SK25093A3 - Detergent containing alkyl sulfate and polyhydroxy fatty acid amide surfactants - Google Patents

Abstract

An alkyl sulphate-based, controlled sudsing liquid or solid laundry detergent compsn. Useful for cleaning fabrics in automatic washing machines comprises: (a) at least 1 wt. % of polyhydroxy fatty acid amide cpd. of formula R2-C-(O)-N(R1)-Z (I) (c) pref. a suds suppressing amt. of a suds suppressor. In (I), R1 = H, 1-4 hydrocarbyl, 2-hydroxyethyl and/or 2-hydroxypropyl; R2 = 5-31C hydrocarbyl; Z = polyhydroxyhydrocarbyl having linear hydrocarbyl chain with at least 3-OH gps. directly connected to the chain or its alkoxylated deriv. The compsn. has a wt. ratio of (a):(b) of 1:10 to 10:1. Also claimed is a detersive particle comprising 5-90 % of cpd. (I) and 10-90% of an alkylsulphate surfactant and 1-30 wt. % of a solubilising agent. The compsn. pref. comprises at least 3% of cpd. (I) and at least 3% alkylsulphate in a wt. ratio of 6:1 to 1:6 (esp. 1.25:1 to 1:4). The compsn. further comprises 1-30% of an auxiliary surfactant component selected from alkyl benzene sulphonate surfactants, alkyl ester sulphonate surfactants, alkyl ethoxylate surfactants, alkyl polyglycoside surfactants, paraffin sulphonate surfactants and/or alkyl phenol alkoxylate surfactants. The suds suppressor is selected from silicone suds suppressors, hydrocarbon suds suppressors and/or monostearyl phosphate suds suppressors (esp. at least 0.5 wt. % of a monocarboxylate fatty acid or its salt).

Description

Technical field

The invention relates to laundry detergent compositions containing an alkyl sulfate surfactant. In particular, the invention relates to laundry detergent compositions comprising mixtures of alkyl sulfates and certain polyhydroxy fatty acid amide surfactant.

The ability of detergents to exhibit good cleaning performance with respect to the various types of dirt and stains on the various fabrics that may constitute the contents of the washing machine is of great importance in evaluating such detergents. Mixtures of linear alkyl benzene sulfonate (LAS) and alkyl sulfate (AS) surfactant formulations are used in granular detergent compositions with high efficiency due to the overall cleaning capability of both cold and hot scrubbing. Surface-active LASs are used more frequently for their ability to have excellent cleaning properties with respect to grease and oil stains. Mixtures of LAS and AS are desirable because they desirably oil (with good soil cleansing and particulate dirt stains. While AS surfactants are readily derived from regenerating plant sources, it is desirable to develop a cleansing compound.

which is comparable or which exhibits better cleaning characteristics, whereby the LAS is either partially or fully replaced by a surfactant which is readily prepared from vegetable, recovering insoluble raw materials.

It is also desirable to incorporate certain AS surfactants (liquid leakage into liquid hollows) on the capabilities, particularly of the scrubber particles for high demands to support them with full regard. While overall well-being, while their excellent chain alkylsulfates easily incorporate the ability of the chain into cleaning agents due to their low demands (light hollow), those skilled in the art are confronted with difficulties in incorporating alkylsulfate surfactants of 14 and higher carbon atoms into liquid cleaners. resources. These additional chain surfactants are generally preferred for laundry detergents and for other uses in fabric cleaning.

In addition, in the case of granular detergents, it would be desirable to promote their solubility and the dissolution of the alkyl sulfate surfactants in aqueous solutions, especially in the case of alkyl sulfates having 14 to more carbon atoms.

The invention relates to a cleaning composition comprising alkyl sulphates, exhibiting a reduced concentration or elimination of LAS while having excellent overall cleaning performance, including with respect to grease and oil stains. The invention relates to detergent compositions which may be in granular form and to detergent compositions which may be in liquid form and contain alkyl sulfate surfactants of 14 carbon atoms or more. The incorporation of such fatty acid polyhydroxyamides into granular detergent compositions may increase their solubility and the solubility of the alkyl sulfate surfactants in aqueous solutions.

The invention further relates to novel detergent particles for alkyl sulfate surfactants and fatty acid polyhydroxyamides as surfactants in granular form, wherein the detergent particles comprise a mixture of two surfactants and a third component to aid dissolution in aqueous solution. These detergent particles are advantageous in that they improve the release of polyhydroxy fatty acid amides into granular detergent compositions in a non-tacky form without the need to use substantial amounts of inert and costly and inactive ingredients. As a rule, polyhydroxy fatty acid amides have a sticky and tacky character which is undesirable for granular compositions. The particles of the invention may exhibit improved dissolution characteristics in aqueous solutions, especially in automatic washing machines.

BACKGROUND OF THE INVENTION

Numerous polyhydroxy fatty acid amides are described in the prior art.

N-acyl, N-methylglucamides are described, for example, by J.V. Goodby,

M. A. Marcus,

E. China

P. L. Firin

Thermotrop i c

Ligue i d-Crystal1 ine Properties of Some Straight Chain

Carbohydrate

Ainphi phi les (Thermotropic liquid-crystalline properties of some straight chain carbohydrate amphiphiles), Liguid

1581 and no.

Muller-Fahrnow, V. Zabel, M. Steif, and R.

Hilgenfeld v

Molecular and

Crysta1

Structure of

Nonionic

detergent

Nonanoy1-N-Methylglucamide (Molecular and crystal structure of nonionic detergents- · Nonanoyl-N-methylglucamide),

J. Chem. Soc. Chem. Commun. , 1986, st. 1573 až

1574. Use

N-alkyl polyhydroxyamide surfactants have recently received particular attention for use in biochemistry, for example in the dissociation of biological membranes (e.g., JEK Hildreth ND-Gluco-N-methylalkariamide Compounds, and the New Class of Non-Ionic Detergents For Membrane Biochemistry ND). Gluco-N-methyl-alkanamide compounds, a new class of nonionic detergents for membrane biochemistry, Biochem J. 1982, Vol. 207, pp. 363-366.

The use of N-alkylglucamides in detergent compositions is also described. U.S. Patent No. 2,965,576 to E. R. Vilson, Dec. 20, 1960;

809060, non-animal

February 18, 1959 (Thomas Hedley & Co. Ltd) discloses cleaning compositions comprising anionic surfactants and certain amide surfactants, which may contain N-methylglucamide added as a low temperature suds booster. These compounds contain

N-acyl group having from 10 to 14 carbon atoms, adjuvants such as straight chain fatty acids These compositions may also contain alkali metal phosphates, alkali metal silicates, sulfates and carbonates.

It is also generally stated that the compositions may contain additional ingredients to impart desirable properties of the composition, such as fluorescent dyes, bleaching agents and perfumes.

U.S. Patent No. 2,707,898 (Mar. 8, 1955) to A. M. Schwartz relates to aqueous cleaning compositions comprising the condensation reaction product of N-alkylglucamine and an aliphatic fatty acid ester. The product of this reaction is said to be usable in aqueous cleaning compositions without further purification. It is also known to prepare a sulfuric acid ester of an acylated glucamine. as described by A. M. Schwartz in U.S. Patent 2,717,894 (September 13, 1955).

PCT International Application WO 83 / 044.12, published December 22, 1983 (J. Hildreth), relates to amphiphilic compounds containing polyhydroxylaliphatic groups and is said to be useful for a variety of purposes, including as surfactant compounds in cosmetics, in pharmaceutical compositions in shampoos, lotions, eye ointments, as emulsifiers and release agents for drugs and in biochemistry for solubilizing membranes, whole cells or other tissue samples, and for preparing liposomes. Included are compounds of the general formula R C0N (R) CH2R and RCON (R) R, wherein R is hydrogen or an organic group, R is an aliphatic hydrocarbon group of at least 3 carbon atoms, and R is an aldose residue.

European Patent Application No. 0 285768, published October 12, 1988 (H. Kekkenberg et al.), Relates to the use of N-polyhydroxy fatty acid amides as thickeners in aqueous cleaning systems. Included are amides of formula

R 1 (O) N (X) R 2, wherein R 1 is C 1 -C 17 alkyl (preferably C 7 -C 17), R 2 is hydrogen, C 1 -C 6 alkyl (preferably C 6 -C 6 alkyl) and thiamino carbon) and / or an alkylene oxide group; and X a C 4 -C 7 polyhydroxyalkyl group, for example Coconut oil fatty acid N-methylglucamide.

Amide thickening properties have been reported to be particularly useful in liquid surfactant systems that contain paraffin sulfonates, although aqueous surfactant systems may contain other anionic surfactants such as alkali metal sulfonates, sulfonates and sulfonates. polyesters of sulfosuccinic acid and ether If fatty alcohol oriates and nonionic surfactants such as polyglycol ether of fatty alcohol, alkylphenol polyglycol ether. polyglycol ester fatty acids; polypropylene oxide polyethylene oxide blend polymers. By way of example, shampoo compositions based on a coconut fatty acid paraffin phonate / N-methylglucamide / nonionic surfactant system are mentioned.

In addition to the thickening effect, N-polyhydroxy fatty acid fatty acid amides are reported to be cut through the skin.

U.S. Pat.

(May 3, 1961) (Boettner et al.) relates to urea-containing detergent bars.

sodium lauryl sulfate nonionic surfactant

N-alkylglucamide nonionic surfactant.

which is selected from the group consisting of

N-mety1,

N-sorbityl lauramide and N-methyl, N-sorbitylmyristam d.

Other glucamide surfactant agents are disclosed, for example, in DT Patent No. 2

226872 CH. IN.

Eckert et al., Published Dec. 20

1973), which relates to detergents containing one or more surfactants and salts of additives (Cbuilder) selected from the group consisting of polymeric phosphates, sequestering agents, laundry alkali, improved by the addition of N-acyl polyhydroxy alkylamine of the general formula

R 1 is C 1 O 3 (R 2) CH 2 (CH ₂ H) _n CH ₂ OH where R 1 is C 1 -C 3 alkyl, R 2 C 10 -C 22 alkyl and n or 3 N-acyl polyhydroxyamino amine is added as a soil suspending agent.

U.S. Patent 3,654,166 to H.V. Eckert et al., U.S. Pat.

4 April 1972) discloses cleaning compositions comprising at least one surfactant selected from the group consisting of anionic.

both zwitterionic and nonionic surfactants; and as a textile emollient, an N-acyl, N-alkylpolyhydroxyalkyl compound of the formula R 1 (Z) C (O) R 2, wherein R 1. R aj is C 10-C aj aj alkyl, R 7 is C až-C alky alkyl, and R a and R obsahujú are from 23 to 39 carbon atoms in total, and Z is a polyhydroxyalkyl group, which may be -CH2 (CHOH) _and CH2OH, where m 3 or 4.

U.S. Pat. No. 4,021,139 to H. Muller et al.

May 3, 1977) relates to skin care cosmetic compositions containing N-polyhydroxyalkylamines which include compounds of the formula R 1 (R) CH (CHOH) _m R 2. where R1 is hydrogen, lower alkyl, hydroxy lower alkyl or aminoalkyl, as well as heterocyclic aminoalkyl, R has the same meaning as R1, but cannot be hydrogen and R2 is CH2OH or COOH-

French Patent Specification No. 1 360018 (April 26, 1963) (Commercial Solvents Corporation) relates to formaldehyde solutions stabilized against polymerization by addition of amides of the formula RC (O) N (R 1) G, wherein R is a carboxylic acid group and at least 7 carbon atoms and a G glycitol group of at least 5 carbon atoms.

German Patent Specification No. 1 261861 CA. Heins, Feb. 29, 1968) relates to glucamide derivatives useful as wetting and dispersing agents of the general formula (RCR) (R1) (R2). wherein R is a glucamine moiety, R 1 is C 1 -C 20 alkyl, and R 2 is C 1 -C 5 acyl.

British Patent No. 745036 (Atlas Povder Company, published February 15, 1956) relates to heterocyclic amides and their carboxylic esters useful, for example, as chemical products of emulsifiers, wetting and dispersing agents, detergents and textile emollients. These compounds have the general formula (RCR) (R 1) C (O) R 2, wherein R is a residue of anhydrous hexanpentol or a carboxylic acid ester, R 1 is a monovalent hydrocarbon group and -C 0 R 2 acyl carboxylic acid having 2 to 25 carbon atoms.

U.S. Pat. No. 3,312,627 to D. T. Hookeri, U.S. Pat.

April 1967) relates to solid toilet bars which are practically free of anionic detergents and alkaline ingredients

(Which include certain lithium soaps of certain fatty acids, nonionic surfactants selected from certain propylene oxide / ethylene oxide / ethylene oxide condensates, propylene oxide / propylene glycol / ethylene oxide condensates and a polymeric composition which may also contain ethylene glycol) a polyhydroxyamide of the formula

RC (O) NR 1 (R 2), wherein RC (O) contains about 10 to about 14 carbon atoms and R 1 and R 6 are each hydrogen or C 1 -C 6 alkyl, these alkyl groups having a total carbon number of 2 to about 7 and a total number of hydroxy group substituents of 2 to about 6. Essentially similar is the subject of the invention of U.S. Patent 3,312,626 (DT Hooker, April 4, 1967).

SUMMARY OF THE INVENTION

The present invention provides a low-foaming detergent suitable

for washing textiles in automatic washing machine them, which It contains weight (a) at least approximately 1 % polyhydroxyamides fatty of of the general formula 0 1 R ² - C - 1 1 - Z

where it means

R ¹ is hydrogen, C 1 -C 4 hydrocarbon, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof

R ² hydrocarbon group of 5-31 carbon atoms, and

Z is a linear hydrocarbon chain polyhydroxy hydrocarbon group having at least three hydroxyl groups directly bonded to the chain or an alkoxylated derivative thereof.

(b) at least about 1% of an alkyl sulfate surfactant; and

c) a suds suppressor amount of a suds suppressor, preferably selected from monocarboxylic fatty acids and salts thereof, silicone suds suppressors, monostearyl-di-alkali metal alkyl phosphates and phosphate esters, hydrocarbon suds suppressors, and mixtures thereof i.

wherein the weight ratio of fatty acid polyhydroxyamides to alkyl sulfate surfactant is about 18 to about 10-1, preferably about 1: 6 to about G: 1, especially about 14 to about 3: 1, and especially about 1-4 to about 1 - 1.

The invention also relates to detergent compositions comprising an alkyl sulfate surfactant and a polyhydroxy fatty acid amide, wherein the weight ratio of alkyl sulfate to polyhydroxy fatty acid amide is about 1.25 L to about 6 = 1, preferably about 1.25 L to about 4 ^:

1, in particular about 1.25 L, wherein the fatty acid polyhydroxamide has the general formula

R ¹

^R2 - C - N - Z wherein R ¹ is methyl, R ² alkyl or alkenyl group having 9 to 17 carbon atoms, Z glycltylovú group derived from a reduced sugar or alkoxylated derivative thereof.

The invention also relates to a liquid cleaning composition comprising by weight

a) at least about 1% of a polyhydroxy fatty acid amide of formula

R ¹

R ² - C - N - Z where is

R ¹ is hydrogen, C 1 -C 4 hydrocarbon, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof

R ² hydrocarbon group of 5-31 carbon atoms, and

Z is a linear hydrocarbon chain polyhydroxy hydrocarbon group having at least three hydroxyl groups directly bonded to the chain or an alkoxylated derivative thereof.

b> at least about 1% alkyl sulfate surfactant c) a liquid carrier, wherein the weight ratio of the polyhydroxy fatty acid amide to the higher alkyl sulfate surfactant is about 1 = 10 to about 10 L, preferably about 1 = 6 to about 6 L, especially about 1-4 to about 3: 1, and especially about 14 to about 1 ^: 1.

The invention also relates to detergent particles suitable for use in granular detergent compositions which contain in the form of an intimate mixture by weight

a) about 5 to about 90%, preferably 50%, of a polyhydroxy fatty acid amide of the formula

R ¹

R ² - C - N - Z where is

R ^{@ 1} is hydrogen, C1 -C4 hydrocarbon, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof

R ² hydrocarbon group of 5-31 carbon atoms, and

Z is a linear hydrocarbon chain polyhydroxy hydrocarbon group having at least three hydroxyl groups directly bonded to the chain or an alkoxylated derivative thereof; and

b) about 10% to about 95, preferably 50%, of an alkylsulfate surfactant, wherein the weight ratio of the alkylsulfate surfactant (b) to the polyhydroxy fatty acid amide (a) is about

20: 1 to about 1 - 1. The invention is therefore relates to a low-foaming detergent. washable fabrics in automatic washing machines which

contains by weight

a) at least about 1% of a polyhydroxy fatty acid amide of formula

ri

R ² - C where is

R ¹ is hydrogen, C 1 -C 4 hydrocarbon, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof

R ² hydrocarbon group of 5-31 carbon atoms, and

Z is a linear hydrocarbon chain polyhydroxy hydrocarbon group having at least three hydroxyl groups directly bonded to the chain or an alkoxylated derivative thereof, and

b) at least about 1% of the alkyl sulfate surfactant is <11; and a

c) a suds suppressor amount of a suds suppressor, preferably selected from the group consisting of monocarboxylic fatty acids and their salts, silicone suds suppressors, monostearyl-di-alkali metal alkyl phosphates and phosphate esters, hydrocarbon suds suppressors and mixtures thereof, wherein: the weight ratio of polyhydroxy fatty acid amide to alkyl sulfate surfactant is about 1:

to about 10: 1, preferably about 1 to 6 to about 6: 1, especially about 1 = 4 to about 3: 1, and especially about 1: 4 to about 1: 1.

Alkyl sulfate surfactant

The composition of the invention comprises at least 1% by weight, preferably about 3 to about 50% by weight, and especially about 5 to about 30% by weight of the alkyl sulfate surfactant.

Alkylsulfate surfactants are known in the art.

Alkyl sulfate surfactants are water-soluble salts or acids of the formula ROSO3M wherein R is a hydrocarbon group having 10 or more carbon atoms, preferably a hydrocarbon group having 10 to 24 carbon atoms, and in particular an alkyl or hydroxyalkyl group having 14 to 18 carbon atoms and M a hydrogen atom or a cation, for example an alkali metal cation (such as sodium, potassium or lithium), an ammonium cation or a substituted ammonium cation (such as a methyl ammonium, dimethylammonium and trimethylammonium cation) and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof. In general, alkyl moieties of 14 carbon atoms or more are preferred for laundry detergent compositions. As a rule, alkyl sulphate surfactants having an alkyl moiety of 12 to 16 and in particular 14 to 16 carbon atoms for lower wash temperatures (e.g. below about 50 ° C) and 16 to 18 carbon atoms are preferred for washing purposes (especially in automatic washing machines). for higher wash temperatures (e.g., above about 50 ° C).

Polyhydroxy fatty acid amide surfactant

The detergent composition of the invention comprises at least 1% by weight, preferably about 3 to about 50% by weight, and more preferably about 3 to about 30% by weight of polyhydroxy fatty acid amide, as a surfactant, as described in more detail below.

The polyhydroxy fatty acid amide surfactant component of the system of the invention has the general formula I

OR ¹

^R2 - C - N - Z (I)

R ^{@ 1} is hydrogen, C1 -C4 hydrocarbon, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, preferably C1 -C4 alkyl, in particular C1 -C2 alkyl and in particular alkyl 1 carbon atom (i.e. methyl)

R ² is a C 5 -C 31 hydrocarbon group, preferably a C 7 -C 19 straight chain alkyl or alkenyl group, especially a C 9 -C 17 straight chain alkyl or alkenyl group, and in particular a straight chain alkyl or alkenyl group with Or a mixture thereof.

Z is a linear hydrocarbon chain polyhydroxy hydrocarbon group having at least three hydroxyl groups directly bonded to the chain or an alkoxylated (preferably ethoxylated or propolylated) derivative thereof.

The group Z is preferably derived from a reducing sugar in a reductive amination reaction i.

preferably Z is a glycityl group. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose. High dextrose corn syrup, high fructose corn syrup and high maltose corn syrup can be used as starting materials as the individual sugars listed above. Corn syrups may be obtained as a mixture of the Z sugar components. However, the above calculation does not exclude other suitable raw materials. The group of symbols Z is preferably selected from the group consisting of the formula

CH2 <CHOH) n CH 2 OH,

CH (C112 OH) - (CHOH) _n CH ₂ OH-L

-CH 2 - (CHOH) 2 (CHOR) (CHOH) -CH ₂ OH

R is a hydrogen atom or a cyclic or aliphatic monosaccharide alkoxylated derivatives thereof.

Most preferred are glycityls wherein n is 4, especially of the formula

-CH 2 - (CHOH) 4 -CH ₂ OH

In formula (I), R ¹ can be, for example, a group

N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl,

Ν-2-hydroxyethyl or Ν-2-hydroxypropyl.

R ² -CO-N? May for example be cocamide stearamide.

oleamide, lauramide, myristamide, capricamide, palmitamide, tallow amide.

A symbol meaning, for example, a group

1-deoxyglucyl,

2-deoxyfructityl,

1-deoxymaltityl

2-deoxylactiyl,

1-deoxygalactityl, 1-deoxymanityl or

1-deoxyma 1 t.

These polyhydroxy fatty acid amides are prepared in a known manner.

Generally, they are prepared by reacting an alkylamine with a reducing sugar to a reductive amination reaction to form the corresponding N-alkyl polyhydroxyamine, and thereafter

The N-alkyl polyhydroxyamine is reacted with a fatty acid ester or triglyceride in the condensation amidation step to form N-alkyl, N-polyhydroxy fatty acid amide. Methods for preparing mixtures containing fatty acid polyhydroxyamides are described, for example, in British Patent Application No. 809060 (Thomas Nedlay & Co., Ltd.) published Feb. 18, 1959. U.S. Patent No. 2,965,576 (ER Wilson, Dec. 20, 1960); U.S. Patent No. 2,703798 (Anthony M. Schwartz, March 8, 1955); and U.S. Patent No. 1,985,424 (Piggott, December 25, 1934).

In one method of preparing N-alkyl

N-depoxyglycitylamides of a fatty acid, and / or N-hydroxyalkyl wherein the glycityl component is derived from glucose

N - alkyl or

An N-hydroxyalkyl group is a group

N-methyl,

N-ethyl,

N-propyl,

N-butyIová,

N-hydroxyethyl or

N-hydroxypropyl, the product is prepared by reaction

N-alkylglucamine or N-hydroxyalkylglucamine with a fatty acid ester selected from the group consisting of fatty acid methyl esters, fatty acid ethyl esters, and fatty acid triglycerides in the presence of catalysts selected from the group consisting of tri-lithium phosphate, trinium phosphate, tricalcium phosphate, tetranopropium phosphate, tetranopropium phosphate lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium carbonate, sodium carbonate, potassium carbonate, disodium titrate. dicalcium tartrate, sodium potassium tartrate, trisodium citrate, three potassium silicate, basic sodium silicate, basic potassium silicate, basic sodium aluminum silicate, and alkaline potassium silicate will dissolve the initiation of such a mixture, preferably about 0.5%, with a catalyst content of about 0.5% mole%, preferably about 2.0 mole% to about 10 mole%, based on the molar basis of N-alkylglucamine or N-hydroxyalkylglucamine. The reactions are preferably carried out at a temperature of about 138-170 ° C, typically for 20-90 minutes. When triglycerides are used in the reaction mixture as a fat ester source, the reaction may also preferably be carried out using about 1 to about 10% by weight of the phase transfer agent, based on the weight of the reaction mixture as a whole, selected from saturated surfactants. fatty alcohol polyethoxylates. alkyl polyglucosides, linear glycamines and mixtures thereof.

Preferably, the method is carried out such that:

(a) preheat es ter 170 ° C fatty acid to a temperature of about 138 to about b) N is added -a 1ky1g 1ukamin or N-hydroxyalkylglutamine The to heated ester fatty of acid and stirred until to

in the formation of a biphasic liquid / liquid mixture,

c) adding the catalyst to the reaction mixture,

d) stirring the reaction mixture for a given time.

When triglycerides are used as the fatty acid ester, it is also preferred to add about 2 to about 20% by weight of the preformed N-alkyl / N-hydroxyalkyl, N-linear fatty acid glucosylamide product to the reaction mixture, based on the weight of the reactants as phase transfer agents. .

This inoculates the reaction and thus increases the reaction rate.

A detailed description of this procedure is part of the examples of the invention.

The polyhydroxy fatty acid amide of the invention provides the advantage to those skilled in the art that it can be fully prepared from primary additional degradable raw materials, i.e. not from petrochemical raw materials.

These raw materials are also low toxic to the environment of natural watercourses.

It should be noted that in addition to the polyhydroxy fatty acid amides of formula I, some non-volatile by-products, such as ester amides and cyclic polyhydroxy fatty acid amides, are also prepared for their production. The concentration of these by-products varies depending on the reactants selected and the reaction conditions. Preferably, the polyhydroxy fatty acid amide introduced into the detergent composition is formulated in a composition comprising a polyhydroxy fatty acid amide composition to contain less than about 10% by weight and preferably less than about 4% cyclic polyhydroxy fatty acid amide. The preferred process described above has the advantage of providing a rather low amount of by-products, including such a cyclic amide by-product.

As mentioned above, they can be incorporated into detergent compositions

The suds suppressors of the present invention incorporate suds suppressors or suds suppressors. The incorporation of such suds suppressors herein is desirable since the fatty acid polyhydroxyamides used as surfactant may increase the foam stability of the composition.

Suds suppressors may be of importance when the cleaning compositions contain a relatively high sudsing agent together with a polyhydroxy fatty acid amide surfactant. Suds suppressors are particularly desirable in the case of cleaners intended for use in front-load automatic washing machines.

Such washing machines are characterized by a laundry and washing drum, with a horizontal axis that rotates about the axis.

This type of mixing can lead to high foaming and, consequently, to a reduced washing effect. The use of suds suppressors may therefore be of particular importance in hot bath washing and high detergent concentration conditions.

A variety of compounds can be used as suds suppressors. Suds suppressors are known in the art.

They are generally described, for example, in Kirk

Othmer

Encyclopedia of Chemical Technology, Third Edition, Volume 7, p. 430-447 (John Viley & Sons, Inc., 1979). One category of suds suppressor that is of particular importance includes monocarboxylic fatty acids and their dissolved salts.

These compounds are described

954347 (Wayne St. John, 27.

in U.S. Patent No. September 1960). The monocarboxylic fatty acids and their salts used as suds suppressors have a hydrocarbon chain of 10 to about 24 carbon atoms.

preferably 12 to 10 carbon atoms. Alkali metal salts such as sodium, potassium and lithium salts, ammonium salts and alkanolammonium salts are suitable. These compounds are believed to be preferred suds suppressors.

The cleaning compositions may also contain non-surfactant suds suppressors. Also, for example; high molecular weight hydrocarbons such as reagents include paraffin, fatty acid esters (e.g., fatty acid triglycerides).

esters of monovalent alcohols of fatty acids, aliphatic ketones

Other agents having 18 to 40 carbon atoms (e.g., stearone).

suppressing foaming of aminotriazines, for example hexaalkylaminamines or di- to tetraalkyldiaminochlorotriazines, formed as the reaction products of cyanuric chloride with 2 to 3 moles of a primary or secondary amine containing carbon atoms, propylene oxide and monosilate phosphate monosearearate esters, monostearyl-diahalic metal phosphate (for example with potassium sodium or lithium as the alkali metal) and phosphate esters.

The hydrocarbons such as paraffin and halogenated paraffin can be used in liquid form. Liquid hydrocarbons may be liquid at room temperature and ambient pressure and have a pouring temperature of about -40 to about +5 ° C and a minimum boiling point of less than about 110 ° C at ambient pressure. It is also known to use wax hydrocarbons, preferably at a melting point below

Mp 100 ° C.

Hydrocarbons represent a preferred category of suds suppressors for the cleaning compositions of the invention.

Hydrocarbon suds suppressors are described, for example, in U.S. Pat.

1982, Gandolfo et al.). These hydrocarbons include aliphatic cyclic, aromatic and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms. As used herein, the term paraffin refers to a suds suppressor mixture of true paraffins and cyclic hydrocarbons.

Another preferred category of suds suppressors is the icon suds suppressor strength.

This category includes the use of polyorganosiloxyn oils, such as polydimethylsiloxane, a dispersion or emulsion of polyorganisilized oils or resins, and mixtures of polyorganosiloxanes with silica particles. wherein the polyorganosiloxane is deposited on silica. Si1 icon chemically sorbed suds suppressors are well known in the art and are described, for example, in U.S. Patent 4,265,779 to Gandolfo et al.

European Patent Application No. 89307851.9 published May

Next

7th

February

1990 C. St. M. S.).

Conical suds suppressors are disclosed in U.S. Pat

No. 455839, which relates to agents and methods for limiting their foaming of aqueous solutions by incorporating small amounts of polydimethylsiloxane liquids.

A mixture of silicones and silanated silicon dioxide is described, for example, in German Published Application No. 124526.

Si 1 icon antifoams and si 1 icon suds suppressors in granular detergent compositions are described in U.S. Patent No. 3

933672 (Bartolotta et al.)

24th

U.S. Pat

652392 (Baginski et al ..

March 1987).

As an exemplary suds suppressor for the purposes of the invention, there is disclosed a suds suppressing amount of a suds controlling agent consisting essentially of the following components;

a polydimethylsiloxane liquid having a viscosity of approximately

500 mm ² / s at 25 ° C.

by weight of about 5 to about 50 parts per 100 parts (i) of 1 icon resin composed of (CH3) 3Sii / 2 units and silica units at a weight ratio of (CH3) 3811/2 units

About 1.0 to about 1.2 parts by weight and about 100 parts by weight per 100 parts of the solid silica gel component (i). The suds suppressors optionally used are used in a suds suppressing amount.

By a suds suppressing amount it is meant that a person skilled in the art will formulate a cleaning composition by selecting the amount of suds suppressing agent to the extent desired.

For example, in the case of high suds surfactants, relatively more suds suppressors are used to achieve the desired suds suppression than low suds surfactants.

The detergent compositions of the present invention generally contain from 0 to about 0.5% suds suppressor. When mono-carboxylic fatty acids and mixtures thereof are used as foaming agents.

are generally present in an amount by weight of up to about the composition, preferably about 3, of the suppressant based on the weight of the laundering agent used, by weight of about 0.5 to% of the fatty acid monocarboxylates as foaming agents. When 1 iconic agents are used as suds suppressors, they are generally contained in an amount of about 2.0 based on the weight of the detergent, although it may be

The upper limit is of a practical nature, quantity.

Preferably, the antifoaming agent strengths are used in an amount of about 0.01% to about 1% by weight, and in particular about 0.25% to about 1% by weight. 0.50%. As mentioned above, these weight percentages include any silica that can be used together with the polyorganosiloxane as well as any adjuvant. Monostearyl phosphates are generally used in an amount of about 0.1 to about 2% by weight of the detergent composition.

Hydrocarbon suds suppressors are generally used in an amount of about 0.1 to about 5.0, although a larger amount may also be used.

The detergent composition of the present invention may further comprise auxiliary surfactants which contain anionic and nonionic surfactants other than the above-mentioned alkyl sulfates and polyhydroxy fatty acid amides and other types of surfactants.

These auxiliary surfactants are optionally present in an amount by weight of at least about 1%, preferably in an amount of about 3 to about 30%, in each case based on the cleaning composition as a whole.

Certain types of surfactant adjuvants, if any, used may contribute to a further surprising improvement in cleaning performance. Such co-surfactants include alkylethoxylated sulfates, alkyl ethoxylates and and alkyl ester sulfonates (especially methyl ester sulfonates) and mixtures thereof. Preferably, the weight ratio of polyhydroxy fatty acid amides to these surfactant aids is about 1 = 10 to about 10 - 1, preferably about 5 - 1 to about: 5, and especially about 1: 4 to about 4 - 1.

Without intending to be limited, it may be desirable to incorporate other surfactants, such as paraffin sulfonates, alkylbenzenesulfonates, alkylpolyglycosides (especially alkylpolyglucosides), and alkylphenolalkoxylates into the detergent compositions of the invention.

Further, these auxiliary agents are suitable for use in the detergent compositions of the present invention.

Auxiliary anionic surfactants

Alkyl ester sulfonate surfactants include linear esters of carboxylic acids having 8 to 20 carbon atoms (i.e., fatty acids) that are sulfonated with sulfur trioxide gas as described in The Journal of the American Oil Chemist Society, 52 (1975), p. 323 to 329. Natural fats such as tallow and palm kernel oil are mentioned as suitable starting materials.

Preferred alkyl ester sulfonate surfactants especially for laundry purposes include alkyl ester sulfonate surfactants of the formula

R ³ -CH-C-OR * ¹

SO3 M where is

R ³ hydrocarbon group having 8 alkyl radical or a mixture of R ¹ hydrocarbon having one alkyl group or a mixture of a soluble salt-forming cation M.

up to 20 carbon atoms, preferably such alkyl groups, up to 6 carbon atoms, preferably such alkyl groups, and

Suitable salts include metal salts such as sodium, potassium and lithium salts and substituted or unsubstituted ammonium salts such as monoethanolamine, diethanolamine and triethanolamine cations and quaternary ammonium cations such as tetramethylammonium and dimethylpyridinium, dione and cationic cations iethanolamine and triethanolamine. Preferably, R ^{3 is} C 10 -C 16 alkyl and R ^{4 is} methyl, ethyl or isopropyl. Particularly preferred are methyl ester sulfonates wherein R ^{3 is} C 14 -C 16 alkyl.

Another category of useful anionic surfactants are alkylalkoxylated sulfate surfactants. Such surfactants are generally water-soluble salts or acids of the general formula

R0 (A) mSO3M, wherein R represents an unsubstituted (C až-C alky alky) alkyl group or a (C až hydroxy-C skupinu alky) hydroxyalkyl group, especially an alkyl or C predovšetkým až 20 (C a 20 20) alkyl group, and in particular an alkyl or hydroxyalkyl group (C 18-C 18 18). The symbol A represents an ethoxy or p-methoxy group, about 6, in particular about 0.5 to about 3, and a hydrogen atom or a cation which may be, for example, a metal cation (e.g. sodium, potassium, lithium, calcium, magnesium) and ammonium or substituted ammonium .

Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl ammonium, ethyl ammonium and trimethylammonium cations, and quaternary ammonium cations such as tetramethyl ammonium, dimethylpiperidinium and alkanolamine derived cations.

for example, from monoethanolamine, diethanolamine and triethanolamine and mixtures thereof. Exemplary surfactants include 12-C18 alkyl (10) carbonate alkyl (10) carbonate, 12-C18 alkyl (2,25) alkyl (2,25) sulfate, and alkyl ( (C12-C18 (2,25) M), C12-C18 alkyl (3,0) sulphate of alkyl (3,0) sulphate (C12-C18Ε (3.0) Μ) alkyl (4,0) sulphate of alkyl of 12 to 18 carbon atoms share

M generally means sodium or potassium. The detergent composition of the invention may include (C 12 -C 16 E (4.0) M), also including other anionic surfactants for detergent purposes.

Salts (including, for example, sodium potassium, ammonium and substituted ammonium salts such as monoethanolamine, diethanolamine triethanolamine salts) of soaps, linear alkylbenzene sulfonates to carbon, carbon atoms, carbon atoms, and sulfonated earth atoms may also be included. primary and secondary alkanesulfonates olefinsulfonates with 8 to polycarboxylic acids, pyrolyzed metal citrate product prepared by alkali atoms, for example, are described in British patent specification

082179, alkyl polyglycol ether sulfates, fatty acylglycerol sulfonates fatty acids glycerol sulfates, and alkylphosphine sulfonates, alkyl phosphates, isethionates such as acyl sulfonates,

N-acyl taurates, methyl tauride fatty acid amides, alkyl succinates and sulfosuccinates, sulfosuccinate monoesters (especially saturated and unsaturated monoesters of 12 to 18 carbon atoms), diesters of sulfosuccinate (especially saturated and unsaturated diesters of 6 to 14 carbon atoms), N-acyl sarcosinates, sulfates and alkyls of polysaccharides such as sulfates and alkylpolyglucosides (nonionic unsulfated compounds described below), branched primary alkylsulfates and alkylpolyethoxycarboxylates, e.g.

R0 (CH ₂ 0) to CH ₂ C00-M ⁺ wherein R is an alkyl radical having 8 to 22 carbon atoms, k is an integer from 0 to 10, and M is a cation forming soluble salts of fatty acids esterified with isethionic acid and neutral izované NaOH.

Also suitable are resin acids and hydrogenated resin acids such as rosin, hydrogenated rosin and resin acids and hydrogenated resin acids contained in tall oil. Other examples of such anionic surfactants are described in Surface Active Agents and Detergents (Volume la II. Schwartz, Perry and Berch). A variety of such surfactants are also disclosed in U.S. Pat. No. 3,929,678 (Laughlin et al., Dec. 30, 1975). column 23, line 58 to column 29, line 23.

Auxiliary nonionic surfactants

Suitable nonionic surfactant detergents are generally described in U.S. Pat. No. 3,929,678 (Laughlin et al., Dec. 30, 1975), column 13, line 14 to column 16, line 6. The following are non-limiting classes. suitable nonionic surfactants -

1- Polyethylene oxide, polypropylene oxide and polybutylene oxide condensates of alkylphenols. These compounds include the condensation products of alkylphenols having an alkyl moiety of 6 to 12 carbon atoms in a straight or branched chain configuration with alkylene oxide. According to a preferred embodiment, the ethylene oxide is present in an amount of about 5 to about 25 moles of ethylene oxide per mole of alkyl phenol. Commercially available nonionic surfactants of this type are, for example, Igepal ^1M C0-630 from GAF Corporation and Triton ™, X-45, X-114, X-100 and X-102, all from Rohm & Haas

Company. The above compounds may be referred to as alkyl phenolalkoxylates, for example alkylphenol ethoxylates.

2- The condensation products of aliphatic alcohols with about e to 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol may be either straight or branched, primary or secondary, and generally contains 8 to 22 carbon atoms. Particularly preferred are the condensation products of an alcohol having alkyl groups of about 10 to about 20 carbon atoms and about 2 to about 10 moles of ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this type include Tergitol ^1M 15-S-9 (a C 11 -C 15 linear alcohol condensation product with 9 moles of ethylene oxide), Tergitol ™

24-L-6-NMV (condensation product of a primary alcohol of 12 to 14 carbon atoms with 6 moles of ethylene oxide and narrow molecular weight distribution), both of which are products of Union Carbide Corporation; Neodol ™ 45-9 (condensation product of linear alcohol of 14 to 15 carbon atoms with 9 moles of ethylene oxide), Neodol ™ 23-6.5 (condensation product of linear alcohol of 12 to 13 carbon atoms with 6.5 moles of ethylene oxide), Neodol ™ 45- 7 (condensation product of linear alcohol of 14 to 15 carbon atoms with 7 moles of ethylene oxide), Neodol ™ 45-4 (condensation product of linear alcohol of 14 to 15 carbon atoms with 4 moles of ethylene oxide) always from Shell Chemical Company and Kyro ™ EOB (condensation product of an alcohol having 13 to 15 carbon atoms with 9 moles of ethylene oxide) from the Procter & Gambie Company. These surfactants may be referred to as alkali ethoxylates.

3. The condensation products of ethylene oxide and a hydrophobic base formed by condensation of propylene oxide with propylene glycol. The hydrophobic portion of these compounds preferably has a molecular weight of about 1,500 to 1,800 and exhibits water insolubility. Addition of the polyoxyethylene moiety to this hydrophobic moiety results in an increase in the water solubility of the molecule as a whole and in the liquid nature of the product to a point where the polyoxyethylene content is about 50% by weight with respect to the total weight of the condensation product.

which corresponds

Examples of compounds of this type include certain commercially available Pluronic ™ surfactants from BASF.

4. The condensation products of ethylene oxide and the product formed by the reaction of propylene oxide and ethylenediamine. The hydrophobic portion of this product consists of the reaction product of ethylenediamine and an excess of propylene oxide and generally has a molecular weight of about 2,500 to about 3,000. This hydrophobic portion is condensed with ethylene oxide to such an extent that the condensation product contains about 40 to about 80% polyoxyethylene molecular weight of about 5,000 to about 11,000. Examples of this type of nonionic surfactant include the commercially available Tetronic ™ compounds from BASF.

5. Semi-polar nonionic surfactants of a particular category of nonionic surfactants which include water-soluble amine oxides containing a C 10 -C 18 alkyl moiety and two moieties specially selected from the group consisting of alkyl and C 1 -C 3 hydroxyalkyl groups; water-soluble phosphine oxides containing an alkyl moiety of 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl groups of 1 to 3 carbon atoms.

Semi-polar nonionic detergent surfactants include amine oxide surfactants of the formula

R ³ (OR ⁴ ) XN (R ⁵ ) 2 wherein is

R ^{3 is an} alkyl, hydroxyalkyl or alkylphenyl group or mixtures thereof having 8 to 22 carbon atoms.

R ^{4 is an} alkylene or hydroxyalkylene group having 2 to 3 carbon atoms or mixtures thereof, x 0 to 3 and

R ^{5 is in} each case an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms or a polyethylene oxide group having about 1 to 3 ethylene oxide groups, wherein the R ⁵ groups can be bonded to each other by, for example, oxygen or nitrogen atoms to form a ring structure.

These amine oxide surfactants particularly include alkyl dimethylamine oxides having from 10 to 18 carbon atoms in the alkyl moiety and alkoxyethyldihydroethyl amine oxides having from 8 to 12 carbon atoms in the alkoxy moiety.

6. Alkyl polysaccharides as described in U.S. Pat. No. 4,556,547 (Llenado)

January 21, 1986) have a hydrophobic carbon atom, preferably about 10 to about 16 carbon atoms, and a polysaccharide such as a polyglycoside as a hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to especially about 1.3 up to about 2.7 carbohydrate units. Any reducing saccharide containing 5 or 6 carbon atoms may be used, for example glucose, galactose and galactosyl moieties may be replaced by glycosyl moieties. (An optional hydrophobic group is attached at the 2, 3, 4 position, etc., and also provides glucose or galactose versus a glucose for example or galactoside.) The intersaccharide linkages may be between the position of the additional carbohydrate units and the positions 2, 3, 4 and / or 6 previous carbohydrate units.

Alternatively, but less desirable, the polyalkylene oxide chain may bind a hydrophobic moiety and a polysaccharide moiety. A preferred alkylene oxide is ethylene oxide. Typical hydrophobic groups include alkyl groups either saturated or unsaturated, branched or unbranched. containing 8 to 18 carbon atoms, preferably 10 to 16 carbon atoms. Preferably, the alkyl group is a straight chain saturated alkyl group.

The alkyl group may contain up to 3 hydroxyl groups and / or the polyalkylene oxide chain may contain up to 10 alkylene oxide moieties, preferably at most 5 alkylene oxide moieties. Suitable alkyl polysaccharides include octyl, nonyldecyl, undecyldodecyl, tridecyl. tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl. di-, tri-, tetra-, penta and hexaglucosides, galactosides, lactosides, glucose, fructoside, fructose and / or galactose. Suitable mixtures include coconut alkyl, di-, tri-, tetra- and pentaglucosides and tallow alkyl tetra-, penta- and hexagucosides.

Preferred alkyl polyglicosides are of the formula R ² O (C 11 H 2 nO) t (glycosyl) wherein R ² is alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein the alkyl moiety contains 10 to 18 carbon atoms, preferably 12 to 14 carbon atoms , n 2 or 3, preferably 2, t 0 to about 10, preferably 0 and x about 1.3 to about 10, preferably about 1.3 to about 3, and especially about 1.3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, an alcohol or an alkylpolyethoxy alcohol is first prepared and then reacted with glucose or a source of glucose to form a glucoside (bound at the 1-position). The additional glucosyl units may then bind between their 1-position

and previous glycosyl units in position 2,3,4 and / or 6 , preferably predominantly in position 2. 7th Fatty acid amide as surface actively agent of of formula 0 R ⁶ - C. - N (R ⁷ ) 2 where R ⁶ means an alkyl group of 7 to 21 carbon alkyl, preferably with 9 to And R ( ⁷⁾ is hydrogen, alkyl group with 1 to 4 carbon atoms, hydroxyalkyl group s 1 to 4 atoms carbon and a group of formula - (C2H4COX H, where

x is about 1 to about 3.

Preferred amides are those having 8 to 20 carbon atoms, monoethanolamides, diethanolamides and triethanolamides.

Cationic surfactants

Cationic surfactants can also be incorporated into the cleaning compositions of the invention. Cationic surfactants include ammonium surfactants such as alkyldimethylammonium halides and surfactants of the general formula [R ² (OR ³ ) _y ] [R ⁴ (OR ³ ) yl R-'N'X where

R ² an alkyl or alkyIbenzolovú having from 8 to 18 carbon atoms in the alkyl,

R ^{3 is} each -CH 2 CH 2 -. -Cl (CH 2 Cl 2) -, CH 2 CH (CH 2 OH) -,

-OH 2 CH 2 CH 2 and mixtures thereof

R ^{4 is} each C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, benzyl, a ring structure formed by joining two R ⁴ groups, -CH 2 CHOH-CHOHCOR ⁶ CHOHCH ² OH, where R ^{6 is} any hexose or a hexose polymer having a molecular weight of less than about 1,000 and a hydrogen atom when y is not zero,

R ⁵ has the same meaning as R ⁴ or is an alkyl chain wherein the total number of carbon atoms R ² plus R ⁵ . is not greater than about 18, y 0 to about 10, and the sum of y values is 0 to about 15 a

X any compatible anion.

Other cationic surfactants suitable for the detergent compositions of the present invention are described in U.S. Pat. No. 4,222,744 (Cambre, Sep. 14, 1980).

Other surfactant auxiliaries h

Ampholytic surfactants can also be incorporated into detergent compositions. These surfactants are described as aliphatic derivatives of secondary or tertiary amines or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety may have a straight or branched chain. One of the aliphatic substituents contains at least 8 carbon atoms, typically 8 to 18 carbon atoms, and at least one contains an anionic water-solubilizing group, for example, a carboxy group, a sulfonate group, and a sulfate group. According to U.S. Pat. No. 3,929,678 to CLaughlin et al., Issued December 30, 1975) column 19, lines 18-35, ampholytic surfactants are used, for example.

Both surfactants can also be incorporated into the detergent compositions of the invention. These surfactants are described as secondary and tertiary amine derivatives, heterocyclic secondary and tertiary amine derivatives, or quaternary ammonium derivatives.

quaternary phosphonium or tertiary sulfonium compounds. Examples of useful zwitterionic surfactants are described in U.S. Pat. No. 3,929,678 to CLaughlin et al.

30 December 1975) column 19, line 38 to column 22, line 48.

Ampholytic and zwitterionic surfactants are generally used with one or more anionic and / or nonionic surfactants.

The invention also relates to a detergent composition with a critically selected ratio of alkyl sulfate to polyhydroxy fatty acid amide to achieve a greater cleaning effect. In particular, the invention relates to a cleaning composition comprising by weight

(a) at least 1% of a polyhydroxy fatty acid amide of the formula I

R ¹

^R2 - C - 'N - Z (I)

R ^{1 is} methyl,

R @ ^{2 is an} alkyl or alkenyl group having from 9 to 17 carbon atoms, preferably an alkyl or alkenyl group having from 11 to 17 carbon atoms and Z is a glycityl group derived from a reducing sugar

b) at least about 1% of an alkyl sulfate surfactant, at a weight ratio of (b) = (a) of about 1.25: 1 to about 1 - 6, preferably about 1.25: 1 to about 1-4, and especially about 1 , 25: 1 to about 11.25.

Surprisingly, a generally good cleaning effect, particularly with regard to the removal of greasy and oily soils, can achieve cleaning conditions in a wide range of cleaning conditions, in particular because of their relatively high weight ratio of fatty acid polyhydroxyamide to alkyl sulfate.

The invention also relates to liquid cleaning compositions containing by weight

(a) at least 1% of a polyhydroxy fatty acid amide of the formula I

OR ¹

^R2 - C - N - Z d) wherein

R ¹ is hydrogen, C 1 -C 4 hydrocarbon, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof

R ² hydrocarbon group of 5-31 carbon atoms, and

Z is a linear hydrocarbon chain polyhydroxy hydrocarbon group having at least three hydroxyl groups directly bonded to the chain or an alkoxylated derivative thereof; and

b) at least about 1% alkyl sulfate surfactant; and a

c) a liquid carrier.

wherein the weight ratio of the polyhydroxy fatty acid amide to the alkyl sulfate surfactant having more than one carbon atom in the alkyl moiety is about up to about 10

1, preferably about 1: 6 to about 6 ^: 1, especially about 1 to about 3, and especially about 1 to about 3

First

As a rule, it is difficult to incorporate alkyl sulfate surfactants having 14 or more carbon atoms in the alkyl moiety into liquid cleaning compositions. This is due, at least in part, to the highly crystalline nature of these surfactants. This is annoying because the alkyl sulfate surfactants of 14 or more carbon atoms are highly desirable detergent surfactants in laundry detergents, especially intended for washing in a bath at about 50 ° C, which usually also contains alkyl sulfate surfactants with 12 atoms atoms. However, the simultaneous use of polyhydroxy fatty acid amides as surfactants makes it much easier to incorporate alkyl sulfates having 14 or more carbon atoms in the alkyl moiety into liquid cleaning compositions.

Preferably, such cleaning compositions comprise from about 3 to about 30% by weight of polyhydroxy fatty acid amides and from about 3 to about 30% by weight of said alkyl sulfate. Liquid cleaning agents may optionally contain alkyl sulfate surfactants having an alkyl chain of less than 14 carbon atoms.

The invention also relates to detergent particles suitable for granular detergent compositions, wherein the detergent particles comprise in the form of a tight composition by weight

a) about 5 to about 50% of a fatty acid polyhydroxymide of formula I

R ¹

Where R ² is

R ^{@ 1} is hydrogen, hydrocarbon, C1 -C4, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof

R ² hydrocarbon group of 5-31 carbon atoms, and

Z is a linear hydrocarbon chain polyhydroxy hydrocarbon group having at least three hydroxyl groups directly bonded to the chain or an alkoxylated derivative thereof; and

b) about 50 to about 95 alkyl sulfate surfactant at a weight ratio of (a) = (b) of about 20 ^: 1 to about 11 L. For mixtures of C 12 -C 14 alkylsulfate to polyhydroxy fatty acid amide, a weight gain is preferred. a ratio of about 20: 1 to about 4 - 1, for a mixture of alkyl sulfate of 14 to 16 carbon atoms in the alkyl moiety to the polyhydroxy fatty acid amide, a weight ratio of about 20 1 to about 3-l is preferred for alkyl sulfate mixtures of up to 18 carbon atoms in the alkyl % to polyhydroxy fatty acid amide, a weight ratio of about 20 to about 1 is preferred.

The detergent particles may contain a solubilizing aid to further promote dissolution of the particles in aqueous solution. Suitable solubilizing particles may be selected from the group consisting of anionic sulfonate surfactants, ethoxylated surfactants having a degree of ethoxylation of at least about 0.5, cyclic fatty acid polyhydroxyamides, alkylpolyglicosides, polyethylene glycol polymers, polyacrylic acid polymers and mixtures thereof. Preferred solubilizing agents include alkyl ethoxylates, alkyl ethoxylated sulfates, alkyl ester sulfonates. cyclic polyhydroxy fatty acid amides, alkyl polyglycosides, polymers of polyethylene glycols or polyacrylic acids and mixtures thereof. Also, other materials may increase the solubility or dissolution of alkyl sulfates and polyhydroxy fatty acid amides.

The amount of solubilizing aids may be from about 0 to preferably not more than 30% by weight of the detergent particles.

By the intimate mixture of alkyl sulfate and polyhydroxy fatty acid amide and optional solubilizing agent it is meant that these ingredients are well mixed before or at the same time as the detergent particles are formed, although the particles may not be perfectly homogeneous. The technique of forming particles from such a tight mixture is known in the art and, for example, a high energy mixer or a high shear mixer may be used.

The method of forming these detergent particles is illustrated in the Examples section. The particle size may vary according to the needs of those skilled in the art.

Generally, for granular detergent compositions, these detergent particles are of a similar size to the other detergent particles. As a rule, the diameter of the detergent particles is about 100 to 1000 microns.

The detergent particles may also contain other detergent builders. processing, aesthetic and other purposes.

The detergent particles may be used alone or may be incorporated into granular detergent compositions containing additional detergent ingredients. Typically, the cleaning composition comprises at least 5% by weight of the detergent particles.

builders

The detergent composition of the invention may also contain detergency builders to control mineral hardness. Both inorganic and organic builders are used. The builder concentration varies widely depending on the end use of the detergent composition of the invention and its physical form.

Liquid detergents generally contain at least about 1% by weight, preferably about 5 to about%, and more preferably about 5 to about 50% by weight of detergency builders. Granular detergent compositions comprise at least about 1% by weight, typically about 10 to about 80% by weight, especially about 15 to about 50% by weight detergent builders. However, greater or lesser amounts of such builders are not excluded.

Inorganic detergency builders include, but are not limited to, alkali metal salts, ammonium and alkanolammonium salts of polyphosphates (e.g., tripolyphosphates, pyrophosphates, and glassy polymeric metaphosphates), -phosphonates, phytic acid silicates, carbonate silicates, carbonate silicates, carbonate silicates ), sulphates and 1umosilicates. Borate builders, as well as borate-containing builders, create materials that can form borates under detergent storage or wash conditions (collectively referred to herein as borate builders) can also be used. Preferably, non-borate builders are used in the compositions of the invention intended for washing at a temperature of less than about 50 ° C, particularly less than 40 ° C.

Examples of silicate builders include alkali metal silicates, in particular silicas having a silica = sodium oxide ratio of 1.6 ^: 1 to 3.2-1 and layered silicates described in U.S. Pat. No. 4,648,339 to HP Rieck, U.S. Pat. May 12, 1987). However, other silicates may also be used, such as magnesium silicate, which serves as a scattering agent in granular compositions, as an oxygen bleach stabilizing agent, and as a suds suppressor component.

Examples of carbonate builders include alkali earth and alkali metal carbonates, including sodium carbonate and sesquicarbonate, and mixtures thereof with ultrafine calcium carbonate, as described in German Patent Application No. 2 321001, published November 5, 1973.

Aluminosilicate builders are particularly preferred according to the invention. Alminosilicate builders are very important in the commercially most common granular cleaning compositions which are subject to high demands (heavy hollow and can also be an important component in liquid cleaning compositions). include compounds of formula

M 2 (zA 102-y S ₁₀ ) wherein M represents sodium, potassium, ammonium and substituted ammonium, from about 0.5 to 2, 1; this material contains magnesium in an ionic capacity of at least about 50 milligrams of calcium carbonate hardness per gram of anhydrous aluminosilicate. Preferred aluminosilicates are zeolite builders having the general formula

= In [(A10 _{2) z} SiO ₂₎ yl. xH ₂ O where y is an integer of at least 6, a polar ratio of z; y is 1.0 to about 0.5 and x is an integer of about 15 to about 264.

Useful aluminum nitric connex materials are commercially available. These aluminosilicates may be crystalline or amorphous and may be naturally occurring aluminosilicates or aluminosilicates synthetically derived. A process for preparing aluminosilicate ion exchange materials is described in U.S. Patent No. 3,985,669 (Krummel et al., Oct. 12, 1976). Preferably, synthetic, crystalline aluminosilicate ion exchange materials suitable in accordance with the invention are commercially available under the designation Zeolite A. Zeolite P (B) and Zeolite X. According to a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has the general formula:

Na 1 E (Al ₂ O ₂ ) ₂ SiO ₂ ) 12 1 - XH ₂ O wherein x is about 20 to about 30 and especially about 27. This material is known as Zeolite A. Preferably, the particle has a particle diameter of about 1 µm. 0.1 to 10 microns.

Specific examples of polyphosphates are alkali metal tripolyphosphates, sodium pyrophosphate, potassium or ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymetaphosphate, the degree of polymerization being about 6 to about 21, and phytic acid salts.

Examples of phosphonate builder salts include the water-soluble salts of ethane-1-hydroxy-1,1-diphosphonate, in particular the sodium and potassium salts, the water-soluble salts of methylenediphosphonic acid, for example trisodium and trisodium salts, and the water-soluble salts of substituted methylenediphosphonic acids. for example, trisodium and tripotassium ethylidene phosphonate, isopropylidene phosphonate.

benzylImethylidene phosphonate and halomethylidene phosphonate.

Phosphonate builder salts of the above type are described, for example, in U.S. Pat.

213030 (Diehl. 1 December 1964 and

Diehl, 19.

October 1965), U.S. Pat

422021 (Roy. 14.

January 1969) and U.S. Pat

400148 and 3,422A37 (Quimby, Sept. 3, 1968, and U.S. Pat

14- January .1969).

Organic detergent builders suitable for the purposes of the invention include, but are not limited to, a variety of polycarboxylate compounds.

The term polycarboxylate refers to compounds having numerous carboxylate groups, preferably at least three carboxylate groups.

Polycarboxylate builders are generally added to the detergent compositions of the invention in acid form, but may also be added in the form of a neutralized salt. When used in salt form, alkali metal salts such as sodium, potassium and lithium are preferred, especially sodium or ammonium salts and substituted ammonium salts such as alkanolammonium.

Polycarboxylate builders include a variety of categories of useful materials. An important category of polycarboxylate builders are ether polycarboxylates. ether polycarboxylates as detergent useful ether polycarboxylates are

Numerous builders have been described. By way of example, oxydisuccinates are described, for example, in U.S. Patent 3,128,287 (Berg, Apr. 7, 1964), and in U.S. Patent 3,635,830 (Lamberti et al., January 18, 1972).

A specific type of ether polycarboxylates useful as builders of the invention also include compounds of formula

CH (A) (COOX) -CH (COOX) -O-CH (COOX) - OH (COOX) (B) wherein A is hydrogen or hydroxyl, B is hydrogen or -O-CH (C00XC) -CH 2 (COOX) and X is a hydrogen atom or a salt-forming cation. For example, if in the above general formula A and B are both hydrogen, then the compound is oxydisuccinic acid and its water-soluble salts. When A is a hydroxyl group and B is a hydrogen atom, then the compound is tetrazmonium monocarboxylic acid (TMS) and its water-soluble salts. If it means A

O-CH (COOX) -CH 2 (CO'OX), a hydrogen atom and

The B group of the formula is a compound of tartrate disuccinic acid (TDX) and its water-soluble salts.

Mixtures of such salts are particularly preferred according to the invention. Particularly preferred are mixtures of TMS and TDS in a weight ratio of TMS

TDS approximately 97 to

80th

These builders are described in U.S. Pat

663071 (Bush et al.,

May 5, 1987).

Preferred ether polycarboxylates also include cyclic compounds, especially alicyclic compounds, as described, for example, in U.S. Pat.

923679.

835263.

158635, 4 120874 and 4 102903.

Detergency builders include ether hydroxy polycarboxylates of the formula

HOIC (R) (COOM) -C (R) (COOM) -OlnH wherein M represents a hydrogen atom or a cation, the resulting salt being water soluble, preferably an alkali metal.

ammonium or a substituted ammonium cation, n about to about 15 (preferably n is about 2 to about and especially n is about 2 to about 4) and each

R has the same or different meanings and represents a hydrogen atom, an alkyl group having a carbon atom or a substituted alkyl group having a carbon atom (preferably R is a hydrogen atom).

represents a hydroxyl group substituted with a sulfo group, a sulfoxy group, or a sulfone group, all of which are described in the aforementioned patents.

Succinate buffers are preferably used in the form of their water-soluble salts, including sodium potassium, ammonium and alkanolammonium salts.

Specific examples of succinate builders include ureasuccinate, myristoyl pentadecenylsuccinate.

Lauryl succinates are preferred builders of this group and are described in European Patent Application Number

86200690.5 / 0,200,263, published

November 5th

1986th

Examples of buffers also include carboxymethyl ethoxylate, carboxymethyl succinate, cis-cyclohexanehexacarboxylate, sodium and potassium cis-cyclopentatetracarboxylates, and water-soluble polycarboxylates (these polycarboylates have a molecular weight of more than about 2000 and are preferably used) also as dispersants) and copolymers of maleic anhydride and vinyl methyl ether or ethylene.

Other suitable polycarboxylates are the polyacetal carboxylates described in U.S. Pat. No. 4,144,226 (Crutchfield et al., Mar. 13, 1979). These polyacetal carboxylates can be prepared by contacting one another under the polymerization conditions of a glyoxylic acid ester and a polymerization initiator. The resulting polyacetyl carboxy ester is then bound to chemically stable end groups to stabilize the polyacetal carboxylates against rapid depolymerization even in an alkaline solution by carrying out the corresponding salt and adding it to the surfactant.

F'olycarbonate bui Idery are also described in U.S. Patent 3,308067 (Diehl, March 7, 1967). Such materials include the water-soluble salts of homopolymers and copolymers of aliphatic carboxylic acids, for example maleic, itaconic, mesaconic, fumaric, aconitic, citraconic and methylenemalonic acids.

Other organic buffers may also be used. Examples are monocarboxylic acids and soluble salts thereof having a long hydrocarbon chain. These materials are generally referred to as soaps. As a rule, a chain length of 10 to 20 carbon atoms is used. The hydrocarbon groups may be saturated or unsaturated.

enzymes

Detergent enzymes can be incorporated into a wide variety of detergents for purposes such as removing protein, carbohydrate or triglyceride stains and, for example, to prevent dye transfer. Included enzymes include proteases, amylases, lipases, cellulases and peroxidases, and mixtures thereof. However, other types of enzymes may also be incorporated. These enzymes may be of any suitable origin, for example vegetable, animal, bacterial, fungal and yeast. However, the choice of enzyme is governed by certain factors such as the pH range of efficacy and / or optimum stability, thermal stability, resistance to the action of active cleaners and builders. In this regard, bacterial and fungal enzymes are preferred, for example bacterial amylase and protease, and fungal cellulase.

Suitable examples of proteases include proteases obtained from separate strains of B. subtills and B.

1icheniforms.

Other suitable proteases are obtained from the strain

Bacillus and have maximum efficacy in the art of pH values of 8 to 8

12> have been developed and are the product of Novo Industries

A / S under the trade name

ESPERASE.

A process for the preparation of these enzymes and similar enzymes is described in British Patent Specification No. 1 243784 (Novo). Proteolytic enzymes suitable for protein-based stain removal are commercially available under the trade names ALCALASE and SAVINASE of Novo Industries A / S (Denmark) and MAXATASE of the company

Dorms She 1 Bio-Synthetics, Inc. (Netherlands).

From the category of proteolytic enzymes, the enzymes referred to herein as Protease A and Protease B are of particular interest for liquid detergent compositions. Proteases A by having the leucine replaced by tyrosine at position 217 in its amino acid new sequence. Protease B is described in the European application of April 1987.

The methods disclosed in European Patent Application No. 87303761.8, filed 28. Proteases B are also described in No. 1130750, published 9.

January 1985 (Bott et al.).

Amylases include, for example, h-amylases obtained from a special strain of B.

licheniforms as described in detail in the aforementioned British Patent Specification No. 1 296839 (Novo).

Amylolytic enzymes include, for example, RAPIDASE enzymes from International Bio-Synthetics Inc.

and TERMANYL of Novo Industries.

Cellulases useful in the present invention include both bacterial and fungal cellulases. They should preferably have an optimum efficiency in the field of pH values of 5 to 9.5. Suitable cellulases are disclosed in Barbesgoard et al., U.S. Patent 4,435,307.

March 6, 1984), which are fungal cellulases produced by Hub

Humicola insolens. Suitable cellulases are also disclosed in British Patent Specifications A-2 075028 and A-2 095275 and in German Published Application

DE-OS-2 247832.

Examples of such cellulases are cellulases produced by Humicola insolens (Humicola grisea var.

thermoidea), especially Humicola strain

DSM 1800 and cellulases produced by Baccilus N or cellulases 212 produced by fungi belonging to the genus Aeromonas and cellulases extracted from hepatopancreas

As suitable marine shellfish (Dolabella Auricula Sonader).

lipase enzymes for detergents are mentioned lipases produced by a microorganism of the Pseudomonas family, for example Pseudomonas stutzeri ATCC 19.154, described in British Patent Specification No. 1 372034. and its purification method is described in Japanese Patent Application Publication No. 53-20487, published February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P 'Amano, referred to herein as Amano-P. Such lipases of the invention should exhibit an immunological cross-linking reaction with the Amano-P antibody, using the known standard immunodiffusion method of Couchterlon (Acta Med. Scan., 133, 76-79, 1950). These lipases and the method of their immunologically cross-linking reaction with Amano-P are also described in U.S. Pat. No. 4,707291 (Thom et al., November 17, 1987). Typical examples of these lipases are Amano-P lipases, lipase produced by Pseudomonas fragi FERM P 1339 (commercially available under the trade name Amano-B), lipase produced by Pseudomonas nitroreducens var. lipolyticum FERM P 1338 (commercially available under the trade name Amano-CES), lipases produced by Chromabacter viscosum, for example Chromabacter viscosum var. lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and Chronatobacter viscosum lipase from U.S. Pat. Biochem. Corp., U. S.A. and Disyonth Co., The Netherlands, and lipases produced by Pseudomonas gladiol i.

Peroxidase enzymes are used in conjunction with an oxygen source such as a peroxide and hydrogen peroxide carbonate, perborate, peroxysulfate

They are used in solution bieaching, i.e. to prevent the transfer of dyes and pigments removed from the substrates during the wash to other substrates in the wash solution.

Peroxidase enzymes are known in the art and include, for example, horseradish Kfen peroxidase, ligninase and haloperoxidase such as chloroperoxidase and bromoperoxidase.

Peroxidase-containing detergent compositions are described, for example, in PCT VO International Application

89099813.

published

Six years old

October 19, 1989 (O. Kirk, Novo Industries Enzyme Materials Department a

A / S).

methods of incorporating them into granules of synthetic detergent compositions are also described in U.S. Patent 3,551,339 to McCarty et al.

January 1971). The enzymes are further described in U.S. Pat. No. 4,101,457 (Plače et al.

July 1978) and U.S. Pat. No. 4,507,219 (Hughes,

March 26, 1985). Enzyme materials suitable for liquid cleaning compositions are a method of incorporating them into such cleaning compositions

I

No. 261868 (above and described in U.S. Pat

Enzymes et al., 14 April 1981).

generally incorporate a sufficient amount of mg. preferably about 0.05 to about 3 mg of active enzyme

For granular detergents per gram of detergent composition, the compositions are preferably treated or processed into beads with enzymes additives that are non-limiting to minimize dust formation and improve shelf life. Techniques for such treatment are known.

In the case of liquid compositions, an enzyme stabilizing system is preferably used. Methods for stabilizing enzymes in liquid cleaning compositions are known. For example, one method of stabilizing enzymes in liquid solutions involves the use of free calcium ions from sources such as calcium acetate.

calcium formate and calcium propionate.

Calcium ions can be used in conjunction with short chain carboxylic acid salts, preferably formates, see, for example, U.S. Pat.

318818 (Lettonn et al., 9.

March 1982!). It is also proposed to use polyols such as glycerol or sorbitol.

Alkoxy alcohols, dialkyl glycol ethers, mixtures of polyhydric alcohols with polyfunctional aliphatic amines (such as diethanolamine, triethanolamine, diisopropylamine) and boric acid or alkali metal borates may also be used for this purpose. Methods for stabilizing enzymes are additionally described and exemplified in U.S. Patent 4,226,868 (Horn et al., April 14, 1981) and U.S. Patent 3,600-19 (Gedge et al., Aug. 17, 1971) and in European Patent Publication No. No. 0 199405, Application No. 86200586.5, published Oct. 29, 1986 (Venegas).

Preferred are boronic acid and borate stabilizers.

Enzyme stabilization systems are also described, for example, in U.S. Patent Nos. 4,226,868, 3,600,319 and 3,519,970.

Bleaching compounds - bleaching active substances and bleach activators

The detergent compositions of the invention may also contain bleaching agents or bleaching compositions containing a bleaching active ingredient and at least one bleach activator.

In the case of a bleaching agent content, the bleaching agent is present in an amount of about 1 to about 20% by weight, and in particular about 1 to about 10% by weight of the detergent composition. Generally, the bleaching ingredients are optional ingredients in non-liquid compositions, for example, granular detergents. When included, the activators are generally present in an amount by weight of about 0.1% to about 60%, and in particular about 0.5 to about 40% by weight of the bleaching additive.

Can any bleach be used? conventional cleaning agents for cleaning textiles, hard surfaces or for other cleaning purposes which are known or become known. Such bleaching agents include oxygen bleaching agents and other agents. For washing conditions below about 50 ° C, and especially below about 40 ° C, it is preferred that the compositions do not contain borate or a material that can form borate in situ (i.e., borate forming material) upon storage of the detergent or under wash conditions. . Under these conditions, it is preferred to use non-borate and borate-free bleaching agents. Preferably, cleaning agents which are substantially free of borate and borate-forming materials at these temperatures should be used. As used herein, the term substantially free of borate and borate-forming material is intended to mean cleaning compositions containing up to about 2% by weight of borate-containing or borate-forming material of any type, preferably at most 1%, and in particular free of such bleaching ingredients.

One category of bleaching agents that can be used includes peroxycarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate oxyhydrate, the magnesium salt of meta-chloroperoxybenzoic acid,

4-nonylamino-4-oxoperoxybutyric acid and di. peroxydodecanedioic acid. Such bleaching agents are described in U.S. Patent 4,483,781 (Hartman, Nov. 20, 1984), U.S. Patent Number (Patent Application No. 740446, Burns et al., Filed June 3, 1985), European Patent Application No. No. 133354 (Banks et al., Issued Feb. 20, 1985) and U.S. Pat. No. 4,412,934 (Chung et al., Nov. 1, 1983). Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,663,551 (Burns et al., Jan. 6, 1987).

Another category of bleaching agents that can be used in the detergent compositions of the invention includes halogen bleaching agents. Examples are hypohalogenic bleaching agents, for example trichloroisocyanuric acid and sodium and potassium dichloroisocyanurates and N-chloroalkanesulfoamides and N-bromoalkalsulfonamides. Such agents are generally added in an amount of 0.5 to 10% by weight based on the weight of the finished product, preferably in an amount of 1 to 5% by weight.

Peroxide bleaching agents are also used. Suitable peroxide bleaching agents include sodium, pyrophosphate peroxyhydrate and sodium peroxide.

Peroxygen bleaching agents with bleach activators that guide the solution (i.e. during the wash) of the bleach activator.

Preferred bleach activators include carbonate peroxyhydrate, urea peroxyhydrate is preferably used in conjunction with in situ production of the aqueous peroxyacid corresponding to the detergent compositions of the present invention wherein R is an alkyl group of about 1 to about 18 carbon atoms, the longest alkyl chain of the carbonyl a carbon atom and comprising a carbonyl carbon atom containing from about 6 to about 10 carbon atoms, L. is a liberated acid conjugate having a pKa of about 4 to about 13. These bleach activators are described in U.S. Patent No. 4,915,854 to Mao et al. et al., April 10, 1990) and U.S. Pat. No. 4,412,934 (supra).

Bleaching agents other than oxygen are also known in the art and are useful in the detergent compositions of the invention. One type of non-oxygen oxygen bleaching agents of particular interest are photoactivated bleaching agents such as sulfonated zinc and / or aluminum phthalocyanines. These materials can be deposited on the substrate during the wash. After irradiation with light in the presence of oxygen, such as when suspended for daylight drying, the sulphonated zinc phthalocianin is activated, and the substrate is then discharged. Preferred zinc phthalocyanines and light-activated bleaching are described in U.S. Patent 4,037,118 (Holcombe et al., Jul. 5, 1977). Generally, the cleaning composition comprises 0.025 to 1.25% by weight of sulfonated zinc phthalocyanine.

Polymeric soil release agents

In addition, any polymeric soil release agent can be used for the detergent compositions of the present invention.

Polymeric hydrophilic soil release agents have both segments that hydrophilize the surface of hydrophobic fibers, such as polyester and nylon fibers, and hydrophobic segments to deposit on hydrophobic fibers.

while remaining clogged even after washing and rinsing are completed, thereby serving to anchor hydrophilic segments. This allows subsequent stains to be cleaned more readily in the presence of a soil release agent.

While it may be beneficial to use soil release agents in each of the detergent compositions of the present invention, these additives are mainly used for laundry detergents or for other uses where it is necessary to release fats and oils from hydrophobic surfaces, the presence of polyhydroxy fatty acid amides in Detergent compositions containing equally anionic surfactants can promote the performance properties of a number of commonly used soil release polymeric types. Anionic surfactants impair the ability of certain soil release agents to deposit and adhere to hydrophobic surfaces. These soil release agents have non-ionic hydrophobic Other segments or hydrophobic segments that interact with arionic surfaces.

The detergent compositions of the present invention which can be improved in soil release efficiency using polyhydroxy fatty acid amides include an anionic surfactant system, an anionic surfactant soil release agent, and a movable hydroxyl amide fatty acid (PFA) in an amount supporting the soil release agent,

I. the anionic surface interaction between the soil release agent and the anionic surfactant cleaning system can be shown by comparing the deposition rate of the soil release agent (SRA) on hydrophobic fibers (e.g., polyester fibers) in aqueous solution between (A) control wash, which measures the deposition of the SRA detergent in an aqueous solution in the absence of other detergents and (B) washing with the system

SRA / anionic surfactant ”, in which the anionic surfactant system is used in the cleaning agent together with

SPA in aqueous solution at the same weight ratio

SRA to the anionic surfactant system in the detergent, while reducing deposition and

II.

at wash (B) as compared to wash (A), indicates an anionic surfactant; and whether the detergent composition contains polyhydroxy fatty acid amide in an amount of soil release promoting agent, can be determined by comparing the SRA deposition in the wash test (B) using the SRA / anionic soil release surfactant with the wash test (C) using of the SRA / anionic surfactant / PFA scrubbing test using the same type and amount of polyhydroxy fatty acid amides in the detergent composition together with the soil release aid and anionic surfactant system corresponding to the SRA scrubbing test / anionic surfactant, with improved deposition of a release promoting agent · dirt in the wash test (C) with respect to the wash test (B) indicates that the amount of polyhydroxy fatty acid support is present ce the effectiveness of soil release agent.

For the purposes of the invention, the tests are to be conducted at concentrations of the surfactant in aqueous solution that are above the critical gel concentration (CMC) of the anionic surfactant and preferably above about 100 ppm. The concentration of the soil release polymeric agent should be at least ppm. A sample of polyester fabric is to be used as the hydrophobic fiber. The same sample is immersed and mixed in a 35 ° C water bath at the appropriate test wash for 12 minutes. it is removed and analyzed. The concentration of the polymeric soil release agent can be determined by radioactivating the soil release agent prior to the assay followed by radiochemical analysis in a known manner.

As an alternative to the aforementioned radiochemical assay, a soil release agent can be determined in the above wash tests (A, B, C) by determining the absorbance of the ultraviolet light (UV) of the test solutions in a known manner.

The decrease in UV absorbance of the test solution after removal of the hydrophobic fiber material corresponds to the increase in the SRA deposition. It is clear to those skilled in the art that UV analysis cannot be used for test solutions containing types and concentrations of materials that cause excessive UV absorbance, such as aromatic surfactants (e.g., alkylbenzenesulfonates).

By the amount of a polyhydroxy fatty acid amide soil release agent is meant a quantity of a surfactant that promotes the deposition of a soil release agent on the hydrophobic fibers as described above, or an amount that promotes the release of fats and oils from fabrics washed by such a detergent in the following washing or cleaning.

The amount of polyhydroxy fatty acid amide required to promote deposition varies according to the surfactant chosen, the amount of anionic surfactant, the type of soil release promoting agent, and the polyhydroxy fatty acid amide chosen. Generally, the cleaning composition should contain from about 0.01% to about 10% by weight of the soil release polymeric agent.

as a rule about 0.1 to about 5% by weight and about 50% to about 50% by weight and especially about 5 to 30% by weight of anionic surfactant.

the compositions should generally contain at least 1% by weight, preferably at least 3%, of polyhydroxyamides, although it is not intended to limit the amounts to these values.

Polymeric soil release agents whose activity is supported by polyhydroxy fatty acid polymers in the presence of anionic surfactants also include one or more hydrophilic components, consisting of

4.6 essentially consisting of (i) polyoxyethylene segments having a degree of polymerization of at least 2, or (ii) oxypropionic or polyoxypropylene segments having a degree of polymerization of 2 to 10, wherein the hydrophilic segment does not include any oxypropylene unit when bound to adjacent portions at each end with ether or (iji) a mixture of oxyalkyl units comprising oxyethyl units and 1 to about 30 oxypropylene units, the mixture containing sufficient oxyethylene units to provide hydrophilicity Another component has a hydrophilicity sufficiently large to increase the hydrophilicity of the surfaces of conventional polyester synthetic fibers after storage. dirt release agents on such a surface and said hydrophilic Other segments preferably contain at least about 25% oxyethylene units, and especially especially those components having about 20 to 30 oxypro at least about 50% of the oxyethyl units, or

(b) one or more hydrophobic components containing (i) 3-carbon oxyalkylene terephthalate segments having an alkyl moiety wherein, when such hydrophobic ingredients also contain exyethylene terephthalate, the ratio of oxyethylene terephthalate unit - oxyalkylene terephthalate unit is less than about 2 atomic alkylene terephthalate units: (ii) alkylene or oxyalkylene segments having from 4 to 6 carbon atoms in the alkylene moiety or mixtures thereof; (iii) poly (vinyl ester) segments, preferably poly (vinyl acetate) segments having a degree of polymerization of at least 2; or Civ) (C1 -C4) alkyl ether substituents. C 4 alkyl atoms or 4-C hydroxyl alkyl ether substituents or mixtures thereof, these substituents being in the form of C 1-4 alkyl ether cellulose derivatives or hydroxyalkyl ether celluloses the C 4 alkyls of the alkyl moiety or mixtures thereof, wherein such cellulose derivatives are amphiphilic and have a sufficient content of C 1 -C 4 alkyl ether units and / or C 4 hydroxyalkyl ether units for storage on conventional polyester synthetic fibers and leave sufficient hydroxyl groups to adhere to the surface of conventional synthetic polyester fibers to increase the surface hydrophilicity of the fibers. The polymeric agents may also comprise a mixture of components (a) and (b).

Generally, the polyoxyethylene segments of (a) (i) have a polymerization degree of 2 to about 200, although the polymerization degree may preferably be 3 to about 150 and especially 6 to about 100. Suitable oxyalkylene hydrophobic segments having 4 to 6 carbon atoms in the alkyl By ion, the moieties include, but are not limited to, endings of soil release promoting polymeric agents, such as MCfCiClClInOCH 2 -, wherein M is sodium and an integer of 4 to 6 are disclosed in U.S. Pat. January 1988).

Polymeric soil release agents suitable for use in the laundry detergent compositions of the present invention include, for example, cellulose derivatives such as hydroxyether cellulose polymers, as well as block copolymers of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate.

Cellulose derivatives that function as soil release agents are commercially available and include cellulose hydroxyethers such as Methocel ^H (Dow).

The cellulosic soil release agents used for the detergent compositions of the present invention also include those selected from the group consisting of C 1-4 alkylcellulose and C 4 alkyl-alkylcellulose, such as methylcellulose.

ethylcellulose, and hydroxybutylmethylcellulose.

hydroxypropylmety1ce1u1óza

A variety of cellulose derivatives useful as soil release agents are described in U.S. Patent No. 4,000093 to Nicol et al.

December 1976).

Soil release agents characterized by poly (vinyl ester) hydrophobic poly (vinyl ester) copolymers, preferably a polyalkylene oxide backbone. Such materials are known and the segments include grafted, for example, vinyl esters of 1 to 6 poly (vinyl acetate) grafted onto a polyethylene oxide backbone.

are described in European Patent Application No. 0 219048, published April 22, 1987 (Kud et al.). Suitable soil release agents of this type are SOKALAN-type materials such as SOKALAN

HP-22, a commercial product of BASF (Germany).

One type of preferred soil release agent is a copolymer having statistical blocks of ethylene terephthalate and polyethylene oxide (PEO) teraphthalate.

In particular, these copolymers containing repeating units of ethylene terephthalate and polyethylene oxide terephthalate in a molar ratio of ethylene terephthalate units to polyethylene oxide terephthalate units of approximately

to about 35

65, wherein the polyethylene oxide terephthalate units have a molecular weight of about 300 to about 2000. The molecular weight of the soil release promoting polymer is about 25,000 to about 55,000. Such compositions are described in U.S. Patent No. 3,952,930 (Hays, May 25, 2005). 1976) and similar copolymers are described in U.S. Patent 3,839,229 (Basadur, Jul. 8, 1975).

Another preferred soil release polymer is a polyester with repeating ethylene terephthalate units containing 10-15% by weight of ethylene terephthalate units together with 90-80% by weight polyoxyethylene terephthalate units derived from a polyoxyethylene glycol having an average molecular weight of 300 to 50%.

000 and with a molar ratio of ethylene terephthalate units to polyoxyethylene terephthalate units in the polymer compound

1 to 6 ^: 1. Commercially available ZELCON 5126 (Dupont) and MILEASE are exemplified by this polymer.

T (ICI). These polymers and methods for their preparation are described in U.S. Pat. No. 4,702,857 (Gosselink, Oct. 27, 1987).

Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprising an oligomeric ester backbone of terephthaloyl and oxyacylerioxy repeating units and terminal moieties covalently bonded to the backbone, said soil release agents being derived from allyl alcohol ethoxylate, 2-propylenediol, wherein, after sulfonation, the terminal portions of each oligomer have a mean total of about 1 to about 4 sulfonate groups. These soil release agents are fully described in U.S. Patent No. 4,968,451 (JJ Scheibel) and U.S. Patent Application No. 07 / 474,709, EP Gosselink, filed January 29, 1990).

Other suitable soil release agents include ethyl or methyl. capped 1,2-propylene terephthalate-polyethylene terephthalate polyesters as disclosed in U.S. Pat. No. 4,711,730 (Gosselink et al., Dec. 8, 1987); anionic depregnated oligomeric esters as described in U.S. Pat. (Gosselink, January 26, 1988), wherein the end caps include sulfopolyethoxy groups derived from polyethylene glycol (PE'G), the block polyester oligomeric compounds described in U.S. Patent 4,708,557 (Gosselink, October 27, 1987) having a polyethoxy terminal cap of the formula X- (OCH 2 CH 2) n, wherein n is 12 to about 43 and X is C 1 -C 4 alkyl, or preferably methyl.

Additional soil release agents include soil release agents described in U.S. Patent 4,877,896 to Maldonado et al.

On Oct. 31, 1989), anionic, especially sulfonic, terephthalate esters end-capped are described. The terephthalate esters contain unsymmetrically substituted oxy-1,2-alkyleneoxy units. U.S. Pat. No. 4,877,896 discloses polyoxyethylene hydrophile materials having other repeating components or repeating 3-carbon oxyalkylene terephthalate units (with the propylene terephthalate hydrophobic units) as mentioned above. (I).

A soil release polymer characterized by one or both of these criteria, which is particularly advantageous for incorporating polyhydroxy fatty acid amides in the presence of anionic surfactants.

When used, soil release agents are generally present in an amount of from 0.01% to about 10.0% by weight, based on the weight of the detergent composition, typically 0.1 to 5% by weight, and more particularly 0.2 to 3.0% by weight. %.

Chelating agents

The detergent compositions of the invention may also optionally contain one or more iron or manganese chelating agents as builder adjuvants. Such chelating agents may be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctional substituted aromatic chelating agents, and mixtures thereof, all defined below. Without intending to be bound by theory, it is believed that the beneficial effect of these materials is due to their extraordinary ability to remove iron and manganese ions from washing solutions to form soluble chelates.

Aminocarboxylates useful as chelating agents in the detergent compositions of the invention have one or more, preferably at least two, units of the formula:

Cll ₂ - N - _{(CH2) x} - C00M wherein M is H, alkali metal, ammonium or substituted ammonium (e.g. ethanolamine) and x 1 to 3, preferably 1-Preferably, these amino phosphonates do not contain alkyl or alkenyl groups with more as 6 carbon atoms. Suitable amino carboxylates include ethylenediaminetetraacetates, N-hydroxyethylenediaminetetracetates. The tri-triacetates, ethylenediaminetetrapropionates, triethylenetetraamine hexaacetates, diethylenetriario pentaacetates and ethanediglycines, their alkali salts, ammonium salts, substituted aroonium salts and mixtures thereof.

Amino phosphonates are also suitable for use as chelating agents in detergent compositions as long as at least a low phosphorus concentration is permitted in the detergent compositions. Compounds with one or more preferably at least two units of the formula

Cll ₂ - N (CH ₂₎ xP0 ₃ M wherein M = H, alkali metal, ammonium or substituted ammonium and x 1 · to 3, preferably 1, are useful and include ethylenediaminetetrakis (methylenephosphonates), add tri 1o-tris (methylphosphonates). adiethylenetriaminepentacis (methylene phosphonates). Preferably, these amino carboxylates do not contain alkyl or alkenyl groups having more than 6 carbon atoms.

Polyfunctional substituted aromatic chelating agents are also useful in the detergent compositions of the invention. These agents may contain compounds of the general formula

OH

wherein at least one R group is -SO ₃ H or -COOH or a salt thereof, and mixtures thereof. Such polyfunctional substituted aromatic chelating and sequestering agents are described in U.S. Pat. No. 3,881,444 (Connor et al., May 21, 1974). Preferred compounds of this type in acid form include dihydroxydisulfobenzenes, for example 1,2-dihydroxy-3,5-disulfobenzene. The alkaline cleaning compositions of the invention may contain these agents in the form of an alkali metal, ammonium or substituted ammonium salt (e.g., in the form of a monoethanolamine, diethanolamine and triethanolamine salt).

When used, the chelating agents are generally present in an amount of from 0.1% to about 10.0% by weight of the detergent composition, preferably from 0.1 to 3.0% by weight of the detergent composition as a whole.

Agents supporting the removal of clay soil and preventing its redeposition

The detergent compositions of the invention may also optionally contain polyethylene glycols in water ethoxylated amines having the ability to remove clay and prevent redeposition.

Polyethylene glycol compounds suitable for; The detergent compositions of the invention generally have a molecular weight of about 400 to 100,000, preferably about 1,000 to about 20,000, especially about 2,000 to about 12,000, and most preferably about 4,000 to about 8,000. Such compounds are commercially available under the designation Carbowax ^1. Carbide, Danbury, Conn.

The water-soluble ethoxylated amines are preferably selected from the following groups:

1. ethoxylated monoamines of the formula (XL -) - N-CR ²⁾ ₂

2. ethoxylated diamines of the general formula

R 2 -N-R 1 -n R ² (R ² ) 2 -NR ¹ -N-CR ² ) 2

l 1 L C> C X or

CX-L- 2 -NR ¹ -N- (R ² ) ₂

Third

4th

ethoxylated polyamines of formula

R ²

R ³ - [(A ¹⁾ q CR ^) tNLX] _L ethoxylated amine polymers of the formula

R2 [(R ² > 2-Ν1 wE R ¹ -N 1 x [R ¹ -N] y [R ¹ -N-LK-X] _Z L

X

5. mixtures thereof.

while meaning

A ^{1 is a} group of the general formula

-NC-NCO,

-NCN-CN0 O

-OCN-, -CO-,

-WHAT- ,

-OCO-,

-0C-,

-CNC54 or an oxygen atom,

R is a hydrogen atom or an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and in the alkyl moiety,

R ^{@ 1 is} alkylene, hydroxyalkyl, C2 -C12 alkenylene, arylene or C1 -C5 arylene or C2 -C3 oxyalkylene having from 2 to 20 oxyalkylene units, provided that no bonds are formed between the nitrogen atom and an oxygen atom,

R ² each hydroxyalkyl group having 1 to 4 carbon atoms, the proportion -LX or two R groups together share ² (CH 2) r A ² - (CH 2) _s, wherein A ² is an oxygen atom or a methylene group, R 1 or 2, 1 or 2, with 1 or 2, and with 3 or 4,

X is a nonionic group, anionic group, or a mixture thereof

R ^{3 is a} substituted alkyl, hydroxyalkyl or C 3 -C 12 alkenyl, aryl or alkaryl group having substitution positions,

R ^{4 is} alkylene, hydroxyalkylene, C 1 -C 12 alkenylene, C 2 -C 3 arylene or alkarylene or C 2 -C 3 oxyalkylene with 2 to 20 oxyalkylene units, provided no bonds are formed between the oxygen atom and the atom an oxygen or nitrogen atom and an oxygen atom,

A hydrophilic chain containing a polyoxyalkylene moiety of the formula

- ^[(R5 0) m (CH ₂ CH ₂ 0) _n] wherein R ⁵ is an alkylene or hydroxyalkyIónovú having 3 to 4 carbon atoms Aaman the number of the units of formula - <CH ₂ CH ₂ 0) n mean weight of at least about 50% of these polyoxyalkylene Smartphones Ionic units, said monoamines, m is from 0 to about 4 an at least about 12, and said diamines, m is from 0 to about 3 n, at least about 6 when R ¹ is alkylene, hydroxyalkyl, or alkenylene kyIónovú a group having 2 to 3 atoms

carbon and at least

3, where R ¹ is not an alkylene group.

a (C 2 -C 3) hydroxyalkylene or alkenylene group; in the case of polyamines and amine polymers, m is 0 to at least about 3; p 3 to 8, q 1 or 0, t 1 or 0 with the proviso that t is 1 when q is 1; v 1 or

0; x + y + z at least 2.

The most preferred soil release agent and anti-soil redeposition agent is ethoxylated tetraethylenepentamine.

Examples of ethoxylated amines are further described in U.S. Pat. No. 4,597,898 (VanderMerr

June 1, 1986). Another group preferred with respect to soil removal and redeposition are the cationic compounds disclosed in European Patent Application, published June 27, 1984 (Oh and Gosselink). Other soil release and anti-redeposition agents are ethoxylated aminated polymers, disclosed in European Patent Application No. 111 984, published June 27, 1984 (Gosselink), and both, polymers, described in European Patent Application No. 1.12,592, published June 4, 1984. 1984 (Gosselink) and the amine oxides described in U.S. Pat. No. 4,548,444 (Connor, Oct. 22, 1985).

Other particulate soil removal and / or anti-redeposition agents may also be used in the detergent compositions of the present invention. Such other preferred agents are, for example, carboxymethyl cellulose materials. Such agents are well known in the art.

Polymeric dispersing agents

Polymeric polycarboxylate dispersing agents may advantageously be used in the detergent compositions of the invention. These agents can assist in the removal of calcium and magnesium hardness of water. They may support the action of builders similarly to polycarboxylates. While not intending to be limited by theory, it is believed that polymeric dispersants promote the utility characteristics of detergency builders when used with other builders (including low molecular weight polycarboxylates) by inhibiting crystal growth, peptizing particulate loosening and antiredeposition.

The polycarboxylate materials used as polymeric dispersing agents in the detergent compositions of the present invention are polymers or copolymers containing at least about 60% by weight of the segments of the general formula

Y COOM n

wherein X, Y and Z are each selected from the group consisting of atom, methyl, carboxy, carboxymethyl, hydroxy and hydroxymethyl;

a salt-forming cation and n is about up to about 400.

Preferably

X is hydrogen or hydroxy, Y is hydrogen or carboxy,

Z is hydrogen and M is hydrogen, alkali metal, ammonium or substituted ammonium.

Polymeric carboxylate materials of this type can be prepared by polymerizing and / or copolymerizing suitable unsaturated monomers, preferably in the form of their acid.

Unsaturated monomeric acids that can be polymerized to form a suitable polymeric polycarboxylate include acrylic acid, maleate (or maleic anhydride), fumaric itaconic acid, acetic mesaconic, citraconic and methylenemalonic acid.

The presence in the polymeric carboxylates of monomeric segments devoid of carboxylate substrates such as vinylmethyl ether, styrene, ethylene and the like is suitable, provided that such segments do not constitute more than 40% by weight.

Particularly suitable polymeric carboxylates may be derived from acrylic acid. Also polymers based on acrylic acid.

which are useful according to the invention are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in acid form is preferably about 2,000 to about 10,000, especially about 4,000 to about 7,000, and especially about 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers include alkali metal salts, ammonium salts and substituted ammonium salts. Soluble polymers of this type are known materials. Useful polyacrylates of this type for use in the detergent compositions of the present invention are described in U.S. Patent No. 3,308,067 (Diehl, March 3, 1967).

Acrylic / melamine-based copolymers can also be used as preferred components of dispersing / anti-redeposition agents. Such include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in acid form is preferably about

000 to

100 000, in particular approximately 6 000 to 60 000 and in particular approximately

The ratio of acrylate to maleate segments in such copolymers is generally about 30: 1 to soluble.

1, particularly about 10 salts of such maleic acid copolymers may include, for example, ammonium and substituted ammonium salts.

1. In water of acrylic and alkali metals:

Soluble copolymers of acrylates and maleates of this type are known and described in the European patent application. 669154 published

December 15th

1,982th

Another polymeric material that can be incorporated into the trisodium metal of the invention is polyethylene glycol (PEG). Polyethylene glycol can have a dispersing effect and at the same time act as a particulate soil removal agent and prevent its redeposition.

The molecular weight of such polyoxyethylenes is approximately for this purpose

500 to approximately

100,000, preferably about 1,000 to about 50,000, more preferably about 1,500 to about 10,000.

Brightening agents

Any optically brightener or other brightener or bleaching agent may be incorporated into the cleaning compositions of the invention.

The choice of brightener for the detergent compositions of the present invention depends on various factors such as the type of detergent, the nature of the other ingredients present in the detergent, the temperature of the wash liquor, the degree of mixing, and the ratio of wash material to container size.

The choice of brightener depends on the type of material to be cleaned, such as cotton, synthetic fiber. Because most detergents are used for cleaning a variety of

Textiles the laundry detergent contains a brightener mixture č i n i d i e 1, which are effective for different types of textiles. Otherwise it is important, the individual components of such a mixture of brighteners

they are compatible.

Commercial brighteners that can be used for the detergent compositions of the invention can be classified into subgroups including, but not limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinoyanines, dibenzothiophene-5,5-dioxide, azoles, five- and six-membered heterocycles and other mixed reagents. Examples of such brighteners are given in The Production and

Application of Fluorescent Brightening Agents, M.

published by John Viley & Sons, Nev York (1982).

As stilbene derivatives that can be used in the compositions of the invention, there is no intention to

For example, garden cleaning restrictions include:

bis (triazines1) amino-benzenes, bisacylamino derivatives of stilbene, triazole derivatives of stilbene oxadiazole derivatives of stilbene.

oxyzole derivatives of stilbene and styryl derivatives of stilbene.

Certain bis (triazinyl1) aminoquinilene derivatives which may be useful in the detergent compositions of the invention may be prepared from 4,4'-diamine-1,4-disulfonic acid.

Coumarin derivatives which can be used in the detergent compositions of the invention include, without limitation, for example:

derivatives substituted at the 3-position, at the 3-position

- 59 7 and in position 3 and 7.

Examples of carboxylic acid derivatives which can be used in the detergent compositions of the present invention include, but are not limited to: fumaric acid derivatives, benzoic acid derivatives, p-phenylene-bis-acrylic acid derivatives, naphthalenedicarboxylic acid derivatives, heterocyclic derivatives acids and cinnamic acid derivatives.

Cinnamic acid derivatives.

which may be used in the detergent compositions of the invention may be further subdivided into groups which include, but are not limited to:

cinnamic, styrylazoles, styrylbenzofurans, styryloxadiazole acid derivatives, styryltriazoles and styrylpolyphenyls, as described on p. 77 of the aforementioned Gardener's publication.

The styrylazoles can be further subdivided into sub-groups including styrylbenzoxyzoles, styrylimidazoles and styrylthiazoles, as described on p. 8 of the aforementioned Gardener's publication.

However, the three subclasses of the brighteners are not an exhaustive overview of the subclasses into which the styrylazoles can be subclassed.

optically

The reagents are derivatives of the dibenzothiophene-5,5-dioxide described on p. 741 to 749

Kirk-Othmer Encyclopedia of

Chemical Technology, Volume 3 and p. 737 and 750 (John Viley & Sons, Inc., 1962) and is included

5,5-dioxide

3,7-diamino-iodo-benzothiophene-2,8-d-isulfonic acid.

Optically brightening agents include azoles which are derivatives of five-membered heterocycles. These compounds are further subdivided into a subclass of monoazoles and bisazoles.

Examples of monoazoles and bisazoles are given in the cited publication

Kirk-Othmer.

Still other optically brightening agents are derivatives of the six-membered heterocycles described in Kirk.

- Othmer.

agents

Examples of such agents include pyridine-derived optically brighteners derived from pyridine

4-aminonaphthalamide.

In addition to the optically brightening agents described above, agents may be used. Examples of such other possible optically brightening agents are set forth on p. 93 to x

Above mentioned Gardener's publications and include 1-hydroxy-3,6-8-pyrene-trisulfonic acid, 2,4-dimethoxy-1,3,5-triazin-6-yl-pyrene, 4,5-diphenylimidazolone disulfonic acid and pyrazoline quinoline derivatives.

Further specific examples of optically brightening agents are disclosed in U.S. Pat. No. 4,790,856 (Vixon, Dec. 13, 1988). Such optically brightening agents include the Phorvhite ™ family of products

Verona. Other optically brightening agents are:

Tinopal

UNPA, Tinopal CBS and Tinopal 5BM from Ciba-Geigy;

Arctic

Get CC and Arctic

Vh i t e

CWD company

H i 1ton

Ta 1iansko;

2- (4-styrylphenyl) -2H-naphthol [1,2-d] triazoles;

4,4-bis- (1,2,3-triazol-2-yl) -stienyl; 4,4-d is (styryl) bisphenyls and γ-aminocoumarins. Specific examples of these optically brightening agents include 4-methyl-7-diethylamino-coumarin; Bisco 1,2-benzimidazol-2-y1) ethylene; 1,3-diphenylpyrazolines;

2,5-bis- (benzoxazol-2-yl) -thiophene, 2-styrylnaphthyl-1,2-d] oxazol-2-ynyl-4-yl) -2H-naphtho [1,2-dl-triazole.

Other optically brighteners which can be used in the detergent compositions of the present invention are described in U.S. Patent 3,646,015 (Hamilton, Feb. 29, 1972).

Other ingredients

The detergent composition of the invention may contain other ingredients suitable for detergent compositions, including, for example, other surfactants, carriers, hydrotropic additives, adjuvants, dyes, pigments and solvents for liquid compositions.

Liquid cleaning compositions may contain water and solvents other than carriers. Low molecular weight primary and secondary alcohols such as methanol, ethanol, propanol and isopropanol are suitable. Monovalent alcohols are preferred for solubilizing surfactants, but polyols containing 2 to about 6 carbon atoms and 2 to about 6 hydroxyl groups (such as propylene glycol, ethylene glycol, glycerin and 1,2 propanediol) may also be used.

The detergent compositions of the invention are preferably formulated such that the wash liquor has a pH of about 6.5 to about 11, preferably about 7.5 to about 10.5 during use in the aqueous cleaning operation. The liquid cleaning compositions preferably have a pH of about 7.5 to about 9.5, preferably about 7.5 to about 9.0. Methods for controlling the pH and the recommended amount include the use of, for example, buffers, alkalis, and acids as known to those skilled in the art.

The invention also relates to a method of cleaning substrates such as fibers, fabrics, hard surfaces and skins by contacting such a substrate with a cleaning composition comprising at least about 1% surfactant and at least 1% fatty acid polyhydroxyamide, wherein (a) such a cleaning composition also comprising (i) a suds suppressor, or (ii) at least 1%, preferably about 3 to about 30%, by weight of a surfactant selected from the group consisting of alkyl ethoxylates, and alkyl ethoxylated sulfates, alkyl ester sulfonates, and mixtures thereof, wherein the weight ratio of alkyl sulfate the surfactant to the polyhydroxy fatty acid amide is about 1 = 10 to about 10 = 1, or preferably at the above weight ratio, or about (b) such a cleaning composition comprises an alkyl sulfate surfactant and a polyhydroxy fatty acid amide, ## STR3 ## wherein R ^{@ 1 is} methyl. A C ² -C 17 alkyl or alkenyl group and a Y moiety derived from a reducing sugar, preferably a glycoside and especially a glucoside group, wherein the weight ratio of alkyl sulfates to polyhydroxy fatty acid amide is about 1.25-1 to about 1-6, preferably about 1.25 to about 1-6 and in particular about 1.25 = 1 to:

about 1 - 1.25. Preferably, the cleaning is carried out by stirring to promote cleaning. Suitable means for such mixing are hand rubbing, but preferably using a brush, sponge, cloth or other cleaning device, an automatic washing machine or an automatic dishwasher.

The invention is illustrated but not limited by the following examples.

DETAILED DESCRIPTION OF THE INVENTION

The N-methyl-1,1-deoxyglucityl lauramide surfactant used in the following examples is prepared as follows ^:

Although one skilled in the art may vary the configuration, the apparatus includes a suitable three-liter four-necked flask apparatus equipped with a motor driven paddle stirrer and a thermometer of sufficient length to contact the reaction mixture. The other two flasks of the flask are fitted with a nitrogen purge side arm and a large orifice side arm (note: a large orifice side arm is important in the case of very rapid methanol evolution) to which an efficient collector condenser and vacuum outlet are connected. The vacuum outlet is connected to a nitrogen source and to a vacuum meter and to a suction and trap. A 500 Watt heating jacket with variable temperature control transformer (Variac), used to heat the reaction, is placed on the laboratory fixture so that it can be easily lifted or lowered to further control the reaction temperature.

N-methylglucamine (195 g, m 1.0 mol, Aldrich, M4700-0) and methyl laurate (Procter & Gambia CE 1270, 220.9 g, 1.0 mol) were charged to a flask. The mixture of solid and liquid is heated with stirring and flushing with nitrogen to form a melt (approximately

125 minutes) When the melt temperature reaches

145 ° C, catalyst (anhydrous powdered sodium carbonate, 10.5

0,1 mol,

J.T. Baker). The nitrogen purge is stopped and the aspirator and the nitrogen outlet are set to obtain a vacuum of 16.95 kPa. From now on, the reaction temperature is maintained at 150 ° C by adjusting the Variac and / or raising or lowering the jacket.

Within seven minutes, the first methanol bubbles appeared on the reaction mixture changer. Then there is an almost violent reaction.

Methanol is distilled off if it is formed. The vacuum is adjusted to about 33.86 kPa. The vacuum is increased approximately as follows (in kPa for a given minute): 33.86 kPa for 3 minutes, 67.72 kPa for seven minutes, 84.65 for ten minutes. Eleven minutes after the start of methanol formation, heating and stirring are discontinued simultaneously with some foaming. The product is cooled and allowed to solidify.

The following examples illustrate the invention without limiting it to Examples 1-6

These examples illustrate cleaning compositions containing alkyl sulfates and polyhydroxy fatty acid amides for washing at temperatures preferably above 40 ° C at a detergent concentration of 6,000 to 8,000 ppm, based on the weight of the washing bath.

Basic granules 1 2 3 CI4-i5alkylsulfát 4.6 4.6 - C16-1ealkylsulfát 2.4 2.4 2.4 Linear Cizalkybenzenesulfonate - - 7.6 C16-18a alkyloxyethoxylate (11 mol) 1.1 1.1 1.1 acrylate (maleate copolymer (molecular weight 60,000) 4.3 5.6 4.3 zeoli t 22.0 24.0 21.3 water and a mixture of ingredients 9.4 9.2 10.1 admixture and spray N-methyl-N-1-deoxyglucitylcocoamide id 7.0 N-methyl-N-1-deoxyglycyl amide 7.0 4.0 sodium citrate 8.0 - 8.0 sodium carbonate 17.5 17.3 17.5 Sodium silicate (SiO 2 / Na 2 O = 1,6) 3.5 3.0 3.5 perfume 0.4 0.4 0.4 si 1 icon liquid 0.5 0.5 0.5 mixture of ingredients (filler salts, enzymes, bleaches, polymers it also helps to relax the spirits and so on) 19.3 26.5 19.4 pretty 100.0 100.0 100.0

The cleaning compositions of Examples 1-3 are preferably used at a concentration of about 6000 ppm, based on the weight of the wash liquor, at a temperature of about 30 to 95 ° C. These cleaners are prepared by suspending the ingredients for the base granules and spray drying them to a final moisture content of 9%. The residual dry powder or granular ingredients are admixed when spraying the final liquid ingredients.

Basic granules 4 5 6 Linear Cisalkylbenzenesulfonate 5.9 - N-methyl-N-1-deoxyglycyl amide tallow fatty acids - - 7.1 alkyl sulfate - 5.9 5.9 C16-18 alkyl sulfate 2.5 2.5 2.5 zeolite 20.5 14.0 20.5 polyacrylate (molecular weight 4500) 3.9 3.9 3.9 sodium citrate - 6.0 - sodium carbonate 12.7 16.0 12.7 water and a mixture of ingredients 8.1 8.2 8.7 admixture and spray N-mety1-N-L-deoxygluclty1lauramid 7.1 - - N-methyl-Ν-1-deoxyglucylcocoamide - 6.6 - mixture of ingredients (filler salts). enzymes, bleaches, polymers for helping to release dirt like you) 39.3 36.9 38.7 pretty 100.0 100.0 100.0

Examples 4 to 6 show standard high performance granulated detergent compositions for wash temperatures of about 30 to about 95 ° C at a concentration of 8,000 ppm, based on the weight of the wash liquor. These cleaning compositions are prepared by suspending the ingredients for the base granules and spray drying them to a final moisture content of 10-13%. The residual dry powder components such as bleaching agents, activators and other excipients are admixed and sprayed onto liquids such as perfume, nonionic surfactants, or suds suppressant.

Examples 7 to 20

These examples exemplify granular cleaning compositions for high nations containing polyhydroxy fatty acid amide, alkyl sulfates and suds suppressors.

Basic granules 7 8 9 10 Ci4-15alkyIsulfát 18.7 10.1 11.3 - C 1-4 -15-alkylene-ethoxy (2.25); - - 5.6 CI2-i8alkylsulfát - - - 16.9 Linear C 12 alkylbenzenesulfonate - 10.1 - - -N-methyl-N-1-deoxyglucity 1- kokoam id 3.8 2.4 5.6 5.6 zeolite A 30.1 18.8 18.8 30.1 sodium citrate - 11.3 11.3 - sodium carbonate 16.9 16.9 16.9 16.9 sodium silicate 3.1 2.5 2.5 2.5 sodium sulfate 15.0 15.0 15.1 15.1 tallow fatty acid 1.1 1.1 1.1 - mixture of ingredients 3.1 3.2 2.7 4.4 admixture and spray Differently 2.5 3.5 3.5 2.5 suds suppressing flakes 0.5 - 0.5 1.0 pretty 100.0 100.0 100 0

The suds suppressing flakes contain approximately 5% of the silica / Si 1 icon oil dispersion encapsulated in the flake containing primary polyethylene glycol (PEG molecular weight 8,000) in an amount of more than 80% and less, optionally water soluble components

The detergent compositions of Examples 7-10 are exemplary compositions for preferred use in an amount of about 1,400 ppm, based on the weight of the wash liquor, at a bath temperature of about 50 ° C.

The cleaning compositions of the above examples are prepared by combining the granular base ingredients in the form of a suspension and spray drying to a residual moisture of about 4-8%. The residual dry ingredients are admixed in the form of granules or powder with the spray-dried granules in a rotary drum blender and sprayed onto the liquid component (nonionic surfactants and perfume).

Basic granules 11 12 Linear Cizalkybenzenesulfonate 7.6 - G14 -15 a 1 k y 1 s u 1 ph 3.3 - tallow fatty acids 3.0 zeo1 i t A 13.4 19.8 polyacrylate (molecular weight 4500) 3.5 4.5 polyethylene glycol (molecular weight 8 000) 2.0 2.0 sodium silicate (SiO 2 / Na 2 O = 1.6) 2.0 2.0 sodium carbonate 15.0 15.0 sodium sulfate 12.0 6.0 mixture of ingredients 1.5 1.0 admixture and spray the detergent particles of Example 29 14.3 - detergent particles according to Example 30 - 30.0 zeolite A 5.0 5.0 sodium citrate 5.0 - suds suppressing flakes ” 0.5 0.5 Differently 7.1 5.0 residual water 7.8 6.2 pretty 100.0 100.0

The suds suppressing flakes contain approximately 5% of the silica / s1 icon oil dispersion encapsulated in a flake containing primary polyethylene glycol (PEG molecular weight 8,000) in an amount of more than 85% and .1.0% of tallow fatty acids.

The cleaning compositions of Examples 11-12 are preferably used in an amount of about 1000 ppm, based on the weight of the wash liquor, at a bath temperature of about 50 ° C. They are prepared by suspending and spray drying the components of the base granule to a residual moisture content of 7 to 10 and mixing with the residual components and spraying the liquid components.

ύ

Basic granules 13 14 15 CI4-isalkylsu1fát 4.3 6.0 - C16-18 fatty acids 2.2 - 2.2 zeo1 i t A 7.0 7.0 7.0 polyacrylate (molecular weight 4500) 3.3 3.3 3.3 Polyethylene glycol (molecular weight 8000) 1.3 1.3 1.3 sodium carbonate 10.7 10.7 10.7 sodium sulfate 5.0 5.0 5.0 sodium silicate (SiO 2 / Na 2 O = 1.6) 5.0 5.0 5.0 mixture of ingredients 7.1 7.1 7.1 admixture and spray Zeo1 i t A 5.0 5.0 5.0 N-Methyl-N-1-deoxyglucocycloamide - 6.4 6.4 detergent particles according to the example 28 21.3 - - CI2-i8alkylsulfát - 13.1 13.1 C 12-18 alkylethoxy (2.25) with 1 ph - - 6.0 suds suppressing flakes' - 1.0 0.5 possible ingredients 17.2 17.2 16.5 C12-13 alkyl ethoxylate (6.5 mol) 2.0 2.0 2.0 perfume 0.5 0.5 0.5 water and various 8.2 9.4 8.4 pretty 100.0 100.0 100.0

The suds suppressing flakes contain approximately 5% of the silica / Si 1 icon oil dispersion encapsulated in the flake containing primary polyethylene glycol (PEG molecular weight 8,000) in an amount of more than 80% and less, optionally water soluble components

The cleaning compositions of Examples 13-15 are condensed compositions and are prepared by suspending and spray drying the constituent granules to a residual moisture content of 5% and mixing with the residual granular or powder constituents. The mixture is sprayed onto the liquid components.

The composition is intended to be used in a concentration of 1000 ppm, based on the weight of the scrubbing bath, and for a scrubbing bath temperature of about 30 ° C.

Basic granules 16 17 CI4-isalkyIsulfát - 4.6 Ci-18 alkylsulfate 2.4 2.4 Linear BlushesBenzenesulfonate 7.6 - C16-18alkyl ethoxylate (11 mol) 1.1 1.1 tallow fatty acids 1.1 1.1 zeolite 21.3 22.0 acrylate / maleate copolymer (molecular weight 60,000) 4.3 5.6 water and a mixture of ingredients 10.1 9.2 Admixture and spray N-methyl-N-1-deoxyglucocycloamide 7.0 N-mety1-N-l-deoxyglucityl 4.0 - tallow fatty acids sodium citrate 8.0 - sodium carbonate 17.5 17.3 sodium silicate (SiO 2 / Na 2 O = 1.6) 3.5 3.0 perfume 0.4 0.4 si 1 icon liquid 0.5 0.5 mixture of ingredients (filler salts, enzymes) bleachers, bullders, etc.) 18.3 25.7 pretty 100.0 100.0

The cleaning compositions of Examples 16 and 17 are preferably used at a concentration of about 6000 ppm, based on the weight of the wash liquor, at a temperature of about 30 to 95 ° C. These cleaners are prepared by suspending the ingredients for the base granules and spray drying them to a final moisture content of 9%. The residual dry powdered or granulated components are mixed in a rotary mixing drum and the final liquid components are sprayed.

Basic granules 18 19 20 Linear C 12 alkylbenzenesulfonate 5.9 - - N-methyl-N-1-deoxyglucidyl id tallow fatty acids - - 7.1 C14-15 alkyl sulfate - 5.9 5.9 C16 -18 and 1 s u 1 ph 2.5 2.5 2.5 zeolite 20.5 14.0 20.5 tallow fatty acids 1.1 1.1 - polyacrylate (molecular weight 4500) 3.9 3.9 3.9 c i trát - 6.0 - sodium carbonate 12.7 15.6 12.7 water and a mixture of ingredients 8.1 8.2 8.7 admixture and spray N-methyl-N-1-deoxyglucyl tyllauramide 7.1 N-methyl-N-1-deoxyglucitylcocoamide - 7.1 - perfume 0.4 0.4 0.4 si 1 icon liquid 1.0 0.5 0.5 mixture of ingredients (filler salts, enzymes) bleaches, builders and the like) 36.8 34.8 37.8 pretty 100.0 100.0 100.0

The cleaning compositions of Example 20 are granular cleaning compositions for high demands.

intended for use in an amount of about 8,000 ppm.

based on the weight of the bath, at a temperature of about 30 to 59 ° C. They are prepared by suspending and spray-drying the components of the base granule to a residual moisture content of 10-13% and mixing with the residual dry ingredients such as bleaching agents, activators and other auxiliary components, and spraying liquid ingredients such as perfumes, nonionic surfactants and suds suppressors. .

Examples 21 to 27

The following examples illustrate high performance cleaning compositions containing alkyl sulfates and polyhydroxy fatty acid amides.

ingredients 21 22 23 24 C 12-18 alkylsulfate 12.9 12.9 9.0 11.5 N-methyl-N-1-deoxyglucyl 1 - cocamide 8.4 - 8.4 - N-methyl-N-1-deoxyglucyl- o 1eam i d - 8.4 - - oleic acid 1.8 1.8 3.5 2.0 citric acid 4.1 4.1 10,0 9.0 they acidified on dodecy1 amber 11.1 11, 1 4.0 5.0 1 icon oil 0.2 0.2 0.2 0.2 various (e.g. solvents. enzymes, brighteners, stabilizers sources, buffers) 16, 1 16, 1 16.6 17.7 Water 45.5 45.5 48.3 48.1 together 100.0 100.0 100.0 100.0

The cleaning compositions of Examples 21-24 are preferably used in an amount of about 12,000 ppm based on the weight of the wash liquor, at a temperature of 30 to 95 ° C.

ingredients 25 26 27 N-methyl-N-1-deoxyglucylcycloam id 4.2 3.1 3.1 N-mety1-N-l-deoxyglucityl oleamide CI4-isalkyletoxy (2.5) sulfate 8.4 6.1 - Ci 4 -1 s and 1 s 1 s u f 4.2 3.1 - C12-18 and alkyloxyethoxylate - 6.2 Ci2-14alkylsulfát - 3.1 CI2-i4alkyletoxylát 3.4 - dodecy11r imety1amon i umeh 1or i d 0.5 - dodecyIsukc i ná - 5.0 c i trát. 3.4 15.0 TMS / TDS (80/20) ~ 3.4 - C12-14 fatty acids 3.0 - oxyd isuction i - 20.0 - ethoxylated tetraethylenepentamine 1.5 - - polyacrylates (molecular weight 4500) - 1.5 1.5 mixture of ingredients (enzymes, brighteners, release promoting agents s, s bil s, and other s) 15.3 14.09 14.9 Water 52.7 51.2 51.2 ce1 kom 100.0 100.0 100.0

* TMS / TDS is a tartrate monosuccinate / tartrate disuccinate system

The detergent compositions of Examples 25 to 27 are preferably used in an amount of about 2000 ppm, based on the weight of the wash liquor having a temperature below about 50 ° C.

The detergent compositions of Examples 21 to 27 are prepared by mixing a non-aqueous solvent, an aqueous paste or a surfactant solution, molten fatty acids, aqueous solutions of polycarboxylate builders and other salts, aqueous ethoxylated tetraethylene pentamine, buffers, alkalis and residual water. The pH is adjusted to about 8.5 using either aqueous sodium citric acid solution or aqueous hydroxide solution. After adjusting the pH, ingredients such as soil release agents, enzymes, dyes and perfumes are added and mixed until a uniform phase is achieved.

Examples 28-30

The following examples illustrate detergent particles containing alkyl sulfate and polyhydroxy fatty acid amides suitable for direct addition to granular detergent compositions for high demands.

ingredients 28 29 30 C12-1-4 alkyl sulfate 75.0 - - C 1-4 -15 and 1 s .1 ph - 65.0 83.0 N-methyl-N-1-deoxyglucitylcocoamid 18.7 21.7 12.0 Differently 1.3 8.3 - residual water and various 5.0 5.0 5.0 pretty 100.0 100.0 100.0

The detergent particles of Examples 28-30 are prepared by mixing a melt of a polyhydroxy fatty acid amide at a temperature of 70-100 ° C to an alkylsulfate paste. The product is then allowed to dry to a residual moisture of less than 5% and finally milled to a particle diameter of about 0.1 to 1.0 mm.

Example 31

An alternative process for preparing polyhydroxy fatty acid amides is as follows.

A reaction mixture containing 84.87 g of fatty acid methyl ester (supplied by Procter & Gambia, methyl ester CE1270), 75.00 g of N-methyl-D-glucamine (supplied by Aldrich Chemical Company M4700-0), 1.04 g of sodium methoxide ( supplier: Aldrich Chemical Company 16, 499-2) and 68.51 g of methanol (30% by weight of the reaction mixture). The reaction vessel has standard equipment for reflux, a drying tube, a condenser and a stirring bar. In this process, N-methylglucamine is mixed with methanol under stirring under argon and heating is started with good stirring (stirring bar, reflux). After 15 minutes the solution is at the desired temperature and the ester and sodium methoxide are added as catalyst. Samples are taken periodically to monitor the progress of the reaction, with the solution clearing well in 63.5 minutes. It is believed that at this point the reaction is virtually complete. The reaction mixture is refluxed for 4 hours. The reaction mixture obtained weighs 156.16 g. After vacuum drying, the total yield is 106.92 g of granulated purified product, which can be easily crushed into small particles. The percentage yield is not calculated on this basis since sampling during the reaction affects the overall yield. The reaction can be carried out by weight at 80% and 90% concentration of the reactants for up to 6 hours, yielding the product with extremely low by-product formation.

The following is not intended to limit the invention, but merely to further elucidate the technological aspects to be taken into account by one skilled in the art in the manufacture of a variety of detergent compositions using polyhydroxy fatty acid amides.

It is clear that polyhydroxy fatty acid amides are unstable under highly basic or highly acidic conditions because of their amide bond. Although some decomposition can be tolerated, it is preferred that these materials are not exposed to pH above

11th

preferably above 10 or below 3 for an unsuitable period of time. The pH of the final product (liquid) is generally 7.0 to 9.0.

In the preparation of polyhydroxy fatty acid amides, it is generally necessary to at least partially neutralize the basic catalyst used for the formed amide bonds. Although any acid may be used for this purpose, it will be apparent to those skilled in the art that it is simple and convenient to use acids whose anion is otherwise useful and desirable in the finished detergent composition. For example, citric acid may be used for neutralization purposes and the resulting citrate ion (about 1%) suspended in about 40% of the polyhydroxy fatty acid amides and pumped to the next stage of the finished detergent production process. Similarly, acid forms of chemicals such as oxydisuccinate, nitrilotriacetate, ethylenediaminetetraacetate and the tartrate / succinate system can be used.

The polyhydroxy fatty acid amides derived from coconut fatty acid alkyls (predominantly 12 to 14 carbon atoms) are more soluble than their tallow fatty acid alkyl counterparts (predominantly 16 to 18 carbon atoms), so materials of 12 to 14 carbon atoms are somewhat easier to formulate in liquid compositions and are more soluble in cold water wash liquors. However, 16 to 18 carbon atoms are also good, especially in circumstances where warm to hot water is used in the wash. Therefore, C16-C18 materials can be better detergent compositions than their C12-C14 counterparts. A person skilled in the art can therefore balance the ease of preparation with the utility properties by choosing a particular polyhydroxy fatty acid amide for a particular detergent composition.

It is also noted that the solubility of polyhydroxyamides into fatty acids may increase depending on the unsaturation and / or branching of the fatty acid portion of the chain. Materials such as polyhydroxy fatty acid amides derived from oleic acid and isostearic acid are much more soluble than their n-alkyl counterparts.

Similarly, the solubility of polyhydroxy fatty acid amides.

prepared from disaccharides, trisaccharides, etc. it is generally greater than the solubility of their monosaciiaride derived counterparts. This higher solubility can particularly assist in the formulation of liquid compositions. In addition, the polyhydroxy fatty acid amides whose polyhydroxy groups are derived from maltose appear to be particularly detergent when used in admixture with conventional alkylbenzerisulfonate (LAS) surfactants. Although not intended to be limited by theory, it appears that a mixture of LAS with higher carbohydrate polyhydroxyamides derived from higher carbohydrates, such as maltose, exhibits a substantial and unexpected decrease in the inphasis voltage in the aqueous environment, thereby promoting a cleansing action. (The process for preparing maltose-derived polyhydroxy fatty acid amide is described below.)

Polyhydroxy fatty acid amides may be prepared not only from purified sugars, but also from hydrolysed starches, for example, corn starch, potato starch or other suitable vegetable starch containing the necessary monosaccharides, disaccharides and the like. This is of particular importance from an economic point of view. For example, such high glucose corn syrup, high maltose corn syrup can be used easily and economically. The feedstock for the preparation of polyhydroxy fatty acid amides may also be deligified hydrolyzed pulp.

As mentioned above, polyhydroxy fatty acid amides derived from higher carbohydrates such as maltose and lactose are much more soluble than their counterparts. In addition, it appears that the more soluble polyhydroxy fatty acid amides may assist in varying degrees of solubility of their less soluble counterparts. A person skilled in the art may therefore choose, for example, as a raw material instead of a high glucose corn syrup a syrup containing a small amount of maltose (for example, 1% by weight or more). The polyhydroxy fatty acid mixture obtained generally has more advantageous solubility characteristics over a wide range of temperatures and concentrations than polyhydroxy fatty acid amide. derived from pure glucose. In addition to the economic advantages of using sugar blends over pure sugar, the polyhydroxy fatty acid amides prepared from the sugar blend have the advantage of being easy to handle during manufacture. However, in some cases, there is a decrease in fat removal (at dishwashing) at a fatty acid concentration of maltamide above approximately 25 certain foaming losses at a concentration of a percentage of maltamides derived from polyhydroxy fatty acids as opposed to e1 from polyhydroxy fatty acid amides derived from change. are possible depending on the length of the glucose chain). Some fatty acid. One of ordinary skill in the art can choose compositions that he considers preferred for polyhydroxy fatty acid amides having a ratio of monosaccharides (e.g. glucose) to disaccharides and to higher saccharides (e.g. maltose) of about 4-1 to about 99: 1.

The preparation of preferred non-cyclized fatty acid polyhydroxyamides from fatty acid esters and N-alkyl polyols can be approximately carried out in alcoholic solvents at a temperature of up to about 90 ° C, preferably about 50 to 80 ° C.

It has now been found that it may be convenient for the person skilled in the art to work in a 1,2-propylene glycol solvent, for example, in the preparation of liquid detergents.

whereas the glycol solvent may not be completely removed from the reaction product prior to use in the preparation of the finished detergent composition. Similarly, it is appropriate for those skilled in the art to prepare a solid, generally granulated, detergent composition at a temperature of 30 to 90 ° C in solvents containing ethoxylated alcohols such as ethoxylovary (EO 3-8) alcohols having 2 to 14 carbon atoms, which are a commercial product 23 E06.5 (Shell). When ethoxylates are used, it is preferred that they do not contain a substantial amount of unethoxylated alcohol, and in particular do not contain a substantial amount of monoethoxylated alcohol (designation T '·).

Although methods for preparing polyhydroxy fatty acid amides per se are not within the scope of the present invention, other possibilities for preparing polyhydroxy fatty acid amides are also discussed and are described below.

Generally, the reaction sequence on an industrial scale for preparing preferably acyclic polyhydroxy fatty acid amides comprises the following steps: Step 1. - Preparation of an N-alkyl polyhydroxyamine derivative from the desired sugar or desired sugar mixture by formation of an N-alkylamine-sugar adduct followed by reaction with hydrogen in the presence of a catalyst. degree

2. - Reaction of the aforementioned polyhydroxyamine, preferably with a fatty acid ester, to form an amide bond. Although a wide variety of N-alkyl polyhydroxyamines are suitable for the Stage 2 reaction sequence, sugar syrups are suitable for the process and for economic reasons. The best results when using such syrups as raw material are obtained when selecting syrups which are light in color or preferably colorless (water white).

Preparation of N-alkyl polyhydroxyamine from sugar syrup obtained from plants

1. Adduct preparation

According to a standard method, about 420 g of about 55% glucose solution (corn syrup about

231 g of glucose - about 1.28 mol) with a Gardner color of less than 1 and about 119 g of an approximately 50% aqueous solution of methylamine (59.5 g methylamine 1.92 mol). The methylamine (MMA) solution is purged with nitrogen and cooled to about 10 ° C or below. Corn syrup is poured and nitrogen is introduced at a temperature of about 10 to 20 ° C. Corn syrup is added slowly to the methylamine solution at the above reaction temperature. The Gardner color number is spaced at the following time intervals, in minutes.

Table I

Time in minutes 10 30 60 120 180 240 Reaction temperature ° C Gardner color (aprox to cut through) 0 1 1 1 1 1 1 20 1 1 1 1 1 30 1 1 2 2 4 5

From the above, it is apparent that the Gardner color for the adduct is much worse when the temperature rises above 30 ° C and at about 50 ° C the time during which the Gardner adduct is below 7 is only 30 minutes. For the next reaction and / or duration, the temperature should be less than about 20 ° C. The Gardner color should be less than about 7 and preferably less than about 4 to achieve a good glucamine color.

When a lower temperature is used to form an adduct, the time to reach an equilibrium adduct concentration is reduced using a higher amine to sugar ratio. At a molar ratio of 1.5

- 1 amine to sugar is equilibrated in about two 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 three hours. Because of the good color, the combination of the amine to sugar ratio, the reaction temperature and the reaction time to achieve a substantially equilibrium conversion are chosen. for example, greater than about 90%, preferably greater than about 95%, and even greater than about 99, based on sugar and adduct color, which is less than about 7, preferably less than about 4, and especially about less than 1.

In the above process, the reaction temperature is less than about 20 ° C and corn syrup of different Gardner color and MMA adduct color (after reaching substantially equilibrium within at least two hours) is shown in Table II.

Table II

Gardner color (approx.) corn syrup 1 1 1 1+ 0 0 0+ adduct 3 4/5 7/8 7/8 1 2 1

ARp is clear from the table, the starting sugar must be almost colorless to produce an acceptable adduct. If the sugar has a Gardner number of approximately 1.

the adduct is sometimes acceptable, sometimes unacceptable.

If the Gardner number is above 1, the adduct obtained is unacceptable. The better the initial color of the sugar.

the better the color of the adduct.

II. Reaction with hydrogen

The adduct obtained by the above process and having a Gardner color of 1 or less is hydrogenated by the following process:

Approximately 539 g of the adduct in water and about 23.1 g of the G49B nickel catalyst (United Catalysts) are charged into a one liter autoclave and purged twice with hydrogen at positive pressure.

380 kPa at 20 ° C. The hydrogen pressure is raised to 9 660 kPa and the temperature is raised to 50 ° C. The overpressure is raised to 11040 kPa and the temperature is maintained at 50 to 55 ° C for three hours. At this point, the product is hydrogenated from 95. The temperature is then raised to about 85 ° C for about 30 minutes and the reaction mixture is decanted and the catalyst is filtered off. The product and water and methylamine were removed by evaporation to give 95% N-methylglucamine as a white powder.

The above process is repeated with about 23.1 g of Raney nickel catalyst as follows. The catalyst is washed three times and the reactor with the catalyst in the reactor is purged twice with hydrogen at an atmospheric pressure of 1480 kPa, after which the hydrogen pressure in the autoclave is adjusted to 11040 kPa for two hours, relieved in one hour and repressurized in the reactor.

II 040 kPa. The adduct is then pumped to a reactor at a hydrogen pressure of 1480 kPa and a temperature of 20 ° C and the reactor is purged with hydrogen at a pressure of 1380 kPa, which is repeated.

In any case, the resulting product is more than 95% N-methylglucamine, which contains less than 10 ppm nickel, based on glucamine, and has a Gardner color of less than 2.

Crude N-methylglucamine is color stable under short term exposure to temperatures up to about 140 ° C.

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

In another method, the adduct is prepared from about 159 g of about 50% methylamine in water, which is washed and shielded with nitrogen at a temperature of about 10 to 20 ° C. About 330 g of about 70% corn syrup (almost white water) is degassed with nitrogen at about 50 ° C and slowly added to the methylamine solution at a temperature of less than about 20 ° C. The solution is stirred for about 30 minutes until about 95% adduct is obtained, which is a very light yellow solution.

About 190 g of this adduct in water and about 9 g of the GE9B (United Catalyst) Ricket Catalyst are charged into an 200 mL acetonitrile and purged three times with hydrogen at about 20 ° C. The hydrogen pressure is raised to about 1380 kPa and the temperature is raised to about 50 ° C. The pressure is raised to 1715 kPa and the temperature is maintained at about 50-55 ° C for three hours. The temperature of the product, which is hydrogenated to about 95%, is increased to about 85 ° C for about 30 minutes, and the product after removal of water and evaporation is about 95% of N-methylglucamine as a white powder.

It is also important to minimize the contact of the adduct and the catalyst under a hydrogen pressure of less than 6.9 MPa to minimize the nickel content of the glucamine. The nickel content of N-methylglucamine in this reaction is about 100 ppm compared to less than 10 ppm in the previous reaction.

The following reaction with hydrogen is performed to directly compare the effect of the reaction temperature.

An autoclave containing 200 ml is used in a typical process similar to that described above for the preparation of the adduct and the reaction with hydrogen is carried out at different temperatures.

The glucamine adduct is prepared by mixing approximately 420 g of approximately 55% glucose solution (corn syrup) (231 g glucose, 1.28 mol) (prepared using CarBill 99DE corn syrup, Gardner color number less than 1). ) and about 119 g of 50% methylamine (59.5 g MMA, 1.92 mol) (from Arir Products).

The reaction is carried out as follows:

1. Charge about 119 g of a 50% methylamine solution into a nitrogen shielded nitrogen purged reactor and cool to less than about 10 ° C.

2. degassing and / or flushing the 55% corn syrup solution at 10 to 20 ° C with nitrogen to remove oxygen from the solution;

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

4. when all solution is added. corn syrup, mixed for one to two hours.

The adduct is used to react with hydrogen directly as it is produced or after storage at low temperature to prevent degradation.

The reaction of the glines of the adduct is carried out as follows:

1. Charge approximately 134 g of adduct (Gardner color number less than 1) and approximately 5.8 g of G49B nickel catalyst into a 200 ml autoclave,

2. purge the reaction mixture with hydrogen at a pressure of approx

380 kPa twice at 20 to 30 ° C,

3. The hydrogen pressure is raised to about 100 psig and the temperature is raised to about 50 ° C.

4. The pressure is raised to about 3.45 MPa, the reaction is allowed to proceed for three hours, maintaining the temperature at about 50-55 ° C, and sampling 1 is taken.

5. The temperature is raised to approximately 85 ° C for approximately 30 minutes.

6. decant and filter the catalyst, sample 2 is taken.

The conditions for the constant temperature reaction are as follows ^:

1. About 134 g of adduct and about 5.8 g of nickel catalyst are introduced into an autoclave containing 200 ml,

2. purge the reaction mixture with hydrogen at a pressure of approx

380 kPa twice at low temperature,

3. The hydrogen pressure is raised to about 2760 kPa and the temperature is raised to about 50 ° C.

4. The pressure is raised to about 3.45 MPa, the reaction is allowed to proceed for three and a half hours while maintaining the temperature as above;

5. Decant and filter the catalyst. Sample 3 corresponds to about 50-55 ° C, sample 4 corresponds to about 75 ° C, and sample 6 corresponds to about 85 ° C. (Reaction time for about 85 ° C is about 45 min.)

All processes give N-methylglucamine of similar purity (approximately 94%) and a similar Gardner color number. However, only a two-stage heat treatment provides good color fastness, and in the reaction at 85 ° C there is only a slight coloration immediately after the reaction.

Example 32

The tallow (hardened) N-methylmaltamine fatty acid Arnide for use in detergent compositions is prepared as follows:

Step 1. Reagents: Maltose monohydrate (Aldrich lot 01318KW), methylamine (40% by weight in water) (Aldrich lot 03325TM), Raney nickel, 50% suspension (HAD 52-73D, Aldrich lot 12921LW).

The reactants are introduced into a glass cartridge (250 g of maltose, f

428 g of methylamine solution, 1 200 g of catalyst suspension - 50 g of Raney nickel) and the insert is placed in a 3 liter fluctuating autoclave, which is purged with nitrogen (at a pressure of 3.45 MPa three times) and hydrogen (at a pressure of 3, 45 MPa, twice) and the autoclave varies in a hydrogen atmosphere at 28-50 ° C over the weekend. The crude reaction mixture was vacuum filtered twice through a microfiber glass microfiber filter. The filtrate was concentrated to give a viscous material. The final traces of water are removed azeotropically by dissolving the material in the metapolis and then removing the methanol / water system on a rotary evaporator. Final drying is carried out under high vacuum. The crude product was dissolved in refluxing methanol, filtered, cooled to crystallization, filtered and the filter cake dried in vacuo at 35 ° C. This is a cut = 1. The filtrate is concentrated until a precipitate is formed and stored in a refrigerator overnight. The solid was filtered off and dried in vacuo. This is a cut = 2. The filtrate of the sieve is again concentrated to half its volume and crystallization occurs. A very small amount of precipitate is formed. A small amount of ethanol is added and the solution is left in the freezer over the weekend. The solid material was filtered off and dried in vacuo. The combined solids contained n-methylmaltamine, which was used in step 2, step 2. - Reagents - N-methylmaltamine (from step 1), solid tallow methyl ester, sodium methoxide (25% solution in methanol), absolute methanol (solvent) mole ratio of amine ester 1 L, the initial catalyst concentration of 10 mol% (based on the weight of maltamine) is increased to 20 mol%, the weight concentration of the solvent 50%.

In a sealed flask, 20.36 g of tallow methyl ester is heated to its melting point (in a water bath) and placed in a 250 ml three-necked round-bottomed flask with mechanical stirring. The flask is heated to about 75 ° C to avoid ester stiffening. Separately, 25.0 g of N-methylamine is mixed with 45.36 g of methanol and the suspension obtained is added to the tallow fatty acid ester with good stirring. Add

1.51 g of 25% sodium methoxide in methanol. After four hours, the reaction mixture did not clear, so

An additional 10 mol% catalysts (to a total of 20 mol%) were added with Cl and the reaction was allowed to proceed overnight (approximately 68 ° C), after which time the mixture became clear.

The reaction flask is then adjusted for distillation.

The temperature was raised to 110 ° C. Distillation at ambient pressure was continued for 60 minutes. High vacuum distillation is then started for 14 minutes, at which time the product becomes highly dense. The product is kept in the reaction flask at 110 ° C (outside temperature) for 60 minutes. The product was removed from the flask and triturated 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. Any residual N-methyl maltamine is removed from the product using silica gel. The silica gel slurry in 100% methanol was added to the funnel and washed several times with 100% methanol. A concentrated sample of the product (20 g in 100 mL of methanol) was loaded onto silica gel and eluted several times under vacuum and evaporated several times to dryness washed with methanol. Collected eluent (on a rotary evaporator) - Any tallow fatty acid ester was removed by trituration in ethyl acetate overnight and filtered.

The filter cake is dried under vacuum overnight.

The product is tallow alkyl N-methyl maltamide.

In a varied process of Step 1, the above reaction sequence may be carried out using commercial corn syrup containing glucose or glucose mixtures and typically 5% or more maltose. The polyhydroxy fatty acid amides obtained and the compositions can be used in any detergent.

In another method, step 2 of the above reaction can be carried out in 1,2-propylene glycol or NEODOL. At the discretion of the worker, propylene glycol or NEODOL need not be removed from the reaction product prior to use in the formulation of the detergent composition. Again, at the discretion of the worker, the methoxide catalyst can be neutralized with citric acid to form sodium citrate, which does not need to be separated from the polyhydroxy fatty acid amide.

Depending on the needs of a person skilled in the art, the cleaning composition of the invention may contain a greater or lesser amount of various suds reducing agents. High sudsing is generally desirable for dishwashing detergents so that no suds suppressors are used. For washing in top-filled washing machines some foaming limitation may be desirable and for washing in front-filled washing machines a significant foaming limitation may be advantageous. A variety of agents are known to reduce energy and can be selected as desired.

The choice of suds control agent or mixtures of such agents for each particular detergent composition depends not only on the content and amount of polyhydroxy fatty acid amide used, but also on the content of other detergent ingredients. For use with polyhydroxy fatty acid amides, various types of icon-based suds suppressors seem to be more effective (i.e., less can be used) than different types of suds-suppressors.

Particularly preferred are the foaming-limiting strength of the icon designation agent

AE X2-3419, Q2-3302

DC-544 (Dov

Corn i ng).

Those skilled in the art of laundry detergent compositions containing soil release additives may choose from a variety of agents (described, for example, in U.S. Patent Nos. 3,962,152, 4,116,885, 4,237,531,

702857, 4 721580 and 4,877896). Additional soil release agents include a nonionic oligomeric esterification reaction product of a mixture comprising a C 1 -C 4 alkoxy-terminated source of polyethoxy units (e.g.

CH 3 [OCH ₂ Cl ₂ 16H), a source of terephthaloyl units (e.g. dimethyl terephthalates), a source of poly (oxyethylene) oxy units (e.g. polyethylene glycol 1500), a source of oxisopropyleneoxy units (e.g. 1,2-propylene glycol) and a source of oxyethyleneoxy units (especially ethylene glycol) The ratio of oxyethyleneoxy units ^: oxyisopropyleneoxy units of at least about 0.5 ^: 1. Such nonionic soil release agents have the general formula:

CH ₂ O) y

(CH ₂ CH ₂ O) x R ¹ wherein R ¹ represents a lower alkyl group (for example having 1 to 4 carbon atoms), especially a methyl group, x and y in each case an integer of about 6 to about 100, m an integer of about 0.75 to about 30 , an integer of about 0.25 to about 20, and R ^{2 is a} mixture of hydrogen and methyl groups at a molar ratio of oxyethyleneoxy oxyisopropyleneoxy of at least about 0.5 L.

Another preferred type of soil release agent is the anionic agent generally described in U.S. Pat. No. 4,877,896, provided that such agents are substantially free of monomers

R is propylene or higher alkyl

HpROH, where it means soil release agents

No. 877896, as in the United States Example, the ether oil, ethylene glycol, group. As a patent, the reaction product of propylene glycol additional agent is used

1,2- and 3-di-benzoic acid sulfide-disinfecting agents may contain, for example, the reaction product of dimethyl terephthalate, ethylene glycol,

5 th three uinsu 1 f oixophthala a

3-sodium sulfobenzoic acid.

Such agents are preferably used in granular detergent compositions.

The person skilled in the art can also determine that it is advantageous to use non-perborne whitening agents and additives, especially in high-duty granular detergent compositions. Various peroxy bleach additives are commercially available and can be used, but percarbonates are common and economical.

The compositions according to the invention may contain solid percarbonate additives, generally in the form of the sodium salt and in an amount of from 3 to 20, preferably from 5 to 18% and in particular from 8 to 15%.

Sodium percarbonate is an additive and corresponds to the formula 2Na2CO3-3H2O and is commercially available as a crystalline solid. The most common material includes a small amount of heavy metal sequestrants such as ethylenediaminetetraacetic acid (EDTA), 1-hydroxyethylidene-1,1-diphosphonic acid (HEDPO) or amine phosphonates which are introduced during production. According to the invention, the percarbonate is introduced into the detergent composition without further protection, but preferably such composition is used in coating form. Although a wide variety of coatings can be used, the most economical is sodium silicate with a silica ratio of sodium 1.6 to 1.8-1, preferably 2.0 to 1, used as an aqueous solution and dried to a weight of 2 to 10%, as a rule 3 to 5% of a silicate dry weight by weight of percarbonate. Magnesium silicate and a chelating agent, for example, may also be used to form the coating.

The particle size of the crystalline percarbonate is 350 to 450 microns with a mean size of approximately 400 microns. After optional coating, the crystals have a size of 400 to 600 microns.

Although the heavy metals contained in the sodium carbonate used for the production of percarbonate can be limited by incorporating sequestering agents into the reaction mixture, the percarbonate must always be protected from heavy metal clays contained as impurities in other detergent ingredients. It has been found that the total content of iron, copper and manganese ions should be less than 20 ppm in order to avoid an unacceptable adverse effect on percarbonate stability.

Example 33

This example illustrates the composition of a modern condensed detergent in the form of granules.

Component Mass quantities (%) The C 14 -isalkyl-alkylsulfonic acid was acidified to 13,00 CI4-isa1kylpolyetoxy (2.25) sulfonic acid they acidified 5.60 C ¹² ' ³ ' and ¹ 'polypolyethoxylate (6,5) 1.45 C12-14 fatty acid N-methylglucamide 2.50 sodium aluminosilicate (such as Zeolite A, 2 to 5 micron size) 25.20 crystalline layered silicate builder ¹ 23,30 citric acid 10.00 sodium carbonate to achieve pH 9.90 sodium polyacrylate (molecular weight 2,000 to 4,500) 3.20 diethylenetriaminepentaacetic acid 0 "45 Savinase ² 0 "70 6-nonanoylamino-6-oxo-peroxykaproová they acidified 7.40 sodium peroxyborate monohydrate 2, 10 nonanyloxybenzenesulfonic acid 5.00 optical brightener 0.10

¹ layered silicate builders are known in the art. Layered sodium silicates are preferred. For example, layered sodium silicate builders are described in U.S. Patent 4,666,559 (HP Rieck, May 12, 1987). For example, a layered silicate builder of the company SKS-6 is suitable

Hoechst ² product company

Novo Nordisk

A / S, Copenhagen

Highly preferred are granules of this type which contain approximately

0.0001% to about 2% of an active acid enzyme of about 1% and in particular granules,% of polyhydroxy fatty acid whose anionic surfactant is not an alkylbenzenesulfonate surfactant

Example 34

This example illustrates a detergent composition with a perborate bleaching additive and a bleach activator additive according to the invention, which is prepared by mixing the ingredients in a mixing drum.

In this case, Zeolite A is a hydrated crystalline Zeolite A containing about 20% water and having a mean particle size of 1 to 10, preferably 3 to 5 microns. LAS means linear sodium alkylbenzenesulfonate having an average of 1.2.3 carbon atoms in the alkyl moiety. AS is sodium alkyl sulfate with 14 to 15 carbon atoms in the alkyl moiety. By nonionic surfactants is meant a coconut alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol and a stripped nonethoxylated and monoethoxylated alcohol, also referred to as CnAE6, 5T. DTPA refers to sodium diethyltetramine pentaacetate.

Parts by weight of the composition% granules

Basic granule ¹ 51.97 100.00 AS 9.44 18.16 LAS 2.92 5.62 at 1 hour 4.47 8.60 sodium silicate (ratio 1,6) 1.35 2.60 sodium sulfate 6.47 12.45 sodium polyacrylate 2.61 5.02 PEG 8,000 1.18 2.27 nonionic surface active ingredients 0.46 0.89 sodium carbonate 13.29 25.57 of the brightener 0.20 0.38 and 1 µm sodium sodium nitrate 9.11 17.53 DTPA 0.27 0.52 perfume 0.20 0.38 NAPAA granula ² 6.09 100.00 NAPM 2.86 49.96 LAS 0.30 4.93 S force? 3Π cl ΖΙΠθΞ 2.93 48.11 NOBS granula ³ 3.88 100.00 NOBS 3.15 81.19 LAS 0.12 3.09 PEG 8,000 0.19 4.90 Differently 0.42 10.82 Zeolite granules ⁴ 12,00 100.00 and sodium luminosilate 7.39 61.58 PEG 8,000 1.50 12.47 nonionic surface active agents 1.16 9.70 in 1 hour 1.66 13.83 Differently 0.29 2.42 rharium SKS-6 layered silicate 15.84 protease (0.078 mg / g potency) 0.52 sodium perborate monohydrate 1.33 acid to ctrone 6.79 Ci 2 -1 <4 N -methy 1 g 1 ukam i d 1.58 pretty 100.00

^{1 The} basic granules are prepared by spray-drying a mixture of the above ingredients ² A freshly prepared wet cake of a NAPAA sample is prepared which typically contains about 60% water by weight, about% available oxygen about 36% NAPAA and as (AvO) peroxyacids (corresponding to material). is a crude reaction product of NAPAA (adipic acid monononylamide), sulfuric acid and hydrogen peroxide, to which is subsequently added water, filtering, washing with distilled water, phosphate buffer, and suction filtration to obtain a wet cake.

and finite

A portion of the wet dries in the air at a dry sample, which as a rule cake is measured.

contains about 90% NAPAA) and about 1.0% unreacted material. After drying, the sample has a pH of about 4.5.

NAPAA granules are prepared by mixing approximately 51.7 parts dry

NAPAA cake (containing 10% unreacted material), approximately

11.1 parts of a linear alkyl benzene sulphonate (LAS) paste with an average number of carbon atoms in the alkyl fraction

12.3 (45% active ingredient), approx

43.3 parts of sodium sulfate and about 30 parts of water in the mixer

Cuisinart.

After drying, the granules (which contain about 47% NAPAA) are passed through a Tyler rnesh # 14 sieve and any particles not passed through the Tyler Mesh # 65 sieve are left. The mean particle size of the peroxyacid amide (agglomerate) is approximately up to 40 microns and the mean particle size is approximately 10 to microns according to Malvern particle size analysis.

³ NOBS (nonanoyloxybenzenesulfonate) granules are prepared according to the method of U.S. Pat. No. 4,997596 to Bovling et al.

March 1991).

^The zeolite granules have the following composition and are prepared

Zeoitite A with PEG 8,000 and CnAE6,5T in an Eirich high energy mixer

Weight parts before drying after drying Zeolite A (including bound water) 70.00 76.99 PEG 8,000 10.80 12.49 CnAE6.5T ^M 8.40 9.72 free water 10.80 0.80

PEG B 000 is in aqueous form containing 50% by weight of water and has a temperature of about 12.8 ° C. CnAE6.5T is in liquid form and maintained at a temperature of about 32.2 ° C. The two liquids are combined by pumping through a 12 element static mixer. The binder obtained has an outlet temperature of about 23.9 ° C and a viscosity of about 5,000 mPa s. The weight ratio of PEG 8000 and CnAE6.5T in the static mixer is approximately 72: 28.

The Eirich 80 high-energy mixer works in a batch mode. First, weigh 34 kg of powder into the bowl of the blender

Zeoli here

A. The blender is started, first by rotating the bowl counterclockwise with a new hand with a rotational speed of approximately 75 / min.

rotate the rotor blades clockwise with a speed of 1

800 / min. The binder is then pumped from the static mixer directly into the Eirich high energy mixer

ROS containing zeolite

A. Fast application of the binder is approximately 2 minutes. The blender is then operated for an additional one minute for a total batch processing time of 3 minutes. The batch is then withdrawn and loaded into a fiber drum.

The process is repeated until 225 kg of wet product are obtained. The product is then dried in a fluidized bed at 116-132 ° C. Drying removes most of the free water and yields the final product. The total energy input to the mixer is approximately 1.31 x 1P ¹² erg / kg at a rate of approximately 2.18 x 10 ⁹ erg / kg

Example 35

Granular detergent, suitable for use in relatively high concentrations in automatic front-loading washers, used mainly in Europe, is suitable for a wide range of temperatures.

Component Mass quantity (¾) SOKALAN CP5 C100% active as Per salt) ¹ 3.52 DEQUEST 2066 (100% active as an acid) ² 0.45 TINOPAL DMS ³ 0.28 magnesium sulfate 0.49 Zeo1 i t A (anhydrous) 17.92 carboxymethylcellulose (100% active) ⁴ 0.47 sodium carbonate 9.44 acidic to thionic acid 3.50 sew the repentant SKS-6 12.90 tallow alkyl sulfate (100% active, Per salt) 2.82 C 14-15 alkylsulfate (100% active. Per salt) 3.50 Cl2-i5alkyl (E0 (3) sulfate 1.76 C18-18 N-methylglucamide 4.10 DOBANOL Ci2-15EO (2) 3:54 LIPOLASE (100,000 LU / g) ⁵ 0.42 SAVINASE (4.0 KNPIJ) ⁶ 1.65 mullets 0.53 X2-3419 0.22 starch 1.08 stearyl 0.35 sodium peroxycarbonate (coated) 22,30 tetraethylethylenediamine (TAED) 5.90 zinc phthalocyanine 0.02 water (ex zeolite) to 100,%

¹ SOKALAN is sodium polyacrylate / inaleát Hoechst t pentafosfónometyldietyléntriairiín ^{2 3} Monsanto optical brighteners Ciba Geigy * ⁴ product FINNFIS of Metasaliton ⁵ LIPOLASE lipolytic enzyme of ⁶ Novo Savinase protease enzymes of Novo ⁷ X2-3419 is sllikonový antifoaming agent Company and Dow Corn i ng

The process for preparing granules includes, for example, various tower drying, agglomeration, dry blending. Percentages are by weight.

1. Wooden and spray-dried

Using conventional methods, it is crushed and spray dried.

van ím ^: SOKALAN CP5 3.52 DEQUEST 2066 00:45 TINOPAL DMS 0.28 magnesium sulfate 00:42

Zeolite A in anhydrous form

7.10% of boxes of ethylcellulose

0.47%

B. Agglomerates of surfactants

BI. Agglomeration of tallow alkyl sulfate salt and C12-15E0 (3) sulfate sodium salt% active tallow alkyl sulfate paste and 70% sodium salt of C12-15L (3) sulfate salt are agglomerated with zeolite A and sodium carbonate according to the formulation (detergent additive) after drying the agglomerate) tallow alkyl sulfate

C12-15 E0 (3) sulfate

Sodium carbonate

2.82%

1,18%

5 ^ 30%

4.50%

B2. C15-C15 alkyl sulfate agglomerate and C12-C15 alkyl ethoxylate, Dobanol

C12-15E0 (3) and N-methylglucosamide having from 16 to 18 carbon atoms

The C 16 -C 18 glucosamide nonionic material is synthesized with the Dobanol (C 12-15 EOO) contained during the reaction of the methyl ester and N-methylglucamine. C12-15E (3) acts as a melting point depressant, allowing the reaction to proceed without forming undesired cyclic gucosamides.

A surfactant mixture of 20% Dobanol C12-15 E0 (3) and 80% N-methylglucosamide of 16 to 18 carbon atoms was prepared and coagglomerated with 10% sodium carbonate.

Said particles are then coagglomerated with a highly active paste (70

%) sodium alkyl sulfate of up to 15 carbon atoms, p

Dobanol C12-isE0 (3), with Zeolite

And with extra sodium carbonate. The particles obtained exhibit good cold water solubility of N-methylglucosamide having 16 to 18 carbon atoms.

to the composition after drying the agglomerate) has the following composition:

4,10%

Cig-1b N-methyl 1 g1 ukosam i d

Dobanol Ci2-isE0

0,94%

sodium carbonate 4.94 QZ b Zeo1 i t A 5.30 -ABOUT Na C14-15 alkyl sulfate 3.50 about • Na C12-15E0 (3) sulfate 0.59 <JZ -Ό

C. Dry ingredients

The following ingredients are added

peroxycarbonate 22,30% TAED (tetraacetylene iam in) 5,90% SKS 6 silicate from Hoechst 12,90% citric acid 3.50% L i polase 0.42% 100,000 LU / g SAVINAŠE 4,0 KNPU 1,65% Night phthalocyanine (bleach) 0.02% D. Injection DOBANOL Ci2-15E0 2,60% perfume 0.53% E- Foaming suppressant

Force iconic suds suppressor X2-3419 (95 to 97% high molecular weight linear silicone, 3 to 5% hydrophobic silica (Dov Corning) coagglomerates with Zeolite A (size

r.

2 to 5 microns), with starch and a stearyl alcohol binder. These particles have the following composition:

Zeolite starch

X2-3419

0.22%

1,08%

0.22% stearyl alcohol

0.35%

The prepared detergent has excellent solubility, higher performance and excellent foam control when used in European automatic washing machines, for example using 85 g of AEG detergent for wash cycles at 30 ° C, 40 ° C, 60 ° C and 90 ° C .

Example 36

In all of the foregoing examples, the fatty acid glucamide surfactant can be replaced with an equivalent amount of mal tamide surfactant or a surfactant glucanide / maltamide mixture derived from natural sugar sources. In the detergent compositions of the invention, the use of ethanolamides appears to help maintain cold stability of the finished detergent compositions. In addition, the use of sulfobetaine (such as sultaine) surfactants shows increased foaming.

For detergents where high sudsing is desired (e.g. in the case of dishwashing detergents), it is preferred that they do not contain any suds suppressors. Since fatty acids containing 14 or more carbon atoms can act as suds suppressors, it is preferred that the dishwashing compositions contain less than about 5% by weight, preferably less than about 2%, fatty acids of 14 or more carbon atoms, and in particular, to contain no fatty acids with or more carbon atoms. Therefore, those skilled in the art should avoid, in the case of high suds cleaners, introducing an amount of such suds suppressing fatty acids into high suds cleaners containing polyhydroxy fatty acid amides and / or avoid the formation of 14 or more carbon fatty acids when storing finished cleaning compositions according to the invention. A simple method is the use of ester reagents with 12 and thiamine and carbon for the preparation of polyhydroxy fatty acid amides.

Fortunately, the use of amine oxide or sulphobetaine surfactants can prevent negative. effects on foaming caused by fatty acids.

A person skilled in the art _intending to add anionic brighteners to liquid cleaning compositions containing relatively high concentrations (e.g., 10% or greater) of anionic or polyanionic substituents such as polycarboxylate builders may find it beneficial to prepare an optical brightener premix with water. and polyhydroxy fatty acid amide and then introducing the premix into the finished detergent composition.

In the case of detergents containing zeolite builders, polyglutamic acid or polyaspartic acid may be used as dispersants.

Examples of suds suppressors include AE liquid or flakes and DC-544 (from Dow Corni ng).

Those skilled in the art will recognize that the preparation of polyhydroxy fatty acid amides using disaccharides and higher carbohydrates such as maltose results in the formation of polyhydroxy fatty acid amides wherein the linear substituent Z is protected by a capped polyhydroxy ring structure. Such materials are fully encompassed within the scope of the invention and thus do not depart from the scope of the invention.

Industrial usability

Liquid or solid detergent with a limited foaming content of polyoxyethylene polymers in a given ratio is suitable for washing laundry and without limiting the washing machine.

i * λγ ι-: νγ by vi-: häroicy

Claims (12)

CLAIMS 1. A detergent composition comprising an alkyl sulfate and a polyhydroxy fatty acid amide, liquid or solid with limited foaming, comprising: (a) at least 1% of a polyhydroxy fatty acid amide of the formula I 0 R ¹ L ^R2 - C - N - Z b (I) wherein ri R ² is H, a hydrocarbon group having 1 to 4 carbon atoms, A 2-hydroxyethyl group, a 2-hydroxypropyl group, or a mixture thereof. a C 5 -C 31 hydrocarbon group and a linear hydrocarbon polyhydroxy hydrocarbon group; b) at least 1% behind the chain c) and at least three per chain or alkylsulfate hydroxyl groups, directly an alkoxylated derivative thereof. a surfactant, and preferably a suds suppressor, a weight ratio of (a) (b) 1 to a suds in an amount. 10 to 10 - 1. A cleaning composition according to claim 1 1, characterized by. comprising at least 3% by weight of polyhydroxy fatty acid amide with at least 3% of alkyl sulfate at a weight ratio of 6 = 1 to 1; 6th A cleaning composition according to claim 2, characterized in that. The composition further comprises from about 1% to about 30% by weight of ancillary surfactants selected from the group consisting of alkylbenzene sulfonate surfactants, alkyl ester sulfonate surfactants, alkyl ethoxylate surfactants, alkyl polyglycoside surfactants, paraffin sulfonate surfactants or a mixture thereof. . 4- A detergent composition according to claim 1, characterized in that it comprises suds suppressors selected from the group consisting of silage conical hydrocarbons, monostearyl phosphate agents for foams and foams, and mixtures thereof. The cleaning composition according to claim 1, characterized in that it comprises at least 0% by weight of fatty acid monocarboxylate or a salt thereof as a suds suppressor. 6th A detergent composition according to claim 1, wherein in formula I, R ^{1 is a} methyl group. ^R2 alkyl or alkenyl group of from 11 to And Z is a group of formula -CH ₂ (CHOH) _n CH ₂ OH, -CH (CH ₂ OH) (CHOH) 1 -CH ₂ OH, or -CH ₂ - (CHOH) ₂ (CHOR) (CHOH) -CH ₂ OH wherein n is an integer from 3 to 5 inclusive and R is a hydrogen atom or a cyclic or aliphatic monosaccharide group. 7. A detergent composition according to claim 1 wherein Z is a maltose group. A detergent composition according to claim 1, characterized in that in formula I Z is a group derived from a mixture of monosaccharides, disaccharides and optionally higher carbohydrates, containing at least 1% by weight of at least one disaccharide, preferably maltose. A cleaning composition according to claim 1, characterized in that. that further comprises at least 20 wt 1% detergency builder. A cleaning composition according to claim 9, characterized in that. (a) at least 1% of a polyhydroxy fatty acid amide of the formula I OR ^{1 R2} - C - N (I) wherein R ^{1 is} methyl. ^R2 alkyl or alkenyl group having 9 to 17 carbon atoms Z is a glycityl group derived from reducing sugars, preferably an N-methylglucamide group 11 to 17 carbon atoms, a group N-methylImaltamide with 11 to 11 Or a mixture of such glucamide and maltamide groups, or alkoxylated derivatives thereof; and b) at least 1% of an alkyl sulfate surfactant of 14 to 18 carbon atoms in the J-moiety. with a weight ratio of component (a) (b) of 1.25: 1 to 1: 6. preferably 1.25 1 to 1-4. 11. A method according to claim 1, characterized in that the washed fabrics are contacted with a water bath containing a cleaning agent according to claim 1. A process according to claim 11, wherein Z is a group derived from a mixture of monosaccharides, disaccharides and polysaccharides available from plant sources. A process according to claim 11, characterized in that in formula I, R ^{2 represents an} alkyl or alkenyl group having 15 to 17 carbon atoms or a mixture thereof. 14. Detergent particles comprising from 5 to 90% by weight of polyhydroxy fatty acid amide and from 10 to 90% by weight of alkyl sulfate surfactant, characterized in that they contain from 1 to 30% by weight of the solubilizing agent.