylene oxy It is a copolymer with random blocks of (PEO) terephthalate. Yo More specifically, these polymers contain ethylene terephthalate units versus PEO terephthalate units. Ethylene terephtha in a molar ratio of rate units from 25:75 to about 35:65 consisting of a repeating unit of rate and PEO terephthalate (the PEO terephthalate The units contain polyethylene oxide having a molecular weight of about 300 to about 2000. ). The molecular weight of this polymeric antifouling agent is within the range of about 25,000 to about 55,000. be. Hayes U.S. Patent No. 3'959.230, issued May 25, 1976. See the detailed booklet (incorporated here as a reference). 197 disclosing similar copolymers U.S. Patent No. 3,893,929 to Basnow, issued July 8, See also (incorporated as a document).

Another preferred polymeric antifouling agent is polyoxyethylene with an average molecular weight of 300 to 5.000. 90 to 80 polyoxyethylene terephthalate units derived from lene glycol Ethylene containing 10-15% by weight of ethylene terephthalate units together with mass% is a polyester with repeating units of terephthalate units, and is a polymer compound Ethylene terephthalate units vs. polyoxyethylene terephthalate units in The molar ratio of is from 2:1 to 6:1.

Examples of this polymer and 1. Now, let's use the commercially available material Zeleon® 5126. (manufactured by DuPont) and Millies (MiicaseR) T (manufactured by ICI) Can be mentioned. These polymers and their manufacturing methods were published in Gosselink in October 1987. U.S. Pat. No. 4,702,857, issued May 27th (incorporated).

Another preferred (7) high content preventive staining agent is aminophthaloyl and oxyalkylene oxide. from the oligomeric ester backbone of the repeat unit and the terminal portion covalently bonded to the backbone. (The antifouling agent is a sulfonated product of a substantially linear ester oligomer. Allyl alcohol ethoxylate, dimethyl terephthalate, and 1,2-propylene derived from lopylene diol, the terminal portions of each oligomer average a total of about 1 to about 4 sulfonate groups). These anti-slip agents are J. J. Siebel. and U.S. Patent No. 4968 issued November 6, 1990 to E. P. Gosselink. No. 451, U.S. patent application Ser. No. 07/474.7, filed January 29, 1990. It is detailed in the specification of No. 09 (incorporated herein by reference 1-2).

Other suitable high content preventive staining agents include Goiselink et al., published February 8, 1987. ethyl- or methyl-blocked 1 of U.S. Pat. No. 4,7118,730, 2-probylene terephthalate-polyoxyethyl non-terephthalate or one polyester U.S. Patent No. 4, 72 issued January 26, 1988 to Stell, Gosselinck et al. 1, 58 C1 specification anion end-blocked oligomer ester (anion The end cap is a sulfo-polyethoxy derived from polyethylene glycol (PEG). (consisting of groups), formula X-(OCBI2CH2)n- (wherein is 12 to about 43 and X is C-C a Goals with polyx-toxy end caps of 70% or preferably (7 are methyl) U.S. Patent No. 4,702.857 issued October 27, 1987 to Vaselink Specification Block Polyester Suribok Compound (all of these patents here References and 17) are listed.

If the additional antifouling polymer is used, -C is an anion, especially a sulfaroyl end-capped polymer. Disclosure of phthalate esters (7 rQ 1989 to Martonato et al. 311 ] issued U.S. Pat. No. 4,877.896 (which patent is hereby incorporated by reference). Antifouling polymers (incorporated) are included. Te1 knockrate ester is an asymmetrically substituted Contains oxy-1,2-alkyleneoxy units.

If utilized, the soil release agent generally comprises from about 0.01 to about 10.0 weight? 6. Preferable 1. < is about 0.1 to about 5.0 weight96, more preferably 1. < will occupy about 012 to about 3.0 weight ji196.

chelating agent Laundry detergent compositions of the present invention may also contain one or more iron/manganese chloride-noting agents. 4 may be added as a builder auxiliary substance. Chelating agents such as is an aminocarboxylate, ``aminophosphonate, polyfunctional compound'' as defined below. Functionally substituted aromatic chelating agents and their 71! You can choose from a group consisting of . Without attempting to be limited by theory, the benefits of these substances may be due in part to their soluble Exceptional ability to remove iron and manganese ions from cleaning solutions by forming chelates It is thought to be due to force.

Aminocarboxylates useful as optional chelating agents in the compositions of the invention include: 1 or more 2 (preferably at least 2) unit substructures re) [wherein M is hydrogen, alkali metal, ammonium or substituted ammonium (e.g. ethanolamine) and X is 1 to about 3, preferably 1. can be a. Preferably, these aminocarboxylates are about 6 Contains no alkyl or alkenyl group having more than 17 carbon atoms. messenger Possible amine carboxylates include ethylenediaminetetraacetate , N-hydroxyethylethylenediamine triacetate, nitrilotriacetate ethylenediaminetetraprobionate, ethylenediaminetetraprobionate, ethylenediaminetetraprobionate Saacetate, diethylenetriaminepentaacetate and ethanol digly Synths, their alkali metal salts, ammonium salts, and substituted ammonium salts and mixtures thereof.

Aminophosphonates also allow at least a small amount of total phosphorus in detergent compositions. suitable for use as a chelating agent in the laundry detergent compositions of the present invention when . Substructure of one or more (preferably at least two) units (wherein M is hydrogen, alkali metal, ammonium or substituted ammonium, and X is from 1 to about 3, preferably is 1) Compounds having ethylenediaminetetrakis ( methylene phosphonate), nitrilotris (methylene phosphonate) and diene Examples include tylenetriamine pentakis (methylene phosphonate). preferably These aminophosphonates are alkylene phosphonates having more than about 6 carbon atoms. or alkenyl groups. Alkylene groups are shared by substructures. Wear.

Polyfunctionally substituted aromatic chelators are also useful in the present compositions. these substances is the general formula (wherein at least one R is -5O3H or -COOH) or their soluble salts and mixtures thereof. Wear. U.S. Patent No. 3,812,044 issued May 21, 1974 to Connor et al. The specification (incorporated herein by reference) describes polyfunctionally substituted aromatic chelation/metallic On sequestering agents are disclosed. A preferred compound of this type in acid form is 1,2-dihydro Dihydroxydisulfobenzene such as Roxy-3゜5-disulfobenzene . Alkaline detergent compositions combine these substances with alkali metal salts, ammonium salts or or in the form of substituted ammonium salts (e.g. heptano or triethanolamine salts) It can be contained in

If utilized, these chelating agents are generally included in the laundry detergent compositions of the present invention. It will account for about 0.1 to about 10% by weight. More preferably, the chelating agent is Such compositions will represent from about 0.1 to about 3.0% by weight.

Clay stain removal/redeposition prevention agent Clay stain removers/anti-redeposition agents useful in the laundry detergent compositions of the present invention include polyester Water-soluble ethos that removes tyrene glycol and clay stains and prevents redeposition. Oxylated amines may be mentioned.

Polyethylene glycol compounds useful in the laundry detergent compositions of the present invention typically include , molecular weight from about 400 to about 100.000, preferably from about 1,000 to about 20.00. 0, more preferably about 2,000 to about 12,000, most preferably about 4,000 0 to about 8.000. Such compounds are commercially available and Carbovax (Union, Panbury, CT) available from Carbide).

The water-soluble ethoxylated amine is preferably selected from the group consisting of:

Ethoxylated monoamine with (2) Formula Ethoxylated diamine with (3) Formula Ethoxylated polyamine with (4) General formula and (5) a mixture thereof [wherein A1 is or -〇-; R is H or C1-C4 alkyl or hydroxyalkyl R1 is 02-C12 alkylene, hydroxyalkylene, alkenylene arylene, arylene or alkarylene, or 2 to about 20 oxyalkylenes A 02-C3 oxyalkylene moiety having a unit, provided that an O-N bond is not formed. each R2 is C-04 or hydroxyalkyl, moiety -L-X is -CH2- 1r is 1 or 2, S is 1 or 2, r+8 is 3 or 4); is an on group, an anion group, or a mixture thereof, and -R3 is a group having a substitution site. Substituted 03-C12 alkyl group, hydroxyalkylene group, alkenylene group, aryl group R4 is 01-C12 alkylene, hydroxyl group, or alkaryl group; sialkylene, alkenylene, arylene or alkarylene, or from 2 to about a C2-C3 oxyalkylene moiety having 20 oxyalkylene units; , but no 0-0 bond or O-N bond is formed; L is a polyoxyalkylene moiety minutes R5 is C-C alkylene or hydroxyalkylene, m and n are moieties -(CHCH20) n- is the polyoxyalkylene moiety, and the oldest is about 50 It is a hydrophilic chain having 3 (the number is such that it accounts for 3% by weight) of the monoamine. in which m is from O to about 4 and ■ is at least about 12; in which m is θ ~ about 3 and D is R is C2-C3 alkylene, hydroxya when it is alkylene or alkenylene, at least about 6, R1 is C2-C3 Argi! When it is other than non, hydroxyalkylene or alkenylene, it is less at most about 3; in the case of the polyamines and amine polymers, m is from 0 to about 3; 10'? ? and p is at least about 3; p is 3 to z3; q is 1 or is O; t is 1 or 0; (Ill, t is 1 when q is 1; W is 1 or O; x + y + Z is at least 2; y +7° is at least 2] The most preferred soil release/anti-redeposition agent is ethylated amine-silicone. It's Tamin. Exemplary etgylated amines include Pandel, published July 1, 1986. Mir U.S. Pat. No. 4,597,898, incorporated herein by reference and 1- ) is further described. Another group of preferred sticky stain removers/anti-redeposition agents is 1 O and Gosselink European Patent Application No. 111°9 published June 27, 984 It is a cationic compound disclosed in No. 65, incorporated herein by reference and No. 17).

Other clay stain removers/restick inhibitors that can be used include Ethoxylation as disclosed in Gosselink European Patent Application No. 111,984 Amine polymer. 1.Gosselink European Patent Application No. 11 published on July 4, 984 No. 2,592; The amine oxides disclosed in Connor U.S. Pat. No. 4,548,744 include (all of which are included here as bibliography).

Eel is also preferred (7) Antifouling/anti-redeposition agent is ethoxylated tetraethyl 1/bentamine. and poly-1-ethylene glycol having a molecular weight of about 4,000 to about s, ooo. Ru.

Granular detergent compositions containing compounds such as - typically contain about 0 clay remover. 601 to about 10.0% by weight: Liquid detergent compositions typically contain about 0.60% to about 10.0% by weight. ], ~50% by weight.

Polymer dispersant Polymeric polycarboxylic one-note dispersants are advantageously utilized in the laundry detergent compositions of the present invention. can. These substances can aid in calcium and magnesium hardness control . As a builder additive, similar to the polycarboxylic notes mentioned above in the builder description. In addition to acting, these higher Molecular weight dispersants can be used in combination with other builders, including low molecular weight polycarboxylate-1. By suppressing the crystal growth of inorganic substances, it reduces the vegetation of granular dirt. Therefore, by preventing redeposition in step 1, it is possible to further improve the overall cleaning performance. It is thought that it can be done.

High molecular weight polycarboxylic 1 note dispersant and 1. Polycarboxylate that can be used as Substances are -squeezed (In the formula, X1Y and 2 are each hydrogen, methyl, carboxy, carboxymethyl, selected from the group consisting of hydroxy and hydroxymethyl; salt-forming cations and and n is about 30 to about 400) These polymers or copolymers containing at least about 60% by weight of segments having It is a polymer. Preferably, X is hydrogen or hydroxy and Y is hydrogen or carboxylic. xy, Z is hydrogen, M is hydrogen, alkali metal, ammonia or substituted ammonium It is.

Polymeric polycarboxylate materials of this type are suitable for the present saturated intermediates (preferably It can be produced by polymerizing or copolymerizing (acid form). Suitable polymer polymer unsaturated monomeric acids that can be polymerized to form boxylates (7) and acrylic acids, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconite Acids include mesaconic acid, citraconic acid and methylenemalonic acid.

Non-carboxylate groups, such as vinyl methyl ether, styrene, edione A monomer segment containing such as The presence of such segments means that such segments should not constitute more than about 40% by weight. Mule is suitable.

A particularly preferred polymer, polycarboxylate-1, can be derived from acrylic acid. here Such acrylic acid-based polymers are useful in polymerized acrylic It is a water-soluble salt of acid. In the acid form, the average molecular weight of the di-like polymer is approximately 2.0 00-10,000. More preferably about 4,000 to 7,000. most preferred is approximately 4,000 to 5,000. Water solubility of such acrylic acid homopolymers Salts include, for example, alkali metal salts, ammonium salts and substituted ammonium salts. Salt is an example. Soluble polymers of this type are known substances. This kind of polya The use of acrylates in detergent compositions is described, for example, in No. 3,308,067 to Diehl. This patent is incorporated herein as a reference.

Acrylic acid/maleic acid based copolymers are also preferred components of dispersants. You may also use it. Such substances include copolymers of acrylic acid and maleic acid. Water-soluble salts of combinations are mentioned. The average molecular weight of such copolymers in acid form is approximately 5 ,000~100,000. Preferably [7 or about 6,000 to 60,000. better Preferably, it is about 7,000 to 60,000. Acrylic in such copolymers The ratio of maleate to maleate segments is generally from about 30:1 to about 1 :1, more preferably about 10=1 to about 2:1. Acrylic acid like this /Maleic acid copolymer water-soluble salts include, for example, alkali metal salts, ammonia salts, ammonium salts and substituted ammonium salts. This type of soluble acrylate/ Maleate copolymers are disclosed in European Patent Application No. 6691 published on December 15, 1982. It is a known substance described in Specification No. 5 (this publication is incorporated herein by reference). Ru.

If utilized, the polymeric dispersant generally accounts for about 0.2 to about 10% of the laundry detergent composition. % by weight, preferably from about 1 to about 5% by weight.

brightener Optical brighteners or other brighteners or whitening agents known to those skilled in the art may also be used in the laundry detergent of the present invention. Can be incorporated into compositions. However, the choice of brightener depends on the type of detergent, the detergent composition properties of other components present in the wash water, temperature of wash water, degree of agitation, ratio of tub size to object to be washed It will depend on a number of factors such as rate.

Brightener selection also depends on the type of material to be cleaned, e.g. cotton, synthetic, etc. Exists. Most laundry detergent products are used to clean a variety of fabrics. So the detergent composition should contain a mixture of brighteners that will be effective on a variety of fabrics. be. Of course, the individual components of such brightener mixtures need to be compatible. It is.

Commercially available optical brighteners can be classified into subgroups, including, but not limited to, Stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanine, dibenzothi Phen-5,5-dioxide, azole, 5-membered and 6-membered heterocyclic compounds derivatives, and other miscellaneous agents. Examples of such brighteners are “fluorescent” "Production and Application of Brighteners", M. Zaladnik, John Wie, New York. Published by Lee & Sons (1982) (the disclosure of which is incorporated herein by reference) ) is disclosed.

Stilbene derivatives include, but are not limited to, bis(triazinyl)amino - derivatives of stilbene; bisacylamino derivatives of stilbene; Riazole derivative; oxadiazole derivative of stilbene; oxadiazole derivative of stilbene sol derivatives; and styryl derivatives of stilbenes.

The derivative of bis(triazinyl)aminostilbene is 4,4'-diamine- It may also be prepared from stilbene-2,2'-disulfonic acid.

Coumarin derivatives include, but are not limited to, the 3rd, 7th, and 3rd and 7th positions. Examples include derivatives substituted with.

Examples of carboxylic acid derivatives include, but are not limited to, fumaric acid derivatives; benzoic acid derivatives; Conductor; p-phenylene-bis-acrylic acid derivative; naphthalene dicarboxylic acid derivative heterocyclic acid derivatives; and cinnamic acid derivatives.

Cinnamic acid derivatives can be further subclassified into several groups, and these groups are not necessarily Cinnamic acid derivatives, salts, as disclosed, without limitation, on page 77 of the Zaradnik literature. Tyrylazole, styrylbenzofuran, styryloxadiazole, styryl triazole, and styryl polyphenyl.

Styryl azole is a styryl azole as disclosed on page 78 of the Zaradnik literature. Further down to benzoxazole, styryl imidazole and styryl thiazole. Can be classified by rank. These three aforementioned subclasses subclassify styrylazole. It is understood that this may not necessarily reflect an exhaustive list of subgroups that may be used. 750 pages (John Willie & Sons, Incorporated) , 1962) (the disclosure of which is incorporated herein by reference), pp. 741-749. a derivative of dibenzothiophene-5,5-dioxide disclosed on page 3.7; -Diamitudibenzothiophene-2,8-disulfonic acid 5,5 dioxide is mentioned. It will be done.

Other optical brighteners are azoles, which are derivatives of five-membered heterocyclic compounds. this can be further subcategorized into monoazoles and diazoles. Monoazole and Examples of diazoles and diazoles are disclosed in the Kirk-Othmer literature.

Other brighteners include the derivatives of six-membered heterocyclic compounds disclosed in the Kirk-Osmer literature. It is a conductor. Examples of such compounds include brighteners derived from pyrazine and Examples include derivatives derived from 4-aminonaphthalamide.

In addition to the brighteners already mentioned, miscellaneous agents may also be useful as brighteners. child Examples of miscellaneous drugs such as and 1-hydroxy-3,6,8-pyrene trisulfonic acid; 2.4- Dimethoxy-1,3,5-triazin-6-yl-pyrene; 4,5-di-phenylene and pyrazoline-quinoline derivatives. Ru.

Other specific examples of optical brighteners include US Pat. No. 4,790,856 (the disclosure of which is incorporated herein by reference) Identified. These brighteners include Holwhite from Verona (Ph orvhite(TM) series of brighteners.

Other brighteners disclosed in this document include Chinoper, available from Ciba Geigy. Tlnopal UNPA, Tynopal CBS and Tlnopal 5 8M; Arctic, which can be manned by Hilton-Davis located in Italy. White CC and Arctic White CWD, 2-(4-styrylphenyl)-2H-naphthol[1,2-d] ) Riazole, 4,4'-bis-(1,2,3-triazo-2-yl) -stilbene; 4,4'-bis(styryl)bisphenyl; and y-aminoc Marine is an example. Specific examples of these brighteners and 17 include 4-methyl-7-di Nithylaminocoumarin, 1,2-bis(benzimidazol-2-yl)-ethyl 1non, 1,3-diphenylfraziline: 2+5=bis(penzoxazole- 2-yl)-1,000-off J,n;2-styryl-naphtho-[1,2-d]-oxazo and 2-(stilben-4-yl)-2H-naphtho[1,2-tJ]! - Liazole.

Other optical brighteners include the one published in Hamilton, July 29, 1972. No. 3,646,015, the disclosure of which is incorporated herein by reference. Included are those disclosed in (in).

If utilized, the optical brightener will generally be present in the laundry detergent composition from about ('3.05 to about 2.0 weight j196, preferably about 0.1 to about 1. It will occupy 06 DI amount.

Foam suppressant Known or becoming known compounds for reducing or inhibiting foam formation are included in the present invention. It can be incorporated into laundry detergent compositions.

The polyhydroxy fatty acid amide surfactants here can increase the foam stability of detergent compositions. The inclusion of such substances (hereinafter referred to as "foam suppressants") may be desirable as they can

Foam control is achieved by detergent compositions combined with polyhydroxy fatty acid amide surfactants. This may be of particular importance when including relatively high foaming surfactants. Foam control is particularly desirable for compositions intended for use in front-load automatic washing machines.

These washing machines typically have a horizontal axis and rotational action around this axis Characterized by having a drum for containing washing/washing water. child Agitation of the seeds can result in high foam formation and therefore reduced cleaning performance. be. The use of foam suppressants is recommended under hot water wash conditions and high surfactant concentration conditions. It can also have significance.

Various materials may be used 17 with foam suppressants. Foam suppressants are well known to those skilled in the art. Ru. The sleds are generally, for example, Kirk-Othmer Encyclope. dia or Che+m1cal Teehnology.

3rd Edition, Volume 7, Pages 430-447 ・Incoho 1 Notes, 1979). I have a specific interest 1 Two categories of foam suppressants are monocarboxylic fatty acids and their derivatives.

and soluble salts thereof. , these substances were found in Uniin St. John 196 U.S. Patent No. 2, 954, 3/47 issued September 2711, 0 ( The patents are discussed in References 1-2). Foam suppressant and 1. The messenger The fatty acids and their salts for use typically have a carbon number of 1 0 to about 2/i, favorable 1-.　　　has a 12 to 18 carbon atoms humanobfulpyl chain Ru. Suitable salt and 1. In the case of alkali metal salts, e.g. tzitorium salt, potassium salts, and lithium salts, and ammonium salts and alkanol ammonium salts Salt is an example. , these materials are a preferred category of anti-foam in detergent compositions. It is a drug.

The laundry detergent composition of the present invention may also contain a non-surfactant foam inhibitor. . These include, for example, high molecular weight hydrocarbons, such as paraffins, fatty acid esters, etc. esters (e.g. fatty acids; liglycerides), fatty acid esters of -hydric alcohols , aliphatic C18-C40 ketones (eg, stearone), and the like. other Foam suppressants include N-alkylated aminotriazines, such as those having 1 to 24 carbon atoms. Produced as a product of 2 or 3 moles of a primary or secondary amine and cyanuric chloride. from trialkylmelamine to hexaalkylmelamine, or From chlortriazine to tetraalkyldiamine chlortriazine , propylene oxide, and monostearyl phosphate, e.g. Allyl alcohol phosphate esters and monostearyl dialkali metals (e.g. , sodium, potassium, lithium) phosphates and phosphate esters. It will be done. Hydrocarbons such as paraffin and helobaraffin are available in liquid form.

Liquid hydrocarbons will be liquid at room temperature and atmospheric pressure and have a pour point of -40°C to 17°C. It will have a minimum boiling point of about 110°C or higher (at atmospheric pressure). Also, row It is already possible to use hydrocarbons, preferably those having a melting point of 1 to less than 100°C. It is knowledge. Hydrocarbons are preferred in detergent compositions.1. constitutes a new category of foam suppressants. . Hydrocarbon foam suppressants are described, for example, in Gandolho et al., published May 5, 1981. As described in Patent No. 4,265,779 (incorporated herein as a reference and 17) There is. Hydrocarbons include aliphatic and alicyclic groups having about 12 to about 70 carbon atoms. , aromatic and heterocyclic saturated or unsaturated hydrocarbons.

The term "paraffin" as used in this foam suppressor discussion refers to true paraffin and cyclic charcoal. It is intended to include mixtures with hydrogen chlorides.

Another preferred category of non-surfactant foam inhibitors consists of silicone foam inhibitors. . This category includes polyorganosiloxanes such as polydimethylsiloxane. Dispersions or emulsions of sun oils, polyorganosiloxane oils or resins, and Combination of polyorganosiloxane oil and silica particles (polyorganosiloxane Examples include the use of silica (chemically adsorbed or fused) on silica. silicone suppressor Foaming agents are well known in the art and are described, for example, in Gandolho et al., published May 5, 1981. U.S. Pat. No. 4,265,779 and M.S. Starch, 1990 European Patent Application No. 89307851.9 published on February 7, 2017 (both here (incorporated as a reference).

Other silicone suds suppressors can be used to water the composition and small amounts of polydimethylsiloxane fluids. U.S. Patent No. 3 for a method for defoaming an aqueous solution by incorporating it into a solution , 455.839.

Mixtures of silicone and silanized silica can be used, for example, in German patent application DO5 No. 2, No. 124,526. Silicone in granular detergent compositions Defoamers and antifoam agents are described in U.S. Pat. No. 3,933,672 to Paltrotsuta et al. U.S. Patent No. 4,652 to Baginski et al., issued March 24, 1987. No. 392.

Exemplary silicone-based foam suppressants for use herein are essentially (i) Polydimethylsiloxane having a viscosity of about 20 cs to about 1500 cs at 25°C. Sun fluid: (i) from about 5 to about 50 parts per 100 parts by weight of (CH3)3Si0112; (CH3)3s in the ratio of units to S t 02 units from 0.6:1 to about 1.2:1 A siloxane resin consisting of io1/2 units and Sio2 units; and (ill ) (i) from about 1 to about 20 parts solid silica gel per 100 parts by weight; It is an antifoam agent with a foam suppressing amount consisting of:

Foam suppressants, when utilized, are present in "foam suppressing amounts."

"Foam control amount" is the amount of foam control that the formulator of the composition will provide to the desired degree of foam control. This means that the amount of agent can be selected. The degree of foam control depends on the detergent surfactant selected. It will change accordingly. For example, in the case of high foaming surfactants, relatively large amounts foam control agents are used to achieve the desired foam control than are the case with low-foaming surfactants. It will be done.

Laundry detergent compositions of the present invention will generally contain from 0% to about 5% suds suppressor. Foam control When utilized as agents, monocarboxylic fatty acids and their salts are typically , may be present in an amount up to about 5% by weight of the detergent composition. Preferably fatty foods About 0.5% to about 3% carboxylate suds suppressor is utilized. Even if you use a large amount Although silicone suds suppressants typically make up up to about 2.0% by weight of detergent compositions, used in quantity. This upper limit is primarily used to keep costs to a minimum and to effectively control foam. Due to the concern regarding the effectiveness of small amounts of water, it is practical in nature. Preferably, Silicone foam suppressors range from 0.01% to 1% to about 1%, preferably from about 0.25% to about 0.0%. 5% is used. These weight percent values used here are Includes silica that may be used in conjunction with the sun, as well as auxiliary materials that may be utilized. mono Stearyl phosphate is generally utilized in an amount of about 0.1% to about 2% by weight of the composition. be done.

Although higher amounts can be used, hydrocarbon suds suppressants typically range from about 0.01% to about 5.0%. It is used in the amount of %.

other ingredients Various other ingredients that can be incorporated into the laundry detergent compositions of the present invention include other active ingredients, Carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, etc. Can be mentioned.

Liquid detergent compositions can contain water and other solvents as carriers. methanol, Low molecular weight exemplified by tanol, propatool, and isopropatool Primary or secondary alcohols are preferred. -hydric alcohol acts as a surfactant Preferred for solubilization are polyols, such as those having about 2 to about 6 carbon atoms and and those containing about 2 to about 6 hydroxy groups (e.g., propylene glycol , ethylene glycol, glycerin, and 1,3-propanediol) are also used. Can be used.

The laundry detergent compositions of the present invention preferably, when used in aqueous cleaning operations, The wash water has a p++ of about 6.5 to about 11, preferably about 7.5 to about 10.5. I would prescribe sea urchins. Liquid product formulations preferably have a pH of about 7.5 to about 9. 5, more preferably about 7.5 to about 9.0. p) Control I to the recommended usage level Techniques for this include the use of buffers, alkalis, acids, etc., and are well known in the art. It is well known to the public.

Furthermore, the present invention provides a method for treating substrates such as fibers, fabrics, hard surfaces, skin, etc. with water, water-miscible solvents ( The non-ionic compounds of the invention can be used in the presence of solvents such as primary and secondary alcohols). Detergent compositions containing surfactant systems (polyhydroxy in nonionic surfactant systems) The weight ratio of sialic acid amide to additional surfactant ranges from about 1=5 to about 5:1. providing a method for cleaning a substrate by contacting it with . Agitation is preferably provided to enhance cleaning. Good for stirring Suitable means include manual scrubbing, preferably a brush or other cleaning method. With the help of devices, scrubbing by hand, automatic washing machines, automatic dishwashers, etc. It will be done.

This is the N-methyl-1-deoxygludityllaurin aliquot for use here. A method for producing a mido surfactant will be exemplified. A skilled chemist can change the shape of the equipment, but this One device suitable for use here is a heated Consists of a 3 liter 4 day flask equipped with a thermometer and a motor driven paddle stirrer. . The other two necks of the flask are connected to the nitrogen sweep and wide bore side arms (Caution: wide bore side arms). The side arm is equipped with a is coupled with an efficient collection cooler and vacuum outlet. The latter is nitrogen bleed/true Connected to the empty gauge and then to the aspirator and trap. anti Variable transformer temperature controller used to heat the reaction mixture A 500W heating mantle with a placed on the love-jack so that it can be easily raised and lowered for control.

N-Methylglucamine (195g, 1.0mol, Aldrich, M4700-0 ) and methyl laurate (Broctanaendo or Gamble CE1270.2 2 (1.9 g, 1°0 mol) into a flask. Stir solid//liquid mixture Prepare the melt by heating under a nitrogen sweep (approximately 25 minutes). Melting temperature is 145℃ When the catalyst (anhydrous powdered sodium carbonate, 10.5 g.

[]71 mol, J, T, Baker) is added. Stop nitrogen sweep d=　l,　,as Adjust the pilator and nitrogen bleed to 5 inches (5/31 atm) Hg. give the sky From this point on, the reaction temperature can be adjusted by adjusting the barrier and /or Maintain at 150"C by raising or lowering the mantle.

Within 7 minutes, the first methanol bubble is seen at the meniscus of the reaction mixture. Geki 1 ．． A reaction quickly accompanies it.

Methanol is distilled until the rate decreases. Adjust the vacuum to 17 to approximately 10 inches. Apply a vacuum of Hg (10/31 atm). Increase the vacuum approximately as follows (by a predetermined amount) Inch Hg): 10 at 3; 20 at 7; 25 at 10° Start of methanol generation? After 11 minutes, heating and stirring are stopped (slight foaming occurs at the same time). product Cool and solidify.

The following examples are intended to illustrate compositions of the invention, but do not limit the scope of the invention. does not necessarily mean that the claims below (determined according to the range).

The invention is illustrated by the following examples. All quantities are by weight unless otherwise specified .

In the examples, abbreviated compound identifications have the following meanings.

CLAS: Linear C12 alkylbenzene sulfonate TG A Nigel dityl tallow fatty acid amide TAS: tallow alcohol sulfate Thorium CAS: C14-C15 alkyl sodium sulfate AE S: Alkylsa CI2~C containing an average of 3 moles of ethylene oxide per 1 mole of Lefey 15 alkyl ether sodium sulfate TAE: Ethoxylation with n moles of ethyl nonoxide per alcohol IT-ru Tallow alcohol 45E7: condensed with an average of 7 moles of ethylene oxide 014-15 Mainly linear primary alcohol 25E3: average of 3 moles of ethylene C12-15 primary alcohol condensed with oxide TAED: Tetraacetylethylenediamine silicate: Amorphous silicate um (usually carbonate described below: anhydrous sodium carbonate) CMC: Carboxymethyl cellulose sodium zeolite A secondary particle size 1-1 Formula % Formula % with 0μm Sodium minosilicate Sideley 1: Tristrium citrate dihydrate MA/AA + maleic anhydride /acrylic acid 1:4 copolymer, average molecular weight approximately 80,000 Berborate monohydrate: Empirical formula NaBO-H2O2 Anhydrous Sodium Perborate Bleach Enzyme: Mixed proteolysis sold by Novo Industries AS/ Starch degrading enzyme brightener: 4,4'-bis(2-morpholino-4-anilino-s -triazin-6-ylamino)stilbene-2:2'-disulfonic acid dinato Rium DETPMP: Marketed by Monsanto under the trade name Dequest 2060 diethylenetriaminepenta(methylenephosphonic acid) Foam inhibitor: paraffin wax (melting point 50°C) 25%, hydrophobic silica 17%, paraffin 58% oil The following granular detergent composition was prepared.

A B C T A S 2.43 TGA 3.5 6.5 - 2 5 E 3 3. B - 6.5 Zeolite A 15.0 Site rate 6.5 Silicate (ratio 2.0) 3.5 Carbonate 13.6 M A / A A 4.25 D E T P M P 0.38 CM CO, 48 T A E D 5.0 Belborate 18.0 Enzyme 1.4 Brightener 0.19 Foam suppressant 3.0 The performance of the three compositions was evaluated in both the tergotometer test and the full scale washing machine test. compared.

tergotometer test 12″ crack hard water (Ca:Mg-4:1) in a 6 x 2 liter metal pot was filled and heated to 60"C.

14g of product was added to each pot and dissolved/dispersed to give a product weight concentration of 0.7%.

Dirty 7.5cm x 7.5cm cotton and polycotton fabric samples are treated with artificial sebum, Spread separate strips of shoe polish and dirty motor oil (DMO) evenly onto each fabric swatch. Prepared by applying one. Next, place the swatches of each fabric type on the pads of each pot. The paddle was then stirred in the pot for 45 minutes. About each product The total number of replicates was 6. The swatches were then rinsed in cold water and allowed to dry overnight. and then evaluated by an expert panel using the 5-point Scheffe scale.

washing machine test Similar products using AEG Lavasat 980 automatic washing machine A comparison was made. Select 45 minute main wash cycle at 60”C 0112°Clarke A product concentration of 0.796 in hard water (Ca:Mg-471) was used. For each product The experiment was repeated six times. Each wash load, along with a set of dirty swatches, Cotton: Cotton fabric together with polycotton product to give polycotton weight ratio 3=1 It consisted of 3 pieces of actual soiled ballast fabric consisting of suits and towels.

The stain set consisted of the following: Two types of grease stains on the brocade (lips) Tick,’ DMO) Two types of grease stains on polyester (makeup, shoe polish) After rinsing with cold water, each swatch was dried and then tested using a 5-point Scheffe scale. The results were evaluated by an expert panel.

Results for both test techniques are shown below.

The LH column shows the benefits of composition A over composition 8, while the RH column shows the advantages of composition A over composition 8. The advantages of Composition A over Product C are shown.

Tergotometer A/B A/C cotton Sebum -0,3-0,3 Shoe polish 10, li 40.2 D　M　O+1.1(s)　+o,g polycotton Sebum +0.2 40.4 Shoe polish +0.8 +0.5 D　M　O+1.5(s)　+0.5 washing machine Lipstick/Cotton Village, 5(s) +0.2DMO/Cotton +1.2 +0. 5 Makeup/polyester +1.0 +0.3 Shoe polish/polyester +1. 4(s) + 1.1(s)(s) - Statistically significant at the 95% confidence level Product C is Comparison A/C represents the composition of the prior art and shows that composition A according to the invention has a broad spectrum. Provides stain removal benefits compared to Composition C across stain types and fabrics Show that. A comparison between composition A and composition B shows that a large amount of polyhydroxy fatty acid amide The use of the composition according to the invention compared to that provided by the use of D alone. It shows the incredible benefits that can be provided.

Example■ Composition A of Example I contains 45AS, 25AE3SSTGA and 25E3 components at C1 ゜When replaced with LAS7.6%, 45E73% and TAE1□1.1% Composition A was compared with a different commercially available detergent composition (D). Washing conditions of Example 1 and Method and use of various smears on cotton, polycotton and polyester fabric swatches A comparison was made in an AEG Lavamat 980 washing machine. 5 points The evaluation of cleaning fabric samples by an expert panel using It has been shown to give benefits on stain removal.

On shoe polish made from polyester> 2 On DMO made from psu polyester> 1　>1.5 psu carp on no cap made from psu cotton The performance of Composition A of Example I was determined by combining the 25E3 components with 68E3 and 68E5 ( 68E3 and 68E5 are condensed with an average of 3 and 5 moles of ethylene oxide, respectively. 018-018, which is mainly a linear primary alcohol) Two further detergent compositions were compared with those of A and E, which differed only in the following. Example I Performance comparisons were made using the tergotometer test conditions and methods of

Evaluation of cleaning fabric samples by an expert panel using a 5-point Schietzfe scale: Both the composition A according to the present invention is not a composition according to the present invention and the composition E It has been shown to provide significant stain removal benefits over other methods.

The results of the comparison are shown below.

The LH column shows the advantages of Composition A over Composition A, while the RH column shows the advantages of Composition A over Composition A. The advantages of composition A over product E are: sebum +0.8s +o, a Shoe polish -0,3-0,6 D　M　O+1.8s　+2.0s polyester Sebum +2.8s +2.7s Shoe polish village, 8s ◆0.5 D　M　O+0.8s　+1.5s (s) - Statistically significant at 95% confidence level (*corresponding application) US Patent Application No. 071578,760 - WO 92/06160 PCT/US9 European Patent Application Box No. 87303761.8 published as Particulars - European Patent No. 0.251,446 published on January 7, 1988 U.S. Patent Application No. 740,446 - European Patent Application No. 0.170,386 book Continuation of front page (81) Designated countries EP (AT, BE, 'CH, DE.

DK, ES, FR, GB, GR, IT, LU, MC, NL, SE), 0A (BF , BJ, CF, CG, CI, CM, GA, GN, ML, MR, SN, TD, TG. ), AU, BB, BG, BR, CA, C3, FI, HU, JP.

KP, KR, LK, MG, MN, MW, No, PL, RO, SD , U.S.

Claims (11)

[Claims] 1. A laundry detergent composition useful for cleaning fabrics in an automatic washing machine, The composition comprises one or more water-soluble anionic detergent surfactants, cationic detergent surfactants. , amphoteric detergent surfactants or zwitterionic detergent surfactants or mixtures thereof and containing a detersive builder compound depending on the combination; (a) At least 1% by weight of the composition ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R1 is H, C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydrocarbyl, droxypropyl or a mixture thereof, R2 is a C5-C31 hydrocal pill and Z is a line with at least three hydroxy groups directly attached to the chain Polyhydroxyhydrocarbyl having a hydrocarbon chain, or its alkoxylation and (b) a polyhydroxy fatty acid amide having a derivative of Contains at least 1% by weight of an average of not more than 5 ethylene oxide groups per mole and substantially water-insoluble ethoxy having an ethylene oxide content of less than 50% by weight. Laundry detergent composition characterized by containing a C11 to C15 primary aliphatic alcohol thing. 2. Component (a) is the formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (wherein R2 is a C11-C19 straight chain alkyl or alkenyl group) The laundry detergent composition according to claim 1, which is a polyhydroxy fatty acid amide. 3. R2 is a C15-C19 straight chain alkyl or alkenyl group or a mixture thereof The laundry detergent according to claim 1 or 2, wherein R1 is methyl and R1 is methyl. agent composition. 4. Claim wherein R2 is a C15-C17 straight chain alkyl group derived from tallow fat. 4. The laundry detergent composition according to any one of items 1 to 3. 5. Component (b) is ethoxylated with an average of 3 ethoxy groups per mole of alcohol substantially linear fats having an average of 12 to 15 carbon atoms in the alkyl chain, The laundry detergent composition according to any one of claims 1 to 4, comprising a group alcohol. thing. 6. 3 to 15% by weight of anionic surfactant, 1% to 10% of component (a) and component ( b) Containing 1% to 10%, weight of anionic surfactant versus component (a) and component (b) Any one of claims 1 to 5, wherein the total weight ratio of The granular laundry detergent composition described in Section 1. 7. Anionic surfactants include water-soluble C12-C18 alkyl sulfates, alkaline C containing on average up to 3 ethoxy groups per mole of kill ethoxy sulfate 12-C18 alkyl ethoxy sulfates and mixtures thereof. The granular laundry detergent composition according to claim 6. 8. Claim in which the anionic surfactant does not contain an alkylbenzene sulfonate. 7. The granular laundry detergent composition according to 7. 9. The anionic surfactant accounts for the main proportion (by weight) of the mixture in water-soluble C14-C15 alkyl sulfate and a small proportion (by weight) of the mixture alkyl ethoxy sulfate C12-C15 alkyl ethoxylic acid containing an average of 3 ethoxy groups per unit according to any one of claims 6 to 8, consisting of a mixture with cisulfate. Granular laundry detergent composition. 10. Any of claims 6 to 9, comprising a non-phosphate detersive builder system. The granular laundry detergent composition according to item 1. 11. Detergent builders are synthetic crystalline or amorphous zeolite aluminosilicate alkali metal carbonates, bicarbonates and organic polycarboxylates, alkali gold silicates, crystalline layered sodium silicates, acrylic acid homopolymers or anhydrous polymers Water-soluble salts of acrylic acid copolymers with leic acid, aminopolycarboxylates and and a mixture of any of the foregoing. agent composition.