JP3119873B2 - Nonionic surfactant system containing polyhydroxy fatty acid amide and one or more additional nonionic surfactant - Google Patents

Description

Description: TECHNICAL FIELD The stain removal performance of detergent compositions is improved by the use of a non-ionic surfactant system comprising one or more polyhydroxy fatty acid amides and one or more additional non-ionic surfactants. Is done.

BACKGROUND OF THE INVENTION Conventional laundry detergent compositions can be formulated in a number of different ways to address a number of different laundry problems. For example, such detergent compositions may contain builders, optical brighteners, dispersants, and the like to address various cleaning problems encountered in the washing operation. In addition, consumers need detergent compositions that are effective against the broadest possible spectrum of stains and stains. Detergent formulators address this need by providing detergent compositions containing mixed surfactants that are widely effective in cleaning performance.

One particular problem that must be considered and dealt with when formulating detergent compositions is cumbersome grease / oil spots,
For example, removal of body stains and food stains. The incorporation of the nonionic surfactant into the laundry detergent composition is carried out using grease /
It would improve the effectiveness of such compositions against oil stains, but only under limited laundry conditions.

The present invention provides a non-ionic surfactant system comprising one or more polyhydroxy fatty acid amides and one or more additional non-ionic surfactants. The present invention also provides laundry detergent compositions containing these non-ionic surfactant systems. When incorporated into such laundry detergent compositions, these nonionic surfactant systems unexpectedly improve the effectiveness of such compositions against grease / oil stains over a wide range of laundry conditions.

Various polyhydroxy fatty acid amides have been described in the art. For example, N-acyl-N-methylglucamide is available from JW Goodbye, MA Marcus, E. Tin, and PL
Finn, "Thermotropic Liquid Crystallinity of Some Linear Carbohydrate Amphiphiles", Liquid Crystals, 1988, 3rd.
Vol. 11, pp. 1569-1581, and A. Muller
"Nonionic detergents: nonanoyl-N-" by Farnau, V. Zabel, M. Stafa and R. Hilgenfeld.
Molecular and Crystal Structure of Methylglucamide "J. Chem.S
oc. Chem. Commun., 1986, pp. 1573-1574. The use of N-alkyl polyhydroxyamide surfactants has recently become of substantial interest for use in biochemistry, for example, in dissociation of biofilms.
See, for example, the journal article "ND-gluco-N-methyl-alkaneamide compounds for membrane biochemistry, a new class of nonionic detergents" by JEK Hildress, Biochem. J. (198
2), volume 207, pages 363-366.

The use of n-alkylglucamides in detergent compositions has also been discussed. US Patent No. 2,965,576 issued December 20, 1960 to ER Wilson and February 1, 1959.
British Patent No. 809,060, issued on August 8 and assigned to Thomas Hedley End Company Limited, describes an anionic surfactant and an amide surfactant, which is N- Which can include methylglucamide). These compounds include the N-chain of higher linear fatty acids having 10 to 14 carbon atoms.
Acyl groups are mentioned. These compositions may also contain auxiliary substances, such as alkali metal phosphates, alkali metal silicates, sulfates, carbonates and the like. It is also generally pointed out that additional components that impart desirable properties to the composition, such as fluorescent dyes, bleaches, fragrances and the like, can be incorporated into the composition.

U.S. Patent No. 2, issued March 8, 1955 to AM Schwartz
No. 703,798 relates to an aqueous detergent composition containing a condensation reaction product of an N-alkylglucamine and an aliphatic ester of a fatty acid. The product of this reaction is said to be usable in aqueous detergent compositions without further purification. AM
U.S. Patent No. 2,717,89 issued to Schwartz on September 13, 1955
It is also known to prepare sulfated acylated glucamines as disclosed in US Pat.

PCT International Application No. WO 83/04412, published December 22, 1983 by J. Hildress, describes cosmetics, medicines, shampoos,
Lotions and eye ointments as surfactants, as medical emulsifiers and dispensers, and for solubilizing membranes, whole cells or other tissue samples and including various uses in biochemistry for the production of liposomes. To amphiphilic compounds containing polyhydroxyl aliphatic groups which are said to be useful for the purpose of This disclosure includes the formula R'CON (R) CH ₂
R "and R" CON (R) R '(where R is hydrogen or an organic atomic group, R' is an aliphatic hydrocarbon group having at least 3 carbon atoms, and R "is a residue of aldose. ) Is included.

EP 0 285 768, issued October 12, 1988 to H. Kelkenberg, relates to the use of N-polyhydroxyalkyl fatty acid amides as thickeners in aqueous detergent systems. Formula R ₁ C (O) N (X) R _{2 wherein} R ₁ is C ₁ -C
₁₇ (preferably C ₇ -C ₁₇ ) alkyl, wherein R ₂ is hydrogen, C
₁ -C ₁₈ (preferably C ₁ -C ₆₎ alkyl or alkylene oxide, X is an amide of a) polyhydroxy alkyl of 4-7 carbon atoms, for example, N- methyl coconut fatty acid glucamide and the like. Aqueous surfactant systems include other anionic surfactants, such as alkyl aryl sulfonates, olefin sulfonates, sulfosuccinic acid half ester salts, and fatty alcohol ether sulfonates, and nonionic surfactants, such as fatty alcohol polyglycol ethers, Alkyl phenol polyglycol ether, fatty acid polyglycol ester,
Although it may contain polypropylene oxide-polyethylene oxide mixed polymers, etc., the thickening of amides has been indicated to have particular use in liquid surfactant systems containing paraffin sulfonates. Paraffin sulfonate
A / N-methyl coconut fatty acid glucamide / nonionic surfactant shampoo formulation is illustrated. In addition to thickening properties, N-polyhydroxyalkyl fatty acid amides are said to have excellent skin tolerating properties.

US Patent No. 2, issued May 2, 1961 to Boettner et al.
No. 982,737 discloses urea, sodium lauryl sulfate anionic surfactant, and N-alkylglucamide selected from N-methyl-N-sorbicyllaurinamide and N-methyl-N-sorbicylmyristamide. Detergent solid containing an ionic surfactant.

Other glucamide surfactants are, for example, of the formula R ₁ C (O) N (R ₂ ) CH ₂ — (CHOH) _n CH ₂ OH, where R ₁ is C ₁ -C ₃ alkyl; ₂ is C ₁₀ -C ₂₂ alkyl and n is 3 or 4), which has been improved by the addition of N-acyl polyhydroxyalkylamines,
Announced on December 20, 1973 for a detersive composition comprising a builder salt selected from one or more surfactants and polymeric phosphates, a sequestering agent and a detersive alkali.
HW Eckert et al., DT 2,226,872. N-acyl polyhydroxyalkylamines are
Add as a stain settling inhibitor.

U.S. Patent issued on April 4, 1972 to HW Eckert
No. 3,654,166 describes at least one surfactant selected from the group of anionic surfactants, zwitterionic surfactants and nonionic surfactants and a formula as a fabric softener.
R ₁ N (Z) C (O) R _{2 wherein} R ₁ is C ₁₀ -C ₂₂ alkyl, R ₂ is C ₇ -C ₂₁ alkyl, and R ₁ and R ₂ are 23- has 39 carbon atoms, Z is _{-CH 2 (CHOH) m CH 2} O
H (where m is 3 or 4 is a polyhydroxyalkyl)] N-acyl-N-alkyl polyhydroxyalkyl compound.

U.S. Patent No. 4,021, issued May 3, 1977 to H. Meller et al.
No. 539 describes the formula R ₁ N (R) CH (CHOH) _m R ₂ (wherein R ₁
Is H, lower alkyl, hydroxy-lower alkyl, or aminoalkyl, as well as heterocyclic aminoalkyl, where R is the same as R ₁ but not both can be H and R ₂ is CH ₂ OH or A skin treatment cosmetic composition containing an N-polyhydroxyalkylamine including a compound of the formula

French Patent No. 1,360,018 assigned to Commercial Solvents Corporation (April 26, 1963)
Day) has the formula RC (O) N (R ₁ ) G, where R is a carboxylic acid functionality having at least 7 carbon atoms, R ₁ is hydrogen or a lower alkyl group, and G is at least 5 carbon atoms. Glycidyl groups) are added to the solution of formaldehyde stabilized against polymerization.

German Patent 1,261,861 (February 29, 1968, A.
Hines) have the formula N (R) (R ₁ ) (R ₂ ) where R is the sugar residue of glucamine, R ₁ is a C ₁₀ -C ₂₀ alkyl group, and R ₂ is a C ₁ -C ₂₀ alkyl group. C about ₅ useful glucamine derivative as a wetting agent / dispersant acyl group is).

UK Patent No. 745,036, issued February 15, 1956 and assigned to Atlas Powder Company, is useful as a chemical intermediate, emulsifier, wetting / dispersing agent, detergent, fabric softener, and the like. Heterocyclic amides and their carboxylic esters. The compound is
Formula N (R) (R ₁ ) C (O) R _{2 wherein} R is the residue of anhydrous hexanepentol or a carboxylic acid ester thereof, R ₁ is a monovalent hydrocarbon group, (O) R ₂ is an acyl group of a carboxylic acid having 2 to 25 carbon atoms).

US Patent 3,312, issued April 4, 1967 to DT Hooker
No. 627 discloses lithium soap of certain fatty acids substantially free of anionic detergents and alkaline builder substances,
Containing a non-ionic surfactant selected from certain propylene oxide-ethylene diamine-ethylene oxide condensates, propylene oxide-propylene glycol-ethylene oxide condensates and polymerized ethylene glycol and also having the formula RC (O) NR ¹ (R ² ) (Where RC (O) is about 10
Has about 14 carbon atoms, and R ¹ and R ² are each H or
A C ₁ -C ₆ alkyl group, the alkyl group having a total number of 2 to about 7 carbon atoms and a total number of substituent hydroxyl groups of 2
(Having from about 6 to about 6) are disclosed. Substantially the same disclosure is given to DT Hooker in April 1967.
It is found in U.S. Pat. No. 3,312,626, issued on Jan. 4, 2016.

The use of non-ionic surfactants in detergent compositions is
It is known in the art. U.S. Pat. No. 3,654,166 issued Apr. 4, 1972 to Eckert et al. Describes a surfactant selected from anionic surfactants, zwitterionic surfactants and nonionic surfactants and N-alkyl-N- Acyl-N-
A detergent composition comprising a polyhydroxyalkyl compound is disclosed.

DISCLOSURE OF THE INVENTION Wherein R ¹ is H, C ₁ -C ₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof, R ² is C ₅ -C ₃₁ hydrocarbyl, and Z is directly One or more polyhydroxy fatty acid amides having a linear hydrocarbyl chain having at least three hydroxyl groups attached thereto or an alkoxylated derivative thereof); and (b) one or more additional A non-ionic surfactant, wherein the weight ratio of the polyhydroxy fatty acid amide (a) to the additional non-ionic surfactant (b) is in the range of about 1: 5 to about 5: 1. Related to ionic surfactant systems.

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

Further, the present invention provides a method for improving the stain removal performance of a detergent composition by incorporating the nonionic surfactant system into such a composition.

BEST MODE FOR CARRYING OUT THE INVENTION The nonionic surfactant system of the present invention consists of one or more polyhydroxy fatty acid amides and one or more additional nonionic surfactants. In these nonionic surfactant systems, the weight ratio of polyhydroxyfatty acid amide to additional nonionic surfactant is from about 1: 5 to about 5: 1, preferably from about 1: 3 to about 3: 1, More preferably, it is in the range of about 1: 1.5 to about 1.5: 1.

The components of the nonionic surfactant system of the present invention are described below.

The polyhydroxy fatty acid amide surfactant component of the present invention has a structural formula Wherein R ¹ is H, C ₁ -C ₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof, preferably C ₁ -C ₄ alkyl, more preferably C ₁ or C ₂ alkyl, Most preferably, it is C ₁ alkyl (ie, methyl); R ² is C ₅ -C ₃₁ hydrocarbyl, preferably linear C ₇ -C ₁₉ alkyl or alkenyl, more preferably linear C ₉ -C ₁₇ alkyl or alkenyl. , and most preferably lies in linear C ₁₁ -C ₁₇ alkyl or alkenyl, or mixtures thereof,; Z is polyhydroxy hydrocarbyl or alkoxylated with a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain Derivatives (preferably ethoxylated or propoxylated)]. Z will preferably be 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 raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars described above. These corn syrups can be used to prepare a mix of Z sugar components. It should be understood that no other suitable raw materials are ever excluded. Z is preferably _{-CH 2 - (CHOH) n -CH} 2 OH, -CH (CH 2 OH) - (CHOH)
_n-1 CH ₂ OH, —CH ₂ — (CHOH) ₂ (CHOR ′) (CHOH) —CH ₂
OH, wherein n is an integer from 3 to 5 and R 'is H or a cyclic or aliphatic monosaccharide, and their alkoxylated derivatives. n is 4
Glycityls, particularly -CH ₂ is - _(CHOH) 4 -CH ₂ OH is
Most preferred.

In the formula (I), R ¹ is, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N
-2-hydroxyethyl, or N-2-hydroxypropyl.

R ² —CO—N <is, for example, cocoamide, stearamide, oleamide, laurinamide, myristamide,
It can be caprinamide, palmitoamide, tallowamide and the like.

Z is 1-deoxyglucityl, 2-deoxyfructyl, 1-deoxymultityl, 1-deoxylactyl, 1-deoxygalacticyl, 1-deoxymannityl, 1-deoxymaltotriothytyl, Can be

Most preferred polyhydroxy fatty acid amides have the general formula Wherein R ² is a C ₁₁ -C ₁₇ linear alkyl or alkenyl group.

The preparation of polyhydroxy fatty acid amides is known in the art. Generally, they react an alkylamine with a reducing sugar in a reductive amination reaction to produce the corresponding N-alkyl polyhydroxyamine, which is then reacted in a condensation / amidation step with a fatty aliphatic ester or React with triglyceride to give N-
It can be made by producing an alkyl-N-polyhydroxy fatty acid amide product. The method for producing a composition containing a polyhydroxyfatty acid amide is, for example, Thomas
19 by Hedley End Company Limited
British Patent No. 809,060 published February 18, 59, ER
U.S. Patent No. 2,965, issued to Wilson on December 20, 1960
No. 576 and Antony M. Schwartz U.S. Pat.
No. 424, each of which is incorporated herein by reference.

The glycityl moiety is derived from glucose and the N-alkyl or N-hydroxyalkyl functionality is N-methyl,
In one process for the preparation of N-alkyl or N-hydroxyalkyl-N-deoxyglycityl fatty acid amides which are N-ethyl, N-propyl, N-butyl, N-hydroxyethyl, or N-hydroxypropyl, the product is , N-alkyl- or N-hydroxyalkyl-glucamine with trilithium phosphate, trisodium phosphate, tripotassium phosphate, tetrasodium pyrophosphate, pentapotassium tripolyphosphate, lithium hydroxide, sodium hydroxide,
Potassium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, disodium tartrate, dipotassium tartrate, potassium sodium tartrate, trisodium citrate, tripotassium citrate, basic sodium silicate, basic potassium silicate Formed by reacting with a fatty acid ester selected from fatty methyl esters, fatty ethyl esters and fatty triglycerides in the presence of a catalyst selected from the group consisting of basic sodium aluminosilicate, and basic potassium aluminosilicate, and mixtures thereof. I do. The amount of catalyst is preferably N
From about 0.5 mole% to about 50 mole%, more preferably from about 2.0 mole% to about 10 mole%, based on moles of -alkyl or N-hydroxyalkyl-glucamine. The reaction is preferably performed at about 138 ° C to about 170 ° C, typically for about 20 to about 90 minutes. When triglycerides are utilized in the reaction mixture as a source of fatty acid ester, the reaction is preferably from about 1 to about 10% by weight, calculated on the weight percent of the total reaction mixture, of saturated fatty alcohol polyethoxylate, alkyl polyglycoside, linear The reaction is performed using a phase transfer agent selected from the form of glucamide surfactant and a mixture thereof.

Preferably, the method is performed as follows: (a) preheating the fatty acid ester to about 138 ° C. to about 170 ° C .; (b) adding the N-alkyl or N-hydroxyalkyl glucamine to the heated fatty acid ester (C) mixing the catalyst into the reaction mixture; (d) stirring for a predetermined reaction time.

Also preferably, if the fatty acid ester is a triglyceride, from about 2 to about 20% by weight of the reactants of the preformed linear N-alkyl / N-hydroxyalkyl-N-linear glucosyl fatty acid amide product is: It is added to the reaction mixture as a phase transfer agent. This facilitates the reaction, thereby increasing the rate of the reaction. Detailed experimental procedures are given below in the experiments.

The polyhydroxy "fatty acid" amide materials used herein also provide the detergent formulator with the advantage that they can be made from all or predominantly natural renewable non-petrochemical feedstocks and are degradable. Also, they show low toxicity to aquatic organisms.

Together with the polyhydroxy fatty acid amides of the formula (I), the methods used to prepare them also typically produce certain amounts of non-volatile by-products such as ester amides, cyclic polyhydroxy fatty acid amides. It should be recognized that The amounts of these by-products will vary depending on the particular reactants and process conditions. Preferably, the polyhydroxyfatty acid amide incorporated into the detergent composition herein is such that the polyhydroxyfatty acid amide-containing composition added to the detergent contains less than about 10%, preferably less than about 4%, cyclic polyhydroxyfatty acid amide. Will be provided in the form. The above-described preferred method is advantageous because it produces rather small amounts of by-products, including such cyclic amide by-products.

Nonionic Surfactants The nonionic surfactant systems of the present invention comprise, in addition to the polyhydroxyfatty acid amide component, one or more of the nonionic surfactants described herein. The non-ionic surfactants described herein will be referred to hereinafter as “additional non-ionic surfactants”. Non-ionic compounds other than these additional non-ionic surfactants may optionally be included in the non-ionic surfactant systems of the present invention. These other optional nonionic compounds will hereinafter be referred to as "optional nonionic compounds". Without intending to be limiting, when such non-ionic compounds are included in the non-ionic surfactant systems of the present invention, they are believed not to provide the unexpected stain benefit described herein.

Polyethylene oxide condensates of alkylphenols,
Polypropylene oxide condensates and polybutylene oxide condensates are suitable for use as additional nonionic surfactants in the nonionic surfactant systems of the present invention, with polyethylene oxide condensates being preferred. These compounds include condensates of alkylphenols with alkylphenols having alkyl groups having about 6 to about 14 carbon atoms, preferably about 8 to about 14 carbon atoms, in a linear or branched configuration. Is mentioned. In a preferred embodiment, the ethylene oxide is present in an amount equivalent to about 5 to about 25 moles, more preferably about 3 to about 15 moles of ethylene oxide per mole of alkylphenol. Commercially available nonionic surfactants of this type include Igepal ^™ CO-63, marketed by GAF Corporation.
0; Triton ^™ X-45, X-114, X-1 marketed by Rohm and Haas Company
00 and X-102. These surfactants are commonly referred to as alkylphenol alkoxylates (eg, alkylphenol ethoxylates).

Condensates of primary and secondary aliphatic alcohols with about 1 to about 25 moles of ethylene oxide are suitable for use as additional nonionic surfactants in the nonionic surfactant systems of the present invention. The alkyl chain of the aliphatic alcohol can be straight or branched primary or secondary and generally has about 8 to about 22 carbon atoms. About 8 carbon atoms
About 20, more preferably about 2 to about 10 per mole of alcohol having an alkyl group having about 10 to about 18 carbon atoms.
Condensates with moles of ethylene oxide are preferred. Examples of commercially available nonionic surfactants of this type include Tergitol ^™ 15-S-9 (condensate of C ₁₁ -C ₁₅ linear alcohol with 9 moles of ethylene oxide), Tergitol ^™ 24-L- 6NMW (C ₁₂ ~C ₁₄ condensation product of primary alcohols with ethylene oxide 6 moles with a narrow molecular weight distribution)
(Both marketed by Union Carbide Corporation); Neodol marketed by Shell Chemical Company _{^{(Neodol TM) 45-9 (C 14}} ~C
Condensates of ₁₅ linear alcohol with 9 moles ethylene oxide), Neodol ^TM 23-6.5 (C ₁₂ ^~C ₁₃ linear alcohol condensation products of ethylene oxide 6.5 moles), Neodol
^TM 45-7 (C ₁₄ ^~C ₁₅ linear alcohol condensation products of ethylene oxide 7 moles), Neodol ^TM 45-4 (C ₁₄ ^~C ₁₅ linear alcohol condensation products of ethylene oxide 4 mol)
Km marketed by The Procter end Gamble Company _{^{(Kyro TM) EOB (C 13}} ~C 15 condensates of alcohols with 9 moles ethylene oxide) and the like.

In addition, carbon number of about 6 to about 30, preferably carbon number of about 10 to about 30
January 21, 1986 having 16 hydrophobic groups and a polysaccharide (eg, polyglycoside) hydrophilic group containing about 1.3 to about 10, preferably about 1.3 to about 3, and most preferably about 1.3 to about 2.7 saccharide units. The alkyl polysaccharides disclosed in Lenado U.S. Pat. No. 4,565,647 issued to Sun are useful as additional nonionic surfactants in the nonionic surfactant systems of the present invention. Any reducing sugar having 5 or 6 carbon atoms can be used, for example, glucose, galactose and galactosyl moieties can be used in place of the glucosyl moieties (optionally, the hydrophobic group can be attached at the 2-, 3-, 4-, etc. To give glucose or galactose as opposed to glucoside or galactoside). The intersugar linkage may be, for example, at position 1 of the additional sugar unit and at positions 2, 3 on the previous sugar unit,
It can be between the 4th and / or 6th position.

In some cases, although less desirable, there may be a polyalkylene oxide chain linking the hydrophobic and polysaccharide moieties. The preferred alkylene oxide is ethylene oxide. Typical hydrophobic groups include those having about 8 to about
18, preferably from about 10 to about 16 saturated or unsaturated branched or unbranched alkyl groups. Preferably, the alkyl group is a linear saturated alkyl group. The alkyl group can contain up to about 3 hydroxy groups, and / or
Alternatively, the polyalkylene oxide chain can contain up to about 10, and preferably less than 5, alkylene oxide moieties. Suitable alkyl polysaccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucoside, galactoside, lactoside, glucose, Fructoside, fructose and / or
Or galactose. Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucoside and tallowalkyl tetra-, penta-, and hexaglucoside.

Preferred alkyl polyglycosides are those wherein ^{_{R 2 O (C n H 2n}} O) t ( glycosyl) _{x (formula,} R ² is selected alkyl, alkylphenyl, hydroxyalkyl, hydroxyl alkyl phenyl, and mixtures thereof And the alkyl group has about 10 to about 18, preferably about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2, and t is 0 to about 1
0, preferably 0; x is about 1.3 to about 10, preferably about
1.3 to about 3, most preferably about 1.3 to about 2.7). Glycosyl is preferably derived from glucose. To produce these compounds, first, an alcohol or alkyl polyethoxy alcohol is produced,
Then reacting with glucose or a glucose source,
Produces glucoside (linked at position 1). Additional glycosyl units can then be linked between their 1-position and the 2-, 3-, 4- and / or 6-position of the previous glycosyl unit, preferably mainly 2.

Although not preferred, condensates of ethylene oxide with a hydrophobic base resulting from the condensation of propylene oxide with propylene glycol are also suitable for use as additional nonionic surfactants in the nonionic surfactant systems of the present invention. . The hydrophobic portion of these compounds preferably has a molecular weight of about
It will have a water solubility between 1500 and about 1800 and will be water insoluble. The addition of a polyoxyethylene moiety to this hydrophobic moiety tends to increase the water solubility of the molecule as a whole and the liquid properties of the product are such that the polyoxyethylene content is up to about 50 of the total weight of the condensate (Corresponding to condensation with up to about 40 moles of ethylene oxide). Examples of such compounds include Pluronic (Pluronic) marketed by BASF.
onic ^™ ) surfactants.

Also, condensates of the product of the reaction of propylene oxide with ethylenediamine and ethylene oxide are suitable, but not preferred, for use as additional nonionic surfactants in the nonionic surfactant systems of the present invention. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally
It has a molecular weight of about 2500 to about 3000. The hydrophobic moiety condenses with ethylene oxide to the extent that the condensate contains about 40 to about 80% by weight polyoxyethylene and has a molecular weight of about 5,000 to about 11,000. Examples of such nonionic surfactants include certain of the Tetronic ^™ compounds marketed by BASF.

Polyethylene oxide condensates of alkylphenols,
Condensates of primary and secondary aliphatic alcohols with about 1 to about 25 moles of ethylene oxide, alkyl polysaccharides, and mixtures thereof can be used as additional nonionic surfactants of the nonionic surfactant systems of the present invention. Preferred for use as
3-15 C ₈ having ethoxy groups -C ₁₄ alkyl phenol ethoxylates and 2-10 C ₈ having ethoxy groups -C ₁₈ alcohol ethoxylates (preferably having an average C
₁₀ ), and mixtures thereof are most preferred.

Detergent composition In addition, 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
A laundry detergent composition comprising 25% by weight. The surfactant of such a laundry detergent composition can consist solely of the nonionic surfactant system of the present invention, or other surfactants,
For example, it may comprise a nonionic surfactant system in combination with an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a zwitterionic surfactant and a semipolar surfactant. Cationic surfactants useful herein are those having one long-chain hydrocarbyl group.

Also, while it is believed that any of the non-ionic compounds described herein do not provide the unexpected stain removal benefits of the non-ionic surfactant systems of the present invention, the laundry detergent compositions of the present invention include:
Here, any of the nonionic compounds described above can be contained. When the laundry detergent composition of the present invention contains a nonionic surfactant system and any such other detergent surfactant, the weight ratio of the nonionic surfactant system to the other detergent surfactant is about 5%.
It will range from 0: 1 to about 1:10, preferably from about 10: 1 to about 1: 5. Additionally, the laundry detergent compositions of the present invention may optionally include other components typically found in detergent compositions,
For example, it can contain builders, soil release agents, chelating agents and the like.

When incorporated into such laundry detergent compositions, the non-ionic surfactant systems of the present invention act to improve the grease / oil stain release properties of such laundry detergent compositions over a wide range of laundry conditions.

Anionic Surfactants The laundry detergent compositions of the present invention can contain, in addition to the nonionic surfactant system of the present invention, one or more anionic surfactants as described below.

Alkyl Ester Sulfonate Surfactant Examples of the alkyl ester sulfonate surfactant include “The Journal of the American Oil Chemistry Society”, 52 (975), pp. 323-329.
C ₈ -C ₂₀ carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO ₃ according to include linear esters. Suitable starting materials will include natural fatty substances such as those derived from tallow, palm oil and the like.

Alkyl ester sulfonate surfactants particularly preferred for laundry applications have the structural formula Wherein R ³ is C ₈ -C ₂₀ hydrocarbyl, preferably alkyl, or a combination thereof, R ⁴ is C ₁ -C ₆ hydrocarbyl, preferably alkyl, or a combination thereof, and M is an alkyl ester An alkyl ester sulfonate surfactant (which is a cation that forms a water-soluble salt with the sulfonate).
Suitable salt-forming cations include metals, for example, sodium, potassium and lithium, and substituted or unsubstituted ammonium cations, for example, monoethanolamine, diethanolamine, and triethanolamine. Preferably, R ³ is C ₁₀ -C ₁₆ alkyl and R ⁴ is methyl, ethyl or isopropyl. R ³
Particularly preferred are methyl ester sulfonates in which is C ₁₀ -C ₁₆ alkyl.

Alkyl sulfate surfactants The alkyl sulfate surfactants here have the formula ROSO ₃ M
Wherein R is preferably C ₁₀ -C ₂₄ hydrocarbyl, preferably alkyl or hydroxyalkyl having a C ₁₀ -C ₂₀ component, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, and M is H or positive. Ions, such as alkali metal cations (eg, sodium, potassium, lithium), or ammonium or substituted ammonium (eg, methyl-, dimethyl-, and trimethylammonium cations and quaternary ammonium cations, such as tetramethyl-) Ammonium and dimethylpiperidinium cations and ethylamine,
Quaternary ammonium cations derived from alkylamines such as diethylamine, triethylamine, and the like, and mixtures thereof). Typically, C ₁₂ -C ₁₆ alkyl chains are preferred for lower wash temperatures (eg, less than about 50 ° C.) and C ₁₆ -C ₁₈ alkyl chains are preferred for higher wash temperatures (eg, than about 50 ° C.). High temperature).

Alkyl alkoxylated sulfate surfactant alkyl alkoxylated sulfate surfactants herein, wherein RO (A) _m SO _{3 M} [wherein, R is an unsubstituted C ₁₀ -C ₂₄ alkyl having a C ₁₀ -C ₂₄ alkyl component or hydroxyalkyl group, preferably a C ₁₂ -C ₂₀ alkyl or hydroxyalkyl, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, a is an ethoxy or propoxy unit, m is greater than zero, typically About 0.
5 to about 6, more preferably about 0.5 to about 3, wherein M is H or, for example, a metal cation (eg, sodium, potassium, lithium, calcium, magnesium, etc.),
Cations which can be ammonium or substituted ammonium cations]. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethylpiperidinium cations and ethylamine, diethylamine, triethylamine and the like. Examples thereof include those derived from alkylamines, and mixtures thereof. Exemplary surfactants, C ₁₂ -C ₁₈ alkyl polyethoxylate (1.0) sulfate (C ₁₂ -C
_{18 E (1.0) M),} C 12 ~C 18 alkyl polyethoxylate (2.25) sulfate _{(C 12 ~C 18 E (2.25} ) M), C 12 ~
C ₁₈ alkyl polyethoxylate (3.0) sulfate _{(C 12 ~C 18 E (3.0} ) M), and C ₁₂ -C ₁₈ alkyl polyethoxylate (4.0) sulfate _{(C 12 ~C 18 E (4} .
0) M), where M is conveniently selected from sodium and potassium.

Other Anionic Surfactants Other anionic surfactants useful for cleaning purposes can also be incorporated into the laundry detergent compositions of the present invention. These include soap salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts, such as monoethanolamine, diethanolamine, and triethanolamine salts), C ₉ -C ₂₀ linear. Pyrolysis of alkyl benzene sulfonates, C ₈ -C ₂₂ primary or secondary alkane sulfonates, C ₈ -C ₂₄ olefin sulfonates, e.g., alkaline earth metal citrates as described in GB 1,082,179 sulfonated polycarboxylic acids prepared by sulfonation of the product, C ₈ -C ₂₄
Alkyl polyglycol ether sulfates (containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates,
Fatty oleyl glycerol sulfate, alkyl phenol ethylene oxide ether sulfate, paraffin sulfonate, alkyl phosphate, isethionate such as acyl isethionate, N-acyl taurate, alkyl succinate and sulfosuccinate, monoester of sulfosuccinate (particularly saturated and unsaturated C ₁₂ -C ₁₈ monoesters) and sulfosuccinates diesters (especially saturated and unsaturated C ₆ -C ₁₂ diesters), acyl sarcosinates, alkyl polysaccharides sulfates, for example, alkyl polyglucosides Sulfates (non-ionic non-sulfated compounds are described below), branched primary alkyl sulfates, and alkyl polyethoxycarboxylates, for example, of the formula RO (CH ₂ CH ₂ O) _k
—CH ₂ COO ⁻ M ⁺ , wherein R is C ₈ -C ₂₂ alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation. Resin acids and hydrogenated resin acids such as rosin, hydrogenated rosin, and resin acids present in or derived from tall oil are also suitable. Still other examples are described in "Surfactants and Detergents" (Volumes I and II by Schwartz, Perry and Birch). Various such surfactants are generally described in U.S. Pat.No. 3,929,678 issued Dec. 30, 1975 to Laurin et al., Column 23, lines 58-29.
It is also disclosed in column 23, incorporated herein by reference.

When incorporated herein, the laundry detergent composition of the present invention comprises:
Typically, such an anionic surfactant comprises about 1 to about 40% by weight, preferably about 3 to about 20% by weight.

Other Surfactants The laundry detergent compositions of the present invention include cationic surfactants, amphoteric surfactants, zwitterionic surfactants, and semipolar surfactants, as well as nonionic surfactants other than those described herein. An activator may also be included. However, without intending to be limited thereby, non-ionic surfactants other than those described herein, such as the semi-polar non-ionic amine oxides described below, are compatible with the non-ionic surfactant systems of the present invention. It is believed that it will not provide the associated blotting benefits.

Suitable cationic detergent surfactants for use in the laundry detergent compositions of the present invention are those having one long chain hydrocarbyl group. Examples of such cationic surfactants include alkyl dimethyl ammonium halogenide and formula [R ² (OR ³⁾ y] [R ⁴ (OR ³⁾ y] ₂ R ⁵ N ⁺ X ^- wherein, R ² Is an alkyl or alkylbenzyl group having about 8 to about 18 carbon atoms in the alkyl chain,
R ³ is -CH ₂ CH _2- , CH ₂ CH (CH ₃ )-, -CH ₂ CH (CH ₂ OH)
—, —CH ₂ CH ₂ CH ₂ — and mixtures thereof; each R ⁴ is a C ₁ -C ₄ alkyl, a C ₁ -C ₄ hydroxyalkyl, linking two R ⁴ groups A benzyl ring structure formed by: —CH ₂ CHOH—CHOHCOR ⁶ CHOHCH ₂ OH (where R ⁶ is hexose or a hexose polymer having a molecular weight of less than about 1000) and hydrogen (when y is not 0)
R ⁵ is the same as R ⁴ or is an alkyl chain, and the total number of carbon atoms of R ² + R ⁵ is about 18 or less; each y is 0 to about 10, The sum of the values is from about 0 to about 15; X is a compatible anion].

Other cationic surfactants useful here are also available from October 1980
No. 4,228,044, issued May 14, issued to Cambrai, incorporated herein by reference.

When incorporated herein, the laundry detergent composition of the present invention comprises:
Typically, such cationic surfactants comprise 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 surfactants are aliphatic derivatives of secondary or tertiary amines in which the aliphatic groups can be straight or branched, or aliphatic derivatives of heterocyclic secondary and tertiary amines. It can be widely described as a derivative. One of the aliphatic substituents has at least 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one has an anionic water solubilizing group, for example, carboxy, sulfonate, sulfate. It contains. For examples of amphoteric surfactants, see U.S. Pat. No. 3,929,678 to Dec. 30, 1975, column 19, lines 18-35 (incorporated herein by reference).

When incorporated herein, the laundry detergent composition of the present invention comprises:
Typically, such amphoteric surfactants comprise 0 to about 15% by weight, preferably about 1 to about 10% by weight.

Zwitterionic surfactants are also suitable for use in laundry detergent compositions. These surfactants include derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Can be widely described. For examples of amphoteric surfactants, see December 30, 1975.
See U.S. Pat. No. 3,929,678 to Laurin et al., Column 19, line 38 to column 22, line 48, incorporated by reference herein.

When incorporated herein, the laundry detergent composition of the present invention comprises:
Typically, such zwitterionic surfactants comprise 0 to about 15% by weight, preferably about 1 to about 10% by weight.

Semipolar nonionic surfactants are a special category of nonionic surfactants. Examples thereof include one alkyl moiety having about 10 to about 18 carbon atoms and about 1 to about 3 carbon atoms.
A water-soluble amine oxide containing two moieties selected from the group consisting of an alkyl group and a hydroxyalkyl group;
One alkyl moiety having about 10 to about 18 carbon atoms and about 1 carbon atom;
A water-soluble phosphine oxide containing two moieties selected from the group consisting of an alkyl group of about 3 and an alkyl group of hydroxyalkyl; and one alkyl moiety of about 10 to about 18 carbon atoms and alkyl of about 1 to about 3 carbon atoms. And a water-soluble sulfoxide containing one moiety selected from the group consisting of hydroxyalkyl moieties.

As a semipolar nonionic detergent surfactant, the formula Wherein R ³ is an alkyl, hydroxyalkyl, or alkylphenyl group having from about 8 to about 22 carbon atoms or a mixture thereof; R ⁴ is an alkylene or hydroxyalkylene group having from about 2 to about 3 carbon atoms, or a mixture thereof. A mixture; x
Is from 0 to about 3; each R ⁵ is an alkyl or hydroxyalkyl group having about 1 to about 3 carbon atoms or a polyethylene oxide group containing about 1 to about 3 ethylene oxide groups. Agents. R ⁵ groups can, for example, can be bonded together to form a ring structure through an oxygen or nitrogen atom.

These amine oxide surfactants include, in particular, C
₁₀ -C ₁₈ alkyl dimethyl amine oxides and C ₈ -C ₁₂
Alkoxyethyl dihydroxyethylamine oxide is exemplified.

When incorporated herein, the laundry detergent composition of the present invention comprises:
Typically, such semi-polar nonionic surfactants are from 0 to about 15
% By weight, preferably from about 1 to about 10% by weight.

Builders The laundry detergent composition of the present invention can include an inorganic or organic detersive builder to help control mineral hardness.

The amount of builder can vary widely depending on the end use of the composition and the desired physical form. Liquid formulations typically comprise at least about 1%, more typically about 5 to about 50%, preferably about 5 to about 30%, by weight of the detersive builder. Granular formulations typically comprise at least about 1%, more typically about 10 to about 80%, preferably about 15 to about 50%, by weight of the detersive builder. However, smaller or larger amounts of builders are not meant to be excluded.

Inorganic detergency builders include, but are not limited to, polyphosphoric acid (exemplified by tripolyphosphate, pyrophosphate, and glassy polymeric metaphosphate), phosphonic acid, phytic acid, silicic acid, carbonic acid (including bicarbonate and sesquicarbonate) ), Sulfuric acid, and alkali metal, ammonium and alkanol ammonium salts of aluminosilicate. Borate builders as well as builders containing borate-forming substances capable of forming borate under detergent storage or washing conditions (hereinafter collectively "borate builders") can also be used. Preferably, non-borate builders are used in the compositions of the present invention that are to be used under wash conditions of less than about 50 ° C, especially less than about 40 ° C.

Examples of silicate builders are alkali metal silicates,
In particular those having an SiO ₂ : Na ₂ O ratio of 1.6: 1 to 3.2: 1 and layered silicates, for example, US Pat. No. 4,664,839 issued May 12, 1987 to HP Ricke, incorporated herein by reference. And the layered sodium silicate described in 1. above. However, other silicates may also be used, such as magnesium silicate, which can serve as a crispness agent in granular formulations, as a stabilizer for oxygen bleaches, and as a component of a foam control system.

Examples of carbonate builders include sodium carbonate and sodium sesquicarbonate and those disclosed in German Patent Application No. 2,321,001, published Nov. 15, 1973, the disclosure of which is incorporated herein by reference. Alkaline earth metal and alkali metal carbonates, including mixtures with fine calcium carbonate.

Aluminosilicate builders are particularly useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions and can be a significant builder component in liquid detergent compositions. As an aluminosilicate builder, the empirical formula M _z (zAlO ₂ .y SiO ₂ ) wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2;
Is 1). This material has a magnesium ion exchange capacity of at least 50 mg equivalent of CaCo ₃ hardness per gram of anhydrous aluminosilicate. Preferred aluminosilicates have the formula Na _z [(AlO ₂ ) _z (SiO ₂ ) _y ] .xH ₂ O, where z and y are integers of at least 6, and the molar ratio of z to y is from 1.0 to about 0.5. Where x is from about 15 to about
Which is an integer of 264).

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally occurring aluminosilicates or synthetically derived.
The method for producing aluminosilicate ion-exchange materials was October 1976.
No. 3,985,669 issued to Krumel et al. On May 12, which is incorporated herein by reference. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are designated Zeolite A, Zeolite P
(B), and zeolite X. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula Na _{12 [(AlO 2) 12 (SiO 2} ) 12 ] · xH ₂ O (wherein, x is from about 20 to about 30, especially about 27 There is). This material is known as zeolite A. Preferably, the aluminosilicate has a diameter of about 0.1
It has a particle size of ~ 10μ.

Specific examples of polyphosphates include alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphates, sodium, potassium and ammonium pyrophosphates, sodium and potassium orthophosphates, having a degree of polymerization of about 6 to about 21. Certain sodium polymetaphosphate and salts of phytic acid.

Examples of phosphonate builder salts are the water-soluble salts of ethane-1-hydroxy-1,1-diphosphonic acid, especially the sodium and potassium salts, the water-soluble salts of methylene diphosphonic acid, such as the trisodium and tripotassium salts and Water-soluble salts of substituted methylene diphosphonic acids, such as trisodium and tripotassium ethylidene, isopropylidenebenzylmethylidene and halomethylidene diphosphonates. Phosphonate builder salts of the foregoing type are disclosed in U.S. Pat.Nos. 3,159,581 and 3,213,030 issued to Deal on December 1, 1964 and October 19, 1965; U.S. Pat. Patent 3,422,021
Issued September 3, 1968 and 1969 to Quinby
No. 3,400,148 and U.S. Pat. No. 3,422,137, issued Jan. 14, 1998, the disclosure of which is incorporated herein by reference.

The polycarboxylate builder can generally be added to the composition in the acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metal salts such as the sodium, potassium and lithium salts, particularly the sodium or ammonium and substituted ammonium salts (eg, alkanol ammonium salts) are preferred.

Polycarboxylate builders include various categories of useful substances. One important category of polycarboxylate builders includes ether polycarboxylates. A number of ether polycarboxylates for use as detergency builders have been disclosed. Examples of useful ether polycarboxylates include U.S. Pat. No. 3,128,28 issued to Berg on April 7, 1964.
And oxydisuccinates as disclosed in US Pat. No. 3,635,830 to Lamberke et al., Issued Jan. 18, 1972, both of which are incorporated herein by reference.

Specific types of ether polycarboxylates useful as builders in the present invention include those of the general formula CH (A) (COOX) -CH (COOX) -O-CH (COOX) -CH
(COOX) (B) wherein A is H or OH; B is H or -O-CH
(COOX) a -CH ₂ (COOX), X can be mentioned those having a a a) H or a salt-forming cation. For example, in the above general formula, A
If and B are both H, the compound is oxydisuccinic acid and its water-soluble salts. A is OH, B is H
If is, the compound is tartrate monosuccinic acid (TMS) and its water-soluble salts. A is H, B is -O
If a _{-CH (COOX) -CH 2 (COOX} ), the compound,
Tartrate disuccinic acid (TDS) and its water-soluble salts. Mixtures of these builders are particularly preferred for use herein. TMS to TDS weight ratio of about 97: 3 to about 20:80
Particularly preferred is a mixture of TMS and TDS. These builders are disclosed in U.S. Pat. No. 4,663,071, issued May 5, 1987 to Bush et al.

Suitable ether polycarboxylates include cyclic compounds, especially alicyclic compounds, for example, U.S. Pat.Nos. 3,923,679, 3,835,163, 4,158,
No. 635, No. 4,120,874 and No. 4,102,903
And those described in the above specification (all of which are incorporated herein by reference).

Other useful detergency builders include the structure HO- [C (R) (COOM) -C (R) (COOM) -O] _n
-H wherein M is hydrogen or a cation (the resulting salt is water-soluble), preferably an alkali metal, ammonium or substituted ammonium cation, and n is from about 2 to about 15 (preferably, n is About 2 to about 10, more preferably n averages about 2 to about 4), each R being the same or different, hydrogen, C
Selected from _1-4 alkyl or C _1-4 substituted alkyl (preferably, R is hydrogen)].

As other ether polycarboxylates, a copolymer of maleic anhydride and ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-
Trisulfonic acid, and carboxymethyloxysuccinic acid.

Organic polycarboxylate builders also include various alkali metal, ammonium and substituted ammonium salts of polyacetic acid. Examples of polyacetic acid builder salts are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid and nitrilotriacetic acid.

Also included are polycarboxylates such as melitic acid, succinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, benzenepentacarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

Citric acid-based builders, such as citric acid and its soluble salts, are polycarboxylate builders of particular importance to heavy duty liquid detergent formulations, but can also be used in particulate compositions. Suitable salts include metal salts, for example, sodium, lithium and potassium salts, and ammonium and substituted ammonium salts.

Another carboxylate builder, March 1973
Carboxylated carbohydrates disclosed in Deal U.S. Pat. No. 3,723,322 issued on Nov. 28, which is incorporated herein by reference.

Also, U.S. Pat.
The 3,3-dicarboxy-4-oxa-1,6-hexanediate and related compounds disclosed in US Pat. No. 566,984, incorporated herein by reference, are suitable in the laundry detergent compositions of the present invention. Useful succinic acid builders include C ₅ -C
₂₀ alkyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenyl succinic acid. Alkyl succinic acids typically have the general formula R—CH (COOH) CH ₂ (COOH), ie, are derivatives of succinic acid, wherein R is a hydrocarbon, eg, C ₁₀ -C ₂₀
Alkyl or alkenyl, preferably C ₁₂ -C ₁₆ , or R is hydroxyl, as described in said patent,
Substituted with sulfo, sulfoxy or sulfone substituents).

The succinate builder is preferably used in the form of a water-soluble salt, including sodium, potassium, ammonium and alkanolammonium salts.

Specific examples of succinate builders include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate, and the like. Lauryl succinate is a preferred builder of this group and is described in European Patent Application No. 86200690.5 / 0,200,263 published Nov. 5, 1986.

Examples of useful builders include sodium and potassium carboxymethyloxymalonates, carboxymethyloxysuccinates, cis-cyclohexanehexacarboxylate, cis-cyclopentanetetracarboxylate, water-soluble polyacrylic acid Salts (these polyacrylates having a molecular weight of greater than about 2,000 can also be usefully employed as dispersants), and salts of maleic anhydride and vinyl methyl ether or ethylene copolymers.

Other suitable polycarboxylates are the polyacetal carboxylates disclosed in U.S. Pat. No. 4,144,226 issued March 13, 1979 to Curtchfield et al., Which is incorporated herein by reference. These polyacetal carboxylates can be produced as described below.
The ester of glyoxylic acid and the polymerization initiator are placed together under polymerization conditions. The resulting polyacetal carboxylate is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, convert it to the corresponding salt, Add to the agent.

Polycarboxylate builders are also disclosed in Deal U.S. Pat. No. 3,308,067, issued Mar. 7, 1967, incorporated herein by reference. Examples of such a substance include water-soluble salts of homopolymers and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid, and methylenemalonic acid.

Other organic builders known in the art can also be used. For example, monocarboxylic acids having long chain hydrocarbyl and their soluble salts can be utilized. These include substances commonly referred to as "soaps". Chain length of C ₁₀ -C ₂₀ are typically utilized. Hydrocarbyls can be saturated or unsaturated.

Enzymes Detergent enzymes can be used as the laundry detergent compositions of the present invention for a variety of reasons, including, for example, protein-based stains, carbohydrate-based stains, or triglyceride-based stain removal and prevention of runaway dye transfer. Can be blended. Enzymes to be included include proteases, amylases, lipases, cellulases, and peroxidases, and mixtures thereof. They may have any suitable origin, for example, plant, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors, such as pH activity and / or stability optima, thermal stability, stability to active detergents, builders, and the like. In this regard, bacterial or fungal enzymes such as bacterial amylase and protease, and fungal cellulase are preferred.

Suitable examples of proteases are Bacillus subtilis and Bacillus
It is a subtilisin obtained from a specific strain of Licheniforms. Another suitable protease is obtained from a strain of Bacillus that has maximum activity over a pH range of 8 to 12, developed by Novo Industries A / S and sold under the trade name Esperase. The preparation of this and similar enzymes is described in Novo GB 1,243,784. A protein as commercial proteolytic enzymes suitable for removing stains based the trade names Alcalase by Novo Industries A / S (Denmark) (ALCALASE ^TM) and Savinase (SAVINASE ^TM)
And those sold under the trade name MAXATASE ^™ by International Bio-Synthetics, Inc. (Netherlands).

Enzymes designated herein as Protease A and Protease B are of particular interest in the category of proteolytic enzymes for liquid detergent compositions. Protease A and its preparation are described in European Patent Application No. 130,756 published Jan. 9, 1985.
The description is incorporated herein by reference (incorporated herein by reference). Protease B is a proteolytic enzyme that differs from protease A in that it has leucine instead of tyrosine at position 217 in the amino acid sequence. Protease B contains 19
It is described in European Patent Application No. 87303761.8 filed Apr. 28, 1987, which is incorporated herein by reference. Also, the method for producing Protease B is disclosed in European Patent Application No. 130,756, Bot et al., Published Jan. 9, 1985, which is incorporated herein by reference.

Amylases include, for example, α-amylases obtained from a special strain of Bacillus licheniformus, described in more detail in GB 1,296,839 (Novo) previously incorporated herein by reference. The amylolytic proteins, e.g., International Bio - Synthetics Inc. made Rapidaze (RAPIDASE ^TM), and Novo Industries Ltd. of Termamyl (TERMAMYL ^TM) can be mentioned.

Cellulases that can be used in the present invention include both bacterial and fungal cellulases. Preferably, they will have a pH optimum of 5 to 9.5. Suitable cellulases are described in U.S. Patent No. 4,435,307, issued March 6, 1984 to Barvesgoad et al., Which discloses a fungal cellulase produced from Humicola insolens, incorporated herein by reference. It has been disclosed. Suitable cellulases are also described in GB 2.075.028, GB 2.095.2.
No. 75 and DE-OS 2.247.832.

Examples of such cellulases include Humicola insolens [Humicola grisea bal thermo idea (Hu
micola grisea var. thermoidea)], in particular, a cellulase produced by a Humicola strain DSM1800, a cellulase produced by a fungus of Bacillus N belonging to the genus Aeromonas or a cellulase 212-producing fungus, and a seawater mollusk [Drabella auricular solander] (Dolabella Auricula Solander)] from the hepatopancreas.

A lipase enzyme suitable for detergent use is disclosed in British Patent No.
No. 1,372,034 (herein incorporated by reference) as disclosed in Pseudomonas st.
utzeri) produced by microorganisms of the Pseudomonas group, such as ATCC 19.154. Suitable lipases include the microorganism Pseudomonas fluorescens (Pseu
domonas Fluorescens) which show a positive immune cross-reactivity with antibodies to lipase produced by IAM1057. This lipase and its purification method are described in Japanese Patent Application No. 53-20487 published on Feb. 24, 1978 for the convenience of the public. This lipase is available from Amano Pharmaceutical Co., Ltd., Nagoya, Japan, under the trade name Lipase P "Amano" (hereinafter referred to as "Amano-P"). Such a lipase according to the present invention can be used as a standard well-known immunodiffusion method for octalony (Acta. Med. Sca).
n., 133, 76-79 (1950)) should be used to demonstrate positive immune cross-reactivity with Amano-P antibodies. Methods for these lipases and their immune cross-reactivity with Amano-P are also described in Tom et al., U.S. Pat.
No. 7,291, incorporated herein by reference. Typical examples thereof are Amano-P lipase, lipase ex Pseudomonas fragi FERM P1339 (available under the trade name Amano-B), lipase ex Pseudomonas nitrore
ducens var.lipolyticum FERM P1338 (trade name Amano-
Available at CES), Lipase ex Chromobacter viscosu
m, for example, Chromobacter viscosum var.commercially available from Toyo Joeso Company of Takata, Japan.
lipolyticum NRRLB3673; and US Biochemical Corporation in the United States and Desoint
Yet another Chromobacter viscosum lipase from the company, and the lipase ex Pseudomonas gladioli.

The peroxidase enzyme is used in combination with an oxygen source, for example, percarbonate, perborate, persulfate, hydrogen peroxide and the like. They are used for "solution bleaching", i.e. to prevent the transfer of dyes or pigments removed from the substrate during the washing operation to other elements in the washing liquor. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxidase, such as chloroperoxidase and bromoperoxidase. Peroxidase-containing detergent compositions are described, for example, in PCT International Application WO 89/099 by O. Kirk, assigned to Novo Industries A / S, published October 19, 1989.
No. 813, incorporated herein by reference.

A wide range of enzymatic substances and means of incorporation into synthetic detergent granules are also disclosed in McCarty et al., US Pat.
No. 3,553,139, which is incorporated herein by reference. Enzymes are further described in U.S. Pat. No. 4,101,457 issued to Place et al., Jul. 18, 1978, and U.S. Pat. No. 4,507,219 issued to Hughes Mar. 26, 1985, both incorporated herein by reference. ). Enzyme substances useful in liquid detergent formulations and methods of incorporation into such formulations are disclosed in Hora et al., U.S. Pat. No. 4,261,868, issued Apr. 14, 1981, incorporated herein by reference. .

Enzymes are usually up to about 5 mg of active enzyme per gram of composition,
More typically, it is incorporated in an amount sufficient to provide from about 0.05 mg to about 3 mg.

In the case of granular detergents, the enzyme is preferably coated or prilled with an additive inert to the enzyme to minimize dust formation and improve storage stability. Techniques for accomplishing this are well known in the art. In liquid formulations, an enzyme stable system is preferably utilized. Enzyme stabilization techniques for aqueous detergent compositions are well known in the art. For example, one enzyme stabilization technique in aqueous solution involves the use of free calcium ions from sources such as calcium acetate, calcium formate, calcium propionate, and the like. Calcium ions can be used in combination with short-chain carboxylate, preferably formate. See, for example, U.S. Patent No. 4,318,818, issued March 9, 1982 to Retton et al., Which is incorporated herein by reference. It has also been proposed to use polyols such as glycerol and sorbitol. Alkoxy-alcohols, dialkyl glycoethers, mixtures of polyhydric alcohols with polyfunctional aliphatic amines (e.g. alkanolamines such as diethanolamine, triethanolamine, diisopropanolamine), and boric acid or alkali metal borates. Enzyme stabilization techniques are additionally disclosed in Horn et al., US Pat. No. 4,261,868, issued Apr. 14, 1981, and Gedge et al., US Pat. No. 3,600,319, issued Aug. 17, 1971 (both in US Pat. And published and exemplified in Venezuean European Patent Application Publication No. 0 199 405 and Application No. 86200586.5 published October 29, 1986.
Stabilizers that are not boric acid and borates are preferred. Also, enzyme stable systems are described, for example, in U.S. Pat. Nos. 4,261,868, 3,600,319 and 3,519,570.

Bleaching Compounds-Bleaching Agents and Bleaching Activators The laundry detergent compositions of the present invention may contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleaching activators. When formulated, the bleaching compounds will typically comprise from about 1% to about 20%, more typically from about 1% to about 20%, of such laundry detergent compositions. Generally, the bleaching compound is an optional ingredient in non-liquid formulations, such as granular detergents. If present, the amount of bleach activator will typically be from about 0.1% to about 60% of the bleaching composition, more typically from about 0.5% to about 40%.

The bleach used herein can be any bleach useful in detergent compositions for fabric cleaning, hard surface cleaning, or other now known or known cleaning purposes. These include oxygen bleaches as well as other bleaches. Less than about 50 ° C, especially about 40 ° C
For less washing conditions, the composition preferably does not contain borates or substances capable of forming borates in situ under detergent storage or washing conditions (ie, borate-forming substances). Thus, under these conditions, it is preferred to use a non-borate, non-borate forming bleach. Preferably, the detergents to be used at these temperatures are substantially free of borate and borate producing substances. As used herein, "substantially free of borate and borate-forming substances" means that the composition contains no more than about 2%, preferably no more than 1%, more preferably no more than 0% by weight of borate-containing and borate-forming substances of any kind. Would mean containing.

One category of bleaches that can be used includes percarboxylic acid bleaches and their salts. Preferred examples of this type of bleach include magnesium monoperoxyphthalate hexahydrate, magnesium salt of m-chloroperbenzoic acid,
4-nonylamino-4-oxoperoxybutyric acid and diperoxidedecanedioic acid. Such bleaches are disclosed in Hartman, U.S. Pat.
No. 483,781, U.S. Patent Application No. 740,446 to Barnes et al. Filed on Jun. 3, 1985, European Patent Application No. 0,133,354 to Banks et al.
U.S. Patent No. 4,412,934 issued to Chung et al. On Nov. 1, 1991, all of which are incorporated herein by reference.
Is disclosed. Highly preferred bleaches include US Pat. No. 4,634,551 issued Jan. 6, 1987 to Vans et al.
Also mentioned are 6-nonyl-amino-6-oxoperoxycaproic acid described in the specification (herein incorporated by reference).

Another category of bleaches that can be used includes halogen bleaches. Examples of hypohalite bleaches include, for example, trichloroisocyanuric acid and sodium dichloroisocyanurate and potassium dichloroisocyanurate and N-chloro and N-bromoalkanesulfonamides. Such materials are usually
It is added at 0.5 to 10% by weight, preferably 1 to 5% by weight.

Peroxygen bleaches can also be used. Suitable peroxygen bleaching compounds include sodium carbonate hydrogen peroxide, sodium pyrophosphate hydrogen peroxide, urea hydrogen peroxide, and sodium peroxide.

The peroxygen bleach is preferably combined with a bleach activator, which results in in-situ formation in an aqueous solution of the peroxyacid corresponding to the bleach activator (ie, during the washing process).

Preferred bleaching activators 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 the longest linear alkyl chain extending from and including the carbonyl carbon has about 6 to about 10 carbon atoms. , L is a leaving group, the conjugate acid pK _a about 4
(Having about 13). These bleach activators were supplied to Mao et al. In April 1990.
It is described in U.S. Pat. No. 4,915,854, issued on Dec. 10, which is hereby incorporated by reference, and in U.S. Pat. No. 4,412,934, hereby incorporated by reference herein.

Bleaches other than oxygen bleaches are known in the art and can be used herein. One type of non-oxygen bleach of particular interest includes light activated bleach, such as sulfonated zinc phthalocyanine and / or aluminum phthalocyanine. These substances can be deposited on the substrate during the cleaning process. Upon irradiation with light in the presence of oxygen by hanging the cloth to dry in sunlight, the sulfonated zinc phthalocyanine is activated and thus the substrate is bleached. Preferred zinc phthalocyanine and light activated bleaching methods are described in U.S. Pat. No. 4,033,718, issued Jul. 5, 1977, to Holcombe et al., Incorporated herein by reference. Typically, the detergent composition comprises
About 0.025 to about 1.25% by weight of sulfonated zinc phthalocyanine
Will be contained.

Polymeric Soil 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. Polymer stain release agent,
A hydrophilic segment for hydrophilizing the surface of hydrophobic fibers such as polyester, nylon, etc., and adhere to the hydrophobic fibers and remain adhered throughout the washing and rinsing cycle, thus as an anchor for the hydrophilic segment It is characterized by having both a hydrophobic segment to serve. This may allow stains that occur after treatment with the soil release agent to be more easily cleaned up in a later cleaning procedure.

Examples of the polymer soil release agent include cellulose derivatives such as hydroxyether cellulose polymers, and copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide terephthalate or polypropylene oxide terephthalate.

Cellulosic derivatives that function as soil release agents are commercially available, and examples thereof Methocel (Methocel ^R)
(Dow) and the like.

Cellulosic soil release agents include methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose, C ₁ ~ such as hydroxybutyl methylcellulose
Also included are those selected from the group consisting of C ₄ alkyl and C ₄ hydroxyalkyl cellulose. Various cellulose derivatives useful as soil release polymers are available from Nicol et al.
It is disclosed in U.S. Patent No. 4,000,093, issued December 28, 76, incorporated herein by reference.

Soil release agents characterized by poly (vinyl ester) hydrophobic segments include poly (vinyl esters), for example, graft copolymers of C ₁ -C ₆ vinyl esters, preferably polyalkylene oxides such as polyethylene oxide backbones Poly (vinyl acetate) grafted on the main chain is mentioned. Such materials are known in the art and are described in European Patent Application 0 291 048 published April 22, 1987 by Kood et al. Suitable commercial soil release agents of this type include Sokalan ^™ .
Substances such as Sokaran ^™ HP-22 available from BASF (West Germany).

One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. More specifically, these polymers have a molar ratio of ethylene terephthalate units to PEO terephthalate units of from about 25:75 to about 3
It consists of a 5:65 repeating unit of ethylene terephthalate and PEO terephthalate, said PEO terephthalate unit containing polyethylene oxide having a molecular weight of about 300 to about 2000. The molecular weight of this polymeric soil release agent is about 25,000
In the range of ~ 55,000. See Haze, U.S. Pat. No. 3,959,230, issued May 25, 1976, incorporated herein by reference. July 1975 discloses a similar copolymer
See also U.S. Pat. No. 3,893,929 to Basder, issued on May 8, incorporated by reference.

Another preferred polymeric soil release agent has an average molecular weight of 300-300.
A polyester having repeating units of ethylene terephthalate units containing 10 to 15% by weight of ethylene terephthalate units together with 90 to 80% by weight of polyoxyethylene terephthalate units derived from 5,000 polyoxyethylene glycols; The molar ratio of ethylene terephthalate units to polyoxyethylene terephthalate units is from 2: 1 to 6: 1. Examples of this polymer is commercially available materials Zerukon (Zelcon ^R) 5126 (DuPont) and Milly's (Milease ^R) T (manufactured by ICI) and the like. These polymers and their preparation are described in detail in U.S. Pat. No. 4,702,857 issued Oct. 27, 1987 to Gosselink, which is incorporated herein by reference.

Another preferred polymeric soil release agent is the sulfonation product of a substantially linear ester oligomer consisting of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and a terminal moiety covalently bonded to the backbone (as described above. The release agent is derived from allyl alcohol ethoxylate, dimethyl terephthalate, and 1,2-propylene diol, with the terminal portion of each oligomer having an average of about 1 to about 4 sulfonate groups). These soil release agents are described in U.S. Pat. No. 4,968,451, issued Nov. 6, 1990 to JJ Schebel and EP Gosselink, U.S. patent application Ser.
No. 09, incorporated herein by reference.

Other suitable polymeric soil release agents include ethyl- or methyl-blocked 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters of U.S. Patent No. 4,711,730 issued December 8, 1987 to Gosselink et al. U.S. Pat. No. 4,721,580, issued Jan. 26, 1988 to Gosselink et al., Wherein the anionic endblocking oligomeric ester comprises a sulfo-polyethoxy group derived from polyethylene glycol (PEG); _{X- (OCH 2 CH 2) n} - ( wherein, n is 12 to about 43, X
October 1987 Gosse link having polyethoxy endcapping of C ₁ -C ₄ alkyl or, preferably, methyl) is
No. 4,702,857, issued on the 27th, which includes block polyester oligomer compounds, all of which are incorporated herein by reference.

Additional soil release polymers include, for example, U.S. Pat.
No. 877,896, which patent is incorporated herein by reference. Terephthalate esters contain asymmetrically substituted oxy-1,2-alkyleneoxy units.

If utilized, the soil release agent will generally comprise from about 0.01 to about 10.0% by weight of the laundry detergent composition of the present invention, preferably from about 0.
It will comprise from 1 to about 5.0% by weight, more preferably from about 0.2 to about 3.0% by weight.

Chelating Agents The laundry detergent compositions of the present invention may also optionally contain one or more iron / manganese chelating agents as builder auxiliary substances. Such chelators can be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally-substituted aromatic chelators as defined below, and mixtures thereof. Without wishing to be limited by theory, it is believed that the benefits of these materials are due, in part, to the exceptional ability to remove iron and manganese ions from the wash liquor by the formation of soluble chelates.

Aminocarboxylates useful as optional chelating agents in the compositions of the present invention comprise one or more (preferably at least two) units of substructure. Wherein M is hydrogen, alkali metal, ammonium or substituted ammonium (eg, ethanolamine) and x is from 1 to about 3, preferably 1. Preferably, these aminocarboxylates do not contain alkyl or alkenyl groups having more than about 6 carbon atoms. Examples of usable amine carboxylates include ethylenediaminetetraacetate, N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, triethylenetetraaminehexaacetate, diethylenetriaminepentaacetate and ethanoldiglycine, and alkali metal salts thereof. Ammonium salts, and substituted ammonium salts and mixtures thereof.

Aminophosphonates are also suitable for use as chelating agents in the laundry detergent compositions of the present invention when at least a small amount of total phosphorus is allowed in the detergent composition. 1
Substructure of above (preferably at least 2) units Wherein M is hydrogen, alkali metal, ammonium or substituted ammonium and x is from 1 to about 3, preferably 1
Are useful, examples include ethylenediaminetetrakis (methylene phosphonate), nitrilotris (methylene phosphonate) and diethylenetriamine pentakis (methylene phosphonate). Preferably, these aminophosphonates are
It does not contain alkyl or alkenyl groups having more than about 6 carbon atoms. Alkylene groups can be shared by substructures.

Also, polyfunctionally substituted aromatic chelators are useful in the present compositions. These substances have the general formula (Wherein at least one R a is -SO ₃ H or -COOH) may be a compound or their soluble salts, and mixtures thereof having. May 21, 1974 to Conner
U.S. Pat. No. 3,812,044, issued to Japan, incorporated herein by reference, discloses polyfunctionally substituted aromatic chelating / sequestering agents. A preferred compound of this type in the acid form is dihydroxydisulfobenzene, such as 1,2-dihydroxy-3,5-disulfobenzene. Alkaline detergent compositions use these materials as alkali metal salts, ammonium salts or substituted ammonium salts (eg, mono-
Or triethanolamine salt).

If utilized, these chelators are generally
It will comprise from about 0.1 to about 10% by weight of the laundry detergent composition of the present invention. More preferably, the chelating agent will make up from about 0.1% to about 3.0% by weight of such compositions.

Clay Smear Removal / Reattachment Prevention Agents Clay stain removal / reattachment inhibitors useful in the laundry detergent compositions of the present invention include polyethylene glycol and water soluble ethoxylated amines having clay stain removal and antiredeposition properties. Can be

Polyethylene glycol compounds useful in the laundry detergent compositions of the present invention typically have a molecular weight of about 400 to about 100,000,
Preferably about 1,000 to about 20,000, more preferably about 2,000
To about 12,000, most preferably from about 4,000 to about 8,000. Such compounds are commercially available and sold as Carbowax, available from Union Carbide, located in Danbury, CT.

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

(1) Ethoxylated monoamine having the formula (XL-)-N- (R ² ) ₂ (2) Or an ethoxylated diamine having (XL-) ₂ -NR ¹ -N- (R ² ) ₂ (3) Ethoxylated polyamines having the general formula (4) An ethoxylated amine polymer having the formula: (5) a mixture thereof, wherein A ¹ is Or -O- and it is; R is H or C ₁ -C ₄ alkyl or hydroxyalkyl; R ¹ is C ₂ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or from 2 to about 20, A C ₂ -C ₃ oxyalkylene moiety having an oxyalkylene unit, provided that no O—N bond is formed; each R ² is a C ₁ -C ₄ or hydroxyalkyl, moiety -LX or two R ² together form a moiety — (CH ₂ ) _r , —A ² — (CH ₂ ) _s — (where A ² is —O
— Or —CH ₂ —, r is 1 or 2, s is 1 or 2,
r + s forms 3 or 4); X is a non-ionic group, anionic group or a mixture thereof; R ³ is a substituted C ₃ -C ₁₂ alkyl group having a substitution site, a hydroxyalkylene group, an alkenylene group, an aryl group group or alkaryl group,; R ⁴ is C ₁ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene,
Or C2- having from ₂ to about 20 oxyalkylene units
A C ₃ oxyalkylene moiety, provided that O-O bond or O-N bonds are not formed; L is a polyoxyalkylene moiety - _{^{[(R 5 O) m (CH}} 2 CH 2 O) n ] - (wherein , R ⁵ is C ₃ -C ₄ alkylene or hydroxyalkylene, m and n are part _{- (CH 2 CH 2 O)} n - is a number such to occupy at least about 50% by weight of said polyoxyalkylene moiety M) is from 0 to about 4 and n is at least about 12 in the case of the monoamine; m is 0 to about 3 in the case of the diamine; n
The R ¹ is C ₂ -C ₃ alkylene, hydroxyalkylene least about 6, R ¹ is when or alkenylene, is C ₂ ~
C ₃ alkylene, at least about 3 when is other than hydroxy alkylene or alkenylene; in the case of the polyamines and amine polymers, m is from 0 to about 10, n is at least about 3; p is 3 8; q is 1
Or 0; t is 1 or 0, where t is q is 1
Is 1 when is; w is 1 or 0; x + y + z
Is at least 2; y + z is at least 2. The most preferred soil release / anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in Vandermeal U.S. Pat. No. 4,597,898, issued Jul. 1, 1986, which is incorporated herein by reference. Another group of preferred clay soil removal /
The anti-redeposition agent is a cationic compound disclosed in Oh and Gosselink European Patent Application No. 111,965, published June 27, 1984, which is incorporated herein by reference. Other clay stain removal / anti-redeposition agents that can be used include 19
Gosselink European Patent Application No. 111, published June 27, 1984
Ethoxylated amine polymer disclosed in specification 984; July 1984
And the amine oxide disclosed in Conner U.S. Pat. No. 4,548,744 issued Oct. 22, 1985. (All of them are incorporated herein by reference).

The most preferred soil release / anti-redeposition agent is ethoxylated tetraethylenepentamine and a molecular weight of about 4,000 to about 8.0.
00 is a polyethylene glycol.

Granular detergent compositions containing such compounds typically contain about 0.01 to about 10.0% by weight of a clay remover; liquid detergent compositions typically contain about 0.01 to about 5.0% by weight. I do.

Polymeric Dispersants Polymeric polycarboxylate dispersants can advantageously be utilized in the laundry detergent compositions of the present invention. These substances are
Can help control calcium and magnesium hardness.
In addition to acting as builder adjuvants in the same manner as the polycarboxylates described above in the builder description, without wishing to be limited by theory, these high molecular weight dispersants have other properties, including low molecular weight polycarboxylates. It is believed that when used in combination with a builder, total detergency builder performance can be further enhanced by suppressing inorganic crystal growth, by particulate soil peptization, and by preventing redeposition.

A polycarboxylate substance that can be used as a polymer polycarboxylate dispersant has a general formula Wherein X, Y and Z are each selected from the group consisting of hydrogen, methyl, carboxy, carboxymethyl, hydroxy and hydroxymethyl; a salt-forming cation and n is from about 30 to about 400. These polymers or copolymers contain about 60% by weight. Preferably, X is hydrogen or hydroxy, Y is hydrogen or carboxy, Z
Is hydrogen and M is hydrogen, alkali metal, ammonia or substituted ammonium.

Such polymeric polycarboxylate materials are prepared by polymerizing or copolymerizing a suitable unsaturated monomer, preferably in the acid form. Unsaturated monomeric acids that can be polymerized to produce suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and Methylene malonic acid. The presence of monomeric segments containing non-carboxylate groups, such as vinyl methyl ether, styrene, ethylene, etc., in the polymeric polycarboxylates of the present invention indicates that such segments do not constitute more than about 40% by weight If so, it is preferable.

Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid based polymers useful herein are water soluble salts of polymerized acrylic acid. The average molecular weight of such an acid form polymer is about 2,
From 000 to 10,000, more preferably from about 4,000 to 7,000, most preferably from about 4,000 to 5,000. Examples of the water-soluble salt of the acrylic acid polymer include an alkali metal salt, an ammonium salt and a substituted ammonium salt. Such soluble polymers are known substances. The use of this type of polyacrylate in detergent compositions is described, for example, in Deal U.S. Pat. No. 3,308, March 7, 1967.
No. 067. This patent is incorporated herein by reference.

Acrylic / maleic acid based copolymers are also
You may use as a preferable component of a dispersing agent. Examples of such a substance include a water-soluble salt of a copolymer of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form is about 5,000-100,000, preferably about 6,000-60,00.
0, more preferably about 7,000 to 60,000. The ratio of acrylate segments to maleate segments in such copolymers will generally be from about 30: 1 to about 1: 1, more preferably from about 10: 1 to about 2: 1. Examples of the water-soluble salt of the acrylic acid / maleic acid copolymer include an alkali metal salt, an ammonium salt and a substituted ammonium salt. This type of soluble acrylate / maleate copolymer is disclosed in European Patent Application No. 66915 published December 15, 1982.
The known substances are described in the specification of this publication, which is incorporated herein by reference.

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

Brighteners Optical or other brighteners or whitening agents known to those skilled in the art can be incorporated into the laundry detergent compositions of the present invention. However, the choice of whitening agent depends on a number of factors, such as the type of detergent, the nature of the other components present in the detergent composition, the temperature of the wash water, the degree of agitation, and the ratio of tub to tub size. There will be.

Brightener selection also depends on the type of material to be cleaned, for example, cotton, synthetics, and the like. As most laundry detergent products are used to clean various fabrics, the detergent composition should contain a mixture of brighteners that will be effective in various fabrics. Of course, the individual components of such brightener mixtures need to be compatible.

Commercially available optical brighteners can be classified into subgroups, and as a subgroup, stilbene, pyrazoline,
Coumarins, carboxylic acids, methine cyanines, dibenzothiphene-5,5-dioxides, azoles, derivatives of 5- and 6-membered heterocyclic compounds, and other miscellaneous agents are included. Examples of such brighteners are disclosed in "Production and Application of Optical Brighteners", M. Zaradnik, published by John Willie and Sons of New York (1982), the disclosure of which is incorporated herein by reference. ing.

Examples of the stilbene derivative include, but are not limited to, bis (triazinyl) amino-stilbene derivatives; stilbene bisacylamino derivatives; stilbene triazole derivatives; stilbene oxadiazole derivatives;
Oxazole derivatives of stilbene; and styryl derivatives of stilbene.

Certain derivatives of bis (triazinyl) aminostilbene may be prepared from 4,4'-diamine-stilbene-2,2'-disulfonic acid.

Coumarin derivatives are not necessarily limited,
And 7-positions, and derivatives substituted at the 3- and 7-positions.

Examples of the carboxylic acid derivative include, but are not limited to, fumaric acid derivatives; benzoic acid derivatives; p-phenylene-bis-
Acrylic acid derivatives; naphthalenedicarboxylic acid derivatives; heterocyclic acid derivatives; and cinnamic acid derivatives.

Cinnamic acid derivatives can be further subdivided into a plurality of groups, and these groups are not necessarily limited, as disclosed on page 77 of Zaradonic literature, styrylazoles, styrylazoles, styrylbenzofurans, styryloxanes. Examples include diazole, styryltriazole, and styrylpolyphenyl.

Styrylazoles can be further subdivided into styrylbenzoxazoles, styrylimidazoles and styrylthiazoles as disclosed on page 78 of the Zaradonic literature. It will be appreciated that these three subclasses may not necessarily reflect an exhaustive list of subgroups that may subclass styrylazole.

Other optical brighteners are available from The Kirk-Othmer Encyclopedia.
of Chemical Technology, Vol. 3, pp. 737-750 (John Willy End Sun, Inc., 1962), the disclosure of which is incorporated herein by reference.
Dibenzothiophene-5,5 disclosed on pages 741 to 749 of
-Derivatives of dioxide and 5,7-diaminodibenzothiophene-2,8-disulfonic acid 5,5 dioxide.

Another optical brightener is azole, which is a derivative of a 5-membered heterocyclic compound. These can be further subdivided into monoazoles and diazoles. Examples of monoazoles and diazoles are disclosed in Kirk-Osmer's literature.

Still other optical brighteners are derivatives of the 6-membered heterocyclic compounds disclosed in Kirk-Osmer's literature. Examples of such compounds include pyrazine-derived brighteners and 4-
Derivatives derived from aminonaphthalamide are exemplified.

In addition to the brighteners already described, miscellaneous drugs may also be useful as brighteners. Examples of such miscellaneous agents are disclosed in the Zaradonic literature at pages 93-95 and include 1-hydroxy-3,6,8-pyrenetrisulfonic acid; 2,4
-Dimethoxy-1,3,5-triazin-6-yl-pyrene;
4,5-di-phenylimidazolone disulfonic acid; and pyrazoline-quinoline derivatives.

Another specific example of an optical brightener is that identified in U.S. Patent No. 4,790,856, issued December 13, 1988 to Wixon, the disclosure of which is incorporated herein by reference. These whitening agents include Forwhite from Verona (Ph
orwhite ^™ ) series brighteners. Other brighteners disclosed in this document include Tinopal UNPA, Tinopal CBS and Tinopal 5BM available from Ciba Geigy; Arctic Whit available from Hilton-Davis, Italy.
e) 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-aminocoumarin. Specific examples of these brighteners include: 4-methyl-7-diethylaminocoumarin; 1,2-bis (benzimidazol-2-yl) -ethylene; 1,3-diphenylfurazoline; 2,5-bis ( Benzoxazol-2-yl) -thiophene; 2-styryl-naphtho- [1,2-d] -oxazole; and 2- (stilben-4-yl) -2H-naphtho [1,2-
d] triazole.

Other optical brighteners include Hamilton in 1972
No. 3,646,015, issued on Jan. 29, the disclosure of which is incorporated herein by reference.

If utilized, the optical brightener will generally comprise from about 0.05 to about 2.0% by weight of the laundry detergent composition, preferably from about 0.1 to about 1.0%.
% By weight.

Foam Inhibitors Known or becoming known compounds for reducing or inhibiting foam formation can be incorporated into the laundry detergent compositions of the present invention. The incorporation of such substances (hereinafter "foam inhibitors") may be desirable because the polyhydroxy fatty acid amide surfactants here can increase the foam stability of the detergent composition. Foam control may be of particular importance when the detergent composition includes a comparatively high foaming surfactant in combination with a polyhydroxy fatty acid amide surfactant. Foam control is particularly desirable for compositions intended to be used in front-loading automatic washing machines. These washing machines are typically characterized by having a horizontal axis and a drum for containing the wash / wash water having a rotating action about this axis. This type of agitation can result in high foam formation and thus reduced cleaning performance. The use of foam inhibitors can also have particular importance under hot water washing conditions and under high surfactant concentration conditions.

Various substances may be used as foam inhibitors. Foam suppressants are well known to those skilled in the art. They are generally, for example,
Kirk-Othmer Encyclopedia of Chemical Technology,
Third Edition, Volume 7, pages 430 to 447 (John Willy End Sons, Inc., 1979). One category of foam inhibitors of particular interest includes monocarboxylic fatty acids and their soluble salts. These substances are available to Wayne St. John
Discussed in U.S. Pat. No. 2,954,347, issued Sep. 27, 1960, which patent is hereby incorporated by reference. Monocarboxylic fatty acids and their salts for use as foam inhibitors typically have a hydrocarbyl chain of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts, for example, the sodium, potassium, and lithium salts, and the ammonium and alkanolammonium salts.
These substances are a preferred category of foam inhibitors for detergent compositions.

Further, the laundry detergent composition of the present invention may contain a non-surfactant foam inhibitor. These include, for example, high molecular weight hydrocarbons, for example, paraffins, fatty acid esters (eg, fatty acid triglycerides), fatty acid esters of monohydric alcohols, and aliphatic C ₁₈ -C ₄₀ ketones (eg, stearone). Other suds suppressors include N-alkylated aminotriazines, such as trialkylmelamines formed as the product of 2 or 3 moles of a primary or secondary amine having 1 to 24 carbon atoms and cyanuric chloride. Hexaalkylmelamine, or dialkyldiaminechlorotriazine to tetraalkyldiaminechlorotriazine, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate and monostearyl dialkali metal (eg, sodium, potassium, lithium) phosphate And phosphoric esters. paraffin,
Hydrocarbons such as haloparaffins are available in liquid form. The liquid hydrocarbon will be liquid at nitrogen and atmospheric pressure and will have a pour point of about -40C to about 5C and a minimum boiling point of about 110C.
(Atmospheric pressure). It is also known to utilize wax hydrocarbons, preferably those having a melting point below about 100 ° C. Hydrocarbons constitute a preferred category of foam inhibitors for detergent compositions. Hydrocarbon foam inhibitors
For example, it is described in U.S. Pat. No. 4,265,779, issued May 5, 1981 to Gandolho et al., Which is incorporated herein by reference. As a hydrocarbon, the carbon number is about
12 to about 70 aliphatic, cycloaliphatic, aromatic and heterocyclic saturated or unsaturated hydrocarbons. The term "paraffin" as used in this defoamer discussion is intended to encompass a mixture of true paraffins and cyclic hydrocarbons.

Another preferred category of non-surfactant suds suppressors consists of silicone suds suppressors. This category includes polyorganosiloxane oils such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins,
And the use of a combination of polyorganosiloxane oil and silica particles, where the polyorganosiloxane chemisorbs or melts on the silica. Silicone foam inhibitors
It is well known in the art, for example, US Patent No. 4,265,779 issued May 5, 1981 to Gandolho et al. And European Patent Application 8930 published February 7, 1990 by MS Starch.
No. 7851.9 (both incorporated herein by reference)
Is disclosed.

Other silicone suds suppressors are disclosed in U.S. Pat.
No. 839.

Mixtures of silicone and silanized silica, for example,
It is described in German patent application DOS 2,124,526. Silicone defoamers and antifoams in granular detergent compositions are disclosed in U.S. Pat. No. 3,933,672 to Bartrotta et al. And U.S. Pat. No. 4,652,392 to Bangginsky et al. Issued Mar. 24, 1987. .

Exemplary silicone-based suds suppressors for use herein are essentially: (i) a polydimethylsiloxane fluid having a viscosity at 25 ° C. of about 20 cs to about 1500 cs; (ii) (i) per 100 parts by weight about 5 to about 50 parts, (CH _3)
3 The ratio of SiO _1/2 units to SiO ₂ units from about 0.6: 1 to about 1.2: 1 (C
A and (iii) (i) anti-foaming amount of suds control agent comprising from about 1 to about 20 parts of a solid silica gel per 100 parts by weight; H _{3) 3} SiO _1/2 units and consisting of SiO ₂ Metropolitan siloxane resin.

Foam suppressants, when utilized, are present in a "foam suppressant amount".
By "foam suppression amount" is meant that the formulator of the composition can select the amount of this foam control agent that will control the foam to the desired degree. The degree of foam control will vary depending on the detergent surfactant chosen. For example, in the case of high foaming surfactants, a relatively large amount of foam control agent is used to achieve the desired foam control than in the case of low foaming surfactants.

The laundry detergent compositions of the present invention will generally contain from 0% to about 5% of a foam inhibitor. When utilized as suds suppressors, the monocarboxylic fatty acids and their salts will typically be present in amounts up to about 5% by weight of the detergent composition. Preferably, from about 0.5% of a fatty monocarboxylate foam inhibitor
About 3% is utilized. Although large amounts may be used, silicone suds suppressors are typically utilized in amounts up to about 2.0% by weight of the detergent composition. This upper limit is practical in nature mainly due to concerns about small amounts of effectiveness to keep costs to a minimum and to effectively control foam. Preferably, about 0.01% to about 1%, more preferably about 0.25% to about 0.5%, of a silicone suds suppressor is used. As used herein, these weight percent values include silica that may be used with the polyorganosiloxane, as well as auxiliary materials that may be utilized. Monostearyl phosphate is generally utilized in an amount of about 0.1 to about 2% by weight of the composition.

Although large amounts can be used, hydrocarbon suds suppressors are typically utilized in amounts of about 0.01% to about 5.0%.

Other Ingredients Various other ingredients that can be included in the laundry detergent composition of the present invention include other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, and the like.

Liquid detergent compositions can contain water and other solvents as carriers. Preferred are low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol. Monohydric alcohols are preferred for solubilizing surfactants, but polyols, such as those containing about 2 to about 6 carbon atoms and about 2 to about 6 hydroxy groups (eg, propylene glycol, ethylene Glycol, glycerin, and 1,3-propanediol) can also be used.

The laundry detergent compositions of the present invention will preferably be formulated so that when used in an aqueous cleaning operation, the wash water has a pH of about 6.5 to about 11, preferably about 7.5 to about 10.5. The liquid product formulation preferably has a pH of about 7.5 to about 9.5,
More preferably it has from about 7.5 to about 9.0. Techniques for controlling the pH to the recommended use level include buffers, alkalis,
The use of acids and the like is mentioned and is well known to those skilled in the art.

Further, the present invention provides a method for preparing a substrate comprising water, a water-miscible solvent (eg,
Detergent compositions containing a nonionic surfactant system of the present invention (polyhydroxyfatty acid amide in a nonionic surfactant system versus additional surfactant) in the presence of a solvent such as primary and secondary alcohols). (A weight ratio of from about 1: 5 to about 5: 1) provides a method for cleaning substrates such as fibers, fabrics, hard surfaces, skin, and the like. Agitation is preferably provided to enhance cleaning. Suitable means for providing agitation include hand rubbing (preferably with a brush) or other cleaning devices, automatic washing machines, automatic dishwashers, and the like.

Experiment This illustrates the preparation of N-methyl-1-deoxyglucityl lauramide surfactant for use herein. Although skilled chemists can vary the device configuration, one device suitable for use herein is a three-unit device equipped with a thermometer long enough to contact the reaction medium and a motor driven paddle stirrer. It consists of a four-neck flask. The other two ports of the flask were equipped with a nitrogen sweep and a wide bore arm (Note:
The wide bore arm is important in the case of very rapid methanol generation), which is connected to an efficient collection cooler and vacuum outlet. The latter is connected to a nitrogen bleed / vacuum gauge and then to an aspirator and trap. A variable transformer temperature controller used to heat the reaction mixture [Varia
c) ") is placed on the lab-jack so that it can be easily raised and lowered to further control the temperature of the reaction mixture.

N-methylglucamine (195 g, 1.0 mol, Aldrich, M4700-0) and methyl laurate (Procter & Gamble CE1270, 220.9 g, 1.0 mol) are placed in a flask. The solid / liquid mixture is heated under stirring and a nitrogen sweep to prepare a melt (about 25 minutes). Melting temperature
When 145 ° C. is reached, the catalyst (anhydrous sodium carbonate in powder form, 10.5 g, 0.1 mol, JT Baker) is added. Stop the nitrogen sweep and adjust the aspirator and nitrogen bleed to give a vacuum of 5 inches (5/31 atm) Hg. From this point, the reaction temperature is raised to 150 ° C. by adjusting the variac and / or by raising or lowering the mantle.
To hold.

Within 7 minutes, primary methanol bubbles are visible at the meniscus of the reaction mixture. A vigorous reaction is immediately associated.
The methanol is distilled until the rate decreases. Adjust the vacuum to give a vacuum of about 10 inches Hg (10/31 atm).
Increase the vacuum approximately as follows (inches Hg at a given minute): 3
At 10; 7 at 20; 10 at 25. Heating and stirring are discontinued 11 minutes after the start of methanol evolution (simultaneous foaming occurs). The product cools and solidifies.

The following examples are intended to illustrate the compositions of the present invention, but do not necessarily limit or otherwise define the scope of the present invention, which is determined according to the following claims. ).

EXAMPLES The following examples of liquid detergent compositions are prepared according to the description below.

A surfactant paste is prepared by first combining the desired surfactant with water and alcohol. The surfactant contained in the surfactant paste includes the polyhydroxy fatty acid amide of the present invention. Ideally, the surfactant paste should be pumpable at room or elevated temperature.

Separately combine the non-aqueous solvent, surfactant paste or solution, molten fatty acid, aqueous solution of polycarboxylate builder with other salts, aqueous ethoxylated tetraethylenepentamine, buffer, caustic, and water in a mixing vessel .
The pH is adjusted to a level of about 8.5 using aqueous citric acid or aqueous sodium hydroxide. After adjusting the pH, the final ingredients, such as soil release agents, enzymes, colorants and fragrances are added. Stir the resulting mixture until a single-phase composition is obtained.

Examples 1-2 These examples relate to heavy duty liquid detergent compositions containing a polyhydroxy fatty acid amide / additional non-ionic surfactant system.

Examples 3-7 These examples show heavy duty liquid detergent compositions containing a polyhydroxyfatty acid amide / additional nonionic surfactant system in combination with an anionic surfactant.

Examples 8-10 These examples show a high builder heavy duty liquid detergent composition containing a polyhydroxy fatty acid amide / additional nonionic surfactant system in combination with an anionic surfactant.

Examples 11-13 Examples of heavy duty liquid detergent compositions containing an alkyl polysaccharide as an additional non-ionic surfactant in a non-ionic surfactant system are as follows. These examples are based on a wash temperature of less than about 50 ° C and about 2,000 ppm by weight of wash water.
And are prepared in the same manner as the compositions of Examples 1-10.

Examples 14-15 The following examples of heavy duty granular detergent compositions containing a polyhydroxyfatty acid amide / additional nonionic surfactant system. These compositions are intended to be used at less than about 50-60 ° C and at a concentration of about 800 ppm (based on wash water weight). These compositions are prepared by mixing a thick paste containing the amide, alkyl ethoxylate, brightener and about 20% by weight of water with the required dry ingredients in a high-speed shear mixer such as an Eirich RV02 mixer. I do. Other dry optional ingredients in granular or powdered form may be mixed with the thick paste and the required dry ingredients in a high shear mixer or may be added subsequently in a rotating mixing drum.

Example 16 Another process for preparing the polyhydroxy fatty acid amide used herein is as follows. Fatty acid methyl esters (Source: Procter & Gamble Methyl Ester CE 12
70) 84.87 g, 75 g of N-methyl-D-glucamine (source: Aldrich Chemical Company MD4700-0), 1.04 g of sodium methoxide (source: Aldrich Chemical Company 16,499-2) and 68.51 of methyl alcohol
The reaction mixture consisting of g is used. The reaction vessel is equipped with standard reflux equipment equipped with a drying tube, condenser and stir bar. In this method, N-methylglucamine is combined with methanol under argon under stirring and heating is started while mixing well (stir bar; reflux). After 15-20 minutes, when the solution has reached the desired temperature, the ester and sodium methoxide catalyst are added. Samples are taken periodically to monitor the course of the reaction and the solution is found to be completely clear at 63.5 minutes. The reaction is in fact judged almost complete at this point. The reaction mixture is kept under reflux for 4 hours. After removing methanol, the recovered crude product is
156.16g. After vacuum drying and purification, purified product 10
A total yield of 6.92 g is recovered. However, yields are not calculated on this basis since regular sampling over the course of the reaction renders the overall yield value meaningless. The reaction can be performed at 80% and 90% reactant concentrations for up to 6 hours to produce product (with very little by-product formation).

The following are not intended to limit the invention, but merely to further illustrate additional aspects of the technology that can be considered by formulators in preparing various detergent compositions using polyhydroxy fatty acid amides. .

It will be readily recognized that polyhydroxy fatty acid amides are susceptible to some instability under highly basic or highly acidic conditions due to amide bonds. Although some degradation is acceptable, these substances can
It is preferred not to be subjected to a pH above 11, preferably above pH 10, below about 3. Final product pH (liquid)
Is typically between 7.0 and 9.0.

During the production of the polyhydroxy fatty acid amide, it will typically be necessary to at least partially neutralize the base catalyst used to form the amide bond. Although any acid can be used for this purpose, detergent formulators will recognize that it is a simple and convenient matter to use an acid that would otherwise be useful and give the desired anion in the finished detergent composition. There will be. For example, citric acid can be used for neutralization purposes and allows the resulting citrate ions (about 1%) to remain with the about 40% polyhydroxyfatty acid amide slurry and is pumped to a manufacturing stage after the entire detergent process. Let it be supplied. Acid form substances such as oxydisuccinate, nitrilotriacetate, ethylenediaminetetraacetate, tartrate / succinate and the like can likewise be used.

Polyhydroxy fatty acid amides derived from coconut alkyl fatty acids (predominantly C ₁₂ -C ₁₄₎ are more soluble than tallow alkyl (predominantly C ₁₆ -C ₁₈₎ equivalents. Thus, C ₁₂ -C ₁₄ materials are soluble in easy and and cold water washing bath to be formulated is slightly more to the liquid composition. However, C ₁₆ -C ₁₈ materials are also quite useful, especially in situations where warm to hot wash water is used. In fact, C ₁₆
-C ₁₈ materials may be better detergent surfactants than C ₁₂ -C ₁₄ equivalents. Thus, formulators may want to balance manufacturability vs. performance when selecting a particular polyhydroxy fatty acid amide for use in a given formulation.

It will also be appreciated that the solubility of the polyhydroxy fatty acid amide can be increased by having unsaturation and / or chain branch points in the fatty acid moiety. Thus, materials such as polyhydroxy fatty acid amides derived from oleic and isostearic acids are more soluble than their n-alkyl equivalents.

Similarly, the solubility of polyhydroxy fatty acid amides made from disaccharides, trisaccharides, etc. will generally be greater than the solubility of monosaccharide-derived equivalents. This high solubility can have particular help in formulating liquid compositions. In addition, polyhydroxy fatty acid amides in which the polyhydroxy groups are derived from maltose appear to perform particularly well as detergents when used in conjunction with conventional alkylbenzene sulfonate ("LAS") surfactants. Without wishing to be limited by theory, the combination of polyhydroxyfatty acid amides derived from higher sugars such as maltose with LAS results in a substantially unexpected decrease in interfacial tension in aqueous media, thereby resulting in a net wash. It seems to improve performance (the production of polyhydroxy fatty acid amide derived from maltose will be described later).

Polyhydroxyfatty acid amides can be produced not only from purified sugars, but also from starches derived from hydrolyzed starches, such as corn starch, potato starch, or other convenient plants containing monosaccharides, disaccharides, etc. as desired by the formulator. Can also be manufactured. This has particular importance from an economic point of view. Thus, "high glucose" corn syrup, "high maltose" corn syrup and the like can be used conveniently and economically. Delignified hydrolyzed cellulose pulp can also provide a source of raw materials for polyhydroxy fatty acid amides.

As mentioned above, polyhydroxy fatty acid amides derived from higher sugars such as maltose and lactose are more soluble than their glucose equivalents. In addition, more soluble polyhydroxy fatty acid amides may help solubilize less soluble equivalents to varying degrees. Thus, the prescriber may, for example, decide to use a raw material comprising high glucose corn syrup,
A syrup containing a small amount of maltose (eg, 1% or more) may be selected. The resulting mixture of polyhydroxy fatty acids will generally exhibit more favorable solubility over a wide range of temperatures and concentrations than "pure" glucose-derived polyhydroxy fatty acid amides. Thus, in addition to the economic advantages of using a sugar mixture rather than a pure sugar reactant, polyhydroxy fatty acid amides made from mixed sugars have very substantial performance and / or ease of formulation. Benefits can be provided. However, in some cases, some loss of grease removal performance (dishwashing) may be observed at fatty acid maltamide levels greater than about 25% and some loss of foaming properties is greater than about 33% It may be found in an amount (the percentage is the percentage of maltamide-derived polyhydroxy fatty acid amide VS glucose-derived polyhydroxy fatty acid amide in the mixture). This can vary slightly depending on the chain length of the fatty acid moiety. Typically, and formulators who decide to use such mixtures, the ratio of a monosaccharide (eg, glucose) to a disaccharide / higher sugar (eg, maltose) will include a ratio of about 4: 1 to about 99: 1. It can be found to be advantageous to choose a polyhydroxy fatty acid amide mixture which is:

The preparation of a preferred acyclic polyhydroxy fatty acid amide from a fatty ester and an N-alkyl polyol is carried out in an alcoholic solvent at about 30C to 90C, preferably about 50C to 80C
Temperature. For example, it is advantageous for liquid detergent formulators to perform such a process in 1,2-propylene glycol solvent because the glycol solvent does not need to be completely removed from the reaction product prior to use in the finished detergent formulation. Is now confirmed. Similarly, for example, solid detergent compositions, the formulator will typically granular detergent composition, ethoxylated process (EO3~8) C ₁₂ ~C ₁₄
It can be found to be convenient to work at 30 ° C. to 90 ° C. in a solvent consisting of an ethoxylated alcohol such as an alcohol, for example, neodol 23EO6.5 (shell). When such ethoxylates are used, they preferably do not contain substantial amounts of non-ethoxylated alcohols, and most preferably do not contain substantial amounts of monoethoxylated alcohols (designation "T").

Although the preparation of the polyhydroxyfatty acid amide itself does not form part of the present invention, the formulator may recognize other methods of synthesizing the polyhydroxyfatty acid amide as described below.

Typically, an industrial scale reaction sequence to produce the preferred acyclic polyhydroxy fatty acid amide comprises a step 1: N
An N-alkyl polyhydroxyamine derivative is produced from the desired saccharide or saccharide mixture by reacting with hydrogen in the presence of a catalyst after forming an adduct of the alkylamine and the saccharide, Is preferably reacted with a fatty acid ester to form an amide bond. The various N-alkyl polyhydroxyamines useful in step 2 of the reaction sequence can be prepared by various technically disclosed methods, but the following methods use a convenient and economical sugar syrup as a raw material. For best results when using such syrup ingredients, it should be understood that the manufacturer should choose a syrup that is completely pale or preferably almost colorless ("water-white"). .

Preparation of N-alkyl polyhydroxyamines from sugar syrups derived from plants I. Adduct formation-The following are standard methods. In this standard method, 420 g of an approximately 55% glucose solution having a Gardner color of less than 1 (corn syrup-approximately 231 g of glucose)
-About 1.28 mol) to about 50% methylamine (methylamine 5
(9.5 g-1.92 mol) aqueous solution. Purge the methylamine (MMA) 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 <0> C. Slowly add to the MMA solution at the indicated reaction temperature, indicating corn syrup. The Gardner color is measured at the approximate display time (minutes).

As can be seen from the above data, the Gardner color of the adduct is much worse as the temperature rises above about 30 ° C., and at about 50 ° C., the adduct has less than about 30 Gardner colors for about 30 hours. Minutes. For longer reactions and / or retention times, the temperature may be about 20
It should be below ° C. The Gardner color should be less than about 7, and preferably less than about 4, for a good color glucamine.

When using low temperatures to produce the adduct, the time to reach a substantial equilibrium concentration of the adduct is reduced by using a higher amine to sugar ratio. For the amine to sugar molar ratio of interest 1.5: 1, equilibrium is achieved in about 2 hours at a reaction temperature of about 30 ° C. At a molar ratio of 1.2: 1, under the same conditions, the time is at least about 3 hours. For good color, the combination of amine: sugar ratio, reaction temperature and reaction time should be substantially equilibrium conversion, for example, about 90% or more, more preferably about 95% or more, more preferably Is selected to achieve a color of at least about 99%, and in the case of an adduct, less than about 7, preferably less than about 4, more preferably less than about 1.

Using the process at a reaction temperature of less than about 20 ° C. and using corn syrup having a different Gardner color as indicated, the MMA adduct color (after reaching substantial equilibrium in at least about 2 hours) It seems like an indication.

As can be seen from the foregoing, the starting sugar material should be almost colorless so that it has consistently acceptable adducts. When the sugar has a Gardner color of about 1, the adduct is sometimes acceptable and sometimes unacceptable. When the Gardner color is greater than 1, the resulting addendum is unacceptable. The better the initial color of the sugar, the better the color of the adduct.

II. Hydrogen reaction-The adduct from the above having a Gardner color of 1 or less is hydrogenated according to the following method.

About 539 g of the adduct in water and about 23.1 g of United Catalyst G49B Ni catalyst are added to one autoclave and purged twice at about 20 ° C. and 200 psi H ₂ . Increase H ₂ pressure to about 1400psi and temperature to about 50 ° C
Temperature. The pressure is then increased to about 1600 psig and the temperature is maintained at about 50-55 ° C for about 3 hours. The product is about 95% hydrogenated at this point. Then raise the temperature to about 85 ° C for about 30 minutes
, The reaction mixture is decanted and the catalyst is filtered off. The product, after removal of water and MMA by evaporation, is about 95% N-methylglucamine, a white powder.

Using about 23.1 g of Raney Ni catalyst with the following changes,
Repeat the above method. The catalyst was washed three times, the reactor (the catalyst is in a reactor) was purged twice with 200PsigH _2, released reactor 2 hours pressurized with H ₂ at 1600psig and the pressure in 1 hour, the reactor To 1600 psig. The adduct is then pumped into the reactor at 200 psig, 20 ° C., and the reactor is purged with 200 psig H ₂ or the like as described above.

The product obtained in each case is higher than about 95% N
-Methylglucamine; about 10% Ni for glucamine
with less than about 2 ppm; and having a solution color of less than about 2 Gardner.

Crude N-methylglucamine is color stable at short exposure times of about 140 ° C.

It is important to have a good adduct with a low sugar content (less than about 5%, preferably less than about 1%) and a good color (less than about 7, preferably less than about 4, more preferably less than about 1 Gardner) It is.

In another reaction, adduct, starting from about 50% methylamine about 159g of water, purged, prepared by shielded with N ₂ at about 10 to 20 ° C.. About 70% corn syrup (water-
About 330 g (near white) was degassed with N ₂ at about 50 ° C.
Slowly add to the methylamine solution at a temperature below ℃. The solution is mixed for about 30 minutes to give a very pale yellow solution, about 95% adduct.

About 190 g of adduct in water and about 9 g of United Catalyst G49B Ni catalyst were added to a 200 ml autoclave,
Purge three times with H ₂ at about 20 ° C. H ₂ pressure about 200psi
And raise the temperature to about 50 ° C. The pressure is increased to 250 psi and the temperature is held at about 50-55 ° C for about 3 hours. The product is
At this point it is about 95% hydrogenated and then raised to a temperature of about 85 ° C. for about 30 minutes and the product is about 95% N-methylglucamine, a white powder, after removal of water by evaporation.

When H ₂ pressure is less than about 1000psig to minimize Ni content in the glucamine, it is also important to minimize contact between the adduct and the catalyst. The nickel content in N-methylglucamine in this reaction is about 100 ppm compared to less than 10 ppm in the previous reaction.

Perform the following reaction of H ₂ for direct comparison of reaction temperature effects.

A 200 ml autoclave reactor is used according to a typical procedure similar to that described above to produce adducts and to carry out the hydrogen reaction at various temperatures.

The adduct used to produce glucamine is about 55%
About 420 g of glucose (corn syrup) solution (glucose
231 g; 1.28 mol) (the solution was prepared using 99DE corn syrup from Cargill, the solution has a color of less than Gardner 1) and about 119 g of 50% methylamine (59.5 g MMA;
1.92 mol) (manufactured by Air Products).

 The reaction method is as follows.

1. addition of 50% methyl amine solution to about 119g in N ₂ purged reactor, shield with N _2, and cooled to below about 10 ° C..

2. degassed and / or purged with N ₂ at 10 to 20 ° C. and 55% corn syrup solution to remove oxygen in the solution.

3. Slowly add the corn syrup solution to the methylamine solution and keep the temperature below about 20 ° C.

4. Once all the corn syrup has been added, add about 1
Stir for ~ 2 hours.

The adduct is used for the hydrogen reaction immediately after production or stored at low temperatures to prevent further degradation.

 The glucamine adduct hydrogen reaction is as follows.

1. Additionals Gardner less than 1) about 134g and G49B
About 5.8 g of Ni is added to a 200 ml autoclave.

2. Bring the reaction mixture to about 200 psi H ₂ at about 20-30 ° C.
Purge twice.

3. Pressurize to about 400 psi with H ₂ and raise the temperature to about 50 ° C.

4. Increase the pressure to about 500 psi and let it react for about 3 hours. Keep the temperature at about 50-55 ° C. Sample 1 is collected.

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

6. Decant the Ni catalyst and filter off. Sample 2 is taken.

 The conditions of the isothermal reaction are as follows.

1. Add about 134 g of the adduct and about 5.8 g of G49B Ni to a 200 ml autoclave.

2. Purge twice at about 200 psi H ₂ at low temperature.

3. Pressurize to about 400 psi with H ₂ and raise the temperature to about 50 ° C.

4. Increase the pressure to about 500 psi and react for about 3.5 hours. Keep the temperature at the indicated temperature.

5. Decant the Ni catalyst and filter off. Sample 3 is at about 50-55 ° C .; Sample 4 is at about 75 ° C .;
This is the case at 85 ° C (the reaction time at about 85 ° C is about 45 minutes).

All runs gave a similar purity of N-methylglucamine (about 94%); the Gardner color of the run was similar to that immediately after the reaction, but only the two-step heat treatment gave good color stability; 8
A run at 5 ° C gives a trivial color immediately after the reaction.

Example 17 The process for preparing a tallow (cured) fatty acid amide of N-methylmaltamine for use in a detergent composition according to the present invention is as follows.

Step 1-Reactant: Maltose monohydrate (Aldrich,
lot 01318KW); Methylamine (40% by weight in water) (Aldrich, lot 03325TM); Raney nickel, 50% slurry (UAD52-73D, Aldrich, lot 12921LW).

Add the reactants to a glass liner (maltose 250 g, methylamine solution 428 g, catalyst slurry 100 g-Runny Ni 50
g) Place in a 3 rocking autoclave and place the autoclave in nitrogen (3 x 500 psig) and hydrogen (2 x 500 psig).
purged with g), swings over the weekend at a temperature of 28 ° C. to 50 ° C. at room temperature under H _2. The crude reaction mixture is filtered twice through a glass microfiber filter with a silica gel plug. Concentrate the filtrate to a viscous material. The final traces of water are azeotroped by dissolving the viscous material in methanol and then removing the methanol / water on a rotary evaporator. Final drying is performed under high vacuum. The crude product is dissolved in refluxing methanol, filtered, recrystallized on cooling, filtered and the filter cake is dried under vacuum at 35 ° C. This is cut # 1. Concentrate the filtrate and store in the refrigerator overnight until a precipitate begins to form. The solid is filtered and dried under vacuum. This is cut # 2. The filtrate is again concentrated to half the volume to achieve recrystallization. Little precipitate forms. Add a small amount of ethanol and leave the solution in the freezer over the weekend. The solid material is filtered and dried under vacuum. The combined solids consist of N-methylmaltamine used in step 2 of the total synthesis.

Step 2-Reactant: N-methylmaltamine (from Step 1);
Cured tallow methyl ester; sodium methoxide (25% in methanol); anhydrous methanol (solvent); amine:
Ester molar ratio 1: 1; initial crystallization amount 10 mol% (w / r maltamine), increased to 20 mol%; solvent amount 50% (weight).

In a sealed bottle, tallow methyl ester 20.3
6 g are heated to the melting point (water bath) and charged to a 250 ml 3-neck round bottom flask with mechanical stirring. Heat the flask to about 70 ° C. to prevent the ester from coagulating. Separately, N-
Combine 25.0 g of methyl maltamine with 45.36 g of methanol,
The resulting slurry is added to the tallow ester with good mixing. 1.51 g of 25% sodium methoxide in methanol
Add. After 4 hours, the reaction mixture is not clear and therefore an additional 10 mol% of crystals (20 mol% total) is added,
The reaction is allowed to continue overnight (about 68 ° C.), after which time the mixture is clear. The reaction flask is then modified for distillation. Increase temperature to 110 ° C. The distillation at atmospheric pressure is continued for 60 minutes. Then start high vacuum distillation and continue for 14 minutes,
At that point the product is very thick. The product is left in the reaction flask at 110 ° C. (external temperature) for 60 minutes. The product is scraped from the flask and rubbed in ethyl ether over the weekend. The ether is removed on a rotary evaporator and the product is stored in an oven overnight and ground to a powder. The remaining N-methylmaltamine is removed from the product using silica gel. A silica gel slurry in 100% methanol is charged to the funnel and washed several times with 100% methanol. A concentrated sample of the product (20 g in 100 ml of 100% methanol) is loaded onto silica gel and eluted several times using vacuum and several methanol washes. The collected eluate is evaporated to dryness (rotary evaporator). The remaining tallow ester is removed by trituration in ethyl acetate overnight and then filtered. Vacuum dry the filter cake overnight. The product is a tallowalkyl N-methylmaltamide.

In another embodiment, step 1 of the reaction sequence can be performed using commercially available corn syrup consisting of glucose or a mixture of glucose and typically at least 5% maltose. The resulting polyhydroxy fatty acid amides and mixtures can be used in any of the detergent compositions of the present invention.

In yet another aspect, step 2 of the reaction sequence comprises:
It can be carried out in 1,2-propylene glycol or neodol. At the discretion of the formulator, it is not necessary that propylene glycol or neodol be removed from the reaction product prior to use to formulate the detergent composition. Again, according to the needs of the formulator, the methoxide catalyst can be neutralized with citric acid to provide sodium citrate, which can remain in the polyhydroxy fatty acid amide.

Depending on the needs of the formulator, the composition may contain more or less of various antifoaming agents. Typically, when washing dishes,
High foaming properties are desirable and therefore no foam control agents will be used. In the case of fabric washing with a top loading washing machine,
Some control of the foam may be desirable and, in the case of a front-loader, a certain degree of foam control may be preferred. Various foam control agents are known in the art and can be routinely selected for use herein. In fact, the choice of foam control agent or mixture of foam control agents for a particular detergent composition will not only depend on the presence and amount of the polyhydroxyfatty acid amide used therein, but also on the other surfactants present in the formulation. Will also depend. However, when used in conjunction with polyhydroxy fatty acid amides, various silicone-based foam control agents appear to be more efficient (ie, smaller amounts can be used) than various other types of foam control agents. . Silicone foam control agents available as X2-3419 and Q2-3302 (Dow Corning) are particularly useful here.

Formulators of fabric laundry compositions that can advantageously contain a soil release agent have a variety of known materials to choose from (e.g.,
U.S. Pat.Nos. 3,962,152, 4,116,885,
No. 4,238,531, No. 4,702,857, No. 4,721,
No. 580 and 4,877,896). Additional soil release materials useful herein include C ₁ -C ₄ alkoxy-terminated polyethoxy unit sources (eg, CH ₃ [OCH ₂ CH ₂ ] ₁₆ O
H), a terephthaloyl unit source (eg, dimethyl terephthalate); a poly (oxyethylene) oxy unit source (eg, polyethylene glycol 1500); an oxyisopropyleneoxy unit source (eg, 1,2-propylene glycol); and oxyethyleneoxy Unit source (for example,
(E.g., ethylene glycol), a non-ionic oligomeric esterification product of a reaction mixture (particularly, the molar ratio of oxyethyleneoxy units to oxyisopropyleneoxy units is at least about 0.5: 1). Such nonionic soil release agents have the general formula Wherein R ¹ is lower (eg, C ₁ -C ₄ ) alkyl, especially methyl; x and y are each an integer from about 6 to about 100;
m is from about 0.75 to about 30 integer; n is about 0.25 to from about 20 integer; R ² is an oxyethylene oxy pair oxyisopropylene propyleneoxy mole ratio of at least about 0.5: H and CH to give 1 ₃ is a mixture of both).

Another preferred class of soil release agents useful herein is U.S. Pat. No. 4,877,896, except that such agents are substantially free of monomers of the HOROH type, where R is propylene or higher alkyl. It has the general anionic type described in the specification. Thus, the soil release agent of U.S. Pat.No. 4,877,896 can comprise, for example, the reaction product of dimethyl terephthalate, ethylene glycol, 1,2-propylene glycol, and 3-sodeiosulfobenzoic acid, while these Additional soil release agents are, for example, dimethyl terephthalate, ethylene glycol and 5
-Sodiosulfoisophthalate and 3-sodeiosulfobenzoic acid. Such agents are preferred for use in granular laundry detergents.

The formulator may determine that it is advantageous to incorporate the non-perborate bleach, especially in heavy duty granular laundry detergents. Various peroxygen bleaches are commercially available and can be used here, of which percarbonate is convenient and economical. Thus, the composition may comprise from 3 to 20% by weight of the composition, more preferably from 5 to 20%.
18% by weight, most preferably 8-15% by weight solid percarbonate bleach (usually in the form of the sodium salt)
Can be contained.

Sodium percarbonate is an adduct having the formula corresponding to 2Na ₂ CO ₃ .3H ₂ O ₂ and is commercially available as a crystalline solid. Most commercially available substances include small amounts of EDTA, 1-hydroxyethylidene 1,1-
Heavy metal ion sequestering agents such as diphosphonic acid (HEDP) and aminophosphonate. For use herein, percarbonate can be incorporated into the detergent composition without additional protection, but a preferred embodiment of the present invention utilizes a stable form of the material (FMC). A variety of coatings can be used, but with an SiO ₂ : Na ₂ O ratio of 1.6 applied as an aqueous solution and dried to give an amount of silicate solids of 2-10% (usually 3-5%) by weight of percarbonate. :from 1 to 2.
8: 1, preferably 2.0: 1, sodium silicate is the most economical. Magnesium silicate can also be used and chelating agents, such as one of the foregoing, can be incorporated into the coating.

The particle size range of the crystalline percarbonate is from 350 μm to 450
μm (about 400 μm on average). When coated, the crystals have a size in the range of 400-600 μm.

While the heavy metals present in the sodium carbonate used to make percarbonate can be controlled by the incorporation of the sequestering agent into the reaction mixture, the percarbonate is derived from heavy metals present as impurities in other components of the product. You still need protection. The total amount of iron, copper and manganese ions in the product is 25 to avoid unacceptable adverse effects on percarbonate stability.
It has been found that it should not be above ppm, and preferably below 20 ppm.

The following relates to the preparation of a preferred liquid heavy duty laundry detergent according to the present invention. It will be appreciated that the stability of the enzyme in such compositions is much lower than in granular detergents. However, by using typical enzyme stabilizers such as formate, boric acid, lipase and cellulase enzymes can be protected from degradation by protease enzymes. However, lipase stability does not depend on alkylbenzene sulfonate ("LAS")
Still relatively poor in the presence of surfactants. Apparently, LAS partially denatures lipase, and more denatured lipase appears to be more susceptible to attack by proteases.

In view of the above considerations, which can be particularly cumbersome with liquid compositions as described above, it is an object to provide a liquid detergent composition that contains a lipase, a protease and a cellulase enzyme together. It is a particular challenge to provide such a ternary enzyme system in a stable liquid detergent with an effective blend of detergent surfactants. Additionally, it is difficult to stably incorporate peroxidase and / or amylase enzymes into such compositions.

Various mixtures of lipases, proteases, cellulases, amylases, and peroxidases are suitably stable in the presence of certain non-alkylbenzene sulfonate surfactant systems, and therefore can formulate even effective heavy duty solid and liquid detergents. Now confirmed. In fact, the formulation of a stable liquid enzyme-containing detergent composition constitutes a highly advantageous preferred embodiment provided by the technology of the present invention.

In particular, prior art liquid detergent compositions typically include LA
Mixture of surfactant of the the S or _{LAS RO (A) m SO 3} M type ( "AES"), i.e., containing LAS / AES mixtures. In contrast, the liquid detergents of the present invention preferably comprise a binary mixture of AES and a polyhydroxy fatty acid amide of the type disclosed herein. It will be appreciated that a minimal amount of LAS can be present, but the stability of the enzyme will be reduced thereby. Thus, it is preferred that the liquid composition be substantially free of LAS (ie, contain less than about 10%, preferably less than about 5%, more preferably less than about 1%, and most preferably 0%).

The present invention provides: (a) about 1% to about 50%, preferably about 4% to about 40%, of an anionic surfactant; (b) about 0.0001% to about 2% of an active detergent enzyme; Wherein R ¹ is H, C ₁ -C ₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof, R ₂ is C ₅ -C ₃₁ hydrocarbyl, and Z is directly An enzymatic performance-enhancing amount (preferably about 0.5% to about 12%) of a polyhydroxyfatty acid amide material of a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain having at least three linked hydroxyls or an alkoxylated derivative thereof; (d) a nonionic surfactant, in particular comprises ₁₂ -C ₁₈ about 1% to 20% alcohol alkoxylated C having 3 to 10 EO groups, the composition and characterized in that it is substantially free of alkyl benzene sulfonate A liquid detergent composition is provided.

Water-soluble anionic surfactants of the present invention is preferably _{RO (A) m SO 3 M} ( wherein, R is an unsubstituted C ₁₀ -C ₂₄ alkyl or hydroxyalkyl (C ₁₀ ~C ₂₄₎ group, A is an ethoxy or propoxy unit, m is an integer greater than 0,
M is hydrogen or a cation) ("AES"). Preferably, R is an unsubstituted C ₁₂ -C
₁₈ alkyl groups, A is an ethoxy unit, m is about 0.5 to about 6,
M is a cation. The cation is preferably a metal cation [eg, sodium (preferred), potassium,
Lithium, calcium, magnesium, etc.] or ammonium or substituted ammonium cations.

The ratio of the surfactant ("AES") to the polyhydroxyfatty acid amide of the present invention is from about 1: 2 to about 8: 1, preferably from about 1: 1 to about 5: 1, most preferably about 1: 1. And preferably about 4: 1.

The liquid compositions of the present invention, or polyhydroxy fatty acid amide, AES, and C ₈ -C ₂₂ (preferably C ₁₀ -C ₂₀₎
About 1 to about 25 per mole of linear alcohol and alcohol,
Preferably, it may contain about 0.5% to about 5% of a condensate with about 2 to about 18 moles of ethylene oxide.

As described above, the liquid composition of the present invention preferably comprises
It has a pH of about 6.5 to about 11.0, preferably about 7.0 to about 8.5 in a 10% solution in water at 20 ° C.

The composition preferably comprises from about 0.1% of a detersive builder.
Further includes about 50%. These compositions preferably comprise from about 0.1% to about 20% of citric acid or a water-soluble salt thereof, and from about 0.1% to about 20% of a water-soluble succinate tartrate, especially its sodium salt and mixtures thereof, or Oxydisuccinate or a mixture thereof with the builder
0.1 to about 20% by weight. Alkenyl succinate 0.1%
~ 50% can be used.

Preferred liquid compositions of the present invention have, on an active basis, about 0.00
It contains from 01% to about 2%, preferably from about 0.0001% to about 1%, most preferably from about 0.001% to about 0.5% of detergent enzyme. These enzymes are preferably selected from the group consisting of proteases (preferred), lipases (preferred), amylase, cellulase, peroxidase, and mixtures thereof. Compositions having two or more enzymes are preferred, most preferably one in which one is a protease.

Various descriptions of detergent proteases, cellulases and the like are available in the literature, but detergent lipases are somewhat unknown. Thus, to assist the formulator, lipases of interest include Amano AKG and Bacillis Sp lipase (eg, Solvay enzyme).
Also, EP A 0399 681 published on November 28, 1990, EP A 0 218 272 published on April 15, 1987, and PCT / DK 88 published on May 18, 1989. See lipases described in US Pat. No./00177, all incorporated herein by reference.

Suitable fungal lipases include Humicola lanuginosa
And those that can be produced by Thermomyces lanuginosus. Humicola as described in European Patent Application No. 0 258 068, incorporated herein by reference.
Clone the gene from lanuginosa and replace the gene with Asp
Lipases obtained by expression in ergillus oryzae (commercially available under the trade name LIPOLASE) are most preferred.

From about 2 to about 20,000 per gram of product, preferably from about 10 to about 20,000
6,000 lipase units of lipase (LU / g) can be used in these compositions. Lipase units are pH stats (pH is
7.0, temperature 30 ° C, substrate is emulsion tributyrin and gum arabic) Ca ⁺⁺ and Na in phosphate
The amount of lipase that produces 1 μmol of titratable butyric acid per minute in the presence of Cl.

Examples 18A-C The following examples illustrate light duty liquid detergent compositions that are particularly suitable for dishwashing and other hard surface cleaning operations. In the example A through C, the surfactant is composed of various alkyl ethoxy sulfate surfactants, which are abbreviated to indicate an average ethoxylation degree using standard nomenclature, C ₁₂ -C ₁₃ Te nuclear EO (0.8) sulfate indicates a sulfated mixed C ₁₂ -C ₁₃ alcohol fraction having an average degree of ethoxylation 0.8. These anionic ethoxy sulfates are preferably used in Na ⁺ salt form or NH ₄ ⁺ salt form. C ₁₂ -C ₁₃ amine oxides, mixed C ₁₂ -C ₁₃ (average)
It is dimethylamine oxide. C ₁₂ -C ₁₄ AP betaine is _{C 12/14 H 25/29 CONH (CH 2} ) 3 N + (CH 3) 2 -CH 2 CO 2 H.. C ₁₂ -C ₁₄ AP sultaine _{is, C 12/14 H 25/29 CONH (CH} 2) 3 N + (CH 3) 2 - is _{(CH 3) 2 CH 2 CH} (OH) CH 2 SO 3 H. . C ₁₂ -C ₁₄ DM betaine is C _12/14 H _25/29 N ⁺ (CH
₃ ) ₂ CH ₂ CO ₂ H. _Ethoxylated nonionic surfactants _designated C _9-1 EO (8) mean C ₉ -C ₁₁ alcohols ethoxylated with an average of 8 moles of ethylene oxide. C
The a ⁺⁺ and Mg ⁺⁺ cations are conveniently CaCl ₂ and Mg
It is introduced into the composition as Cl ₂ . The rest of the composition consists of citrate / propylene glycol (1-5%) and cumene sulfonate or xylene sulfonate hydrotrope present in water and glucamide surfactant 1-3%
Consists of The pH is typically 6.8 to 7.4 (NH ₄ ⁺ salt), or 7-8.2 (Na ⁺ salt).

Example 19 Liquid laundry detergent compositions suitable for use at relatively high concentrations common to front-loading automatic washing machines over a wide range of temperatures, especially in Europe, are as follows.

^{1 As} SYNPRAX3 from ICI or DTSA from Monsanto.

^{2 As} Protease B as described in EPO 0342177 of November 15, 1989;% at 40 g /.

Amylase from ³ Novo;% at 300 KNU / g.

Lipase from ⁴ Novo;% at 100 KLU / g.

Cellulase from ⁵ Novo;% at 5000 CEVU /.

Available from ⁶ Monsanto.

^{7 As} Lutensol P6105 from BASF.

⁸ Bayer swing hall CPG766.

⁹ Silane corrosion inhibitor available as A1130 from Union Carbide or DYNASYLAN TRIAMINO from Hills.

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

¹¹ Silicone foam control available from Dow Corning as Q2-3302 ¹² Dispersant for silicone foam control available from Dow Corning as DC-3225C.

^★ Preferred fatty acids are topped containing 12% oleic acid and 2% each of stearic and linoleic acid
Balm nucleus.

Example 20 A particulate laundry detergent composition suitable for use in relatively high concentrations common to front-loading automatic washing machines over a wide range of temperatures, particularly in Europe, is as follows.

^One socarane is a polyacrylic acid / sodium maleate available from Hoechst.

² penta-phosphonomethyl diethylenetriamine of Monsanto's brand.

³ Optical brightener available from Ciba Geigy.

⁴ Finnfix (trade name) available from Metasariton.

Lipolase lipolytic enzyme from ⁵ Novo.

Savinase protease enzyme from ⁶ Novo.

⁷ X2-3419 is a silicone foam inhibitor available from Dow Corning.

The production method of the granular material includes various types of tower drying, coagulation, dry addition, and the like as follows. The percentages are based on the finished composition.

A. Clutching and blowing through towers Using standard techniques, the following components are
ch) Dry the tower.

Sokalan CP5 3.52% du Quest 2066 0.45% Tinopal DMS 0.28% Zeolite A 7.1% CMC 0.47% as magnesium sulfate 0.49% anhydride B. Surfactant agglomerate B1. Paste and C ₁₂ -C of the sodium salt of tallow alkyl sulfate ₁₅ EO (3) aggregation of the paste of the sodium salt of sulfuric acid - 50% active paste of tallow alkyl sulfate and C ₁₂ ~C ₁₅ EO (3) 70% paste sulfate agglomerate zeolite a and sodium carbonate according to the following formulation ( Contributes to detergent formulation after drying of aggregates).

Tallow alkyl sulphate _{2.82% C 12~15 EO (3)} 1.18% sulphate Zeolite A 5.3% Sodium carbonate 4.5% B2. C ₁₄ ~C ₁₅ alkyl sulfates, C ₁₂ -C ₁₅ alkyl ethoxysulfate, Dobanol C ₁₂ -C ₁₅ EO
(3) and C ₁₆ -C ₁₈ N-methylglucose amide aggregate-C ₁₆ -C ₁₈ glucose amide non-ionic substance are added to methyl ester and N-methylglucamine in dovanol C _12-15 EO (3 ). C _12-15 EO
(3) acts as a melting point depressant which allows the reaction to take place without producing undesirable cyclic glucose amides.

A surfactant mixture of 20% dovanol C _12-15 EO (3) and 80% C ₁₆ -C ₁₈ N-methylglucoseamide is obtained and co-aggregates with 10% sodium carbonate.

Secondly, then the particles C ₁₄ -C ₁₅ sodium salt and C _{12 to 15} alkyl sulfate EO (3) sulfate and Zeolite A and extra high activity paste and sodium carbonate (70
%). The particles exhibit good dispersibility in cold water of C ₁₆ -C ₁₈ N-methyl glucose amide.

The total formulation of the particles (contributing to the detergent formulation after drying of the agglomerates) is as follows.

C ₁₆ -C ₁₈ N-methylglucose amide 4.1% Dovanol C _12-15 EO (3) 0.94% Sodium carbonate 4.94% Zeolite A 5.3% C ₁₄ -C ₁₅ Sodium alkyl sulfate 3.5% C _12-15 EO (3) Sulfuric acid Sodium 0.59% C. Drying additives Add the following ingredients:

Percarbonate 22.3% TAED (tetraacetyl ethylenediamine) 5.9% Hoechst layered silicate SKS-6 12.90% Citric acid 3.5% Lipolase 0.42% 100,000 LU / g Savinase 4.0KNPU 1.65% Zinc phthalocyanine (photobleach) 0.02% D. Spray-on Dovanol C _12-15 EO (3) 2.60% Fragrance 0.53% E. Foam Inhibitor Silicone foam inhibitor X2-3419 from Dow Corning
(High molecular weight starch 95% -97%; hydrophobic silica 3% -5)
%) With zeolite A (size 2-5 μ), starch and stearyl alcohol binder. The particles have the following formulation.

Zeolite A 0.22% Starch 1.08% X2-3419 0.22% Stearyl alcohol 0.35% Detergent formulations, for example, use 85 g of detergent at 30 ° C., 40 ° C., 60 ° C. and 90 ° C. cycles in an AEG brand washing machine for European laundry. It exhibits excellent solubility, excellent performance and excellent foam control when used on a machine.

Example 21 In any of the foregoing examples, the fatty acid glucamide surfactant can be replaced by an equivalent amount of a maltamide surfactant or a glucamide / maltamide surfactant derived from a plant sugar source. In compositions, the use of ethanolamide appears to promote cold stability of the finished formulation.
In addition, the use of sulfobetaine (aka "sultaine") surfactants provides excellent foaming properties.

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

Examples 22A-D If a particularly high foaming composition is desired (for example,
Dishwashing), C ₁₄ or higher fatty acids, because they may suppress the foaming, C ₁₄ or more fatty acids less than about 5%, there is more preferably less than about 2%, and most preferably that there is no substantial Is preferred. Accordingly, formulators of high foaming compositions desirably avoid introducing low foaming amounts of such fatty acids into high foaming compositions having polyhydroxy fatty acid amides and / or store the finished composition. It would avoid the production of C ₁₄ or more fatty acids when. One simple means is to use C ₁₂ ester reactants to produce the polyhydroxy fatty acid amides of the present invention. Fortunately, the use of amine oxide or sulfobetaine surfactants can overcome some of the negative foaming effects caused by fatty acids.

Formulators who wish to add anionic optical brighteners to liquid detergents containing relatively high concentrations (eg, 10% or more) of anionic or polyanionic surfactants, such as polycarboxylate builders, It may be useful to premix the brightener with water and the polyhydroxy fatty acid amide, and then add the premix to the final composition.

The polyglutamic acid or polyaspartic acid dispersant can be usefully used together with the detergent containing zeolite builder.
AEE fluids or flakes and DC-544 (Dow Corning) are other examples of other foam control agents useful herein.

Preparation of polyhydroxy fatty acid amides using disaccharides and higher sugars, such as maltose, will result in the production of polyhydroxy fatty acid amides in which the linear substituent Z is "blocked" by a polyhydroxy ring structure. Will be recognized by those skilled in the art. Such materials are fully contemplated for use herein and do not depart from the spirit and scope of the invention as disclosed and claimed.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI C11D 1:68) (31) Priority claim number 755,894 (32) Priority date September 6, 1991 (Sept. 1991. 6) (33) Priority countries United States (US) (56) References JP-A-63-270534 (JP, A) US Patent 3,676,340 (US, A) US Patent 3,31,627 (US, A) (58) Searched Field (Int.Cl. ⁷ , DB name) C11D 1/52 C11D 1/72 C11D 1/68

Claims (5)

(57) [Claims] 1. A method for improving the grease and oil bleeding performance of a detergent composition, wherein the detergent composition comprises: Wherein R ¹ is H, C ₁ -C ₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof, R ² is C ₅ -C ₃₁ hydrocarbyl, and Z is directly linked polyhydroxy hydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyl groups, C ₁₁ ~C ₁₇ N- methyl glucamide, C ₁₁ -C
₁₇ N-methyl-Maltese bromide or one or more polyhydroxy fatty acid amides having a mixture or their alkoxylated derivatives) of the glucamides and Marutamido,, C with (b) 3 to 15 ethoxy groups ₈ -C ₁₄ alkyl phenol ethoxylates and 2 to 10 C ₈ -C ₁₈ alcohol ethoxylates having an ethoxy group, and is selected from the group consisting of a mixture thereof, one or more additional nonionic surfactants Wherein the weight ratio of polyhydroxy fatty acid amide to additional nonionic surfactant is in the range of 1: 5 to 5: 1, and wherein the composition has
Improved methods of stain removal performance of the detergent composition, characterized in that does not substantially contain a C ₁₄ or more fatty acids. 2. The method of claim 1, wherein said Z moiety in said polyhydroxy fatty acid amide is derived from mixed monosaccharides, disaccharides and polysaccharides available from plant sources. 3. The polyhydroxy fatty acid amide according to claim 1, wherein
R ² moiety is a C ₁₅ -C ₁₇ alkyl, alkenyl, or mixtures thereof, The method of claim 1. 4. A method for bleeding from a fabric, comprising contacting the fabric with a detergent composition having enhanced bleeding performance according to the method of claim 1. 5. A method for bleeding from a hard surface, comprising contacting the hard surface with a detergent composition having enhanced bleeding performance according to the method of claim 1.