JPH06501505A - Nonionic surfactant system containing polyhydroxy fatty acid amide and one or more additional nonionic surfactants - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] containing a polyhydroxy fatty acid amide and one or more additional nonionic surfactants. Nonionic surfactant system - Technical field The stain removal performance of detergent compositions is determined by the combination of one or more polyhydroxy fatty acid amides and one or more polyhydroxy fatty acid amides. modified by the use of a nonionic surfactant system containing an additional nonionic surfactant and Goodness Conventional laundry detergent compositions have a number of different formulations to treat a number of different laundry problems. It can be prescribed by method. For example, such detergent compositions can be used to Contains builders, optical brighteners, dispersants, etc. to deal with leaning issues. Good too. Additionally, consumers can protect against the broadest possible spectrum of stains and stains. There is a need for detergent compositions that are effective. Detergent formulators are focusing on cleaning performance. By providing detergent compositions containing mixed surfactants that are widely effective in So, we are dealing with this need.

One particular issue that must be considered and addressed when formulating detergent compositions is , removal of troublesome grease/oil stains, such as body stains, food stains, etc. Non The incorporation of ionic surfactants into laundry detergent compositions improves resistance to grease/oil stains. will improve the effectiveness of the composition, but only under limited laundering conditions. Ru.

The present invention comprises one or more polyhydroxy fatty acid amides and one or more additional nonionic A nonionic surfactant system comprising a surfactant. In addition, the present invention A laundry detergent composition containing a nonionic surfactant system is provided. laundry detergent When incorporated into compositions, these nonionic surfactant systems can withstand a wide range of laundering conditions. unexpectedly improves the effectiveness of such compositions against grease/oil stains over .

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, “The thermotoplasty of some straight-chain carbohydrate amphiphiles. Lopic Liquid Crystals J, Liquid Crystals.

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

“Non-ionic detergents: Molecular structure and crystal structure of nonanoyl-N-methylglucamide J J, Ch ew, Soc, CheII.

Commun, 1986, pp. 1573-1574. . The use of N-alkyl polyhydroxyamide surfactants has recently been introduced in biochemistry, e.g. For example, there has been substantial interest for use in biofilm dissociation. example For example, in J.E. Hildreth's journal article "N-D-Glue for Membrane Biochemistry" "Co-N-methyl-alkanamide compound, a new kind of non-ionic detergent", Bio See cheIl, J. (1982), Vol. 207, pp. 363-366. .

The use of N-alkyl glucamides in detergent compositions has also been discussed. E, U.S. Patent No. 2.965,576 issued December 20, 1960 to R. Wilson. Thomas Hedley End. British Patent No. 809,060, assigned to The Company Limited Amide surfactant, which is an ionic surfactant (this is added as a low-temperature foaming agent) methyl glucamide). These transformations Examples of compounds include N-acyl groups of higher straight chain fatty acids having 10 to 14 carbon atoms. There is. These compositions contain alkali metal phosphates, alkali metal silicates, sal Auxiliary substances such as phates, carbonates, etc. may also be included. Also, in general, Additional ingredients that impart new properties to the composition, such as fluorescent dyes, bleaches, fragrances, etc. It has been pointed out that it can also be incorporated into the composition.

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 Departure aWO No. 83, published December 22, 1983, by J. Hildreth. 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 Applications in biochemistry for solubilizing other tissue samples and for the production of liposomes containing polyhydroxyl aliphatic groups, which are said to be useful for a variety of purposes, including It relates to amphipathic compounds having. This disclosure includes the formula R'CON (R)CH2 R' 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 group. compounds which are residues) are included.

European Patent No. 0285 of H. Kerkenberg et al. published on October 12, 1988 No. 768 discloses that N-polyhydroxyalkyl fatty acid amide is enriched in an aqueous detergent system. Concerning use as a sticky agent. formula RC(0)N　(X)R2C In the formula, R1 is C1 to C, a (preferably 07 to C1 7) alkyl, R2 is hydrogen, C1-Cl8 (preferably C1-C6) alkyl; or alkylene oxide, and X is polyhydroxyalkyl having 4 to 7 carbon atoms. including N-methyl coconut fatty acid glucamide, be done. Aqueous surfactant systems may contain other anionic surfactants, e.g. sulfonates, olefin sulfonates, sulfosuccinic acid half ester salts, and and fatty alcohol ether sulfonates, and nonionic surfactants, e.g. Fatty alcohol polyglycol ether, alkylphenol polyglycol ether ether, fatty acid polyglycol ester, polypropylene oxide-polyethylene However, the viscosity of amide is limited by paraffin sulfur. Liquid surfactant systems containing phonates have been shown to have particular utility.

Paraffin sulfonate/N-methyl coconut fatty acid glucamide/nonionic field A surfactant shampoo formulation is illustrated.

In addition to thickening properties, N-polyhydroxyalkyl fatty acid amides have excellent skin tolerability. It is said to have tolerant properties.

U.S. Patent No. 2,982,737 issued May 2, 1961 to Boesotner et al. The specifications include urea, sodium lauryl sulfate anionic surfactant, and N-methyl- N-Sorbityllaurinamide and N-methyl-N-sorbityl myristamide A detergent hardener containing an N-alkylglycamide nonionic surfactant selected from Regarding shapes.

Other glucamide surfactants may be used, e.g. (In the formula, R is c-c alkyl, R is C1゜l　1　3　2 ~C22 alkyl, n is 3 or 4) N-acylpolyhydroxy One or more surfactants and polymers modified by the addition of alkylamines Builder salts selected from phosphates, sequestrants and detergent alkalis H, W, Elacart, published on December 20, 1973 regarding a detersive composition containing et al., DT 2°226.872. N-acyl polyhyde The loxyalkylamine is added as a soil suspending agent.

U.S. Patent No. 3,654.16 issued April 4, 1972 to H.W., Elakart et al. Specification No. 6 describes anionic surfactants, zwitterionic surfactants and nonionic surfactants. At least one surfactant selected from the group of and fabric softener Tositeno type R N (Z)C(0)R2 (wherein, R1 is C1o-C22 alkyl, and R2 is C7-C2]alkyl, R1 and Ro have a total of 23-39 carbon atoms and Z is -CH2(CHOH) lCH20H (where m is 3 or 4) is a polyhydroxyalkyl which can be The present invention relates to a detergent composition containing a droxyalkyl compound.

No. 4,021,539 issued May 3, 1977 to H. Mellor et al. The calligraphy is the expression R, N　(R)CH(CHOH)　llR2 (wherein, R1 is H1 lower alkyl, Hydroxy lower alkyl, or aminoalkyl, as well as heterocyclic aminoalkyl and R is the same as R1, but both cannot be H, and R2 is CH 20H or C0OH) The present invention relates to skin treatment cosmetic compositions containing amines.

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 (R1)G (wherein R is a carboxylic acid function having at least 7 carbon atoms R1 is hydrogen or a lower alkyl group, and G has at least 5 carbon atoms. Formal stabilized against polymerization by adding an amide of glycidol (which is a glycidol group) Concerning solutions of dehydes.

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 Cl0 = C20 alkyl group, R2■ is a C1-C5 acyl group) Glucamine derivatives useful as wetting agents/dispersing agents Regarding.

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 has the formula N(R)(R,)C(0)R2, where R is anhydrous hexane is a residue of nithol 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) It is expressed as

U.S. Patent No. 3,312,627 issued April 4, 1967 to D. T. Hooker. The specification does not substantially contain anionic detergents and alkaline builder substances and consists 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 is 2- having a total number of carbon atoms of about 7 and a total number of substituent hydroxyl groups from 2 to about 6 ) Solid cosmetics that also contain nonionic foaming ingredients that can include polyhydroxyamides A solid substance is disclosed. Substantially similar disclosures were made in D. T. Hooker, 1967, 4. No. 3,312,626, issued May 4th.

The use of nonionic surfactants in detergent compositions is known in the art. Eraka U.S. Patent No. 3,654,166 issued on April 4, 1972 to Hart et al. A surfactant selected from anionic surfactants, zwitterionic surfactants and nonionic surfactants. Surfactants and N-alkyl-N-acyl-N-polyhydroxyalkyl compounds Discloses a detergent composition comprising:

Demonstration of invention The present invention (In the formula, R1 is H, C-C hydrocarbyl, 2-hydroxyethyl, 2-hydrocarbyl, oxypropyl, or a mixture thereof, and R2 is C-C hydrocarbyl. Z is a linear hydroxyl group having at least three hydroxyl groups directly linked to the chain. Polyhydroxyhydrocarbyl or their alkoxy with locarpylic chain derivative) one or more polyhydroxy fatty acid amides having: and (b) contains additional nonionic surfactants greater than or equal to IFli and contains polyhydroxy fatty acids; The weight ratio of amide (a) to additional nonionic surfactant (b) is from about 1=5 to about 5: 1.

The present invention also provides a laundry detergent composition containing the nonionic surfactant system. Ru. When incorporated into such laundry detergent compositions, these nonionic surfactant systems , unexpectedly, such compositions against grease/ura stains over a wide range of washing conditions Improves stain removal performance of objects.

Furthermore, the present invention provides a method for treating such compositions by incorporating the nonionic surfactant system into the composition. Provided are methods for improving the stain removal performance of detergent compositions.

BEST MODE FOR CARRYING OUT THE INVENTION The nonionic surfactant system of the present invention comprises one or more polyhydroxy fatty acid amides and and one or more additional nonionic surfactants. These nonionic surfactants In the system, the weight of polyhydroxy fatty acid amide versus additional nonionic surfactant The ratio is about 1:5 to about 5:1, preferably about 1=3 to about 3:1, more preferably is within the range of about 1=1.5 to about 1.5:1.

The components of the nonionic surfactant system of the present invention are as follows: The fatty acid amide surfactant component 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 C1 alkyl (i.e. methyl) and R2 is C5-C31 hydrocarbyl, preferably linear C7-C19 alkyl Kyl or alkenyl, more preferably straight chain C9-C17 alkyl or alkenyl most preferably straight chain C11-C17 alkyl or alkenyl, or a mixture of these; Z has at least three hydroxyls directly linked to the chain; polyhydroxyhydrocarbyl having a linear hydrocarpyl chain or its an alkoxylated derivative (preferably ethoxylated or propoxylated) Consists of compounds. Z is preferably derived from a reducing sugar in a reductive amination reaction. more preferably Z is glycityl; Suitable reducing sugars include: Glucose, fructose, maltose, lactose, galactose, mannose and xylose. As a raw material, high dextrose corn syrup high fructose corn syrup, and high maltose corn syrup. It can be used in the same way as the individual sugars listed below. These corn syrups contain Z sugar ingredients. Sometimes I prepare mixes. Never try to exclude other suitable raw materials You should understand that. Z is preferably -CH-(CHOH)-CH20 H.

n -CH(CHOH)-(CHOH) CHOH.

2 n-12 -CH-(CHOH)2(CHOR')(CHOH)-CH20H.

(where n is an integer from 3 to 5, and R' is H or a cyclic or aliphatic monosaccharide. ), and alkoxylated derivatives thereof. n is 4, glycityl, 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~C○-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 Tytyl, 1-deoxyglutyl, 1-deoxygalactytyl, 1-deoxyglutyl Nityl, 1-deoxymaltotriothytyl, and the like.

The most preferred polyhydroxy fatty acid amide has the general formula (wherein R2 is C-C straight chain Alkyl or Alkeni 11 1st ) 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, 2013, to E. R. Wilson. U.S. Pat. No. 2,965,576, issued December 20, 1960; and Andrew M. Schwartz U.S. Patent No. 2.7, issued March 8, 1955. No. 03,798 and U.S. Patent issued December 25, 1934 to Pigont. 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 In one method for producing droxyalkyl-N-deoxyglycityl fatty acid amide , the product lyses N-alkyl- or N-hydroxyalkyl-glucamine. Trilithium phosphate, trisodium phosphate, tripotassium phosphate, tetrasodium pyrophosphate um, pentapotassium tripolyphosphate, lithium hydroxide, sodium hydroxide, hydroxide Potassium, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, Disodium tartrate, dipotassium tartrate, potassium sodium tartrate, citric acid trisodium, tripotassium citrate, basic sodium silicate, basic potassium silicate basic sodium aluminosilicate, and basic potassium aluminosilicate fatty methyl ester 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 tel. The amount of catalyst is preferably N-alkyl or about 0.5 moles on a mole basis of N-hydroxyalkyl-glucamine96 to about 5 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 from about 1 to about 10% by weight, calculated on a weight percent basis of the total reaction mixture. Cole polyethoxylate, alkyl polyglycoside, linear glucamide surfactant using a phase transfer agent selected from agents and mixtures thereof.

Preferably, the magazine will: (a) Preheat the fatty acid ester to about 38°C 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 a two-phase liquid-liquid mixture; ( 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 preformed linear N-alkyl/N-hydroxyalkyl- The N-linear glucofur fatty acid amide product was added to the reaction mixture as a phase transfer agent. Ru. This accelerates the reaction and thereby increases the reaction rate. Detailed experimental method is given below in the experiment.

The polyhydroxy "fatty acid" amide materials used herein are also wholly or primarily natural. Detergent formulators benefit from manufacturing from natural, renewable, non-petrochemical feedstocks provided and degradable. They also exhibit low toxicity to aquatic organisms.

Used together with polyhydroxy fatty acid amides of formula (I) to produce them The method also typically involves adding an amount of ester amide, cyclic polyhydroxy fatty acid It should be recognized that non-volatile by-products such as mido will also be produced. these The amount of byproduct will vary depending on the particular reactants and process conditions.

Preferably, the polyhydroxy fatty acid amide blended into the detergent composition herein is a detergent. The polyhydroxy fatty acid amide-containing composition added to the cyclic polyhydroxy fatty acid amide If provided in such a form that it contains less than about 10%, preferably less than about 4%, Dew. The preferred method described above uses rather small amounts of by-products, including such cyclic amide by-products. The nonionic surfactant system of the water invention is only produced by living organisms, so the nonionic surfactant system of the water-based invention is In addition to the fatty acid amide component, it consists of one or more of the nonionic surfactants listed herein. . The nonionic surfactants described herein are hereinafter referred to as "additional nonionic surfactants." will. Nonionic compounds other than these additional nonionic surfactants are Depending on the case, they may be included in the nonionic surfactant system of the present invention. These other duties Any nonionic compound will hereinafter be referred to as "any nonionic compound." limited Although it is not intended that any such nonionic compound be used as a nonionic surfactant of the present invention, When included in a formulation, they provide the unexpected stain removal benefits described herein. I believe it is not possible.

Polyethylene oxide condensate of alkylphenol, polypropylene oxide condensate Compounds and polybutylene oxide condensates can be added to the nonionic surfactant systems of the present invention. Suitable for use as a nonionic surfactant in addition to polyethylene oxide Condensates are preferred. These compounds may contain from about 6 to an alkyl group having about 14 carbon atoms, preferably about 8 to about 14 carbon atoms; Examples include condensates of alkylphenols and alkylene oxides having the following. good In a preferred embodiment, the ethylene oxide is Equivalent to about 5 to about 25 moles of ethylene oxide, more preferably about 3 to about 15 moles of ethylene oxide. exists in large amounts. Commercially available nonionic surfactants of this type include GAF Corp. Igepal™ Co-630, commercially available from ; Triton (Tr), marketed by Rohm & Haas Company; itonTM) X-45, X-114, X-100 and X-102 are listed. It will be done.

These surfactants are typically alkylphenol alkoxylates (e.g. Alkylphenol ethoxylate).

primary and secondary aliphatic alcohols and about 1 to about 25 moles of ethylene oxide. The condensate can be used as an additional nonionic surfactant in the nonionic surfactant system of the present invention. suitable for use. The alkyl chain of the aliphatic alcohol can be linear or branched. primary or secondary and generally has from about 8 to about 22 carbon atoms. . having an alkyl group having about 8 to about 20 carbon atoms, more preferably about 10 to about 18 carbon atoms; alcohol and about 2 to about 10 moles of ethylene oxide per mole of alcohol. A condensate with is preferred. Examples of commercially available nonionic surfactants of this type include T Father-in-law is Tergxtol 15 S 9 (Ctt~015 line condensate of alcohol and 9 moles of ethylene oxide), Tergitol TM24- L-6NMW (CI2~C14 secondary ~alcohol and ethyl alcohol with narrow molecular weight distribution) condensate with 6 moles of ren oxide) (both from Union Carbide Corporation) marketed by Shell Chemical Company); marketed by Shell Chemical Company Neodol TM23-6.5 (condensate with 9 moles of neodol tyrene oxide) (condensation product of C,2-CI3 linear alcohol and 6.5 mol of ethylene oxide), Neodol” 45-7 (014-C15 linear alcohol and 7 moss of ethylene oxide le M ), Neodol 45-4 (C14-CI5 linear alcohol and ethylene condensate with 4 moles of carbon oxide), The Brocter End Gamble Campa KyroTM E OB (C13-C 15 alcohol and 9 moles of ethylene oxide).

In addition, a hydrophobic group having about 6 to about 30 carbon atoms, preferably about 10 to about 16 carbon atoms, and about 1.3 to about 10, preferably about 1.3 to about 3, most preferably about 1.3 to about 2. Polysaccharides (e.g. polyglycosides) containing 7 sugar units 198 with hydrophilic groups No. 4,565,647 to Lenado, issued January 21, 2006. Alkyl polysaccharides are additional nonionic surfactants of the nonionic surfactant system of the present invention. It is useful as Any reducing sugar having 5 or 6 carbon atoms can be used, e.g. Glucose, galactose and galactosyl moieties replace glucosyl moieties , can be used (in some cases, the hydrophobic group is bonded at the 2-position, 3-position, 4-position, etc.) to form a group. Glucose or galactose as opposed to lucoside or galactoside ). The sugar bond is, for example, the 1st position of the additional sugar unit and the 2nd position on the previous sugar unit. , 3rd, 4th and/or 6th position.

In some cases, threading is undesirable, but polyalcohols that bind the hydrophobic and polysaccharide moieties are There can be xylene oxide chains. A preferred alkylene oxide is ethylene oxide. Typical hydrophobic groups have about 8 to about 18 carbon atoms, preferably about From 10 to about 16 saturated or unsaturated branched or unbranched alkyl groups are included. good Preferably, the alkyl group is a straight chain saturated alkyl group. Approximately 3 or more alkyl groups may contain hydroxy groups and/or polyalkylene oxides The chain contains up to about 10, preferably less than 5 alkylene oxide moieties I can do it. Preferred alkyl polysaccharides are octyl, nonyldecyl, undecyl Dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptade sil, and octadecyl, di, tri, tetra, penta, and hexa glucoside, galactoside, lactonde, glucose, fructocyto, fructo galactose and/or galactose. A suitable mixture is coconut oil. Lucyl, di, tri, tetra-1 and pentaglucosides and tallow alkyl Mention may be made of lutetra-, penta-1 and hexaglucosides.

Preferred alkyl polyglycosides have the formula (wherein R2 is alkyl, alkyl hydroxyl, hydroxyalkyl, hydroxyalkylphenyl, and their from about 10 to about 18 alkyl groups, preferably from about 10 to about 18 alkyl groups; has about 12 to about 14 carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; X is from about 1.3 to about 10. Preferably about 1 ．． 3 to about 3, most preferably about 1.3 to about 2.7) has. Glycodyl is preferably derived from glucose. these compounds To produce alcohol, first, alcohol or alkyl polyethoxy alcohol is produced. and then reacted with glucose or a glucose source to form the glucoside (1-position ). Additional glycosyl units are then added to their first position and the previous group. 2nd, 3rd, 4th and/or 6th position of the lycodyl unit, preferably primarily the 2nd position Can be combined between

Although undesirable, it results from the condensation of propylene oxide and propylene glycol. A condensate of a hydrophobic base and ethylene oxide can also be used as a nonionic surfactant of the present invention. Suitable for use as an additional nonionic surfactant in the system. these compounds The hydrophobic portion preferably has a molecular weight of about 1500 to about 1800 and is water insoluble. will show. The addition of the polyoxyethylene moiety to this hydrophobic portion is the overall Polyoxyethylene tends to increase the water solubility of the molecule and the liquid properties of the product 50 of the total weight of the condensate (up to about 40 moles of ethylene oxide). (corresponding to the condensation with). Examples of this type of compound include BASF's Therefore, the composition of commercially available Pluronic surfactants The following can be mentioned.

Also, the products resulting from the reaction of propylene oxide and ethylene diamine and ethylene The condensate with surfactant oxide is an additional nonionic interface of the nonionic surfactant system of the present invention. Suitable or unpreferred for use as an activator. Hydrophobicity of these products The moiety consists of the reaction product of ethylene diamine and excess propylene oxide. generally have a molecular weight of about 1500 to about 3000. This hydrophobic part is the condensate Contains about 40 to about 80% by weight of polyoxyethylene and has a molecular weight of about 5,000 to about 5,000. It condenses with ethylene oxide to an extent of about 11,000 i. This kind of non-ion Examples of surfactants include Tetronic (T etronicTM) compounds.

Polyethylene oxide condensates of alkylphenols, primary and secondary aliphatic condensate of alcohol and about 1 to about 25 moles of ethylene oxide, alkyl polysaccharide, and mixtures thereof or additional nonionic interfaces of the nonionic surfactant systems of the present invention. Preferred for use as an activator.

08-C14 alkylphenol ethoxylate with 3-15 ethoxy groups and C8-C18 alcohol ethoxylates having 2 to 10 ethoxy groups (preferably average C1o), and mixtures thereof are most preferred.

detergent composition Additionally, the present invention provides at least 1% by weight of total surfactant, preferably from about 3 to about 65% by weight. %, more preferably from about 10 to about 25% by weight.

The surfactants in such laundry detergent compositions may be comprised solely of the nonionic surfactant system of the present invention. or other surfactants, such as anionic surfactants, cationic surfactants, etc. combinations with surfactants, amphoteric surfactants, zwitterionic surfactants and semipolar surfactants. The combination may also consist of a nonionic surfactant system. Cations useful here A surfactant is one that has one long chain hydrocarbyl group.

Additionally, any nonionic compounds mentioned herein may be used in the nonionic surfactant system of the present invention. Although it is believed that the laundry detergent compositions of the present invention do not provide unexpected stain removal benefits, can contain any of the nonionic compounds mentioned above. Laundry detergent composition of the present invention or non-ionic surfactant systems and any other such detergent surfactants. The weight ratio of nonionic surfactant system to detergent surfactant ranges from about 50.1 to about 1:10, preferably within the range of about 10:1 to about 1:5. Additionally, the book The laundry detergent compositions of the invention optionally contain other materials typically found in detergent compositions. ingredients such as builders, soil release agents, chelating agents, etc.

When incorporated into such laundry detergent compositions, the nonionic surfactant systems of the present invention are widely used. Improves the grease/stain removal properties of such laundry detergent compositions over a range of laundering conditions. act for the good.

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 of the American Oil Chemistry'' Sutsu Society J, 52 (975), pp.

C8-C2o carbons sulfonated with gaseous SO3 according to 323-329 Included are linear esters of acids (ie fatty acids). Suitable starting materials include Ta Natural fatty substances such as those derived from raw, palm oil and the like may be mentioned.

Particularly preferred alkyl ester sulfonate surfactants for laundry applications have the structural formula (wherein R is C-02o hydrocarbyl, preferably alkyl, or combination, R4 is C1-06 hydrocarbyl, preferably alkyl, or or a combination thereof, where M is an alkyl ester sulfonate and a water-soluble salt. from alkyl ester sulfonate surfactants (which are cations forming Ru.

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 toie and R4 is methyl, ethyl or isopropyl. R is 010 = 01 Particularly preferred are methyl ester sulfonates that are 6 alkyl.

Alkyl sulfate surfactant The alkyl sulfate surfactant herein has the formula RO803M [wherein R is preferably or C1o-024 hydrocarbyl, preferably having a C10""C20 component alkyl or hydroxyalkyl, more preferably 012-018 alkyl or hydroxyalkyl, M is H or a cation, e.g. alkali gold cations (e.g., sodium, potassium, lithium), or ammonium or substituted ammoniums (e.g. methyl-, dimethyl-1 and trimethyl-1) ammonium cations and quaternary ammonium cations, e.g. tetramethyl - ammonium and dimethylpiperidinium cations and ethylamine, di Quaternary amines derived from alkyl amines such as ethylamine and triethylamine water-soluble salts or acids, such as ammonium cations, and mixtures thereof) It is. Typically, C12-C16 alkyl chains or lower wash temperatures (e.g. C16-C18 alkyl chains have higher cleaning temperatures. (e.g., higher than about 50°C).

Alkyl alkoxylated sulfate surfactant here Phate surfactant has the formula RO(A) So MC where R is C10-C24 Unsubstituted C10’=C24 alkyl or hydroxyalkyl having an alkyl component Kyl group, preferably CI2-C2o alkyl or hydroxyalkyl, more preferably Preferably 012-018 alkyl or hydroxyalkyl, and A is ethoxyalkyl. or propoquine units, where m is greater than 0, typically from about 0.5 to about 6, more preferably about 0.5 to about 3, and M is H or, e.g., a metal cation. (e.g., sodium, potassium, lithium, calcium, magnesium, etc.) ), ammonium or substituted ammonium cations is a water-soluble salt or acid. Alkyl ethoxylated sulfates and Rukyl propoxylated sulfates are contemplated herein. Substituted ammonium cation Specific examples of ions include methyl-, dimethyl-, trimethyl-ammonium cations. and quaternary ammonium cations, e.g. tetramethyl-ammonium and dimethylpiperidinium cation and ethylamine, diethylamine, Those derived from alkylamines such as triethylamine, and mixtures thereof. Which can be mentioned. Exemplary surfactants include 012-C18 alkyl polyethoxylates. (1,0) sulfate (C-CE(1,0)M), C12-C18 alkyl polyethoxylate (2,25) sulfate (C-CE (2,25)M ), C, , ~C18 alkyl polyethoxylate (3,0) sulfate ( 012-CE(3,0)M), and CI2-C18 alkyl polyethoxylates (4,0) sulfate (012~Cl8E (4,0)M) (where M is (conveniently selected from sodium and potassium).

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), C9-c2o linear Alkylbenzene sulfonate, 08-022 primary or secondary alkanesul phonates, C-C24 olefin sulfonates, e.g. British Patent No. 1,082 , 179 of the thermal decomposition products of alkaline earth metal citrates. Sulfonated polycarboxylic acids produced by sulfonation, C8-C24 alkyl polyglycol ether sulfate (contains up to 10 moles of ethylene oxide) ): Alkylglycerol sulfonate, fatty acylglycerol sulfonate , fatty oleyl glycerol sulfate, alkylphenol ethyleneoxy Doether sulfate, paraffin sulfonate, alkyl phosphate, Cethionates, such as acyl isethionates, N-acyl taurates, alkyl Rusufucinamate and sulfosuccinate, monoesters of sulfosuccinate (particularly saturated and unsaturated 012-018 monoesters) and sulfoskune diesters (especially saturated and unsaturated C-C, diesters), acyl sarcodiesters (especially saturated and unsaturated C-C, diesters) cinates, sulfates of alkyl polysaccharides, e.g. of alkyl polyglucosides. Sulfates (non-ionic non-sulfated compounds are listed below), secondary alkyl salts ruphate, and alkyl polyethoxy carboxylates, such as formula R○ ( CH2CH20) k-CH2COO-M” (wherein, R is 08-C22 alkyl , k is an integer from 0 to 10, and M is a soluble salt-forming cation). The following can be mentioned. Resin acids and hydrogenated resin acids, e.g. rosin, hydrogenated rosin resin acids present in or derived from tall oil and hydrogenation. Resin acids are also suitable. Yet another example is “surfactants and detergents” (Schwar vol. 1 and vol. Various Such surfactants are generally described in Rollin et al. No. 3,929,678 specification, column 23, line 58 to column 29, line 23 (herein (incorporated as a reference).

When formulated herein, the laundry detergent compositions of the present invention typically contain such anions. The surfactant contains about 1% to about 40% by weight, preferably about 3% to about 20% 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. and semipolar surfactants, as well as nonionic surfactants other than those mentioned herein. It may also contain a sex agent. However, without attempting to limit it thereby, Nonionic surfactants other than those mentioned above, such as the semipolar nonionic surfactants described below, may also be used. The amine oxides described above are associated with the nonionic surfactant systems of the present invention. It is believed that there will be no overriding benefit.

Cationic detergent surfactants suitable for use in the laundry detergent compositions of the present invention include one It has a long chain hydrocarbyl group. Examples of such cationic surfactants and is an alkyldimethylammonium halide and the formula %formula% [wherein R2 is an alkyl group having about 8 to about 18 carbon atoms in the alkyl chain] or an alkylbenzyl group, and each R is -CH2CH2-1-CH2CH(CH 3)-1-CH2CH(CH20H)-1 selected from the group consisting of ~CH2CH2CH2- and mixtures thereof: each R4 is C-C alkyl, C-C4 hydroxyalkyl, in bonding two R4 groups Therefore, the benzyl ring structure formed, (wherein R6 is a hexose or a hexose polymer having a molecular weight of less than about 1000) selected from the group consisting of hydrogen (when y is not ○), R5 is the same as R4 or an alkyl chain, and the total number of R+R'' carbon atoms is about 18 or less; Each y is from 0 to about 10, and the sum of the y values is from O to about 15; X is a compatible anion. Examples include surfactants having the following properties.

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

When formulated herein, the laundry detergent compositions of the present invention typically contain such cations. The surfactant contains 0 to about 25% by weight, preferably about 3 to about 15% by weight.

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 derivatives 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 US Pat. No. 3,929,678 specification, column 19, lines 18 to 35 (references here) (incorporated as).

When formulated herein, the laundry detergent compositions of the present invention typically contain such amphoteric compounds. Contains 0 to 15% by weight surfactant, preferably about 1 to about 10% by weight.

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 No. 3,929,678 to Rollin et al., issued December 30, 1975. See Column 19, Line 38 to Column 22, Line 48 of the specification (incorporated herein as a reference).

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

Semipolar nonionic surfactants are a special category of nonionic surfactants.

Examples of these include one alkyl moiety having about 10 to about 18 carbon atoms; a moiety selected from the group consisting of 1 to about 3 alkyl groups and hydroxyalkyl groups; A water-soluble amine oxide containing 2 alkyl moieties of about 10 to about 18 carbon atoms 1 a group consisting of alkyl groups and hydroxyalkyl groups having about 1 to about 3 carbon atoms A water-soluble phosphine oxyto containing 2 moieties selected from: and about 1 carbon number 1 alkyl moiety of 0 to about 18 and alkyl of about 1 to about 3 carbon atoms and hydro Water-soluble sulfoxy containing one moiety selected from the group consisting of xyalkyl moieties One example is de.

Semi-polar non-ionic detergent surfactants include alkyl and hydrogen having the formula from about 8 to about 22 carbon atoms. droxyalkyl or alkylphenyl group or a mixture thereof; R 4 is an alkylene or hydroxyalkylene group having about 2 to about 3 carbon atoms, or X is 0 to about 3; each R5 is an alkyl group having about 1 to about 3 carbon atoms; or hydroxyalkyl group or about 1 to about 3 ethylene oxide groups Examples include amine oxide surfactants having polyethylene oxide groups (polyethylene oxide groups). Ru. The R5 groups are bonded to each other through oxygen or nitrogen atoms to form a ring structure, for example. can be achieved.

These amine oxide surfactants include C1 (1"01g alkyl Dimethylamine oxide and 08-C12 alkoxyethyl dihydroxydiethyl and amine oxide.

When formulated herein, the laundry detergent compositions of the present invention typically contain such semipolar Contains from 0 to about 15% by weight, preferably from about 1 to about 10% by weight of nonionic surfactant.

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

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 It typically contains 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 About 80% by weight, preferably about 15 to about 50% by weight. However, less No or large 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 capable of producing borates under conditions (hereinafter referred to as Collectively "borate builders") may also be used. Preferably a non-borated bill The product is intended for use under cleaning conditions below about 50°C, especially below about 40°C. used in bright compositions.

Examples of silicate builders are alkali metal silicates, especially SiO:Na2O ratios of 1 ．． 6:1 to 3.2:1 and layered silicates, such as H,P, U.S. Pat. No. 4.664.839 issued May 12, 1987 to Ritte ( (Incorporated herein by reference) is a layered sodium silicate. But long Other silicates, such as magnesium silicate, may also be used; In granular formulations, it can be used as a burr imparting agent, as a stabilizer for oxygen bleaching agents, and as an anti-foaming agent. It can serve as a component of a system.

Examples of carbonate builders are sodium carbonate and sodium sesquicarbonate. German Patent Application No. 2.321.001 published on November 15, 1973 Ultra-fine carbonate carbonate as disclosed in the No. 1 specification (the disclosure of which is incorporated herein by reference) In carbonates of alkaline earth metals and alkali metals, including mixtures with lucium. be.

Aluminosilicate builders are particularly useful in the present invention. aluminosilicate Builder is a major component of most currently commercially available heavy-duty granular detergent compositions. has great importance and can also be a significant builder component in liquid detergent compositions. . 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. CO3 hardness has a magnesium ion exchange capacity of at least 50@g equivalent. good The preferred aluminosilicate has the formula Na ((AIO) (SiO))・xH20z 2z 2y (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

Useful aluminosilicate ion exchange materials are commercially available. these aluminum Nosilicates can be crystalline or amorphous in structure and are naturally occurring aluminum Can be straight or 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 A, zeolite P (B), and zeolite Available at X.

In particularly preferred embodiments, the crystalline aluminone 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 aluminide has a particle size of about 0.1 to 10 microns in diameter.

Specific examples of polyphosphates are alkali metal tripolyphosphates, sodium, carbonate, Lium and ammonium birophosphate, 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, iso 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 using 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 alkanol 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 Help U.S. Patent No. 3,128°287 and issued January 18, 1972 No. 3,635,830 to Lamberke et al. One example is sydisuccinate (both are incorporated herein as bibliography).

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 ogicidicohataic acid and its water-soluble salts. A is 0H If SB or H, the compound is tartrate monosuccinic acid (TNxS ) and its water-soluble salts. A or HSB is -0-CH(COOX)-CH2( COOX), the compound is tartrate disuccinic acid (TDS) and It is its water-soluble salt. A mixture of these builders is particularly preferred for use here. Delicious. The weight ratio of TMS to TDS ranges from 97:3 to about 20:80. Mixtures with DS are particularly preferred. These builders on May 5, 1987 No. 4,663,071 issued to Bush 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 structures HO-[C(R)(C00M)-C (R) (CooM) -03-H [where M is hydrogen or a cation (obtained salts are water soluble), preferably alkali metal, ammonium or substituted ammonium cation, and n is from about 2 to about 15 (preferably, n is from about 2 to about 10, such as preferably n is on average about 2 to about 4), each R is the same or different, hydrogen, Cal 1-4 selected from kill or ct-substituted alkyl 1-4 (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-trihydroxybenzene -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-trical 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 C5-C2o 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 (where R is a hydrocarbon, e.g. Cl0=C20al kyl or alkenyl, preferably C12-C16, or R is Substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents as described in ).

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 succinate and myristic succinate. 2-dodecenyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-dodecenyl succinate Examples include pentadecenyl. Lauryl succinate is the preferred building block of this group. European Patent Application No. 86200690.5 published on November 5, 1986 No. 10,200.263.

Also, examples of useful builders include sodium and potassium carboxymers. Tyloxymalonate, carboxine methyloxysuccinate, cis-cyclohexyl Xanehexacarboxylate, cis-cyclopentanetetracarboxylate, water soluble polyacrylates (these polyacrylates have 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 polymerization initiator together under weight 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.

Polycarboxylate builders are listed in Deal's U.S. special edition 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, and aconic acid. Homopolymers of aliphatic carboxylic acids such as citrate acid, citraconic acid, and methylenemalonic acid and water-soluble salts of copolymers.

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". The chain length of C1o-C2° is typical Generally 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 have a suitable origin, such as plant, animal, bacterial, X fungus and yeast origin. Good too. However, their selection depends on several factors, such as pH 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. ichenif'or ■S). another The preferred protease was developed by Novo Industries A/S and 8 to 12 pages sold under the registered product name Esperase Obtained from strains of Bacillus that have maximum activity throughout the H range. this enzyme and similar enzyme preparations are described in Novo UK Patent No. 1,243.784. It is listed. Commercially available tongues suitable for removing protein-based stains The protein-degrading enzyme is produced by Novo Industries A/S (Denmark). The product names are Alcalase (ALCALASETM) and Savinase (SAVIN). ASETM) and International Biosynthes. Trade name Maxatase ( One example is the one sold at ``M^XATASE'').

The enzymes referred to herein as protease A and protease B, particularly in liquid detergent compositions, Are you interested in something in the category of proteolytic enzymes? protease A and The manufacturing method is described in European Patent Application No. 130.756 published on January 9, 1985. (Incorporated here as a reference). Protease B is an amino acid Protease A is different from Protease A in that it has leucine instead of tyrosine at position 217 in the sequence. They are different proteolytic enzymes. Protease B was filed on April 28, 1987. European Patent Application No. 87303761.8 (herein incorporated 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 Pott et al. (herein incorporated by reference) ) is disclosed.

Amylases include, for example, British Patent No. 1, previously incorporated herein by reference. ．． Bacillus licheniforme as described in more detail in Novo No. 296,839 (Novo) Examples include α-amylase obtained from special strains of bacteria.

Examples of starch degrading proteins include International Biosyn Rapidase (RAPIDASE) manufactured by Cetics Inc. , and Terma Mill (TEI?MAMYLTM) 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 (Hun+1col 1984 discloses a fungal cellulase produced from A. ajnsolens). U.S. Pat. No. 4,435.307 to Barbesgaard et al., issued March 6, (incorporated herein by reference). In addition, suitable cellulases include English National Patent No. 2.075.028 Specification, British Patent No. 2.095.275 Specification and DE-O8 2.247.832.

An example of such a cellulase is Humicola insolens [Humicola grisea]. Pal thermoidea (Humicola grisea var, the rIIoidea)), especially Humicola strain DSM1800. cellulases, and fungi or cells of Bacillus N belonging to the genus Aeromonas. Cellulases produced by 212-producing fungi and marine molluscs Dolabella Aurjcula This cellulase is extracted from the liver, pancreas, and viscera of the 5.

Lipase enzymes suitable for use in detergents include British Patent No. 1.372,034. Pseudomonas stuzeri (P. seudomonas 5 tutzeri) AT CC19, 154, etc. Examples include those produced by microorganisms of the Pseudomonas group. suitable ripper As the enzyme, the microorganism Pseudomonas 1 fluorescens (Pseudollona Anti-lipase produced by S. fluorescens) IAM1057 These include those that show positive immunological cross-reactivity with the body. This lipase and its purification The law is based on a patent application published for public convenience on February 24, 1978. It is described in Publication No. 487. This lipase is manufactured by Amano Fa in Nagoya, Japan. Product name Lipase P "Amano J" from Lumaseutical Co., Ltd. (hereinafter referred to as "Amanor P"). Such lipases of the present invention are of The standard well-known immunodiffusion method according to Ronnie (^eta, Med, 5can,.

133.76-79 (1950)) with Amanor P antibody. It should show a differential response. These lipases and their immunization with Amanor P Methods for cross-reactivity are also described in US Pat. No. 4, Tom et al., issued November 17, 1987. , 707, 291 (incorporated herein as a reference). So Typical examples of these are Amanor P lipase, Pseudomona ex Pseudomona s fragiFERM P13B9 (available under the product name Amanor B), Ripper Zeex Pseudomonas n1troreducens war.

1ipolyticu [IF E RM P 1.338 (Product name Amanor C ES), lipase ex Chro*obactarviscosum , for example, commercially available from the Toyo-Jossey Company of Japan. Chrosobacter viscosulvar, 1ipolyticu v N RRL B 3673; and U.S. Biochemical Corporation of the United States. Polation and further Chr from the Dutch Disoint Company omobaeter viseosum lipase, and lipase exPseu It is Domonas gladioli.

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 known above, e.g. 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. aWO 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. Race et al. U.S. Pat. No. 4,101. .

No. 457 and Hughes U.S. Pat. No. 4.5, issued March 26, 1985. No. 07,219, both incorporated herein by reference. . Enzyme materials useful in liquid detergent formulations and methods of incorporation into such formulations were described in 1981. U.S. Pat. No. 4,261,868 to Hora et al., issued April 14, (incorporated as a research document).

The enzyme will usually contain up to about 5 mg of active enzyme per gram of composition, more typically about 0.5 mg of active enzyme per gram of composition. 0.5 mg to about 3 cm.

In the case of granular detergents, the enzymes are preferably coated with enzyme-inert additives or Lyllation minimizes dust formation and improves storage stability. accomplished this Techniques for doing so are well known in the art. In liquid formulations, the enzyme stabilization system Preferably used. Enzyme stabilization technology for aqueous detergent compositions is well known in the art. Ru. For example, one enzyme stabilization technique in aqueous solution is calcium acetate, calcium formate, Use of free calcium ions from sources such as calcium, calcium propionate, etc. include. Calcium ions can be combined with short chain carboxylates, preferably formates. Wear. For example, U.S. Pat. No. 4,318 to Retton et al., issued March 9, 1982; See specification No. 818 (incorporated herein by reference). Also, glycerol, sol It has also been proposed to use polyols such as Vitol.

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. Patent No. 4,261,868, issued on May 14, 1971, to Gesoji et al. No. 3,600,319, issued Aug. 17, both incorporated herein by reference. (incorporated as a document) and Venegas' European patent publication published on October 29, 1986. Application publication number 0 199 405 specification, application box 86200586.5 specification Disclosed and illustrated. Stabilizers that are not boric acid and borates are preferred. stomach.

Enzyme stabilization systems are also described, for example, in U.S. Pat. No. 4,261°868, 3. 600,319 and 3.51.9,570. Ru.

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. A bleaching composition may also be included. When formulated, the present bleaching compounds typically Typically from about 1% to about 20% of such laundry detergent compositions, more typically from about 1% to about It will account for 20%. Generally, bleaching compounds are used in non-liquid formulations, e.g. It is an optional ingredient in detergents. If present, the amount of bleach activator typically From about 0.1% to about 60% of the white composition, more typically from about 0.5% to about 40%. cormorant.

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. These include oxygen bleach as well as other bleaches. can be lost. For cleaning conditions below about 50°C, especially below about 40°C, the composition can produce borate or detergent in situ under storage or cleaning conditions Preferably, it does not contain any substances (ie, borate-forming substances). Thus, these Preferably, a non-borate non-borate forming bleach is used under conditions of.

Preferably, detergents to be used at these temperatures are borates and borate products. The quality is virtually non-existent. Here we use [borates and borate-forming substances] The composition does not contain borate-containing substances and borate-producing substances of any kind. Contains about 2% by weight or less, preferably 1% by weight or less, more preferably 0% by weight of the substance It would mean that.

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 m-chloroperbenzoic acid, 4-nonylamino- Mention may be made of 4-oxoperoxybutyric acid and diperoxide dodecanedioic acid.

Such bleaching agents are disclosed in Hartman U.S. Pat. No. 83,781, U.S. Patent Application to Burns et al., filed June 1, 1985. No. 740,4464, European Patent of Banks et al., published February 20, 1985. Application No. 0.133,354, published November 1, 1983, by Chung et al. No. 4,412°934, all of which are incorporated herein by reference. .

(incorporated). Highly preferred bleaching agents include Buns et al. U.S. Pat. No. 4,634.551, issued January 6, 1987 (referenced herein) 6-nonyl-amino-6-oxoberoxycabronic acid described in Can be mentioned.

Another category of bleaches that can be used includes halogen bleaches. Hypohara Examples of acid bleaches include, for example, trichloroisocyanuric acid and dichloroisocyanuric acid. Sodium isocyanurate and potassium dichloroisocyanurate and N-chloro and N-bromoalkanesulfonamides. Such substances are usually , 0.5-10%, preferably 1-5% by weight of the finished product.

Peroxygen bleach can also be used. Suitable peroxygen bleaching compounds include sodium carbonate. Muum peroxide, sodium birophosphate peroxide, urea peroxide , and sodium peroxide.

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.

Preferred bleach activators to be incorporated into the laundry detergent compositions of the present invention have the general formula: (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 the leaving group, and the conjugate acid has [)K from about 4 to about 13 have) has. These bleach activators are listed in the US Pat. No. 4,915.854 (incorporated herein by reference) and U.S. Pat. No. 4゜412.934 (earlier incorporated herein by reference) There is.

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.

Polymer stain release agent Any polymeric soil release agent known to those skilled in the art can be used in the laundry detergent compositions of the present invention. Wear. Polymeric soil release agents clean the surface of hydrophobic fibers such as polyester and nylon. A hydrophilic segment for making hydrophilic and a hydrophobic segment for attaching to and cleaning and cleaning. remains attached throughout the completion of the rinsing cycle, thus providing an anchor for the hydrophilic segment. characterized by having both a hydrophobic segment and a It will be done. This makes it easier for subsequent cleaning methods to remove stains that occur after treatment with soil release agents. It can be made possible to purify.

As a polymer stain release agent, cellulose such as hydroxyether cellulose polymer Rose derivatives, ethylene terephthalate or propylene terephthalate and polymers. Liethylene oxymethoterephthalate or polypropylene oxide terephthalate Examples include copolymer blocks with

Cellulose-based derivatives that function as soil release agents are commercially available; For example, cellulose hydroxyesters such as Methocel® (Dow) -tel is mentioned.

Cellulosic soil release agents include methylcellulose, ethylcellulose, and hydroxide. 0 such as roxypropyl methylcellulose and hydroxybutyl methylcellulose selected from the group consisting of 1-C alkyl and C4 hydroxyalkyl cellulose There are also things that can be mentioned. Various cellulose derivatives useful as soil release polymers include: No. 4,000.093 issued December 28, 1976 to Nicol et al. Disclosed in the detailed document (incorporated herein by reference).

Soil release agents characterized by poly(vinyl ester) hydrophobic segments and For example, grafting of poly(vinyl ester), e.g. C-CB vinyl ester. Copolymers, preferably polyalkylene oxides such as polyethylene oxide backbones Examples include poly(vinyl acetate) grafted onto the main chain. Such substances are technically European Patent Application No. 0 which is known and published on April 22, 1987 by Kusodo et al. It is described in the specification of No. 219048. Suitable commercial soil release agents of this kind and SokalanTM type materials, such as BASF C West Germany ) available from Tsukaran TMHP-22.

One type of preferred soil release agent is ethylene terephthalate and polyethylene olefin. It is a copolymer with random blocks of oxide (PEO) and terephthalate. . More specifically, these polymers contain ethylene terephthalate units versus PEO terephthalate units. Ethylene terephthalate with a molar ratio of phthalate units from about 25 nia 5 to about 35:65 consisting of a repeating unit of rate and PEO terephthalate (the PEO terephthalate I/ -t unit contains polyethylene oxide having a molecular weight of about 300 to about 2000 do).

The molecular weight of the polymeric soil release agent ranges from about 25,000 to about 55,000. be. Hayes U.S. Pat. No. 3,959,230, issued May 25, 1976. See the detailed booklet (incorporated here as a reference). 197 disclosing similar copolymers U.S. Pat. No. 3,893.929 to Vasdar, issued July 8, See also (incorporated as a document).

Another preferred polymeric soil release agent is polyoxygenate having an average molecular weight of 300 to 5.000. Polyoxine ethylene terephthalate units derived from ethylene glycol 90-8 10-15 weight units of ethylene terephthalate along with 0 weight fA 96? Contains o is a polyester having repeating units of ethylene terephthalate units, and Ethylene terephthalate units in polymer compounds vs. polyoxyethylene terephthalate The molar ratio with rate units is from 2:1 to 6:1.

An example of this polymer is the commercially available material Zelcon® 5126. (manufactured by DuPont) and Millies (MNease　”) T (manufactured by ICI) Can be mentioned. These polymers and their manufacturing methods were published in Goiselink in October 1987. No. 4,702,857, issued May 27, 2013 (incorporation).

Another preferred polymeric soil release agent is terephthaloyl and oxyalkylene oxide. from the oligomeric ester backbone of the repeat unit and the terminal portion covalently bonded to the backbone. is the sulfonated product of a substantially linear ester oligomer (the soil release The agents are allyl alcohol ethoxylate, dimethyl terephthalate, and 1.2 - derived from propylene diol, the terminal portion of each oligomer averages a total of approximately 1 to about 4 sulfonate groups).

These soil release agents include J. J. Siebel and E.

U.S. Patent No. 4,968,451 issued November 6, 1990 to Gosselinck, P. No. 07/474,709, filed January 29, 1990 It is detailed in the specification (incorporated herein by reference).

Other suitable polymeric soil release agents include Gosselinck et al., December 8, 1987; Ethyl- or methyl-blocked 1 of issued U.S. Pat. No. 4,711,730 , 2-propylene terephthalate-polyoxyethylene terephthalate polyester U.S. Patent No. 4,721,5 issued January 26, 1988 to Tell, Goiselinck et al. No. 80, the anionic end-capped oligomer ester (anionic end-capped is consisting of sulfo-polyethquine groups derived from ethylene glycol (PEG)), formula X-(OCR, CH2) n- (wherein, n is 12 to about 43, and X is C1 to C 4 alkyl or preferably methyl) U.S. Patent No. 4,702.857 issued October 27, 1987 to Ssselink. Specification of block polyester oligomer compounds (see all of these patents here) (incorporated as a reference).

Additional soil-releasing polymers include anionic, especially sulfaroyl end-capped terephthalates. Published October 31, 1989 to Maltonato et al. U.S. Pat. No. 4,877.896 (incorporated herein by reference) soil-releasing polymers. Terephthalate esters are asymmetrically substituted oxy Contains -1,2-alkyleneoxy units.

If utilized, the soil release agent generally comprises about 0.01% of the laundry detergent composition of the present invention. to about 10.0% by weight, preferably about 0.1 to about 5.0% by weight, more preferably about It will account for 0.2 to about 3.0% by weight.

chelating agent The laundry detergent compositions of the present invention may also optionally contain one or more iron/manganese chelating agents. Therefore, it may be contained as a builder auxiliary substance. Such chelating agents include: Aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic Can be selected from the group consisting of aromatic chelating agents and mixtures thereof. by theory Without attempting to limit the benefits of these substances, the benefits are due in part to the production of soluble chelates. This is believed to be due to its exceptional ability to remove iron and manganese ions from cleaning solutions by I get teased.

Aminocarboxylates useful as optional chelating agents in the compositions of the invention include 1 or more (preferably at least 2) units of substructure ) [where M is hydrogen, alkali metal, ammonium or substituted ammonium (e.g. (e.g., ethanolamine), and X is 1 to about 3, preferably 1. can have. Preferably, these aminocarboxylates are about 6 Contains no alkyl or alkenyl groups having more than 1 carbon atoms. use Possible amine carboxylates include ethylenediaminetetraacetate, N-Hydroxyethylethylenediamine triacetate, nitrilotriacetate , ethylenediaminetetrapropionate, triethylenetetrahumine hexa Acetate, diethylenetriamine pentaacetate and ethanol diglycyl salts, their alkali metal salts, ammonium salts, substituted ammonium salts and 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 alkyl phosphonates having more than about 6 carbon atoms. or alkenyl groups. Alkylene groups are shared by substructures. Wear.

In addition, the polyfunctional pupil-converting aromatic chelating agent is Kigumi 5j, @"C. The substance has the general formula (wherein at least one R is -8O3H 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. mono- 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 It will represent from about 0.1 to about 3.0% by weight of such compositions.

Clay stain removal/redeposition prevention agent Clay stain removers/anti-redeposition agents useful in the laundry detergent compositions of the present invention include clay stain removers/anti-redeposition agents. Polyethylene glycol and water-soluble ethylene glycol with anti-removal and redeposition properties. Examples include oxygenated amines.

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 commercially available. Carbowax available from Union Carbide located in Danbury, TN It is sold as (CarboνaX@).

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

Ethoxylated monoamine with or Ethoxylated diamine with (3) Formula Ethoxylated polyamine with (4) General formula and (5) mixtures thereof [wherein A1 is II II 11 1111 -Co-, -0CO-, -QC-, -CNC-.

or -0-; R is H or C1-C4 alkyl or hydroxyalkyl and R1 is C2-C12 alkylene, hydroxyalkylene, alkenyl Ren, arylene or alkali metal, or 2 to about 20 oxyalkylene is a C2-C3 oxyalkylene moiety having an O-N bond. each R2 is C-C4 or hydroxyalkyl, the moiety -L-X is -CH2 -1r is 1 or 2, S is 1 or 2, r+s is 3 or 4): is an ionic group, an anionic group or a mixture thereof; R3 has a substitution site Substituted C-C12 alkyl group, hydroxyalkylene group, alkenylene group, aryl group R4 is C-C alkylene, hydroxyalkyl group, or alkaryl group; Kylene, alkenylene, arylene or alkali run, or 2 to about 20 is a C-03-year-old xyalkylene moiety having an oxyalkylene unit of No 0-0 bond or O-N bond is formed: L is a polyoxyalkylene moiety m and n are parts -(CH2CH20)n- is at least about 50 of the polyoxyalkylene moieties of the monoamine (in such a number as to account for % by weight). in which m is from 0 to about 4 and n is at least about 12: in which m is from 0 to about 3 and n is R1 is C0-C3 alkylene, hydroxy When it is alkylene or alkenylene, at least about 6, R1 is C-03 When it is other than alkylene, hydroxyalkylene or alkenylene, less and in the case of the polyamines and amine polymers, m is from 0 to about 1. 0, n is at least about 3; p is 3 to 8; q is 1 or 0; t is 1 or O, provided that t is 1 when q is 1; W is 1 or O; is 0; x+y+z is at least 2; y+z is at least 2 ] The most preferred soil release/anti-redeposition agent is ethoxylated tetraethylene pentamine. It is. Exemplary ethoxylated amines include Pandelmir, published July 1, 1986; No. 4,597,898 (incorporated herein by reference); Are listed. Another group of preferred clay stain removers/anti-redeposition agents is the 1984 O and Gosselink European Patent Application No. 111°965 published on June 27th It is a cationic compound disclosed in the specification (herein incorporated by reference). can be used Other clay stain removal/redeposition prevention agents include Gosse, published on June 27, 1984. Ethoxylated amine polymerization disclosed in Link European Patent Application No. 111.984 Gososelink European Patent Application No. 112,592 published on July 4, 1984 Zwitter Polymers Disclosed in the Specification: and Conner, U.S.A., published October 22, 1985. Examples include amine oxides disclosed in Patent No. 4,548,744 (which (all of which are incorporated herein by reference).

The most preferred soil release/anti-redeposition agent is ethoxylated tetraethylene pentamine. and polyethylene glycol with a molecular weight of about 4,000 to about 8,000. Ru.

Granular detergent compositions containing such compounds typically contain about 0.01 to about 10.0% by weight; liquid detergent compositions typically contain from about 0.01 to about Contains 5.0% by weight.

Polymer dispersant Polymeric polycarboxylate dispersants are advantageously utilized in the laundry detergent compositions of the present invention. Can be used. These materials can help control calcium and magnesium hardness. Ru.

Like the polycarboxylate mentioned above in the explanation of builders, it can be used as a builder aid. In addition to acting, without trying to limit by theory, these polymers Dispersants may be used in combination with other builders, including low molecular weight polycarboxylates. In addition, by suppressing the crystal growth of inorganic substances, granular dirt veptization , and by preventing re-deposition, the total detergency builder performance can be further improved. Believable.

Polycarboxylate materials that can be used as polymeric polycarboxylate dispersants is the general formula (In the formula, X, Y and Z are 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 contain 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.

High molecular weight polycarboxylate materials of this type are made of suitable unsaturated monomers (preferably acid form) by polymerization or copolymerization. Suitable polymer polycarbo Unsaturated monomeric acids that can be polymerized to form xylate include acrylic acid, Maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, Mesaconic acid, citraconic acid and methylenemalonic acid are mentioned. non-carboxy Containing late groups such as vinyl methyl ether, styrene, ethylene, etc. The presence of monomeric segments in the polymeric polycarboxylate of the present invention indicates that It is preferred if such segments constitute no more than about 40% by weight.

A particularly suitable polymeric polycarboxylate can be derived from acrylic acid. here Such acrylic acid-based polymers that are useful include polymerized acrylic acid It is a water-soluble salt. The average molecular weight of such polymers in acid form is about 2.000 to [0.0 00, more preferably about 4,000 to 7,000, most preferably about 4,000 ~5,000. Examples of such water-soluble salts of acrylic acid polymers include alkali metal salts, ammonium salts and substituted ammonium salts. this species soluble polymers are known substances. This kind of polyacrylate is used in detergent compositions For example, Diehl, U.S. Pat. No. 3, issued March 7, 1967, , 308.067. Reference this patent here Transfer.

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. Examples include water-soluble salts of The average molecular weight of such copolymers in acid form is approximately 5,000 ~100,000, preferably about 6.000-60.000, more preferably about It is 7.000 to 60.000. Acrylate segments in such copolymers The ratio of maleinate segment to maleinate segment is generally from about 30:1 to about 1:1, more preferably or about 10=1 to about 2:1. Such acrylic acid/maleic acid copolymerization Examples of water-soluble salts include alkali metal salts, ammonium salts and substituted salts. Examples include ammonium salts. This type of soluble acrylate/maleate copolymer European Patent Application No. 66915 published on December 15, 1982 (this publication) This is a known substance described in the following article (herein incorporated by reference).

If utilized, the polymeric dispersant generally comprises from 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 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. Ru.

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 include “fluorescent brighteners” "Production and Application of Agents", John Wiley, M. Zaradnisok, New York. ・Published by End Sons (1982) (the disclosure is incorporated here as a bibliography) Disclosed.

Stilbene derivatives include, but are not limited to, bis(triazinyl)amino - Derivatives of stilbene bisacylamino derivatives of stilbene; Oxadiazole derivatives of nistilbene Oxadiazole derivatives of nistilbene 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 reference. Tyrylazole, styrylbenzofuran, styryloxadiazole, styryl triazole, and styryl polyphenyl.

Styryl azole is a styryl azole, as disclosed on page 78 of the Zaladny Nku literature. In addition to rubenzoxazole, styryl imidazole and styryl thiazole Can be subclassified. These three aforementioned subclasses subclass styrylazole. It is understood that this may not necessarily reflect an exhaustive list of subgroups that may be similar. 750 pages (John Willie and Son Inc.) De, 1962) (the disclosure of which is incorporated herein by reference), pp. 741-74. A derivative of dibenzothiophene-5,5-dioxide disclosed on page 9, and 3. 7-diamitudibenzothiophene-2,8-disulfonic acid 5,5 dioxide is mentioned. can be lost.

Other optical brighteners are azoles, which are derivatives of five-membered heterocyclic compounds. this They can be further subcategorized into monoazoles and di7soles. Monoazole and Examples of diazoles and diazoles are disclosed in the Kirk-Othmer literature.

Other optical brighteners include six-membered heterocyclic compounds disclosed in the Kirk-Osmer literature. It is a derivative of 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. mosquito Examples of such miscellaneous drugs are disclosed on pages 93-95 of the Zaladnik article. and 1-hydroxy-3,6,8-pyrenetrisulfonic acid; 2,4-dimetrisulfonic acid; Toxy-1,3,5-triazin-6-yl-pyrene: 4,5-di-phenyl Midacylondisulfonic acid: and pyrazoline-quinoline derivatives.

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" series brighteners.

Other brighteners disclosed in this document include Chinovar, available from Ciba Geigy; Tinopal UNPA, Tinopal CBS and Tinopal 5 8M; Arctic available from Hilton Davis located in Italy. White (Arctic White) CC and Arctic White CWD, 2-(4-styrylphenyl)-2H-naphthol [1,2-d] Triazole; 4,4'-bis-(1,2,3-triazol-2-yl) -stilbene, 4,4'-bis(styryl)bisphenyl; and y-aminoc Marine is an example. Specific examples of these brighteners include 4-methyl-7-mite Thylaminocoumarin: 1,2-bis(benzimidazol-2-yl)-ethyle N: 1,3-diphenylwarazolin. 2.5-bis(benzoxazole-2- yl)-thiophene: 2-styryl-naphtho-[1,2-d)-oxazole: and 2-(stilben-4-yl)-2H-naphtho[:1.2-d])-ly Examples include azoles.

Other optical brighteners include the United States Patent Publication, published by Hamilton on February 29, 1972. No. 3,646,015 (the disclosure of which is incorporated herein by reference) The following are listed.

If utilized, the optical brightener generally comprises about 0.05 to about 2.0% of the laundry detergent composition. It will account for 0% by weight, preferably from about 0.1 to about 1.0%.

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 incorporation of such substances (hereinafter "foam suppressants") may be desirable as they can Foam control compared detergent compositions in combination with polyhydroxy fatty acid amide surfactants. Particular importance may be placed upon the inclusion of high foaming surfactants. Foam suppression is It 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 be important.

Various materials may be used as suds suppressants. Foam suppressants are well known to those skilled in the art.

They are generally, for example, Kirk-Othmer Encyclopedi a　Chemical Technology.

3rd Edition, Volume 7, Pages 430-447 (John Willie End Φ Sands ・Incorporated, 1979). one with a particular interest The category of foam suppressants includes monocarboxylic fatty acids and their soluble salts. Ru. These substances are listed in the U.S. publication dated September 27, 1960 by Unyin Sentong Yong. National Patent No. 2.954,347 (this patent is incorporated herein by reference) being discussed. Monocarboxylic fatty acids and their use as foam suppressants Salts typically contain 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms. It has a locarpil chain. Suitable salts include alkali metal salts, such as sodium ammonium salts, potassium salts, and lithium salts, and ammonium salts and alkanoyl salts. Examples include ammonium salts. These substances are in the preferred category for detergent compositions. Lee's foam suppressant.

The laundry detergent compositions of the present invention may also contain non-surfactant suds suppressants. this Examples include high molecular weight hydrocarbons, such as paraffins, fatty acid esters, etc. (e.g. fatty acid triglycerides), fatty acid esters of -hydric alcohols, aliphatic Examples include C18-C40 ketones (eg, stearone). with other foam suppressants N-alkylated aminotriazines, such as primary or or as a product of 2 or 3 moles of a secondary amine and cyanuric acid chloride. From realkyl melamine to hexaalkyl melamine or dialkyl diamide From chlorotriazine to tetraalkyldiamine chlortriazine, ren oxide, and monostearyl phosphate, e.g. Alcohol phosphate esters and monostearyl dialkali metals (e.g. sodium um, potassium, lithium) phosphates and phosphoric acid esters.

Hydrocarbons such as paraffins and haloparaffins 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 about 5°C and a minimum boiling point of about 110°C or above (atmospheric pressure). Also, wax charcoal It is known to utilize hydrogen hydrides, preferably those having a melting point below about 100°C. Ru. Hydrocarbons constitute a preferred category of suds suppressants for detergent compositions. hydrocarbon water Foam suppressants are described, for example, in U.S. Pat. No. 265.779 (incorporated herein by reference). Carbonization Hydrogen thus includes aliphatic, cycloaliphatic, aromatic and Mention may be made of heterocyclic saturated or unsaturated hydrocarbons. Used in this foam suppressor discussion The term "paraffin" shall encompass mixtures of true paraffins and cyclic hydrocarbons. I try to sleep.

Another preferred category of non-surfactant suds suppressors consists of silicone suds suppressants.

This category includes polyorganosiloxane oils such as polydimethylsiloxane. , dispersions or emulsions of polyorganosiloxane oils or resins, and poly(a) Combination of xane oil and silica particles (polyorganosiloxane is chemisorbed onto silica) It may be used as an adhesive (attached or melted). Silicone foam suppressants are well known in the art. For example, U.S. Pat. No. 4,265, issued May 5, 1981 to Gandolho et al. No. 779 and published by M.S. Starch on February 7, 1990 in Europe. Patent Application Box No. 89307851.9 (both incorporated herein by reference) ) is disclosed.

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 ．． No. 455.839.

Mixtures of silicone and inflated silica can be used, for example, in German patent application DO8 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. No. 4,652 to Panginski 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; (ii) (i) from about 5 to about 50 parts per 100 parts by weight of (CH) 510112; (CH)5iO with a ratio of units to St02 units of 6:1 to about 1.2:1 Siloxane resin consisting of 1/2 unit and S iO2: and N11) (i) 10 from about 1 to about 20 parts solid silica gel per 0 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 level" refers to the amount of foam control that the formulator of the composition will use to control foam to the desired degree. This means that you can choose the amount of foaming agent. 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 high An amount of antifoam agent used to achieve the desired foam control than that of a low-foaming surfactant 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 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 polyorganosiloxane It includes silica, which may be used in conjunction with silica, as well as auxiliary substances, which may be utilized. monoste Allyl phosphate is generally utilized in an amount of about 0.1% to about 2% by weight of the composition. Ru.

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 lost.

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 pH of about 6.5 to about 11, preferably about 7.5 to about 10.5. will be prescribed. Liquid product formulations preferably have a po of about 7°5 to about 9.5 , more preferably about 7.5 to about 9.0. Control pH to recommended usage levels Techniques for this include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art. It is well known.

Additionally, the present invention provides a method for treating substrates with water, water-miscible solvents (e.g., primary and secondary alcohols), Detergent compositions containing the nonionic surfactant system of the invention in the presence of a solvent such as (polyhydroxy fatty acid amide vs. additional surfactant in nonionic surfactant systems) the fiber by contacting it with a sex agent (the weight ratio of the sexing agent is from about 1:5 to about 5:1); A method for cleaning substrates such as fabrics, hard surfaces, skin, etc. is provided. stirring Agitation is preferably provided to enhance cleaning. to give agitation Suitable means include manual rubbing (preferably by brush) or other methods. cleaning equipment, automatic washing machines, automatic dishwashers, etc.

experiment 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 It consists of a 3g 4-day flask equipped with a thermometer and a motor-driven paddle stirrer. Hula The other two ports on the Sco (which is important for very rapid methanol generation), which requires efficiency. connected to a collection cooler and a vacuum outlet. The latter is a nitrogen bleed/vacuum gate. and then to an aspirator and a trap. reaction mixture Variable transformer temperature controller used to heat things [Varia c) 500W heating mantle with J) further controls the temperature of the reaction mixture. placed on the love-jack so that it can be easily raised and lowered to

N-Methylglucamine (195g, 1-0 mol, Aldrich, M4700- 0) and methyl laurate (Brocter & Gamble CE1270. 220.9 g, 1.0 mol) into the flask. solid/liquid mixture under stirring Prepare the melt by heating under nitrogen sweep (approximately 25 minutes). Melting temperature reaches 145℃ When the catalyst (anhydrous powdered sodium carbonate, 10.5 g, 0.1 mol, J, T , Baker). Stop nitrogen sweep, aspirator and nitrogen bleed to provide a vacuum of 5 inches (5/31 atm) Hg. From this point on, the reaction Temperature can be adjusted by adjusting the barrier and/or by raising or lowering the mantle. The temperature is maintained at 150°C by

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

Methanol is distilled until the rate decreases. Adjust the vacuum to about 10 inches H A vacuum of g (10/31 atm) is applied. Increase the vacuum approximately as follows (in a given minute) inch Hg): 3 to 10 to 20.10 to 25° from the start of methanol generation After 11 minutes, heating and stirring are discontinued (some foaming occurs at the same time). the 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).

Example The following examples of liquid detergent compositions are prepared according to the instructions set forth below.

Surfactant paste is made by first combining the desired surfactant with water and alcohol. Prepare by The surfactant contained in this surfactant paste Examples include the polyhydroxy fatty acid amide of the present invention. Ideally, surface activity The sex agent paste should be pumpable at room or elevated temperatures.

Separately, non-aqueous solvents, surfactant pastes or solutions, molten fatty acids, polycarboxylic Aqueous solution of quinlate builder and other salts, aqueous ethoxylated tetraethylene penta Combine mineral, buffer, caustic, and water in a mixing vessel. Citric acid aqueous solution or The pH is adjusted to a level of about 8.5 using aqueous sodium hydroxide solution. Adjust the pH After knotting, final ingredients such as stain release agents, enzymes, colorants and fragrances are added.

The resulting mixture is stirred until a single phase composition is obtained.

Examples 1-2 Examples of these include polyhydroxy fatty acid amide/additional nonionic surfactant systems. The present invention relates to a heavy duty liquid detergent composition having the following properties.

Example breeding (weight%) Ingredient 12 C alkyl N-methylglucamide 10.0015.0012-14 C alkyl ethoxylate (average 15.00 to, o.

12-13 6.5) Coco fatty acid 3.00 3.00 Dodenrutrimethylammonium chloride 0.18 0.18 Citric acid 1.0 OL, 00 Monoethanolamine 2.50 2.50 Ethoxylated Tetraethylene Pentami 1.50 1.50 Protease (IAU/g) 0.53 0.53 Water and miscellaneous ingredients (solvent, stain-releasing polymer, remainder (100% fragrance, dye, etc.) Runo Examples 3-7 These examples include polyhydroxy fatty acid amide in combination with anionic surfactants. Heavy-duty liquid detergent compositions containing additional non-ionic surfactant systems shows.

Example N [L (wt%) Ingredients 34567 C alkyl N-methylglucamide 4.20 5.62 18.88 B, 25 5.0012-14 CI2-13 alkyl ethoxylate (average 6.5) 3.40 2.50 2 ．． 50 7.50 2.50 CI5-16 Sodium baraphin sulfonate - --11,2510,00 tartrate monosuccinate/ Tartrate disuccinate 3.40 - - Coco fatty acid 3.00 3.00 3.00 3.00 3.00 Dodecyltrimethylammonium chloride Lido 0.51 0.18 0.18 0.18 0.18 Citric acid 3.40 1,00 1.00 1.00 1.00 Monoethanolamine 1.05 2 ．． 50 2.50 2,50 2.50 Ethoxylated Tetraethylene Pentamine 1.50 1,50 1.50 1.50 l, 50 brightener 0.11 0.1 1 0.11 - - Protease (1, AU/g) 0.80 0,51 0 ．． 51 0.53 0.53 amylase (325 MAmU) -0,240,2 4--Propanediol 4.5 [14,004,00--Ethanol 1.1 g 3.00 3.00 - -NaOH (pH adjustment) 3.00 1.50 1.50 - - Calcium formate 0.29 0.119 0.119 - - Sodium formate 0.34 0.34 0J4 - -Toluenesulfone Sodium sulfonate 2.91 2.00 2.00 - - Water and miscellaneous components (Solvent, stain-releasing polymer, fragrance, dye, etc.) Remaining portion (100%) Examples 8 to 1 0 Examples of these are polyhydroxy fatty acid amides in combination with anionic surfactants. / High builder heavy duty liquid containing additional nonionic surfactant system 1 shows a body cleansing composition.

brain 11%) Ingredients 8 9 10 C 12 ++ t47 Ruki/L, Nyt Chirgu/1, l’7 Mido 3.1 0 3.10 4.10C12-13 alkyl ethoxylate (average 6.5) 9.30 3.10 2.10C14-15 alkyl ethoxy (average 2, 25 ) Sulfate - 3.00 4.00015-16 Sodium baraffin sulfonate TolJ'7-3.10-C11.8 Linear alkylbenzene sulfonate - - 3.10 Tartrate monosuccinate/ Tartrate disuccinate - 10.00 - Citric acid - 10.00 2 0.00 Oxydisuccinate 20.00 - Polyacrylate (molecular weight 4 5 0 0) 1.50 1.50 1.50 Monoethanolamine 1.0 0 1.00 t. o.

Brightener 0.11 0.11 0.11 Maxacal 0.21 0.21 0. 21 Propanediol 5.50 5,50 5.50 Ethanol 0.87 G. 87 0.87N a O H (pHNJ) 1.39 1.39 1J 9 Calcium formate 0.21 0.21 0.21 Sodium formate 0.34 0.34 0.34 Sodium toluenesulfonate/ Sodium cumene sulfonate 5.00 5.00 5.00 Water and miscellaneous ingredients ( Solvents, stain-releasing polymers, fragrances, dyes, etc.) Remaining portion (100%) Examples 11-1 3 Contains alkyl polysaccharide as an additional nonionic surfactant within the nonionic surfactant system Examples of heavy duty liquid detergent compositions include: These examples are , a wash temperature of less than about 50° C. and about 2,000 ppm by weight of the wash water. The compositions are prepared in the same manner as the compositions of Examples 1-10.

Example Nα (weight%) Ingredients 11 12 13 C12-14 alkyl N-methylglucamide 15.0 10.0 8. OC1 2-14 alkyl polyglycoside (average 1.4) 10.0 10.0 -C I4-15 alkyl ethoxylate (average 7.0) - - 10.0C12~ 14 alkyl ethoxylate (average 7.0) -5.0-dodecyldimethyl Amine oxide --4. OCl. ~14 fatty acids 3.0 3.0-dodecyl Trimethylammonium chloride 0.2 0.2-citalodimethylammo Nium chloride --3.6 Citric acid 1.0 1.0 -- Monoethanolamine 2.5 2.5 -Ethoxylated tetraethylene pentami 1.5 1.5 1.5 Optional components and solvent Remainder (100%) Example 1 4-15 Heavy detergent containing polyhydroxy fatty acid amide/additional non-ionic surfactant system The following examples of utility-granular detergent compositions. These compositions are suitable for temperatures below about 50-60°C. and a temperature of about 800 pp11 (based on the weight of washing water). these The composition includes an amide, an alkyl ethoxylate, a brightener, and about 20% water by weight. Mix a thick paste with an Eirich R V 02 mixer. Prepare by mixing with the required dry ingredients in any high-shear mixer. grain Other dry optional ingredients in solid or powdered form are made into a thick paste in a high shear mixer. and may be mixed with the required dry ingredients or subsequently processed in a rotating mixing drum. You can also

Example k (wt%) Ingredients 14 15 C12-14 alkyl N-methylglucamide 8.0 10. OC Alkyrie Toxilate 12.0 10.012~L5 (Average 7.0) Zeolite A 30.0 15.0 Sodium citrate - 30.0 Sodium carbonate 30.0 20.0 Brightener 1.0 1.0 Optional ingredients 10.4 5.9 Residual water 8.8 8.1 100, 0 100.0 Example 1 Another method for producing the polyhydroxy fatty acid amide used here is as follows. fat Acid methyl ester (source: Brocturnaendo Gamble methyl ester CE 1270) 84.87 g and N-methyl-D-glucamine (source: Aldrich-Ke. Micalya Company M4700-0) 75g and sodium methoxide (source: Al Dolisochi Chemical Company 16,499-2) 1.04g and methylal A reaction mixture consisting of 68.51 g of coal is used. The reaction vessel is a dry tube, a cold Equipped with standard reflux equipment including evaporator and stir bar. In this method, N- Combine the methylglucamine with methanol under argon with stirring and mix well. Start heating (stir bar: reflux). After 15-20 minutes, the solution reaches the desired temperature. When the ester and sodium methoxide catalyst are added. Collect samples regularly to monitor the course of the reaction, and the solution was found to be completely clear after 63.5 minutes. I can't stand it. The reaction is in fact judged to be almost complete at this point. reaction The mixture is kept under reflux for 4 hours. After methanol removal, the recovered crude product was It is 156.16g. After vacuum drying and purification, 06.92 g of purified product] The entire yield is collected. However, regularity throughout the course of the reaction Yield is not calculated on this basis as sampling makes the overall yield value meaningless . The reaction is carried out at reactant concentrations of 80% and 90% for up to 6 hours to produce product. 0% (with very little by-product formation).

The following, without seeking to limit the invention, include polyhydroxy fatty acid amides: Techniques that can be considered by formulators in the preparation of various detergent compositions using It is merely intended to further illustrate additional aspects of the logic.

Polyhydroxy fatty acid amide can be used under highly basic or highly acidic conditions due to the amide bond. It will be readily appreciated that it is susceptible to some instability under conditions. some Although degradation is tolerable, these materials cannot be exposed to pH higher than about 11 for unreasonably long periods of time. Preferably, the pH is higher than 10. It is also preferred not to subject it to a pl of less than about 3.

The final product pH (liquid) is typically between 7.0 and 9.0.

During the production of polyhydroxy fatty acid amides, typically It may be necessary to at least partially neutralize the base catalyst used for this purpose. squid Acids can also be used for this purpose, but detergent formulators may It is simply convenient to use acids that provide useful and desirable anions when They will recognize that this is a serious matter. For example, citric acid is used for neutralizing purposes The citrate ions (about 1%) that can and are obtained are about 40% polyhydroxy fat. Allows the acid amide slurry to remain with the slurry and be added to a later manufacturing step in the entire detergent formulation. supply the pump. Substances in acid form, e.g. oxydisuccinate, nitrilotria acetate, ethylenediaminetetraacetate, tartrate/succinate, etc. can be used similarly.

Polyhydroxy derived from coconut alkyl fatty acids (mainly 012-C14) Siamic acid amides are more flexible than their tallow alkyl (mainly C16-Cl8) equivalents. Soluble.

Therefore, C1°-C14 materials are slightly easier to formulate into liquid compositions. and is soluble in cold water wash baths. However, CI6 to C18 substances also This is particularly useful in situations where warm to hot wash water is used. Fact, C- C substances may be better detergent surfactants than their C1°-C14 equivalents. Ru. Therefore, formulators must specify the specific polyhydroxy fatty acids for use in a given formulation. When choosing an amide, you may want to balance ease of manufacture vs. performance. .

In addition, the solubility of polyhydroxy fatty acid amide is determined by the unsaturation point in the fatty acid moiety and This may be enhanced by having/or chain branch points.

Thus, polyhydroxy fatty acid amines derived from oleic acid and isostearic acid Substances such as midos are more soluble than their n-alkyl equivalents.

Similarly, the solubility of polyhydroxy fatty acid amides produced from trisaccharides, trisaccharides, etc. , typically will be greater than the solubility of monosaccharide-derived equivalents. This high solubility Certain aids can be had in formulating liquid compositions.

Furthermore, polyhydroxy fatty acid amide whose polyhydroxy group is derived from maltose is , used in combination with regular alkylbenzenesulfonate (rLAsJ) surfactants It sometimes seems to work particularly well as a detergent. I don't try to limit it by theory, but , polyhydroxy fatty acid amide derived from higher sugars such as maltose and LAS. The combination produces a substantial and unexpected decrease in interfacial tension in aqueous media, which Therefore, it seems to improve the net cleaning performance (polyhydroxy fat derived from maltose) The production of fatty acid amides will be described later).

Polyhydroxy fatty acid amide can not only be produced from refined sugar, but also by hydrolysis. Starch, e.g. corn starch, potato starch, or by formulator Also from starches derived from other favorable plants that naturally contain the desired monosaccharides, trisaccharides, etc. Can be manufactured. This has particular importance from an economic point of view. (te, ``high guru'' ``coast'' corn syrup, ``high maltose'' corn syrup, etc. It can be used economically. Delignified hydrolyzed cellulose pulp is also It can provide a raw material source for sialic acid amide.

As mentioned above, polyhydroxides derived from higher sugars such as maltose and lactose Syria fatty acid amides are more soluble than their glucose equivalents. Furthermore, more Soluble polyhydroxy fatty acid amides can be prepared by various treatments of their less soluble equivalents. It seems that it can promote solubilization. Therefore, prescribers, e.g. - You may decide to use ingredients that include scone syrup, but with a small amount of malt Optionally, syrups containing a certain amount of sugar (eg, 1% or more) may be selected. polyhydroxy The resulting mixture of fatty acids is generally a "pure" glucose-derived polyhydroxy Shows more favorable solubility over a wide range of temperatures and concentrations than fatty acid amides There will be. Thus, the economics of using sugar mixtures rather than pure sugar reactants In addition to their physical benefits, polyhydroxy fatty acid amides made from mixed sugars offer performance and/or may offer very substantial advantages in terms of ease of formulation. but However, in some cases, a slight loss in grease removal performance (dishwashing) is approximately 25 % of fatty acid maltamide and a slight loss of foaming properties. Loss may be observed in amounts greater than about 33% (said percentage is the amount of Maltese in the mixture). Mido-derived polyhydroxy fatty acid amide vS glucose-derived polyhydroxy fatty acid % of amide). This can vary slightly depending on the chain length of the fatty acid moiety. typical In general, and formulators who decide to use such mixtures, monosaccharides (e.g. (e.g., glucose) to trisaccharides/higher sugars (e.g., maltose) from about 4:1 to about It is advantageous to choose a polyhydroxy fatty acid amide mixture containing 99=1 You can find out things.

Preferred acyclic polyhydroxy from fatty esters and N-alkyl polyols The fatty acid amide is produced in an alcoholic solvent at a temperature of about 30°C to 90°C, preferably about 5°C. It can be carried out at a temperature of 0°C to 80°C. Glycol solvents are not used in finished detergent formulations. It is not necessary to completely remove the reaction product before use, e.g. The drug formulator may perform such a process in a 1,2-propylene glycol solvent. It has now been confirmed that it is convenient.

Similarly, for example, formulators of solid detergent compositions, typically granular detergent compositions, Ethoxylation of processes (EO3-8) Ethoxylation of C12-C14 alcohols, etc. Alcohol, for example also available as Neodol 23EO6,5 (shell) We have found it convenient to carry out the process at 30°C to 90°C in a solvent consisting of can be done. When such ethoxylates are used, they contain substantial amounts of Contains no non-ethoxylated alcohols and most preferably contains substantial amounts of monoethoxylated alcohols. Preferably, it does not contain alcohol (designation "T").

Although the method for producing the polyhydroxy fatty acid amide itself does not form part of the present invention, The manufacturer also accepts other methods of synthesizing polyhydroxy fatty acid amides, such as those described below. can be done.

Typically, the industry for producing the preferred acyclic polyhydroxy fatty acid amides The scale reaction sequence is Step 1: After forming the adduct of N-alkylamine and sugar N-A from the desired sugar or sugar mixture by reaction with hydrogen in the presence of a catalyst. After producing the alkyl polyhydroxyamine derivative, Step 2: the polyhydroxy From reacting an amine preferably with a fatty acid ester to form an amide bond Become. Various N-alkyl polyhydroxyamines useful in step 2 of the reaction sequence include: Although it can be manufactured by various methods disclosed in the art, the following methods are convenient and Use economical sugar syrup as raw material. When using such syrup ingredients For best results, the manufacturer recommends that the color be completely pale or preferably almost colorless. It should be understood that one should choose a syrup that is similar in color (“water-white”).

Production of N-alkyl polyhydroxyamines from plant-derived sugar syrups (2) Adduct formation - The following is a standard method. In this standard method, gar 420 g of approximately 55% glucose solution with donor color less than 1 (corn syrup - Approximately 231 g of glucose (approximately 1.28 mol) was mixed with approximately 50% methylamine (59.5 g - 1.92 mol) aqueous solution. Methylamine ( M　M　A　) Purge the solution, blanket with N2, and cool to below about 10°C.

Purge the corn syrup and blanket with N2 at a temperature of about 10-20°C. Ko Slowly add the syrup to the MMA solution at the indicated reaction temperature. Gar Measure the donor color at the approximate time indicated (in minutes).

As can be seen from the above data, the Gardner color of the adducts increases at temperatures above about 30°C. It gets much worse as you go up to higher temperatures, and at about 50°C, the adducts The time with donor color less than 7 is only about 30 minutes. Longer reactions and/or or hold time, the temperature should be less than about 20°C. garda - Color is less than about 7, preferably less than about 4 for good color glucamine Should.

When low temperatures are used to form the adduct, a substantial equilibrium concentration of the adduct is reached. The time for decontamination is reduced by using a higher ratio of amine to sugar. Attention For a molar ratio of amine to sugar of 1.5+1, equilibrium is approximately Achieved in 2 hours. At a molar ratio of 1.2:1, under the same conditions, the time is less. At least about 3 hours. For good color, the amine:sugar ratio and reaction temperature In combination with reaction time, substantially equilibrium conversion, e.g., about 90% or more for sugar , more preferably about 95% or more, even more preferably about 99% or more, and the adduct. achieve a color that is less than about 7 in some cases, preferably less than about 4, more preferably less than about 1. chosen to do.

Using the process with a reaction temperature below about 20° C. and using different guards as indicated Using corn syrup that has a neutral color, the MMA adduct color (substantially at equilibrium (at least after reaching about 2 hours) seems to be the point.

Corn syrup LLLL+000+ Addition 3 415 7/8 7/it l 2 1 As can be seen from the above Firstly, the starting sugar material is adjusted so that it consistently has adducts that are acceptable. It must be colorless. When the sugar has a Gardner color of about 1, the adduct is Sometimes acceptable, sometimes unacceptable.

When the Gardner color is greater than 1, the resulting adduct is unacceptable. The beginning of sugar The better the initial color, the better the color of the adduct.

■, Hydrogen reaction - adducts from the above with a Gardner color of 1 or less are as follows: Hydrogenate according to the method.

Approximately 539 g of adduct in water and United C atalyst) G 49 B Ni catalyst approximately 23.1 g in 1 g of autoclay purge twice with 200 psi H2 at about 20°C. Approximately N2 pressure Increase to 1400 psi and increase temperature to approximately 50°C. Then increase the pressure to about 160 Increase to 0 psig and maintain temperature at about 50-55°C for about 3 hours. The product is At this point, about 95% hydrogen is added. The temperature is then raised to about 85°C for about 30 minutes, The reaction mixture is decanted and the catalyst is filtered off. The product is obtained by removing water and MMA by evaporation. After removal, it is about 95% N-methylglucamine, a white powder.

Repeat the above method using approximately 23.1 g of Raney Ni catalyst with the following changes: . Wash the catalyst three times and reduce the reactor (catalyst is in the reactor) to 200 psigH2 The reactor was pressurized with N2 at 1600 psig for 2 hours and the pressure The power is released after 1 hour and the reactor is repressurized to 1600 psig. Then add The reactor was pumped to the reactor at 200 psig and 20°C, and the reactor was heated as described above. Purge with 200 psig H2, etc.

The resulting product in each case is greater than about 95% N-methylglucamine. less than about 10 ppm Ni relative to glucamine; and less than about 2 Gardner; has a solution color of

Crude N-methylglucamine is color stable to 140°C for short exposure times.

Low sugar content (less than about 5%, preferably less than about 1%) and good color (Gardner good adhesion (less than about 7, preferably less than about 4, more preferably less than about 1) Having things is important.

In another reaction, the adduct is produced from about 159 g of about 50% methylamine in water. Prepare by venting, purging and shielding with N2 at about 10-20°C. Approximately 70% About 330 g of syrup (water - almost white) was degassed with N2 at about 50°C, Add slowly to the methylamine solution at a temperature below about 20°C. Approximately 3 liters of solution Mix for 0 minutes to give approximately 95% adduct, which is a very pale yellow solution.

Approximately 190 g of adduct in water and United Catalyst G49B Ni catalyst Add about 9g to a 200ml autoclave and purify with N2 three times at about 20℃. page.

Increase the N2 pressure to about 200 psi and the temperature to about 50°C. Pressure 250 psi and maintain temperature at about 50-55°C for about 3 hours. The product is then about 95% hydrogenated at the point, and then raised to a temperature of about 85° C. for about 30 minutes, After removal of water by evaporation, the product is approximately 95% N-methylglucamine, a white powder. be.

N2 pressure is approximately 1000 ps/g to minimize Ni content in glucamine. It is also important to minimize contact between the adduct and the catalyst when the . The nickel content in N-methylglucamine in this reaction is the same as that in the previous reaction. approximately 100 ppm compared to less than 10 ppm.

The following reaction with N2 is performed for direct comparison of reaction temperature effects.

Typical methods similar to those described above can be used to generate adducts and carry out hydrogen reactions at various temperatures. A 200 ml autoclave reactor is used according to a standard procedure.

The adduct used to produce glucamine is approximately 55% glucose (corn syrup). approx. 420 g (1'/l) solution.

course 231g; 1.28mol) (solution is 99DE corn syrup from Kargil) The solution has a color less than 1) and 50% methyl Approximately 119g of Ruamine (MMA59.5g; 1.92mol) (Air Products) (manufactured by).

The reaction method is as follows.

1. Add approximately 119 g of 50% methylamine solution to the 2N purged reactor. , shielded with N2 and cooled to below about 10°C.

2. Degas the 55% corn syrup solution with N2 at 10-20℃ and/or or purge to remove oxygen from the solution.

3. Slowly add the corn syrup solution to the methylamine solution and bring the temperature to approx. Keep below ℃.

4. Once all the corn syrup has been added, stir for about 1-2 hours.

The adducts are either used in hydrogen reactions immediately after production or are dehydrated to prevent further degradation. Store at room temperature.

The glucamine adduct hydrogen reaction is as follows.

1. Adduct (color less than Gardner 1) about 134g and G49B Ni about 5. Add 8g to 200ml autoclave.

2. Purge the reaction mixture twice with about 200 ps IH2 at about 20-30 °C. Ru.

3. Pressurize to about 400 psi with H2 and raise the temperature to about 50°C.

4. Increase the pressure to about 500 psi and react for about 3 hours. Temperature about 50-5 Keep at 5℃. Take sample 1.

5. Raise the temperature to about 85°C for about 30 minutes.

6. Decant the Ni catalyst and filter it out. Take sample 2.

The conditions for the isothermal reaction are as follows.

1. Add 134 g of additive and about 5.8 g of G49B Ni to 200 ml of autoclave. Add to toclave.

2. Purge twice with approximately 200 psi H2 at low temperature.

3. Pressurize to about 400 psi with H2 and raise the temperature to about 50°C.

4. Increase the pressure to about 500 psi and react for about 3.5 hours. pointed out the temperature temperature.

5. Decant the Ni catalyst and filter it out. Sample 3 is about 50-55°C; sample Sample 4 is for the case of about 75°C; Sample 5 is for the case of about 85°C (for the reaction at about 85°C) (about 45 minutes).

All runs gave similar purity of N-methylglucamine (approximately 94%): run The Gardner color is similar to that immediately after reaction, but only the two-step heat treatment provides good color stability. A run at 85°C gives a slight color immediately after the reaction.

Example 17 N-methylmaltamine tallow (cured) for use in detergent compositions according to the invention ) The method for producing fatty acid amide is as follows.

Step 1 - Reactant: Maltose monohydrate (Aldrich, lot O1318KW ); Methylamine (40% by weight in water) (Aldrich, lot 03325T M); Raney nickel, 50% slurry (UAD52-73D, Aldrich, lot 12921LW).

Add the reactants to the glass liner (250 g maltose.

428 g of methylamine solution, 100 g of catalyst slurry - 50 g of Ranney Ni), 3 Place the autoclave in a rocking autoclave with nitrogen (3 x 500p). sig) and hydrogen (2X 500 psig) and store the chamber under H2. Temperatures ranging from 28° C. to 50° C. are rocked over the weekend. Sift the crude reaction mixture. Filter twice through a glass microfiber filter with licage gel plugs. filtrate Concentrate into a viscous substance. The final trace of water dissolves the viscous mass in methanol, then Azeotrop by removing methanol/water on a rotary evaporator. High final drying Perform under vacuum.

Dissolve the crude product in refluxing methanol, filter, cool and recrystallize, filter, filtrate. The cake is dried under vacuum at 35°C. This is cut #1. The precipitation Concentrate the filtrate and store it in the refrigerator overnight until it begins to form.

Filter the solid and dry under vacuum. This is cut #2. Halve the filtrate again volume and achieve recrystallization. Almost no precipitate forms. small amount of ethano Add the solution and leave the solution in the freezer over the weekend.

Filter the solid material and dry under vacuum. The combined solid is used in step 2 of total synthesis. N-methylmaltamine.

Step 2 - Reactant 2N-methylmaltamine (from step 1): Cured tallow methyl ester Sodium methoxide (25% in methanol); Anhydrous methanol (solvent) ; Amine:ester molar ratio 1:1: initial crystal amount 10 mol% (w/r maltamine ), increased to 20 mol%; solvent amount 50% (weight ff1).

In a sealed bottle, heat 20.36 g of tallow methyl ester to melting point. (water bath), placed in a 250 ml 30 round bottom flask under mechanical stirring. flask to about 70° C. to prevent the ester from coagulating.

Separately, 25.0 g of N-methylmaltamine was combined with 45.36 g of methanol; Add the resulting slurry to the tallow ester with good mixing. 2 in methanol Add 1.51 g of 5% sodium methoxide. After 4 hours, the reaction mixture was clear. , therefore an additional 10 mol % of crystals (20 mol % total) was added and the reaction started. It is allowed to continue overnight (approximately 68° C.), after which time the mixture is clear. Then, the reaction tube Fix the lasco for distillation. Increase temperature to 110°C. Distillation at atmospheric pressure Continue for 60 minutes.

High vacuum distillation is then started and continued for 14 minutes, at which point the product is very thick.

The product is allowed to remain in the reaction flask for 60 minutes at 110°C (external temperature). Frass the product Scrape it off and rub it in ethyl ether over the weekend.

The ether was removed on a rotary evaporator and the product was stored in an oven overnight and reduced to a powder. Smash. Remove remaining N-methylmaltamine from the product using silica gel. leave

Charge the silica gel slurry in 100% methanol to the funnel and add 100% methanol to the funnel. Wash several times with water. A concentrated sample of the product (2 in 100 ml of 100% methanol) 0 g) onto silica gel and several times using vacuum and several methanol washes. Elute twice. The collected eluate is evaporated to dryness (rotary evaporator). remaining taroe The stellate is removed by trituration in ethyl acetate overnight, then filtered. filtration case Vacuum dry the cube overnight. The product is tallow alkyl N-methyl maltamide. Ru.

In another form, step 1 of the reaction sequence comprises glucose or glucose. Use commercially available corn syrup, typically a mixture with 5% or more maltose You can do it by doing this. The obtained polyhydroxy fatty acid amide and mixture are Any of the detergent compositions of the invention can be used.

In yet another embodiment, step 2 of the reaction sequence comprises 1,2-propylene glyco It can be carried out in mol or neodol. At the discretion of the prescriber, propylene Recall or Neodol is a reactive product that is used to formulate detergent compositions. It is not necessary to remove it from the composition. Again, per the prescriber's request, methoxy The cid catalyst can be neutralized by citric acid to give sodium citrate; Sodium enoate can remain in the polyhydroxy fatty acid amide.

Depending on the wishes of the formulator, the compositions can contain more or less of each type of antifoam agent. typical Typically, in the case of dishwashing, high foaming is desirable and therefore antifoaming agents are not used. Probably not. For fabric washing in top-loading washers, some control of foam A significant degree of foam control may be desirable and in the case of front charging machines. There are some good things. Various antifoam agents are known in the art and for use herein. can be habitually selected. In fact, antifoam agents or mixtures of antifoam agents for certain detergent compositions The choice of products depends on the presence and amount of polyhydroxy fatty acid amide used therein. It will also depend on the other surfactants present in the formulation. death However, when used in combination with polyhydroxy fatty acid amide, various silicones Foam-based antifoam agents appear to be more efficient than various other types of antifoam agents. (i.e. smaller amounts can be used). X2-3419 and Q2-3302 (da Silicone antifoam agents available as U.S. Corning are particularly useful here. .

Formulators of fabric laundry compositions that can advantageously contain soil release agents have a variety of existing materials to choose from. (e.g., U.S. Pat. No. 3,962,152, No. 4,1) No. 16゜885, No. 4,238,531, No. 4゜702.857 Specification No. 4.721,580 and Specification No. 4,877.896 reference). Additional fouling release materials useful herein include C-C4 alkoxy-terminated polymers. Liethoxy unit source (e.g. CH[OCHCH2) 160H), terephthalo yl unit source (e.g. dimethyl terephthalate): poly(oxyethylene) oxide cy unit [(e.g. polyethylene glycol 1500); oxyisobrobylene a source of oxy units (e.g. 1,2-propylene glycol); and oxyethylene Non-ionic oxidation of reaction mixtures containing a source of oxygen units (e.g. ethylene glycol) Ligomer esterification products (especially oxyethyleneoxy units vs. oxyisopropylene) The molar ratio of lenoxy units is at least about 0.5:1). Kaka Non-ionic soil release agents have the general formula (wherein R is lower (e.g. C-C4) alkyl, especially methyl: X and each y is an integer from about 6 to about 100; m is an integer from about 0.75 to about 30; n is an integer from about 0.25 to about 20; R2 is oxyethyleneoxy vs. H and CH3 to give a molar ratio of sobrobyleneoxy of at least about 5:1. is a mixture of both) has.

Another preferred class of soil release agents useful herein is that such agents are of the HOROH type (formula R is propylene or higher alkyl) Other than the conditions described in U.S. Pat. No. 4,877,896, It has a main type. Thus, the soil release agent of U.S. Pat. No. 4,877,896 is , for example, dimethyl terephthalate, ethylene glycol, and 1,2-propylene Can consist of the reaction product of glycol and 3-sodiosulfobenzoic acid On the other hand, these additional soil release agents include, for example, dimethyl terephthalate and ethylene. glycol, 5-sodiosulfoisophthalate, and 3-sodiosulfoisophthalate It can consist of a reaction product with an acid. Such agents should not be used in granular laundry detergents. preferred for

Formulators should include non-berborate bleaches especially in heavy-duty granular laundry detergents. It may be determined that it is advantageous to Various peroxygen bleaches are available commercially. of these, bell carbonate is convenient and can be used here. It is possible and economical. Thus, the present composition preferably contains 3 to 20% by weight of the composition. The solid base is preferably incorporated in an amount of 5 to 18% by weight, most preferably 8 to 15% by weight. can contain carbonate bleaches (usually in the form of sodium salts).

Sodium percarbonate is an addition compound with the formula corresponding to 2NaCo.3H202 It is a compound and is commercially available as a crystalline solid. Most commercially available substances are A small amount of EDTA, 1-hydroxyethylidene 1,1- added during the manufacturing process. Heavy metal ion sequestrants such as diphosphonic acid (HEDP) and aminophosphonates Can be mentioned.

For use herein, bell carbonate must be added to detergent compositions without additional protection. Although a preferred embodiment of the invention utilizes a stable form of material (FMC), . Various coatings can be used, but are applied as an aqueous solution and to provide a silicate solids content of 2 to 10% (usually 3 to 5%) by weight of the Sea urchin dried S 10: N a 20 ratio 1. ．． 6:1 to 2.8:1, good Preferably, 2.0+1 sodium silicate is the most economical. Magnesium silicate A chelating agent such as one of those mentioned above can also be used in the coating. Can be mixed.

The particle size range of crystalline bell carbonate is 350 μm to 450 μm (average 400 μm μm). When coating, the crystals have a size within the range of 400-600 μm. has.

The heavy metals present in the sodium carbonate used to produce Belcarbonate are , which can be controlled by the incorporation of sequestrants into the reaction mixture; still require protection from heavy metals present as impurities in other components of the product. shall be. The total amount of iron, copper and manganese ions in the product is 251) I) ■ to avoid unacceptable negative effects on carbonate stability. It has been found that there should be no more than 2 Opp layers and preferably less than 2 It was done.

The following are preferred methods of making liquid heavy duty laundry detergents according to the present invention: related. The stability of enzymes in such compositions is considerably lower than in granular detergents. That will be recognized. However, typical By using enzyme stabilizers, lipase and cellulase enzymes can be It can be protected from degradation by the enzyme Aase. However, lipase stability In the presence of killbenzene sulfonate (rLAsJ) surfactants, still relatively It is defective. Apparently, LAS partially denatures lipase and further denatures Lipases appear to be more susceptible to attack by proteases.

In view of the aforementioned considerations, which can be particularly troublesome with liquid compositions, liquid detergent compositions containing together enzymes such as protease, protease and cellulase. It is a challenge to do so. Stable liquid wash with effective blend of detergent surfactants Providing such ternary enzyme systems in pharmaceutical agents is a particular challenge. Additionally, Pero Stably incorporating oxidase and/or amylase enzymes into such compositions It is difficult.

Various types of lipase, protease, cellulase, amylase, and peroxidase The mixture consists of non-alkylbenzene sulfonates Even solid and liquid detergents can be formulated into heavy-duty and therefore effective It has now been confirmed that it can be done. In fact, the formulation of stable liquid enzyme-containing detergent compositions is The present invention constitutes a highly advantageous preferred embodiment provided by the inventive technology.

In particular, prior art liquid detergent compositions typically include LAS or LAS and the R O (A) So3M type■ (rAEsJ) with a surfactant, i.e. a LAS/AES mixture. Ru. In contrast, the liquid detergents of the present invention preferably contain AES and a compound of the type disclosed herein. Contains binary mixtures with polyhydroxy fatty acid amides. The minimum amount of LAS is However, it is recognized that the stability of the enzyme will thereby be reduced. Will. Accordingly, the liquid composition is capable of absorbing LAS with substantially no force (preferably). That is, less than about 10%, preferably less than about 5%, more preferably less than about 1%, most preferably less than about 1%. (preferably contains 0%).

The present invention (a) about 1% to about 50% anionic surfactant, preferably about 4% to about 40%: (b) Active detergent enzymatic 0.0001% to about 2%; (C) Formula (In the formula, R1 is H, C-C4 hydrocarbyl, 2-■ hydroxyethyl, 2-hydroxypropyl, or a mixture thereof; R is C-031 hydrocarbyl and Z is at least 3 directly linked to the chain. Polyhydroxyhydrocarbon with linear hydrocarpyl chain having hydroxyls an enzymatic performance enhancing amount (preferably carbyl or an alkoxylated derivative thereof) of (about 0.5% to about 12%) polyhydroxy fatty acid amide material; (d) nonionic field Surfactants, especially alkoxylated C12-C18 alcos having 3 to 10 EO groups The composition contains about 1% to 20% of the alkylbenzene sulfonate. To provide a liquid detergent composition characterized in that it does not contain any

The water-soluble anionic surfactant of the present invention is preferably RO (A) SO3M ■ (wherein R is unsubstituted C10"" C24 alkyl or hydroxydialkyl (C 10"" C24) group, A is an ethoxy or propoxy unit, m is is an integer greater than 0, and M is hydrogen or a cation) (rAESJ). Preferably, R is an unsubstituted 012-018 alkyl group, A is an ethoxy unit, m is about 0.5 to about 6. M is a cation. Cations are good Preferably, metal cations [e.g., sodium (preferred), potassium, lithium ammonium, calcium, magnesium, etc.] or ammonium or substituted ammonium It is a mu cation.

The ratio of the surfactant (rAESJ) to the polyhydroxy fatty acid amide of the present invention is , about 1:2 to about 8:1, preferably about 1:1 to about 5:1, most preferably about Preferably, the ratio is from 1=1 to about 4:1.

The liquid composition of the present invention alternatively comprises polyhydroxy fatty acid amide, AES, and 08-c2□ (preferably cl.

~C2o) linear alcohol and from about 1 to about 25 per mole of alcohol, preferably 0.5% to about 5% condensate with about 2 to about 18 moles of ethylene oxide good.

As mentioned above, the liquid composition of the present invention preferably contains 10% 0% in water at 20°C. In solution, the average temperature is from 6.5 to about 11.0°, preferably from about 7.0 to about 8.5.

The composition preferably further comprises from about 0.1% to about 50% detersive builder. child These compositions preferably contain from 0.1% to about 20% of citric acid or its water-soluble salt. %, and water-soluble succinate tartrate, especially its sodium salt and that from 0.1% to about 20%, or oxydisuccinate or its predecessor. from 0.1% to about 20% by weight in admixture with said builder. alkenyl succinate 0.1% to 50% can also be used.

Preferred liquid compositions of the invention have an active content of about 0.0001% to about 2%, preferably about 0.0001% to about 2%, on an active basis. or about 0.0001% to about 1%, most preferably about 0.001% to about 0.5%. Contains detergent enzymes. These enzymes are preferably proteases (preferred), lipase (preferred), amylase, cellulase, peroxidase, and selected from the group consisting of mixtures thereof. Compositions containing two or more enzymes are preferred. and most preferably one is a protease.

Although various descriptions of detergent proteases, cellulases, etc. are available in the literature, detergent proteases, cellulases, etc. Pase is somewhat less well known. Therefore, to help prescribers, there is interest in Some lipases include Amano AKG and Bacillis Sp lipase [ For example, Solvay enzyme]. Also, November 1990 Specification of EP A 0399 681 published on April 28, 1987, published on April 15, 1987. Publication EP A No. 0 218 272 and Publication No. 18 May 1989 PCT/D K No. 88100177 (all incorporated herein by reference) See lipase described in (incorporated).

Suitable fungal lipases include Humicola Ianuginosa and Listed below are the substances that can be produced by Theriomyces Ianuginosus. can be lost. European Patent Application No. 0 258 068 (herein incorporated by reference) The gene from Hu+*1 cola lanuginosa as described in and express the gene in Aspergillus oryzae. Lipase obtained by [commercially available under the trade name LIPOLASE] ] is the most preferred.

from about 2 to about 20,000, preferably from about 10 to about 6,000 lipa per H of product. One unit of lipase (LU/g) can be used in these compositions. lipase mono The position is a pH stand (pH is 7.0, temperature is 30°C, substrate is emulsion tributyrin and gum arabic), the presence of Ca”+ and NaCl in the phosphate. The amount of lipase that produces 1 H mole of titratable butyric acid per minute in the presence of

Examples 18A-C The example below shows a light duplex specifically suited for dishwashing and other hard surface cleaning operations. 3 illustrates a liquid detergent composition. In Examples A-C, the surfactants are various of alkyl ethoxy sulfate surfactants, these are defined by the standard academic terminology The abbreviation is used to indicate the average degree of ethoxylation, thus 012~C13EO(0 , 8) Sulfate is a sulfated mixture C12-C1 with an average degree of Etkinization 0.8 3 alcohol fractions are shown. These anionic ethoxy sulfates are preferably is used in Na+ or NH+ salt form. C12-C13 amine oxide is , mixed C12-013 (average) dimethylamine oxide. C12-C14 A P betaine is C12/14H25/29CONH(CH2)3N+(CH 3) 2-CH2CO2H0. CI2~C14A　P sultaine is C1゜ /14H25/29CONH(CH)N+(CH3)2-(CH) CHCH( OH) CH2So3H.

It is. C12~CC14D betaine is C12/14H25129N+ (C H) It is CHC02H. Ethoxylated nonionic interface 9-1 designated as CEO (8) The activator is ethoxylated with an average of 8 moles of ethylene oxide++ means a C9-C11 alcohol. Ca and Mg0 cations are preferred Conveniently it is introduced into the composition as CaCl2 and MgCl2. rest of the composition is the citrate/propylene glycosylation present in water and glucamide surfactants. (1-5%) and cumene sulfonate or xylene sulfonate hydro Consists of Tropes 1-396. The pH is typically 6.8-7.4 (NH4 salt ) or 7 to 8.2 (Na salt).

Ingredients % (weight) C-CN-methylglucamide 11 8 12.7 CI2~C13EO (0,8 ) Sulfate - 18 10. OC-CEO (3) Sulfate 11-2 ．． 7CI2~C13EO(8,5) sulfate -11111 remainder remainder remainder Remaining part Example 19 Relatively high concentrations common in front-loading automatic washing machines over a wide range of temperatures, especially in Europe Liquid laundry detergent compositions suitable for use in water are as follows.

Ingredients Weight% Coconut alkyl (C12) N-methylglucamide 14C, 4-15EO (2,25) Sulfate, Na salt 10. OCt4-t5E O(7) 4. 0 Anhydrous C12-14 alkenylsuccine H' 4.0 CI2-I4 fatty acid *3. .

Citric acid (anhydrous) 4.6 Protease (enzyme) 20.37 Termamil (enzyme) 3 0.12 Lipolase (enzyme)' 0.36 Carezyme zyIle) (enzyme)" 0.12 teyukues) 206 OS 61, 0NaOH (pH to 7.6) 5.5 1.2-Propanediol 4.7 Ethanol 4.0 Sodium metaborate 4. O Ca　C120,014 Ethoxylated tetraethylenepentamine 70.4 Brightener 80.13 , -19 Nff i　0.04 Soil release polymer 10 o, 2 Silicone (foam control, 11 0.4 Silicone dispersant 12 o, 2 Water and trace ingredients balance l Symbrax (5YNPl?AX) from ICI 3 or Monsando? As the DTSA of et al.

2 Protea as described in EPO No. 0342177 of November 15, 1989 As B: 96° at 40 g/l Amylase from 3 Novo; % at 300 KNU/g.

Lipase from 4 Novo; % at 100 KLU/g.

Cellulase from 5 novo; % at 5000 CEVU/Ill.

Available from 6 Mon Sand.

From 7BASF as Rutinsol P6105.

8 Bayer Blanco Hall CPG766゜9 Union Carbide to A11 DYNASYLAN TRI from 30 or Hills Silane corrosion inhibitor available as AMINO).

10 Polyesters of U.S. Pat. No. 4,711,730.

11 Silicone antifoam agent available from Dow Corning as 02-3302 12 Silicone foam control agent available from Dow Corning as DC-3225C Dispersant for use.

★Preferred fatty acids are 12% oleic acid and each of stearic acid and linoleic acid. Topped palm kernel containing 2%.

Example 20 Relatively high concentrations common in front-loading automatic washing machines over a wide range of temperatures, especially in Europe Particulate laundry detergent compositions suitable for use in laundry detergents are as follows.

Ingredients Weight% Tukaran CP5 (active content as Na salt 3.52100%) 1 Duquest 2066 (1009(i) as acid 0.45 Chinopal DM 　530.28 MgSO40,49 Zeolite A (anhydrous, 2-5μ) 17.92CMC (active content 100%) 0.47 layered silicate S K S -612,9 tallow alkyl sulfate 2.82 (Activity 100%; Na salt) C14-C15 alkyl sulfate 3.5 (activity 100%; Na salt) C-C alkyl EO(3) sulfate 1.78CI6~Cl8N-methylglue Camido 4.1 Dopanol C12-C15EO (3) 3.54 Lipolase (1 00,’0OOLU/g) 5 0.42 Sabinase (4,0KNPU) 6 1.85 fragrance 0.53 Stearyl alcohol 0.35 Sodium percarbonate (coated) 22.3 Tetraacetylene diamine (TAED) 5.9 Zinc phthalocyanine 0.02 Water (from zeolite) remainder 1 Tsukaran is polyacrylic acid/sodium maleate available from Hoechst. be.

Monsando brand of 2-pentaphosphonomethyldiethylenetriamine.

3 Optical brightener available from Ciba Geigy.

4. Product name FINNFIX available from Metasaliton.

Noriporase lipolytic enzyme from 5 Novo.

Savinase protease enzyme from 6 Novo.

7X2-3419 is a silicone suds suppressor available from Dow Corning.

The method for producing granules consists of various tower drying, agglomeration, dry addition, etc. as follows. %teeth, For the finished composition.

A. Using standard techniques for clutching and blowing through the column, the following components are clapped: (crutch) and dry in a tower.

Tsukaran CP5 3.52% Duquest 2066 0.45% Chino Pearl DMS 0.28% Magnesium sulfate 0.49% Zeolite A as anhydride 7.1% CMC 0.47% B. Surfactant aggregate B1. Sodium salt of tallow alkyl sulfate basedum 4S■2S■l&Mr. Soil and 4 ships 4 nimmu&n! Niest's agglomeration - 50 of tallow alkyl sulfate % active paste and 70% paste of CI2~C15EO(3) sulfate is aggregated with zeolite A and sodium carbonate according to the following recipe □. Contributes to detergent formulation after drying).

Tallow alkyl sulfate 2.82% C12-15EO (3) sulfate 1.18% Zeolite A 5.3% Sodium carbonate 4.5% Seeing Uni King Yu C is h ending - 竺i 歺迭歭Z" 2" ≧ノh Any P here on the top of the page 22ヱ ! "1 Koni Zuto 11 = Beg 295 Uni 32 L2" Yu 31 ヱ "Yu C Go" f Sou 2 2 Shi -4 52i amide aggregates - CI6 to C18 glucose amide nonionic substances Dopanol CEO ( Synthesize in 3).

12-15 CI2-15EO (3) reacts without producing undesirable cyclic glucose amides. It acts as a melting point depressant, allowing the reaction to take place.

Dopanol CEO (3) 20% and 016~Cl8N12~15 A surfactant mixture was obtained with 80% monomethylglucoseamide and sodium carbonate. Simultaneously coagulates with 10% of aluminum.

Second, the particles are then treated with sodium salt of CI4-C15 alkyl sulfate and CE O(3) sulfate and ze12-15 Simultaneous coagulation with a highly active paste (70%) of Olide A and excess sodium carbonate. Ru. This particle shows good performance of 016-018N-methylglucoseamide in cold water. Shows dispersibility.

The total formulation of this particle (contributing to the detergent formulation after drying of the aggregates) is as follows.

CI6~C18N-methylglucoseamide 4.1% Dopanol 012~15 EO (3) 0.94% Sodium carbonate 4.94% Zeolite A5.3% 014-C15 alkyl sodium sulfate 3゜5% CEO (3) Sodium sulfate 　0.59%12~15 C1 drying additive Add the following ingredients.

Bell carbonate 22.3% TAED (Tetraacetylethylenediamine) 5.9% Hoechst layered silica TOTO S K S-612, 90% citric acid 3.5% Lipolase 0.42% 100.0OOLU/g Sabinase 4.0KNPU L, 65% zinc phthalocyanine (photobleach) 0.0 2% D, spray-on Dopanol 012-15EO (3) 2. eo% fragrance 0.53% B. Foam suppressant Silicone Foam Inhibitor X2-3419 (High Molecular Weight Starch 9) from Dow Corning 5% to 97%: hydrophobic silica 396 to 596) to zeolite A (size 2 to 5μ ), co-agglomerates with starch and stearyl alcohol binder. this particle Take the following prescription.

Zeolite A O, 22% Starch 1.08% X 2-3419 0.22% Stearyl alcohol 0.35% The detergent formulation may be prepared by, for example, washing 85 g of detergent in an AEG brand washing machine at 30°C, 40°C, Excellent when used in European washing machines using 60°C and 90°C cycles exhibits good solubility, excellent performance and excellent foam control.

Example 21 In any of the foregoing examples, the fatty acid glucamide surfactant contains an equivalent amount of maltamide. Depends on surfactants or glucamide/maltamide surfactants derived from plant sugar sources. It can be changed. In the composition, the use of ethanolamide It seems to promote the cold and temperature stability of things.

Additionally, the use of sulfobetaine (also known as "sultaine") surfactant provides superior foaming. Give sex.

The following example illustrates yet another example that is particularly suitable for "light duty" applications such as washing dishes. A liquid composition (both Mg++ and Ca++ as described above) is illustrated.

C12-14 Alki/Izz, Toxysulfate (IEO) 16 9 12 -C12-14 alkyl ethoxy sulfate (3EO)-14-11C alkyl ethoxylate (8EO) 7 3 7 1°1ON-, -ftk a7. KaE l' 8 9 12 612-14 Coconut jetanolamide ------5 dimethyldodecylamineoxy Do-1-2 Cocoamidopropylhydroxysultaine -13 = Cocoamidop Lopil betaine 2 - - - Sodium toluenesulfonate 3 3 3 3 Ethanol 4 4 4 4 Water remainder Especially if a highly foaming composition is desired (e.g. dishwashing Acids may inhibit foaming properties, so use less than about 5% fatty acids of 014 or higher, or more. Preferably less than about 2% is present, most preferably substantially absent. stomach. Therefore, formulators of high foaming compositions desirably use such fatty acids with foam-inhibiting amounts. into the high foaming composition having the polyhydroxy fatty acid amide and and/or will avoid the formation of fatty acids with a CI4 or higher during storage of the finished composition. . One simple approach is to prepare the polyhydroxy fatty acid amides of the present invention. using a C12 ester reactant. Fortunately, amine oxide The use of sulfobetaine or sulfobetaine surfactants avoids the negative foaming properties caused by Some of the effects can be overcome.

Anionic optical brighteners with relatively high concentrations (e.g. 10% or more) of anionic surfactants agents or polyanionic surfactants, such as polycarboxylate builders. Formulators who wish to add brighteners to liquid detergents that contain water and polyhydroxy fatty acids It may be useful to premix with the amide and then add the premix to the final composition. You can find out something.

Polyglutamic acid or polyaspartic acid dispersants are used as zeolite builders. Can be used usefully with detergents. AEE Fluid or Flake and DC-544 (Dow Corning) are other examples of other antifoam agents useful herein.

Polyhydroxy fatty acid amide using trisaccharides and higher sugars, e.g. maltose In the production of de, the linear substituent Z is "blocked" by a polyhydroxy ring structure. It will be recognized by those skilled in the art that this will result in the formation of polyhydroquine fatty acid amide. will be done. Such materials are fully intended and disclosed for use herein. without departing from the spirit and scope of the invention as defined and claimed.

Claims (16)

[Claims] 1. (a) Formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R1 is H, C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydrocarbyl, droxypropyl, or a mixture thereof, and R2 is a C5-C31 hydrocarbon. and Z has at least three hydroxyl groups directly linked to the chain. Polyhydroxyhydrocarbyl or its alkyl having a linear hydrocarpyl chain coxylated derivative) one or more polyhydroxy fatty acid amides having; and (b) containing one or more additional nonionic surfactants; The weight ratio of surfactant (a) to additional nonionic surfactant (b) ranges from 1:5 to 5:1. A nonionic surfactant system characterized by: 2. R1 is a C1-C2 alkyl group, and R2 is C9-C17 alkyl or 2. A nonionic surfactant system according to claim 1, which is an alkenyl group. 3. Polyhydroxy fatty acid amide component (a) has ■▲ mathematical formulas, chemical formulas, tables, etc. Masu▼ (In the formula, R2 is a C11 to C17 straight chain alkyl or alkenyl group, and Z is a group derived from lucose, maltose or mixtures thereof) 3. A nonionic surfactant system according to claim 2, comprising: 4. Additional nonionic surfactant (b) Oxide condensate, primary and secondary aliphatic alcohol and ethylene oxide 1-2 selected from the group consisting of condensates with 5 moles, alkyl polysaccharides, and mixtures thereof 3. The nonionic surfactant system of claim 2. 5. Weight of polyhydroxy fatty acid amide (a) versus additional nonionic surfactant (b) Nonionic surfactant according to claim 4, wherein the quantitative ratio is within the range of 1:3 to 3:1. Drug system. 6. The additional nonionic surfactant (b) is a C8 having 3 to 15 ethoxy groups. ~C14 alkylphenol ethoxylates, having 2 to 10 ethoxy groups selected from C12-C18 alcohol ethoxylates, and mixtures thereof , a nonionic surfactant system according to claim 5. 7. The nonionic product according to claim 1, which substantially does not contain fatty acids with a foam-inhibiting amount of C14 or higher. Surfactant system. 8. Regarding the polyhydroxy fatty acid amide, Z is derived from maltose, The nonionic surfactant system according to claim 1. 9. Regarding the polyhydroxy fatty acid amide, Z is a monosaccharide, a disaccharide, and optionally and higher saccharides (the mixture comprises at least one disaccharide, preferably a malt). 2. The nonionic surfactant of claim 1, wherein the nonionic surfactant is derived from system. 10. (a) Formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R1 is H, C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydrocarbyl, droxypropyl, or a mixture thereof, and R2 is a C5-C31 hydrocarbon. and Z has at least three hydroxyl groups directly linked to the chain. polyhydroxyhydrocarbyl or its alkyl having a linear hydrocarbyl chain coxylated derivative) one or more polyhydroxy fatty acid amides having; and (b) containing one or more additional nonionic surfactants; The weight ratio of surfactant (a) to additional nonionic surfactant (b) ranges from 1:5 to 5:1. A laundry product comprising at least 1% by weight of a nonionic surfactant system, characterized in that: Detergent composition. 11. One or more anionic surfactants, cationic surfactants, amphoteric surfactants, Zwitterionic surfactants, semipolar surfactants and any nonionic surfactants; The laundry detergent according to claim 10, further comprising a surfactant selected from a mixture thereof. Composition. 12. Detergent compositions containing one or more non-ionic detergent surfactants and optional detergent adjuvants In improving the stain removal performance of the composition, the formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R1 is H, C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydrocarbyl, droxypropyl, or a mixture thereof, and R2 is a C5-C31 hydrocarbon. and Z has at least three hydroxyl groups directly linked to the chain. polyhydroxyhydrocarbyl having linear hydrocarbyl chains, preferably C 11-C17N-methylglucamide, C11-C17N-methylmaltamide, or or a mixture of the glucamide and maltamide or an alkoxylated derivative thereof ); and one or more additional polyhydroxy fatty acid amides; Contains an additional non-ionic surfactant, polyhydroxy fatty acid amide vs. an additional non-ionic surfactant. The weight ratio of surfactants is in the range of 1:5 to 5:1. A method for improving the stain removal performance of a detergent composition. 13. The Z moiety in the polyhydroxy fatty acid amide is obtainable from a vegetable source. 13. The method according to claim 12, wherein the method is derived from mixed monosaccharides, disaccharides and polysaccharides. 14. The R2 moiety in the polyhydroxy fatty acid amide is a C15-C17 atom. 13. The method of claim 12, wherein the method is alkyl, alkenyl, or a mixture thereof. 15. A detergent composition whose ability to remove stains from fabric is enhanced by the method of claim 12; A method for removing stains from fabrics characterized by contact. 16. A booster characterized in that it contains a nonionic surfactant system according to claim 7. A dishwashing composition having foaming properties.