SK25493A3 - Detergent composition containing polyhydroxy fattydetergent composition containing polyhydroxy fatty acid amide acid amide and alkyl benzene sulfonate - Google Patents

Abstract

Detergent compositions are disclosed containing alkyl benzene sulfonate and certain polyhydroxy fatty acid amide surfactants in combination with suds suppressors or an auxiliary surfactant component, and combinations thereof. Also disclosed is a method for washing substrates using alkyl benzene sulfonate and certain polyhydroxy fatty acid amide surfactants.

Description

Technical field

The invention relates to low-foaming cleansing compositions comprising alkylbenzenesulfonate and polyhydroxy fatty acid amide surfactants.

The state of the art

The ability of detergents to perform well with respect to various types of dirt and cleaning stains on a variety of fabrics that may form the contents of the washing machine as well as to clean other surfaces (e.g., hard surfaces and hair) is of great importance in evaluating such detergents.

One type of such surfactants, which has the importance of an overall excellent ability to remove fats and oils for its wide temperature range (including relatively low temperatures), includes linearly what

LAS containing surfactant systems behave similarly with respect to the removal of fatty oily soils, alkyl sulfonates, alkylethoxylated sulfates, surfactants are typically added to the alkyl ethoxylates and others to promote cleaning action with respect to a wide range of soils and stains (e.g., particulate soils).

It has now been found that laundry detergent surfactant systems comprising a mixture of alkylbenzene sulfonate surfactants and certain polyhydroxy fatty acid amides exhibit excellent cleaning characteristics with respect to a wide variety of dirt and stains, and are particularly well-suited for removing greasy dirt and oils (e.g. lipsticks and cosmetics, shoe polishes). In addition, the fatty acid polyhydroxyainides can be derived mainly or wholly from natural, renewable non-petroleum raw materials.

Many polyhydroxyamides of N-acyl fatty acids are described in the prior art. N-methylglucamides are described, for example, by J.V. Goodby, M.A. Marcus, E.Chin and P. L. Finn in The Thermotropics Liquid-Crystal1ine Properties of Some Straight Chain Carbohydrate ftmphiphiles (Liquid Crystals). 1988, Volume 3. / Number 11. p.1569 - 1281, and A.Muller-Fahrnov, V.Zabel, M.Stifa and R.Hilgenfeld in the Molecular and Crystal Structure of a Nonionic Detergent: Nonanoy1-N-methylglucamide ”( Molecular acrylic structure of nonionic detergents: Nonanoyl-N-methylglucamide, J. Chem. Soc. Chem. Commun., 1986, p. 1573 to 1574.

The use of reagents should be avoided

N-alkyl polyhydroxyamide surfactants more recently pays close attention to use in biochemistry, for example in (e.g., magazine dissociation of biological membranes)

J.E.K.H i 1dretŔ Article:

"N-D-Gluco-N-methy1-alkanamides

Compounds, a

Nev Class of

Non-Ionic

Detergents

for

membrane

Biochemistry

N-D-Gluco-N-methylalkanamide compounds. new detergents for membrane biochemistry. Biochem.

nonionic class

J .. 1982. Vol

207. p.363 to 366.

The use of N-alkylglucamides in detergent compositions is also described. U.S. Patent No. 2965576 (ERVilson, issued December 20, 1960) and British Patent Application No. 809060, published February 18, 1959 (Thomas Hedley & Com. Ltd), disclose detergent compositions containing anionic surfactants and certain amide surfactants. agents that may contain N-roethylglucamide added as a low temperature suds booster. These compounds contain an N-acyl group of a higher straight chain fatty acid having 10 to 14 carbon atoms. These compositions may also contain adjuvants such as 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 compositions such as fluorescent dyes, bleaching agents and perfumes.

U.S. Pat. No. 2,703798 (issued March 8, 1955) (A. M. Schwartz) relates to aqueous cleaning compositions.

containing the condensation reaction product of an N-alkyl glucamide and an aliphatic fatty acid ester. The product of this reaction is reported. It is useful in aqueous cleaning compositions without further purification. It is also known to prepare a sulfuric acid ester of an acylated glucamide as described by A.M.Schvartz in U.S. Pat. No. 2,717,894 (assigned

September 13, 1955).

International Application PCT WO 83/04412. published

December 22, 1983 (J. Childeth) relates to amphiphilic compounds containing polyhydroxylaliphatic groups and is said to be useful for a variety of purposes including the use of surfactant compounds in cosmetics, pharmaceutical compositions in shampoos, lotions, eye ointments such as emulsifiers and release agents for drugs and biochemistry for solubilizing membranes, whole cells or other tissue samples, and for preparing liposomes. Included are compounds of formula R'CON (R) CH2R''and R''CON (R) R ', where R is hydrogen or an organic group. R @ 1 represents an aliphatic hydrocarbon group having at least 3 carbon atoms and R @ 1 is an aldose residue.

European Patent Application No. 0 285768, published October 12, 1988 (H. Kekkenberg et al.), Relates to the use of thickening N-polyhydroxyalkylamides as thickeners in aqueous cleaning systems. Included are amides of the formula R1C (0) N (X) R2, wherein R 1 represents an alkyl group having 1 to 17 carbon atoms (preferably 7 to 17 carbon atoms), R ₂ a carbon atom, an alkyl group having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms) or an alkylene oxide group and X C 4 -C 7 polyhydroxyalkyl, for example Coconut oil fatty acid N-methylglucamide. The 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 alkylarylsulfonates, olefin sulfonates of sulfosuccinic acid polyesters and non-sulfonate fatty acid ether sulfonates. active agents such as fatty alcohol polyglycol ether, alkylphenol polyglycol ether, polyglycol fatty acid ester, polypropylene oxide-polyethylene oxide mixed polymers. For example, paraffin sulphonate / coconut fatty acid glucamide / nonionic surfactant shampoo compositions are disclosed. In addition to the thickening action, N-polyhydroxy fatty acid amides are said to contribute to better skin tolerance of the compositions.

U.S. Patent No. 2,982,237 (issued May 2, 1961) to Boettner et al. Relates to urea-containing detergent bars, sodium lauryl sulfonate nonionic surfactant, and an N-alkyl alkyl glucamide nonionic surfactant selected from the group consisting of N-methyl. , N-sorbityl lauramide and N-methyl, N-sorbitylmyristamide.

Other glucamide surfactants are disclosed, for example, in DT Patent 2226872 (HWEckert et al., Published Dec. 20, 1973), for laundry detergents containing one or more surfactants and builder salts selected from the group consisting of: polymeric phosphates, sequestering agents, scouring alkali improved by the addition of N-celypolyhydroxyalkylamine of the general formula

R 1 C (O) N (R 2) CH 2 (CHOH) _n CH 2 OH wherein R 1 represents an alkyl group having 1 to 3 carbon atoms. R 2 is an alkyl group having 10 to 22 carbon atoms and n is 3 or 4. N-acylpolyhydroxyamylkylamine is added as a soil suspending agent.

U.S. Pat. No. 3,654,166 (HWEckert et al., Issued April 4, 1972) discloses cleaning compositions comprising at least one surfactant selected from the group consisting of anionic, nonionic surfactants, and as a fabric softener. The N-acyl, N-alkylpolyhydroxyalkyl compound of the general formula R1N (Z) C (O) R2, wherein R1 is a C1-C22 alkyl group, R2 is a C7-C21 alkyl group and R1 and R2 contain a total of 23 to 22 carbon atoms. And 39 is a polyhydroxyalkyl group, which may be of the formula -CHa (CHOH) mCHaOH, wherein m is 3 or 4.

U.S. Pat. No. 4,021,139 (H. Moller et al., Issued 3, 3, 1977); relates to skin care cosmetic compositions containing N-polyhydroxyalkylamines which include compounds of the formula R1N (R) CH ( CH0H) m R 2. wherein R 1 represents a hydrogen atom. 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 (granted April 26, 1963 (Commercial Solvents Corporation)) relates to formaldehyde solutions stabilized against polymerization by the addition of amides of the general formula R ¹ -DEC ( ¹ ) G, wherein R is a carboxylic acid group having at least 7 carbon atoms and G a glycitol group with at least 5 carbon atoms.

German Patent Specification No. 1 261861 (No. Heins, assigned February 29, 1968) relates to glucamide derivatives useful as wetting and dispersing agents of the general formula N (R) (R 1 (R 2), where R is a glucamine sugar moiety, an R 1 alkyl group (C až-C a) and R R2 (C ac-C 5).

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

U.S. Pat. No. 3,312,627 (DTHooker, issued April 4, 1967) relates to solid toilet bars which are practically devoid of anionic detergents and alkaline builders and which contain lithium soaps of certain fatty acids, nonionic surfactants selected from certain propylene oxide-ethylenediamine-ethylene oxide condensates propylene oxide-propylene glycol-ethylene oxide condensates and polymerized ethylene glycol and also contain a nonionic foaming component which may contain a polyhydroxyamide of the formula

RC (O) NR 1 (R 2), wherein RC (O) contains from about 10 to about 14 carbon atoms and R 1 and R 2 are each hydrogen or C 1 -C 6 alkyl, the alkyl groups having an aggregate number of carbon atoms of 2 until; about 7, and a total number of hydroxyl group substituents of 2 to about 6. Essentially similar is the subject of U.S. Patent 3,126,626 (D.T. Hooker, issued April 4, 1967).

SUMMARY OF THE INVENTION

It is an object of the present invention to provide at least a low-foaming detergent composition by weight which

1% alkylbenzenesulfonate surfactant.

(a) at least approximately

1% polyhydroxy fatty acid amide of formula

R ¹

U I where means

R ¹ is H, hydrocarbyl having 1 to 4 carbon atoms, 2-hydroxyethylene, 2-hydroxy propyl, or a mixture thereof,

R ² hydrocarbyl group having 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 alkylbenzenesulfonate surfactant, and optionally very preferably

c) a suds suppressor amount of a suds suppressor, preferably selected from monocarboxylic fatty acids and their salts, silicone suds suppressors, monostearyl phosphate agents such as monostearyl-di-alkali metal phosphates and phosphate esters, hydrocarbon suds suppressors, and their % of the mixture, wherein the weight ratio of fatty acid polyhydroxyamide to alkylbenzene sulfonate is about 10 to about 10 = 1. Preferably R ^{1 is} methyl. R ² is a C 9 -C 17 hydrocarbon group and Z is a glycytyl radical. derived from a reducing sugar, and the weight ratio of polyhydroxy fatty acid amide to alkylbenzene sulfonate is about 5 L to about 1 = 5, and in particular about 2 ^: 1 to about 1 = 3.

s

The incorporation of a suds suppressor may be of importance in formulating detergent compositions with alkylbenzene sulfonates and polyhydroxy fatty acid amides, as such a mixture of surfactants often leads to excessive sudsing, which adversely affects the cleaning performance of the washing machine.

The invention also relates to detergent compositions comprising an alkylbenzene sulfonate surfactant and a polyhydroxy ammonium acid such as the foregoing as well as surfactants selected from the group consisting of alkyl sulfonates, alkylethoxylated sulfates, alkyl ethoxylates and alkyl polyglycosides, and mixtures thereof. Such cleaning compositions generally contain from about 1 to about 25% by weight.

such a co-surfactant. In such compositions, the weight ratio of polyhydroxy fatty acid amide to alkyl benzene sulfonate is about 10 = 1 to about 1 = 10. preferably about 5 = 1 to about 1: 5, and especially about 2 = 1 to about 1 = 3. The weight ratio of alkylbenzene sulfonate to such a cosurfactant is preferably about 5-1 to about 1 = 5, preferably about 4 = 1 to about 1 = 1. It is also preferred that the alkyl ethoxy sulfate has an ethoxylation degree of about 0.5 to about 3.0, and in particular about 1.0 to about 3.0.

Additional surfactant auxiliaries may also be included in the detergent composition as well as optimal detergent ingredients and other ingredients known in the art for detergent compositions.

The invention also relates to the cleaning of substrates. such as fibers, fabrics and hard surfaces by contacting such substrates with a cleaning composition comprising an alkylbenzene sulfonate surfactant and a polyhydroxy fatty acid amide, wherein the weight ratio of alkylbenzene sulfonate to polyhydroxy fatty acid amide is about 1 = 10 to about 10 ^: 1 in the presence of water or a water-miscible solvent (such as a primary and secondary alcohol). In such contacting, the cleaned substrate. with cleaning agent promotes mixing cleaning effect. Suitable types of such mixing are the trend of hands, preferably with the aid of a brush or other cleaning device such as an automatic washing machine or a dishwasher. Advantageously, a considerable improvement in the cleaning action can be achieved at higher temperatures, especially with regard to greasy and oily soils.

Particularly advantageous weight ratios of surfactants as well as suds suppressors or, where appropriate, surfactant adjuvants and other detergent adjuvants may be used in this cleaning process.

Polyhydroxy fatty acid amide surfactant

The cleaning composition according to the invention of at least 1% by weight, as a rule, comprises approximately up to approximately 50% by weight, in particular approximately up to approximately 30% by weight, of polyhydroxy fatty acid amide, as a surfactant, as described in detail below.

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

R ¹

II I

R - C - N - Z (I) where is

R ¹ is H, hydrocarbyl having 1 to 4 carbon atoms, 2-hydroxyethylene, 2-hydroxy propyl or a mixture thereof, preferably C1 -C4 alkyl and especially C1 alkyl (i.e., methyl) .

R ^{2 is} a C 5 -C 31 hydrocarbon group, preferably a C 7 -C 17 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 C 11 to C 17 or a mixture thereof;

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

The group Z is preferably derived from a reducing sugar in a reductive amination reaction. Preferably Z is a glucityl 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 may be used as the starting materials as the above sugars. 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 Z is preferably selected from the group consisting of -CH ₂ - (CHOH ₎ -CH ₂ OH, -CH (CH ₂ OH) - (CHOH) _n CH ₂ OH. -CH ₂ - (CHOH) ₂ CCHOR ') (CHOH) -C 6 OH. wherein n is an integer from 3 to 5 and R 'is a hydrogen atom or a cyclic or allyphatic monosaccharide and its alkoxylated derivatives. Most preferred are glycityls wherein n is 4, especially of the formula

-CH ₂ (CHOH) 4 -CH ₂ OH.

In formula (I), R 'may be, for example, N-methyl, N-ethyl, N-propyl. N-isopropyl, N-butyl, Ν-2-hydroxyethyl or Ν-2-hydroxypropyl.

R ² -CO-N? May be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, tallow amide.

For example, Z may be a group

1- deoxyglucityl. 2-deoxyfctityl, 1-deoxymaltityl,

2-deoxylactyl, 1-deoxygalactyl, 1-deoxymanityl or 1-deoxymethylthiotryltyl.

These polyhydroxy fatty acid amides are prepared in a manner known per se. Generally, they are prepared by reacting an alkylamine with a reducing sugar by a reductive amination reaction to form the corresponding N-alkyl polyhydroxyamine and then reacting the N-alkyl polyhydroxyamine with a fatty acid ester or triglyceride in a condensation amidation step to form N-alkyl, N-polyhydroxyalkyl amide. Methods for preparing mixtures containing polyhydroxy fatty acid amides are described, for example, in British Patent Application No. 809060 (Thomas Nedley & Co., Ltd). published Jan. 18, 1959, U.S. Pat. No. 2,965,576 to E.R. Wilson, issued December 20, 1960. U.S. Patent No. 2,737,898 (Anthony M. Schwartz, issued March 8, 1955); and U.S. Patent No. 1,985,424 (Piggott, issued December 25, 1934).

According to one method of preparing N-alkyl or hydroxyalkyl N-deoxyglycitylamides of a fatty acid, wherein the glycityl component is derived from glucose and the N-alkyl or N-hydroxyalkyl group is -methyl, N-ethyl, N-propyl, N-butyl, N -hydroxyethyl or N-hydroxypropyl is prepared by reacting N-alkylglucamine or -hydroxyalkylglucamine with a fatty acid ester selected from fatty acid methyl esters, fatty acid ethyl esters and fatty acid triglycerides in the presence of a catalyst selected from the group consisting of tri-lithium phosphate, tri-lithium phosphate, tricalcium phosphate, tetranium pyrophosphate, pentakalium tripolyphosphate, lithium hydroxide, potassium hydroxide, sodium hydroxide, calcium hydroxide, calcium carbonate, sodium carbonate, potassium carbonate, disodium tartrate, dicalcium tartrate, sodium sodium tartrate, trisodium citrate, tricalcium triate, tricalcium potassium magnesium, basic sodium aluminum sulfate and basic kallumal aluminum sulfate, and mixtures thereof. The amount of catalyst preferably corresponds to about 0.5 mol% to about 50 mol%, preferably about 2.0 mol% to about 10 mol%, relative to the N-alkylglucamine or N-hydroxyalkylglucamine molar basis. The reaction is 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 from about 1 to about 10% by weight of the phase transfer agent relative to the weight of the reaction mixture as a whole, selected from the group consisting of saturated surfactants. fatty alcohol polyethoxylates, alkyl polyglucosides, linear glucamide and mixtures thereof i.

Preferably, the method is carried out such that

(a) preheating the fatty acid ester to a temperature of about 138 to about 170 ° C; ·?

b) add N-alkylglucamine or N-hydroxyalkylglutamine to the heated fatty acid ester and mix until a biphasic liquid / liquid mixture is formed,

c) adding the catalyst to the reaction mixture,

d) stirring the reaction mixture for a given time.

When a triglyceride is 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 component as phase transfer agent.

the glucosylamide fatty acid product to the reaction mixture, based on the weight of the reaction

Thus, the reaction is inoculated

A detailed description of this procedure and thus increase the reaction rate.

is in the Examples section.

Polyhydroxy fatty acid has the advantage to those skilled in the art that from the primary natural degradable event not from the chemical raw materials. These raw materials are acids according to the invention can be fully raw materials, thus providing to prepare in no also little toxic to the environment of natural watercourses.

It should be noted that in addition to the polyhydroxy fatty acid amides of formula (I), some nonvolatile byproducts such as ester amides and cyclic polyhydroxy fatty acid amides are also prepared for their production. The concentrations of these by-products vary depending on the reactants selected and the reaction conditions. Preferably, the polyhydroxy fatty acid amide introduced into the detergent composition is prepared in such form as a composition comprising the polyhydroxy fatty acid amide to contain less than about 10% by weight and preferably less than about 4% cyclic polyhydroxy fatty acid amide. The above-mentioned preferred method of preparation has the advantage of providing rather lower amounts of by-products, including such cyclic amide by-products.

alkyl benzene sulfonate

Alkylbenzenesulfonate surfactants are known in the art. These surfactants include the alkyl with 9 or more carbon atoms, preferably 9 to 18 carbon atoms, and particularly linear alkyl component, wherein the linear alkylbenzene sulfonates ^(LAS) class of commerical surfactants. Particularly preferred are C 10 -C 14 LAS surfactants in the alkyl moiety. These surfactants can be used either in acid or salt form, with soluble salts being preferred. Suitable salts include metal salts (e.g., sodium, potassium and lithium salts) as well as substituted and unsubstituted ammonium salts (e.g., ethanolamines).

The detergent compositions of the invention comprise at least about 1% by weight of alkylbenzene sulfonate, preferably about 3 to about 50% by weight, and especially about 5 to about 30% alkylbenzene sulfonate by weight.

Foaming suppressors

As mentioned above, suds suppressors or suds suppressors may be incorporated into the cleaning compositions of the invention. The incorporation of such suds suppressors herein is desirable since the polyhydroxy fatty acid amides used as surfactants may increase the foaming of the detergent composition. Suds suppressors may be of particular importance if the cleaning compositions comprise a relatively high suds surfactant together with a polyhydroxy fatty acid amide. Suds suppressors are particularly desirable for laundry detergents intended to be washed in a front-load automatic washing machine. These washing machines generally have drums for washing fabrics and a washing bath, the drums having a horizontal axis about which the drum rotates. This type of movement can lead to considerable foam formation and thus to reduced washing efficiency. The use of suds suppressors is of particular importance for high temperature wash conditions (e.g., above about 50 ° C) and high detergent concentrations (e.g., about 1000 to about 3500 ppm).

A variety of compounds are used as suds suppressors. agents; suds suppressors are well known in the art. For example, they are generally described in Kirk Othmer Encyclopedia of Chemical Technology, 3rd Edition, Volume 7, p. 430-447 (John Viley & Sons, Inc., 1979). One category of suds suppressors of particular interest includes monocarboxylic fatty acids and soluble salts thereof. These compounds are described in U.S. Pat. No. 2,954,347 (Vayne St. John, Sep. 27, 1960). The monocarboxylic fatty acids and their salts for use as suds suppressors have a hydrocarbon chain of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable alkali metal salts are, for example, sodium, potassium and lithium salts, furthermore ammonium salts and alkanolammonium salts. These compounds are considered to be preferred suds suppressors.

Cleaning agents may also contain non-surfactant suds suppressors. Such agents include, for example, high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., triglycerides of fatty acids), esters of monovalent fatty acid alcohols, aliphatic ketones of 18 to 40 carbon atoms (e.g., stearone). ).

'W'

Other suds suppressors include N-alkylated aminotriazines, for example, tri- to hexaalkylmellamines or di- to tetraalkyldiaminochlorotriazines formed as the reaction products of a cyanuric chloride with two to three moles of a primary or secondary amine containing 1 to 24 carbon atoms.

propylene oxide; and monostearyl phosphate, for example, monostearyl and phosphate ester monostearyl dialkyl metal phosphate (for example with potassium, sodium or lithium as the alkali metal) and phosphate esters.

paraffin and halogenated paraffin

Hydrocarbons such as can be used in liquid form. Liquid hydrocarbons may be liquefied at room temperature and at ambient pressure and have a pouring temperature of about -40 to about + 5 ° C and a minimum boiling point of not less than about 110 ° C at ambient pressure. The use of waxy hydrocarbons is also known. preferably having a melting point below about 100 ° C. Hydrocarbons constitute a preferred category of suds suppressors for the detergent compositions of the present invention. Hydrocarbon suds suppressors are disclosed in U.S. Patent 4,265,779 (May 5, 1981) to 9andolfo 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 suds suppressors, mixtures of true paraffins and cyclic hydrocarbons.

Another preferred category of suds suppressors is the iconic suds suppressors.

This category includes the use of polyorganosiloxane oils.

such as polydimethylsiloxane, polyorganosiloxane oil dispersions or or emulsions of resins and mixtures of polyorganosiloxane with silica particles.

wherein the chemically polyorganosiloxane is silicon. The Si icon reagents sorbed and deposited on the foam suppressor are well known in the art and are described, for example, in U.S. Patent 4,265,779 (Gandolfo et al., May 5, 1981) and European Patent Application Publication No. 89307851.9, published

February 7, 1990 (Starch M.S.).

Other icon suds suppressors are disclosed in U.S. Patent 3,455,839, which relates to suds suppressing agents and methods for aqueous solutions by incorporating small amounts of polydimethylsiloxane fluids.

Mixtures of silicones and silicone silica are described, for example, in German Published Application No. 2,124526. Si 1 icon antifoams and 1 icon suds suppressors in granular detergent compositions are described in U.S. Patent No. 3,933,672 to Bartolotta et al. and U.S. Patent 4,652,392 (Baginski et al., Mar. 24, 1987).

An exemplary suds suppressor for the purposes of the present invention is an amount of an anti-baking suppressant consisting essentially of the following components:

i) polydimethylsiloxane mm ² / s to about liquid.

1500 mm ² / s having a viscosity at approximately 25 ° C;

up to about (i) about 1 icon resin, composed of (i) about parts by weight per

100 parts of units and units of silicon dioxide at a unit weight ratio (CH3) of 3SIL / 2 (CH3> 3SIL / 2

1.2: 1; and (i) the weight components according to about 1 to about 20 parts per 100 parts of paragraph (i) of solid silica gel.

For any automatic washing machine cleaner, there is a requirement that the foam generated does not flow out of the machine.

The suds suppressors, optionally used, are used in a suds suppressing amount. By a suds suppressor, it is meant that a person skilled in the art will formulate a cleaning composition by selecting the amount of suds suppressor to the extent desired to obtain a low sudsing agent for the automatic buckle. The amount of suds suppressor depends on the surfactant chosen. For example, in the case of high suds surfactants, relatively more suds suppressors are used to achieve the same degree of suds than a less sudsing surfactant. In general, sufficient suds suppressant is used so that the foam formed during the wash cycle (e.g., after mixing the detergent in an aqueous solution at an appropriate bath temperature and the corresponding detergent concentration) does not exceed about 75% of the free volume of the washing machine drum; 50% of this volume, this free volume being given by the difference between the total volume of the drum and the volume of the bath plus the washed fabrics. 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 contain from 0 to about 5% by weight of suds suppressors.

When monocarboxylic fatty acids and salts thereof are used as suds suppressors, they are generally present in an amount of up to about 5% by weight of the detergent composition. Typically, about 5 to about 3¾ by weight of fatty acid monocarboxylates are used as suds suppressors. When 1 iconic agents are used as suds suppressors, they are generally included in an amount of about 2.0% by weight relative to the weight of the detergent, however greater amounts may be used. The upper limit is of a practical nature since it is primarily considered to minimize the cost and efficiency of a smaller amount to effectively reduce foaming. Preferably, the silicone antifoam agents are used in an amount by weight of about 0.019¾ to about 1¾, and in particular in an amount of about 0.25¾ to about 0.50¾. As mentioned above, these percentages by weight include any silica that can be used in conjunction with a polyorganosiloxane, as well as any adjuvants. Monostearyl phosphates are generally used in an amount of about 0.1 to about 2¾ by weight relative to the weight of the detergent composition.

Hydrocarbon suds suppressors are generally used in an amount of about 0.1 to about 5.0% by weight. however, larger amounts may also be used.

The detergent composition of the invention may further comprise a polyhydroxi fatty acid amide and an alkylbenzene sulfonate surfactant such as the foregoing and further a surfactant selected from the group consisting of alkyl sulfonates, alkyl ethoxylated sulfonates, alkyl ethoxylates and alkyl ester sulfonates (especially methyl ester sulfonates) and mixtures thereof. Generally, the detergent compositions of the present invention contain, by weight, about 1 to about 25% by weight of these auxiliary surfactants. In such cleaning compositions, the weight ratio of polyhydroxy fatty acid amides to alkylbenzene sulfonate is about 10 = 1 to about 1:10, preferably about 5 = 1, and especially about 2 = 1 to about

1 = 3rd The co-surfactant of this embodiment is preferably comprised in a weight ratio of polyhydroxy fatty acid amide to co-surfactant of about 10 = 1 to about 1 = 10. preferably

5 ^: 1 to 1 = 5. When an alkyl sulphate or an alkylethoxylated sulphate or mixtures thereof is used as the auxiliary surfactant. the weight ratio of alkyl sulfonate to these co-surfactants is preferably about 4 = 1 to 1 = 1; It is also preferred that the degree of ethoxylation of the alkylethoxylated sulfate is about 0.5 to about 3.0, especially 1.0 to approximately / 3.0. For detergent compositions according to the invention intended for washing at temperatures above 50 ° C, alkylsuldates having from 16 to 18 carbon atoms in the alkyl moiety are preferred.

Additional surfactant auxiliaries and, where appropriate, detergent adjuvants known to those skilled in the art may be incorporated into the detergent compositions of the present invention. Such co-surfactants are generally present in an amount of 0 to about 25% by weight relative to the weight of the cleaning composition, and may be included in the absence of any of the above-mentioned preferred co-surfactants. It is further stated, without any deliberate limitation, that the cleaning compositions of the invention may contain alkylphenol ethoxylates, paraffin sulfonates and alkyl ester sulfonates. Such auxiliary surfactants are discussed in detail below.

Nonionic auxiliary surfactants

Anionic surfactants suitable for detergent use include salts (including, for example, sodium, potassium ammonium, and substituted ammonium salts, e.g., mono-ethanolamine, diethanolamine, and triethanolamine salts) of soaps, primary or secondary C8-C22 alkanesulfonates, with an olefinic olefin share; Sulfonated polycarboxylic acids prepared by sulfonating a pyrolyzed alkaline earth metal citrate product, such as described in British Patent No. 1,082,179, alkyl glycerol sulfonates. fatty acylglycerol sulfonates, fatty alkylene phenylethylene oxides and detersulfates, alkyl phosphates, isothionates such as oleyl glycerol sulfonates. paraffin sulfonates such as acyl isobutyls;

N-aceltauráty. methyl tauride fatty acid amides, alkyl succinates and sulfosuccinates. sulfosuccinate monoesters (especially saturated and unsaturated monoesters of 12 to 18 carbon atoms), sulfosuccinate diesters (especially saturated and unsaturated di-ethers of 6 to 12 carbon atoms,), N-acyl sarcosinates, alkylpolysaccharide sulphates, such as sulphated alkylpolyglucosisates ), branched primary alkyl sulfates, and alkyl polyethoxy carboxylates such as of the formula R 0 (CH2CH20) kCH2C00-M ⁺ wherein R is an alkyl group having 8 to 22 atómammi alkyl, k is an integer from 0 to 10, and M is a cation forming a soluble salt, and fatty acids esterified with isethionic acid and neutralized with sodium hydroxide. Resin acids and hydrogenated resin acids such as rosin acids, hydrogenated rosin and resin acids and hydrogenated resin acids contained in tall oil are also suitable. Further examples of such anionic surfactants are described in Surface Active Agents and Detergents (Volumes I and II, Schvartz, Perry and Berch). A variety of such surfactants are also described in U.S. Pat. No. 3,929,678 (Laughlin et al., Dec. 30, 1975), column 23, line 58 through column 29, line 23.

Preferred co-surfactants are alkyl sulfate surfactants. These agents include water-soluble salts or acids of the general formula ROSCHM, a hydrocarbon group or a hydroxyalkylalkyl wherein R is preferably carbon, especially alkyl carbon atoms and especially 12 to 18 carbon atoms and, for example, an alkali or lithium cation), a substituted group, e.g. a trimethyl ammonium group having from 10 to 24 atoms, a group having from 10 to 20, or a hydroxyalkyl group is a carbon or cation of a metal (e.g., sodium, potassium or unsubstituted ammonium methylammonium, dimethyl ammonium and quaternary ammonium groups).

for example a tetramethylammonium and dimethylpiperidinium group and a cation derived from alkaloamines such as ethanolamine, diethanolamine, triethanolamine and mixtures thereof. An alkyl chain of up to 18 carbon atoms is preferred for higher temperatures (above about 50 ° C). C 12 -C 16 alkyl chains are preferred for washing temperatures of about 50 ° C and lower temperatures.

A further category of active agents are the active agents. Such useful anionic surfactant alkylalkoxylated sulfate surfactants are soluble salts or acids of the general formula R0 (ä) iqSO3M, wherein

R is an unsubstituted (C až-C alebo) alkyl or (C až-C, hydroxy) hydroxyalkyl group, especially a Cal-C 20 alky (C až alky alky) alkyl or hydroxyalkyl group, and especially a C až až 18 (C alky alky alky) alkyl group. A is ethoxy or propoxy, m is greater than 0, generally about 0.5 to about 6, especially about 0.5 to about 3, and M is a hydrogen atom or a cation, which may be, for example, a metal cation (e.g. sodium, potassium, lithium, calcium, magnesium) and an ammonium or substituted ammonium cation. Alkyl ethoxylated sulfates as well as alkylpropoxylate sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl ammonium, ethylammonium and trimethylammonium cations, and quaternary ammonium cations such as tetramethylammonium, dimethylpiperidinium, cations and cations derived from an alkanolamine alkyl, such as a monoethanolamine, a monoethanolamine, a monoethanolamine with an alkyl portion of an alkylpolyethoxylate (2.25) sulfate with an alkyl portion of an alkylpolyethoxylate (3.0) sulfate with an alkyl portion and an alkylpolyethoxylate (4.0) sulfate with a mixture thereof. Than

agents are mentioned 12 until 18 carbon atoms (C12 -CieEd. 0)), 12 until 18 carbon atoms (Cl 2 18 E (2.25) M), 12 until 18 carbon atoms (C12 CIEE (3.0) M) 12 until 18 carbon atoms

wherein M generally represents in the alkyl moiety (C 12 -C 16 E (4.0) M), sodium or potassium.

Alkyl ester sulfonate surfactants include linear esters of C8-C20 carboxylic acids (i.e., fatty acids). which are sulfonated with sulfur trioxide gas, as reported in The Journal of the American Oil Chemist Society, 52 ¢ 1975), p. 323 to 329. Suitable fats are, for example, natural fats such as tallow and palm and coconut oil.

Preferred alkyl ester sulfonate / surfactants, especially for laundry purposes, include alkyl ester sulfonate surfactants of the general formula (I).

R ³ -CH-C-OR ⁴

I

Where SO3M means

R ^{3 is} a C 8 to C 20 hydrocarbon group, preferably an alkyl group or a mixture of such alkyl groups;

R ^{4 is} a C 1 -C 6 hydrocarbon group, preferably an alkyl group or a mixture of such alkyl groups, and

The cation which forms the water-soluble alkyl ester sulfonate salt i.

Suitable salt-forming cations are metal cations, for example sodium, potassium and lithium, and substituted or unsubstituted ammonium cations, for example monoethanolamine, diethanolamine and triethanolamine cations and quaternary ammonium cations, for example tetramethylammonium and odoromethylamine and dimethylpyridine, 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.

In addition to the anionic surfactants, the detergent compositions of the invention may comprise additional nonionic surfactants and other surfactants.

Auxiliary nonionic surfactants

Suitable nonionic surfactant detergents are generally disclosed in U.S. Pat. No. 3,929,678 (Laughlin et al., Issued Dec. 30, 1975), column 13, line to column 16, line 6. The following are exemplary but not limiting classes of suitable nonionic surfactants. agents =

1. Polyethylene oxide, polypropylene oxide condensates of alkylphenols. These surfactant and polybutylene oxide compounds include condensation products of alkylphenols having an alkyl moiety of 6 to 12 carbon atoms in a straight or branched chain configuration with alkylene oxide. Preferably, it is contained in an amount of about ethylene oxide per mole of alkyl phenol. surfactants of this type are ethylene oxide 5 to about 25 moles. Commercially available nonionic are, for example, Igelpal ™ C0-630 from GAF Corporation and Triton ™ X-45. X-114, X-100 and X-102, all of the Rohm & Haas Company products. The above compounds may be referred to as alkylphenolalkoxylates, for example alkylphenol ethoxylates.

2. The condensation products of aliphatic alcohols with about 1 to 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. Of particular note are the condensation products of an alcohol having alkyl groups of about 10 to about 20 carbon atoms with about 2 to about 10 moles of ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this type are Tergitol (TM) 15-S-9 (9 to 10 moles ethylene oxide linear alcohol condensation product), Tergitol (TM) 24-L-6-NMW (primary alcohol condensation product) 12 to 14 carbon atoms with 6 moles of ethylene oxide and narrow molecular weight distribution), both of which are products of Uion 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 (the condensation product of a linear lacquer alcohol of 14 to 15 carbon atoms with 7 moles of ethylene oxide). Neodol ™ 45-4 (condensation product of 14 to 15 carbon atoms of linear moles with 4 moles of ethylene oxide), always from Shell

Chemical Company and Kyro ™ EOB (condensation product of a C13-C15 alcohol with 9 moles of ethylene oxide) from the Procter & Gambia Company. These surfactants may be referred to as alkyl ethoxylases.

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 1500 to 1800 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 approximately 50% by weight based on the total. which corresponds to the condensation of up to about 40 moles of ethylene oxide. 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 the product consists of the reaction product of ethylenediamine and an excess of propylene oxide and generally has a molecular weight of about 2500 to about 3000. This hydrophobic portion is condensed with ethylene oxide to such an extent that the condensation product contains about 40 to about 80% polyoxyethylene. Examples of this type of nonionic surfactant are the commercially available Tetronic ™ compounds from BASF.

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

R ³ (OR ⁴ ) x N (R 5) ₂ where is

R ³ an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from 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 approximately 1 to 3 ethylene oxide groups, wherein the R ⁵ groups can be bonded to one another, for example by means of an oxygen or nitrogen atom, to form a ring structure.

These amine oxide surfactants particularly include C 10 -C 18 alkyldimethylamine oxides and C 8 -C 8 alkoxyethyldihydroethylamine oxides.

6. The alkylpolysaccharides disclosed in U.S. Patent 4,556,547 (Llenado, Jan. 21, 1986) have a hydrophobic group containing from about 6 to about 30 carbon atoms.

preferably about 10 to about 16 carbon atoms and a polysaccharide.

for example, a polyglycoside as a hydrophilic moiety containing 1.3 about 3 and up to about 10, preferably about 1.3 to especially about 1.3 to about 2.7 saccharide 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 moiety is bound at the 2.3.4 position, etc., and also provides glucose or galactose over a glucoside or galactoside.) The intersaccharide linkages may, for example, be between the area of the additional carbohydrate units and the patches of the 2,3,4 or 6 preceding carbohydrate units.

Alternatively, but less desirable, the plyalkylene oxide chain may bind a hydrophobic moiety and a polysaccharide moiety. The preferred alkylene oxide is ethylene oxide. Typical hydrophobic groups are alkyl groups, either saturated or unsaturated, branched or unbranched, containing from 8 to 18 carbon atoms, preferably from 10 to 16 carbon atoms; Preferably, the alkyl group is a straight chain saturated alkyl group. The alkyl group may contain up to 3 hydroxy groups 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, nonydecyl, undecyldodecyl, tridecyl tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl di-, tri-, tetra-, penta- and hexaglucosides, galactosides, lactosides, glucose, fructose, fructose or fructose. Suitable mixtures include coconut alkyl, di-, tri-, tetra and pentaglucosides and tallow alkyl tetra-, penta and hexaglucosides.

The preferred alkylpolyglycosides have the formula R ² 0 (C _n H ₂ n0) t (glycosyl) x wherein R ² is alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein the alkyl groups contain 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 from a source of glucose to form a glucoside (bound at the 1-position). The additional glycosyl units may then bind between their 1-position and the preceding glycosyl units at the 2,3,4-position;

6. preferably predominantly in position Second 7. Fatty amide of as surface active agent of the general formula 0 H R ⁶ - C - N (R ⁷ ) ₂

wherein R ⁶ represents an alkyl group having 7 to 21 carbon atoms, preferably 9 to 17 carbon atoms and

R ⁷ is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl and - (C 2 H 4 O) x H where x is about 1 to about 3.

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

Cationic surfactants; :

! r

Cationic detergent surfactants can also be incorporated into the detergent 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 ² R ⁵ N ⁺ X where

R ^{2 is an} alkyl or alkylbenzyl group of from about 8 to about 18 carbon atoms in the alkyl moiety;

R ^{3 is} each -CH 2 CH 2 -. -CH ₂ CH (CH 3) -, CH 2 CH (CH 2 OH) -. -CH 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 combining two R ⁴ groups, -CH 2 CHOH-CHOHCOR ⁶ CHOHCH ² OH. wherein R ⁶ represents any hexox or hexose polymer having a molecular weight of less than about 1000 and a hydrogen atom when y is not zero;

R ⁵ has the same meaning as R ⁴ or denotes an alkyl chain wherein the total number of carbon atoms R ² plus R ⁵ is not more than about 18;

γ 0 to about 10 and the sum of γ values is 0 to about 15 and x any compatible anion.

Other cationic surfactants suitable for use in the detergent compositions of the present invention are described in U.S. Patent 4,222,444 (Cambre, Sep. 14, 1980).

Other auxiliary surfactants

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. as a rule 8 to 18 carbon atoms and at least one contains an anionic water-soluble solubilizing group, for example, carboxy, sulfonate and sulfate groups, No. 3,929,678 (Laughlin and Col. 19, line 18-35), surfactants.

According to U.S. Pat

Both surfactants can also be incorporated into the detergent compositions of the invention. These surfactants are described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary sulfonium compounds. Examples of useful zwitterionic surfactants are described in U.S. Pat. No. 3,929,678 to Laughlin et al., Issued December 30, 1975, column 19, line 38 through column 22, line 48.

Ampholithic and zwitterionic surfactants are generally used in admixture with one or more anionic or nonionic surfactants.

builders

The detergent composition of the invention may also contain inorganic or organic detergency builders to control mineral hardness.

The builder concentrations vary widely depending on the end use of the detergent composition of the invention and its physical form. Liquid cleaners generally contain at least 1¾ by weight. in particular about 5 to about 50% and in particular about 5 to about 30% 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 80% by weight

50¾ detergency builders. However, greater or lesser amounts of such buileders 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, soda carbonates, carbonates, silicates, carboxylates, silicates, carboxylates, silicates, carboxylates, silicates , sulphates and aluminosicates. Borate builders as well as builders containing borate-forming 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, especially silicas having a silica: sodium oxide ratio of 1.6 = 1 to 3.2 = 1 and layered silicates, which are described in U.S. Patent 4,666,839 ( HPRieck, 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 component of a suds suppressor system.

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. 2,332,100, published November 5, 1973.

Aluminumuminate builders are particularly preferred according to the invention. Aluminosilicate builders are very important in the commercially most common granular detergent compositions which are subject to high hollow requirements and may also be an important component in liquid detergent compositions. Aluminosilicate builders include compounds of formula

M 2 (from A 102, Y 5 and O 2) wherein M represents sodium, potassium, ammonium and substituted ammonium;

from about 0.5 to 2; y 1; the material comprising magnesium in an ionic capacity of at least about 50 milligrams equivalents of calcium carbonate hardness per gram of anhydrous aluminosic acid. Preferred aluminosilicates are zeolite builders having the general formula

Na 2 L (A 102) 3 SiO 2 → y 1 .XH 2 O, wherein z and y is an integer of at least 6. The molar ratio of z = y is 0, 0 to about 0.5 and x is an integer of about 15 to about 264.

Useful aluminum ion exchange materials are commercially available. These aluminosilicates may be crystalline or amorphous and may be naturally occurring aluminosilicates or aluminosilicates synthetically derived. A process for the preparation of aluminosic ion exchange materials is described in U.S. Pat. No. 3,985,669 to Krummel et al.

1976). Preferred synthetic, crystalline aluminosilicate ion exchange materials suitable in accordance with the invention are commercially available under the designations Zeolite A, Zeolite P (B) and Zeolite X. According to a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has the general formula

Nai2 I (AIO2) i2SiO2 1 -ΧΗ2Ο where x is approximately 20 to approximately 30 and especially approximately

This material is known as Zeolite A. Preferably, the aluminosate has a particle diameter of about 0.1 to 10 microns.

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

Examples of phosphonate builder salts include the water-soluble salts of ethane-1-hydroxy-1,1-diphosphonates, in particular the sodium and potassium salts, the water-soluble salts of methylenediphosphonate acid, for example the tri-sodium and trisodium salts, and the water-soluble salts of substituted methylenediphosphonic acids. such as trisodium and tripotassium ethylidene phosphonate, isopropylidenedene phosphonate, benzylmethylidene phosphonate and halomethylidene phosphonate. Phosphonate builder salts of the above type are described, for example, in U.S. Pat

19 October

159581

1965) v

14 January

1969) and 3 213030 (Diehl. December 1, U.S. Pat

422A37 (Quimby, Sept. 3 - Organic detergents include, however not intended) polycarboxylate polycarboxylate herein refers to carboxylate groups, preferably at least a wide variety of polycarboxylate groups.

1964 and Diehl,

No. 422021 (Roy, U.S. Pat

1968 and January 14, 1969). bui ldery ;. suitable for the purposes of the invention.

like any restriction,

400148 and 3 compounds. The term compounds having numerous three carboxylate groups.

The polycarboxylate builders are generally added in an acid form to the compositions of the invention, and may be added in the form of an neutralized salt. However, when used in the form of salts, alkali metal salts such as sodium, potassium and lithium salts, especially sodium salts, or ammonium salts and substituted ammonium salts such as alkanolammonium salts are preferred salts.

Polycarboxylate builders include a wide variety of useful materials. An important category of polycarboxylate builders are eterpolycarboxylates.

eterpolycarboxylates as detergent useful eterpolycarboxylates are

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

A specific type of eterpolycarboxylates useful as builders according to the invention also includes compounds of the general formula

CH (A) (COOX) -CH (COOX) -O-CH (COOX) -CH (COOX) (B) wherein A represents a hydrogen atom or a hydroxyl group; B is a hydrogen atom or a group of the formula -O-CH (COOX) -CH2 (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 succinic acid and its water-soluble salts. When A is a hydroxyl group and B is a hydrogen atom, the compound is tetrammonosuccinic acid (TMS) and its water-soluble salts.

When A is hydrogen and B is -O-CH (COOX) -CH 2 (COOX), the compound is tartrate succinic 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 TMS: TDS weight ratio of about 97 = 3 to about 20 = 80. These builders are described in U.S. Patent 4,666,3071 (Bush et al., Issued May 5, 1987).

Preferred eterpolycarboxylates also include cyclic compounds, especially alicyclic compounds, as described, for example, in U.S. Patent Nos. 30923679,

3835263, 4 158635, 4 120874 and 4 102903.

Other detergency builders include the ether hydroxy polycarboxylates of the formula

H0 [C (R) (COOM) -C (R) (COOM) -O] _n H wherein M represents a hydrogen atom or a cation, the resulting salt being water soluble, preferably an alkali metal, ammonium or substituted ammonium cation, n about 2 to about 15 (preferably n is about 2 to about 10 and especially n is about 2 to about 4) and each R has the same or different meanings and is hydrogen, C 1 -C 4 alkyl or substituted alkyl C 1 -C 4 (preferably R is hydrogen).

Yet another group of eterpolycarboxylates include copolymers of maleic anhydride with ethylene or vinyl methyl ether.

1,3,5-trihydroxybenzene-2,4-6-trisulfonic acid and carboxymethyloxysuccinic acid.

acid

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

Polycarboxylates of mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid and carboxymethyloxysuccinic acid and their soluble salts are also mentioned.

Of particular importance for high performance laundry detergents are citrate builders, for example citric acid and soluble salts thereof (especially the sodium salt). However, these builders can also be used in granular form for the detergent compositions of the invention. When used in salt form, preferred salts are alkali metal salts such as sodium. potassium and lithium salts, as well as ammonium salts and substituted ammonium salts. Other carboxylate builders include the carboxylated carbohydrates described in U.S. Pat. No. 3,723,322 (Diehl. March 28, 1973).

They are also suitable for the detergent compositions of the invention

3,3-dlcarboxy-4-oxa-1,6-hexanedionates and related compounds.

described in U.S. Patent 4,566984 (Bush,

January 28, 1986). Useful builders based on succinic acid include, in particular, alkyl succinic acids having 5 to 20 carbon atoms in the alkyl moiety and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid.

Alkyl succinic acids generally have the general formula

R-CH (COOH) CH2 (COOH) are generally succinic acid derivatives. wherein R represents a hydrocarbon group, for example an alkyl or alkenyl group having 10 to 20 carbon atoms, preferably having 12 to 16 carbon atoms, because R is a hydroxyl-substituted group.

sulfo, sulfoxy or sulfone, all of which are all described in the above patents.

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

* Specific examples of succinate builders include:

laurylsuccinate, myristysuccinate and pentadecenylsuccinate. '

Lauryl succinates are preferred builders of this group and are described in European Patent Application No. 86200690.5 / 0, 200, 263, published November 5, 1986.

Examples of builders also include carboxymethyloxymalonate. sodium, potassium, and water-soluble polycarboxylates (these polycarboxylates have a molecular weight of more than about 2000, and are preferably also used as dispersants or copolymers) and the copolymers of the maleic copolymer.

Other suitable polycarboxylates are the polyacetal carboxylates disclosed in U.S. Pat. No. 4,142,226 (Crutchfield, et al., Issued March 13, 1979).

conditions of the glycoxy acid ester and the polymerization initiator. The resulting polyacetal carboxylate ester then binds chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization even in an alkaline solution by converting it to the corresponding salt and adding it to the surfactant.

Polycarbonate builders are also disclosed in U.S. Pat. No. 3,308,067 (Diehl, issued March 7, 1967). Such materials include the water-soluble salts of homopolymers and copolymers of aliphatic carboxylic acids. for example maleic acid, itaconic acid. mesaconove j. filmmaker, aconite. citracone and methylenmalon.

Other organic builders may also be used. Examples are monocarboxylic acids and soluble salts thereof. having a long hydrocarbon chain. These materials are commonly 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

B

Detergent enzymes can be incorporated into a 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 plant, animal, bacterial, fungal and yeast. However, the selection of the enzyme is governed by some factors, such as the pH range of the efficacy or optimal stability, thermal stability, resistance to the action of the active cleaning ingredients and additives ( " ^A 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. subtilis and B. lichenorms. Other suitable r proteases are obtained from the Bacillus strain and have maximum potency in the pH range of 8 to 12 and have been developed and are a product of Novo Industries A / S under the trade name ESPERAZA. A process for the preparation of these enzymes and similar enzymes is described in British Patent Specification No. 1 243784 (Novo). Proteolithic enzymes suitable for protein-based stain removal are commercially available under the trade names ALCALAZA and SAVINAZA of Novo Industries A / S (Denmark) and MAXATASE of the company

International 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 detergents. Protease A and the process for its preparation are disclosed in European Patent Application No. 130759, published

9th

January

1985. The protease is a proteolytic enzyme, different from

proteases

And by having the leucine replaced by tyrosine at position 217 in its amino acid sequence. Protease B is disclosed in European Patent Application No. 87303761.8 filed j

April 28, 1987. Methods of Preparation

Protease B is also disclosed in European Patent Application No. 130759 published

January 9, 1985 (Bott et al.).

Amylases include, for example, obtained from a special strain of B.icheniforms.

as detailed in the aforementioned British Patent Specification 1 296839 (Novo).

Amylolithic enzymes include, for example, enzymes

RAPIDAZA company

International Bio-Syntetics Inc. and

TERMAMYL OF COMMUNITY

Novo Industries.

Cellulases useful in the present invention include both bacterial and fungal cellulases.

They should preferably have optimum efficiency in the pH range of 5 to 9.5.

Suitable cellulases are disclosed in U.S. Pat

435307 (Barbesgoard et al.,

On March 6, 1984), which are fungal cellulases produced by the fungus

Humicola insolens. Suitable cellulases are also disclosed in British Patent Nos. 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), in particular Humicola strain DSM 1800; and cellulases spiked with Bacillus N or cellulases 212 produced by a fungus belonging to the genus Aeromonas and cellulase extracted from hepatopancreas of marine molluscs (Dolabella Auricula Sonader).

Suitable lipase enzymes for detergents include lipases produced by a microorganism of the Pseudomonas family, for example Pseudomonas stutzeri ATCC 19.154, disclosed in British Patent Specification No. 1 372034. Lipases which exhibit a positive immunological cross-linking reaction with the lipase enzyme produced by P Lipase and a method for its purification are described in Japanese Patent Application No. 53-20487. published on January 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya Japan, under the tradename Lipase P Amano, referred to herein as Amano-P. Such lipases of the invention are intended to exhibit an immunological cross-linking reaction with the Amano-P antibody, using the standard Ouchterlon standard immunodiffusion method (Acta. Med. Scan., 133. pp. 76-79, 1950) known per se. These lipases and the method of their immunologically cross-linking reaction with Amano-P are also described in U.S. Pat. No. 4,707,291 (Thom et al., Nov. 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 Chromatobacter viscosum lipase from U.S. Pat. Biochem Corp., U.S.A. and Disoynth Co., The Netherlands and lipases produced by Pseudomonas gladiol i.

Peroxydase enzymes are used with oxygen sources such as percarbonate, perborate, peroxysulfate and hydrogen peroxide. They are used in solution bleaching, i.e. to prevent the transfer of dyes and pigments removed from substrates during washing to other substrates in the wash solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloroperoxidase and bromoperoxidase.

Peroxidase-containing cleaning compositions are described, for example, in PCT WO 89 / 0998-3. published October 19, 1989 (0 Kirk, Novo Industries A / S).

A wide variety of enzyme materials and a method for incorporating them into granules of synthetic detergent compositions are also described in U.S. Patent 3,533,139 (McCarty et al., Issued Jan. 5, 1971). The enzymes are further described in U.S. Pat. No. 4,101,457 (Placek et al., Issued July 18, 1978) and in U.S. Pat. No. 4,507,219 (Hughes, March 26, 1985). Enzyme materials suitable for liquid cleaning compositions and methods for incorporating them into such cleaning compositions are described in U.S. Patent 4,226,868 (Hora et al., Issued April 14, 1981).

As a rule, the enzymes are incorporated in a quantity sufficient to provide up to about 5 mg, preferably about 0.05 to about 3 mg of active enzyme per gram of detergent composition.

For granular detergents, the enzymes are preferably coated or processed into beads with enzyme additives inert to minimize dust formation and improve shelf life. Techniques for such treatment are known. In the case of liquid compositions, enzyme stabilizing systems are preferably used. Methods for stabilizing enzymes in liquid cleaning compositions are known. For example, one method of stabilizing the enzyme 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. Patent 4,388,818 (Letton et al., March 9, 1982). It is also proposed to use polyols. such as glycerol or sorbitol. Alkoxy alcohols, dialkyl glycoethers, mixtures of polyhydric alcohols with polyfunctional aliphatic amines (such as diethanolamine, triethanolamine, diisopropylamine) and boric acids or alkali metal borates may also be used for this purpose. Enzyme stabilization techniques are additionally disclosed and exemplified in U.S. Patent 4 261868 (Horn et al. _T .14.apríla 1981) and in U.S. Patent 3 600 319, (Čedgé, et al., August 17, 1971) and in European Patent Publication No. 0 199405, Application No. 86200586.5, Published Oct. 29, 1986 (Venegas). Boric acid and borate stabilizers are disadvantageous. 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, 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%, relative to the bleaching additive.

Any bleaching agents commonly used for cleaning fabrics, hard surfaces or other cleaning purposes that are known or become known may be used. 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) when storing the detergent or after washing conditions. Under these conditions, it is preferable to use non-borate and borate-free bleaching agents. Preferably cleaning agents are substantially free of borate and borate-forming materials at these temperatures. As used herein, substantially free of borate and borate-forming material. cleaning compositions containing a maximum of about 2% by weight of borate-containing or borate-forming material of any type, preferably at most 1%, and especially, are free of such bleaching agents.

One category of bleaching agents that may 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 diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. Pat. No. 4,483,881 (Hartman, issued November 20, 1984), U.S. Pat. No. 7,244,446, Burns et al., Filed Jun. 3, 1985, in European Patent Application No. 0 133354. (Banks et al., Issued Feb. 20, 1985) and U.S. Pat. No. 4,412,934 (Chung et al., Issued Nov. 1, 1983). Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as disclosed in U.S. Patent 4,663,551 (Burns et al., Issued 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 halogen bleaching agents such as trichloroisocyanuric acid and sodium and potassium dichloroisocyanurates and N-chloroalkanesulfonamides and N-bromoalkanesulfonamides. Such agents are generally added in an amount of 0.5 to 10% by weight relative to the weight of the finished product, preferably in an amount of 1 to 5% by weight.

Peroxygen bleaching agents are also used. Suitable sodium peroxide bleaching agents include sodium pyrophosphate peroxyhydrate, sodium carbonate peraxate, peroxyhydrate urea and sodium peroxide.

Peroxygen bleaching agents are preferably used in conjunction with bleach activators which result in in situ production in an aqueous solution (i.e. during the wash) of the peroxyacid corresponding to the bleach activator.

Preferred bleach activators in the cleaning compositions of the invention have the general formula

IN

R-C-L wherein R is an alkyl group of about 1 to about 18 carbon atoms, wherein the longest alkyl chain of the carbonyl carbon atom and comprising the carbonyl carbon atom contains about 6 to about 10 carbon atoms and L is a liberated group, an acid conjugate of The pKa value is about 4 to about 13. These bleach activators are described in U.S. Patent No. 4,915,854 (Mao et al., April 10, 1990) and in U.S. Patent No. 4,412,934 (above).

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-acidic bleaching agents of particular interest are photoactivated bleaching agents such as sulfonated zinc 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 by hanging for daylight drying, the sulphonated zinc phthalocyanine 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., Issued July 5, 1977).

As a rule, 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 soil release agents have both hydrophilic segments that hydrophilize the surface of hydrophobic fibers, such as polyester and nylon fibers, and hydrophobic segments for depositing on hydrophobic fibers, while remaining adhered after washing and rinsing to serve to anchor the hydrophobic fibers. segments. This makes it possible for 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 used separately for detergents or for other uses where it is necessary to release fats and oils from hydrophobic surfaces, wherein the presence of polyhydroxy fatty acid amide in the detergents compositions containing also anionic surfactants can enhance the utility properties of many commonly used types of soil release polymeric agents. 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 segments or hydrophobic segments that interact with anionic surfaces.

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

I) the anionic surface interaction between the soil release agent and the anionic surfactant system of the detergent composition 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 SRÄ from the detergent in aqueous solution in the absence of other detergents and (B) washing with SRÄ / anionic surfactant using the same type and amount of anionic surfactant system

in detergent composition is combined with the SRA, in aqueous solution in the same weight ratio of SRA to the anionic surfactant system of the detergent composition, whereby reduced deposition in (B) in comparison to money (A) shows the interaction of the anionic ^surfactant: and

II) Whether the detergent composition contains polyhydroxy fatty acid amide in an amount of a soil release promoting agent can be determined by comparing the SRA deposition in the wash test (B) using the SRA / anionic soil release surfactant from the wash test (C) using soil release in an SRA / anionic surfactant / PFA wash test using the same type and amount of polyhydroxy fatty acid amide in the detergent composition together with the composition.

promoting the release of dirt. and an anionic surfactant system corresponding to the SRA / anionic surfactant wash test, wherein the improved deposition of the soil release promoting agent in the wash test (C) with respect to the wash test (B) indicates that an amount of polydydroxy fatty acid-enhancing agent is included. the effectiveness of the soil release agent. For purposes of the invention, the tests are to be conducted at surfactant concentrations in aqueous solution that are above the critical micelle concentration (CMC) of the anionic surfactant, and preferably above about 1-10 ppm. The concentration of the soil release promoting polymer should be at least 15 ppm. A sample of polyester fabric is to be used as the hydrophobic fiber. The same sample is immersed and stirred in a 35 ° C water bath under appropriate test washing for 12 minutes. it is removed and analyzed. The concentration of the soil release promoting polymer may be determined by radioactivating the soil release promoting agent prior to assay and subsequent radiochemical analysis in a known manner.

As an alternative to the above radiocheroid test, a soil release agent can be determined in the above wash tests (A, B, C) by determining the ultraviolet light (UV) absorbance of the test solutions in a known manner. The decrease in UV absorption of the test solution after removal of the hydrophobic fibrous material corresponds to the increase in SRA deposition. It is clear to those skilled in the art that UV analyzes cannot be used for test solutions containing types and concentrations; materials that cause excessive UV absorption, such as. surfactants with aromatic groups (e.g. alkylbenzenesulfonates).

By the amount of a polyhydroxy fatty acid amide soil release agent is meant an amount 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 cleaning agent. The amount of polyhydroxy fatty acid amide required to promote deposition varies according to the surfactant selected, the amount of anionic surfactant, the type of soil release agent, and the polyhydroxy fatty acid amide selected. Generally, the detergent composition should contain from about 0.01% to about 10% by weight of the soil release promoting polymer, typically from about 0.1 to about 5% by weight, and from about 4 to 50% by weight, and especially from about 5% to about 30% by weight of anionic surfactant. . Such cleaning compositions should generally contain at least 1% by weight, preferably at least 3%, of polyhydroxyamide, although it is not intended to limit the amounts to these values.

Polymeric soil release agents whose activity is supported by polyhydroxy fatty acid amides in the presence of anionic surfactants include

(a) one or more hydrophilic components consisting essentially of (i) polyoxyethylene segments having a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments having a degree of polymerization of 2 to 10, wherein the hydrophilic segment does not comprise any oxypropylene unit when bound to adjacent portions at each end by ether linkages, or (iii) a mixture of osalkylene units comprising oxyethylene units and from 1 to about 30 oxypropylene units, the mixture containing a sufficient amount of axis of ethylene units such that the hydrophilic component has a hydrophilicity sufficient to increase hydrophilicity surfaces of conventional polyester synthetic fibers after depositing a soil release agent on such a surface and said hydrophile Other segments preferably comprise at least about 25% oxyethylene units, and in particular, in particular for components having about 20 to 30 oxypropylene units, at least about 50% oxyethylene units, or

b) one or more hydrophobic components comprising (i) 3-carbon oxyalkylene terephthalate segments, wherein, when such hydrophobic components also contain 3-carbon oxyethylene terephthalate units of about 2 ^: 1 or less, (ii) alkylene or (4-6C) oxyalkylene segments or mixtures thereof; (iii) poly (vinyl ester segments, preferably poly (vinyl acetate) segments having a degree of polymerization of at least 2; or (iv) (C1-C4) alkyl ether substituents. or a mixture thereof, wherein the substituents are in the form of alkyl ether cellulose derivatives of 1 to 4 carbon atoms in the alkyl moiety or hydroxyalkyl ether ether cellulose derivatives of 4 carbon atoms in the alkyl moiety, or mixtures thereof. mixtures wherein such cellulose derivatives are amphiphilic and have a sufficient content of C 1 -C 3 alkyl ether units and / or C 4 hydroxyalkyl ether ether units to be deposited on the surface of conventional polyester synthetic fibers and retain a sufficient number of hydroxyl groups to adhere to the conventional synthetic surface % of the polyester fibers increased the hydrophilicity of the fiber surface. The polymeric agents may also comprise a mixture of components (a) and (b).

Typically, the polyoxyethylene segments of (a) (i) have a degree of polymerization of from 2 to about 200, although the degree of polymerization may preferably be from 3 to about 150 and especially 6 to about 100. Suitable oxyalkylene hydrophobic segments of 4 to 6 carbon atoms in the alkylene moiety include, but are not limited to, endings of soil release promoting polymeric agents such as MCH 2 SiO 2, OCH 2 CH 2 Cl 2, where M is sodium and integers 4 and 6 are disclosed in U.S. Patent 4,721,580 (Gosselink, Jan. 26, 1988). ).

Polymeric soil release agents useful 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 ^R (from DOV).

Cellulosic soil release agents used in 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, hydroxypropylmethylcellulose and hydroxybutylmethylcellulose. A variety of cellulose derivatives useful as soil release agents are described in U.S. Pat. No. 4,000093 (Nicol et al., Dec. 28, 1976).

Soil release agents characterized by poly (vinyl ester) hydrophobic segments include seeded

copolymers of poly (vinyl ester), for example vinyl esters of 1 to 6 carbon atoms, preferably poly (vinyl acetate) grafted on

a polyalkylene oxide backbone, such as a polyethylene backbone. Such materials are known and 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 promoting agent is a copolymer having ethylene terephthalate and polyethylene oxide (PEO) terephthalate statistical blocks. In particular, these copolymers contain repeating units of ethylene terephthalate and polyethylene oxide terephthalate in a molar ratio of ethylene terephthalate units to polyethylene oxide terephthalate units of about 25: 75 to about 35-65, the polyethylene oxide terephthalate units having a molecular weight of about 300 to about 2000. The molecular weight of the polymeric agent. such compositions are described in U.S. Patent No. 3,952,930 (Hays, issued May 25, 1976), and similar copolymers are disclosed in U.S. Patent No. 3,939,229 (Basadur, issued July 8, 1975). ).

Another preferred soil release polymer is an ethylene terephthalate repeating polyester comprising from about 10% to about 15% ethylene terephthalate units by weight, and from about 90% to about 80% polyoxyethylene terephthalate units derived from polyoxyethylene glycol units having an average molecular weight of about 300 to about 300 molecular weight. to polyoxyethylene terephthalate units in polymer compound 2 1 to 6 ^: 1. Examples of this polymer include the commercially available materials ZELCON 5126 (from Dupont) and MILEASE T (from ICI). These polymers and methods for their preparation are described in U.S. Pat. No. 4,702,857 (Gosselink, issued October 27, 1987).

Another suitable soil release promoting polymeric agent is a sulfonated product of a substantially linear ester oligomer comprising an oligomeric ester backbone of terephthaloyl and oxyacylenoxy repeating units and terminal moieties covalently bonded to the backbone, wherein the soil release and dimethylalcohol-derivative derived dimetyl ester derivative is derived from 1,2-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 to J. J. Scheibel and U.S. Patent Application Serial No. 07 / 474,709, E.P. Gosselink, filed Jan. 29, 1990).

Other suitable soil release agents include capped 1,2-propylene terephthalate-polyethylene terephthalate polyesters described in U.S. Pat. No. 4,711,730 (Gosselink et al., Issued December 8, 1987). ), anionic deducted oligomeric esters as described in U.S. Patent 4,721,580 (Gosseling, issued Jan. 26, 2002).

1988), wherein the end caps include sulfopolyethoxy groups derived from polyethylene glycol (PEG), block polyester oligomeric compounds described in U.S. Pat. No. 4,702857 (Gosselink).

27th

October 1987), having a polyethoxy-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 reagents. soil release enhancers, including soil release agents described in U.S. Patent 4,877,896 (Maldonado et al., issued October 31, 1989), describing anionic, especially sulfoaroyl, end-capped terephthalate esters.

The terephthalate esters contain unsymmetrically substituted oxy-1,2-alkylenoxy units. Other soil repeating polyoxyethylene components or copending U.S. Pat. Nos. 4,877,896 disclose hydrophilic polymers such as the 3-carbon oxyalkylene terephthalate units (with propylene terephthalate hydrophobic units i) as the soil release promoting polymers. ) (i). Polymeric soil release agents. characterized by one or both of these criteria, which are particularly advantageous for incorporating polyhydroxy fatty acid amides in the presence of anionic surfactants.

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

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 aminocarboxylates, aminophosphonates, polyfunctional substituted aromatic chelating agents, and mixtures thereof, all defined below. Without intending to be bound by theory, it has been shown that the beneficial effect of these materials is due to their extraordinary ability to remove iron and manganese ions from the 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:

CH ₂ -N- (CH ₂ ) _X -COOM wherein M represents a hydrogen atom, an alkali metal, ammonium or substituted ammonium (for example, an ethanolamine group) and X 1 to 3, preferably 1. Preferably, these aminocarboxylates do not contain alkyl or alkenyl groups with a plurality of as 6 carbon atoms. Suitable aminocarboxylates include ethylenediaminetetraacetates, N-hydroxyethylenediaminoetriacetates, nitriotriacetates, ethylenediaminetetrapropionates. triethylenetetraamine hexaacetates, diethylenetriaminepentaacetates and ethanediglycines, their alkali salts, ammonium salts, substituted ammonium salts, and mixtures thereof.

Aminophosphonates 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

_CH2 - N _(CH2) xPCbM:

wherein M represents a hydrogen atom, an alkali metal, an aminoium or a substituted ammonium and x 1 to 3, preferably 1, are useful

I:;

and include ethylenediaminetetrakisimethylenephosphonates), nitrilo-tris (methylene phosphonates) and diethylenetriaminepentacisimethylene phosphonates).

Preferably, these aminocarboxylates 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

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 detergent compositions of the invention may contain these agents in the form of an alkali metal, ammonium or substituted ammonium salt (e.g., monoethanolamine, diethanolamine and three ethanolamines).

When chelating agents are used, they are generally included in an amount of 0.1% to about 10.0% by weight of the detergent composition, preferably 0.1 to 0.3% by weight of the detergent composition as a whole.

Agents supporting the removal of clay soil and preventing its redeposition i

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

The polyethylene glycol compounds useful in the laundry detergent compositions of the present invention typically have a molecular weight of about 400 to 100,000, preferably about 1000 to about 20,000, especially about 2000 to about 12,000, and most preferably about 4000 to about 8,000. Such compounds are commercially available under the trade name Carbovax® from Carbide. Danbury Conn.

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

1) ethoxylated monoamines of formula (XL -) - N- (R ² ) 2

2j ethoxylated diamines of general formula

R ² -NR ¹ -NR ² I | (R ² ) 2 -NR ¹ -N- (R ² ) 2 I T 1 1 L L 1 L 1 1 x x 1 x

or (XL-) 2 -NR ¹ -N- (R ² ) ₂

3) ethoxylated polyamines having the formula R ²

I

P-KA ¹ jq-CR 1 Jt-NL-X Jp

4) ethoxylated amine polymers of general formula

R ²

I [(R ² ) 2 -NjutR ¹ -Nlx [R ¹ -N] y [R ¹ -N-LK-X 1 _Z

I

L l

and i) mixtures thereof, wherein

And a group of the formula

0 0 0 0 0 0 -NC- | , -NCO-, I -NCN-, I -CN-. I -OCN-. I -WHAT- 1 R 1 R 1 R R 1 R 1 R 0 0 0 0 0 • 1 » II ·· II -WHAT-, -OCO-, -oc-, -CNC- T

R or O,

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

R ^{@ 1 is} alkylene, hydroxyalkyl, C2 -C12 alkynylene, C2 -C3 arylene or C1 -C3 oxyalkylene or C2 -C20 oxyalkylene, provided that no bonds are formed between the nitrogen atom and the atom oxygen,

R ² each hydroxyalkyl group having 1 to 4 carbon atoms, the proportion -LX, or two R @ ² groups together share (CH 2> r. N ² - (CH 2> 2 when A ² is oxygen or a methylene radical, R 1, or 2, with 1 or 2 and + 3 or 4,

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

R ³ substituted alkyl, hydroxyalkyl, or alkylene of 3 to 12 carbon atoms, aryl or alkaryl group having substitution sites,

R ^{4 is} alkylene, hydroxyalkyl, C 1 -C 12 alkenyl, C 2 -C 3 arylene or alkarylene or C 2 -C 3 oxyalkyl having 2 to 20 oxyalkylene units, provided that 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 general formula

- [CR 2 OM (CH 2 CH 2 O) n] where R is C 3 -C 4 alkylene or hydroxyalkylene and such that the moieties of formula - (CH 2 CH 2 O) n represent at least about 50% by weight of these polyoxyalkylene moieties; m 0 to about 4 and n to at least about 12 and wherein for diamines m is 0 to about 3 and n is at least about 6 when R ¹ is an alkylene, hydroxyalkylene or alkenylene group having 2 to 3 carbon atoms, and at least 3 when R ¹ is not an alkylene, hydroxyalkylene or alkenylene group having 2 to 3 carbon atoms; in the case of polyamines and amine polymers, m is from 0 to about 10 and n is at least about 3; p 3 to 8. q 1 or □, t 1 or O, provided that t is 1 when q is 1; v 1 or 0; x + y + z of at least 2 and y + z of at least 2. The most preferred soil release agent and anti-redeposition agent is ethoxylated tetraethylenepentamine. Examples of ethoxylated amines are further described in U.S. Pat. No. 4,597,898 to VanderMeer, U.S. Pat.

June 1, 1986). Another group preferred with respect to soil removal and redeposition is the cationic compounds disclosed in European Patent Application, published June 27, 1984 (Oh and Gosselink). Other soil release and anti-redeposition agents are ethoxylated amine polymers disclosed in European Patent Application No. 111 984, published June 27, 1984 (Gosselink), and double-faced polymers disclosed in European Patent Application No. 112 592, published June 4, 1984 (Gosselink) and the amine oxides described in U.S. Pat. No. 4,547,444 (Connor, issued October 22, 1985).

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

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. Although not intended to be bound 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 soil release, and antiredeparticle debris.

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

wherein X, Y and Z are each selected from oxygen.

methyl, carboxy, carboxymethyl.

hydroxy and hydroxymethyl:

cation-forming salt 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.

or a substituted ammonium group.

carboxylate polymerization of monomers, with materials of this type, can be or copolymerized suitably in the form of their acid.

may be polymerized to an ammonium group

Polymerizing unsaturated

Unsaturated monomeric acids which form a suitable polymeric polycarboxylate include acrylic acid, maleic acid (or maleic anhydride), fumaric, itaconic, aconitic, mesaconic, citraconic and methylenemalonic acid.

The presence in the polymeric carboxylates of monomer segments, free of carboxylate moieties such as vinyl methyl ether, styrene, ethylene and the like, is suitable provided that such segments do not constitute more than 40 wt.

Particularly suitable polymeric carboxylates may be derived from acrylic acid. Such acrylic acid-based polymers useful in the present invention are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in acid form is preferably about 2000 to about 10,000, especially about 4000 to about 7,000, and especially about 4000 to 5,000. The water-soluble salts of such acrylic acid polymers are, for example, alkali metal, ammonium and ammonium salts. substituted ammonium salts.

Soluble polymers of this type are known materials. Useful polyacrylates of this type for use in the detergent compositions of the invention are described in U.S. Patent No. 3,308,067 (Diehl, issued March 3, 1967).

Acrylic / melain-based copolymers can also be used as preferred components of dispersing / anti-redeposition agents. Such agents 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 5000 to 100000, especially about 6000 to 60000, and especially about 7000 to 60000. The ratio of acrylate to maleate segments in such copolymers is generally about 30-1 to about 11, especially about 10 = 1 to 2 = 1. Water-soluble salts of such copolymers of acrylic acid and maleic acid may include, for example, alkali metal salts of ammonium and substituted ammonium salts. Soluble copolymers of acrylates and maleate species of this type are known and described in the European patent application.

66915 published December 15

1,982th

Other polymeric ^; The detergent compositions of the invention are those which can be incorporated into the 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 i. The molecular weight of such polyethylene polyols for this purpose is about 500 to about 100,000, preferably about 1000 to about 50,000, in particular about 1500 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 the brightener for the detergent compositions of the 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. Since most detergents are used to clean a variety of fabrics. The detergent composition should contain a mixture of brighteners which is effective for various types of fabric. It is important that the individual components of such a brightener mixture be 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.

methanolanine, dibenzothiophene-5 and 6-membered heterocycles and 5-dioxide azoles, 5-membered other blending agents. Examples of such brighteners are given in The

Production)

And published by John Viley É / Sons, New.

York (1982).

Stilbene derivatives which / may be used in the detergent compositions of the invention include, but are not limited to ^, derivatives of bis (trianzines1) aminostilbenes.

stilbene bisacylamino derivatives, stilbene triazole derivatives.

oxadiazole derivatives of stilbene, oxazole derivatives of stilbe ¹ ® and styryl derivatives of stilbene.

Certain bis (triazinyl1) aminostilbene derivatives that may be useful in the detergent compositions of the invention.

can be prepared from 4,4 diaminestilben-2,2 which

disulfonic acid.

Coumarin derivatives can be used in the present invention include derivatives without any intention of limitation ^mentioned: by way of example the 7-position and 3-position and the seventh

substituted in the 3-position,

As the carboxylic acid derivatives that can be used in the detergent compositions of the invention, any limitation is exemplified by:

without intent, filmaric acid derivatives, benzoic acid derivatives, p-phenylene-bis-acrylic acid derivatives, naphthalene and carboxylic acid derivatives, heterocyclic acid derivatives cinnamic acid derivatives.

The cinnamic acid derivatives which can be used in the detergent compositions of the invention can be further subdivided into groups which include, but are not limited to:

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

The styrylazoles with styrylbenzoxazoles can be further subdivided into subgroups which include styrylimidazoles and styrylthiazoles as described on p. 78 of the aforementioned Gardener's publication.

The three subclasses exhaustively reviewed styrylazoles subclassed.

Optically brightening dibenzothiophene-5,5-dioxide.

pub1 i kác i e The

Kirk-Othmer Volume 3, and p. 737 and being

brightening subclasses, into reagents are not which i may be agents They are derivatives described on p. 741 to 749 Encyclopedia of Chemical Technology, 750 (John Viley and Sonš, Inc .. 1962), included R 5 , 5-dioxide

3,7-diaminodibenzothiophene-2,8-disulfonic acid.

In addition to the optically brightening agents already described above, they may; use a variety of other agents. Examples of such other possible optically brightening agents are set forth on p.

up to 95 of the above-mentioned Gardener's publication and include 1-hydroxy-3,6-8-pyrentrisulfonic acid,

2,4-dimethoxy-1,3,5-triazin-6-yl-pyrene,

4,5-Diphenylimidazolone disulfonic acid and pyrazolinequinoline derivatives.

Other specific examples of optically brightening agents are disclosed in U.S. Patent No. 4,790,856 to Wixon, issued December 13, 1988. Such optically brightening agents include the Phorvhite TM products of Verona. Other optically brightening agents are: Tinopal UNPA, Tinopal CBS and Tinopal 5BM from Ciba-Geigy; Arctic Vhite CC and Arctic Vhite CVD from Hilton Davis. Italy;

2- (4-styry1-feny1) -2H-naphthol [1,2-d] triazoles;

4,4-bis- (1,2,3-triazol-2-yl) stilbenes; 4,4 bisistyl) bisphenyls and γ-aminocoumarins. Specific examples of these optically brightening agents include 4-methyl-7-diethylaminocoumarin;

First

2-bis (benzimidazol-2-y1) ethylene;

1,3-diphenylphrazolines;

5-bis (benzoxazol-2-y1) thiophene;

2-styryl-naphth- [1,2-d] oxazole

2- (stilbene-4-yl) -2-naftot1,2-d] triazole. Other optically brightening agents.

which can be used in the detergent compositions of the present invention are described in U.S. Pat. No. 3,664,015 (Hamilton, granted

As optically brightening agents, they are

29th

February 1972).

disclose azoles which are derivatives of five-membered heterocycles. These compounds are further subdivided into subclasses of monoazoles and bisazoles. Examples of monoazoles and bisazoles are given in Kirk-Othmer.

Still other optically brightening agents are derivatives of the six membered heterocycles described in Kirk-Othmer. Examples of such agents include optically brighteners derived from pyridine and optically brighteners derived from 4-aminonaphthalamide.

Next of 1 sts, i

The detergent composition of the invention may contain other ingredients useful in 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.

polyols containing 2 to about 6 carbon atoms and up 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 in such a way.

so that the wash liquor is of value during use in the aqueous cleaning operation

A pH of about 6.5 to about 11, preferably about 7.5 to about 10.5.

have value

The pH is preferably about 7.5

Liquid cleaning agents up to about 9.5.

preferably about 7.5 to about 9.0.

pH values and recommended amounts include

Methods of controlling, for example, buffers, alkalis known.

and acids such as those of ordinary skill in the art

The invention also relates to a method of cleaning substrates such as fibers, fabrics and hard surfaces by contacting such a substrate with a cleaning agent comprising alkylbenzenesulfonate and polyhydroxy fatty acid amides, wherein the weight ratio of alkylbenzene sulfonate surfactant to polyhydroxy fatty acid amide surfactant is about 10%. up to about 10-1 in the presence of water or a water miscible solvent (such as a primary or secondary alcohol). Preferably, the purification is carried out with stirring, which promotes the purification. Suitable means for such mixing are hand rubbing, but preferably using a brush, sponge, cloth or other cleaning device, automatic washing machine or automatic dishwasher.

According to the invention, the above-mentioned most preferred weight ratios and suds-reducing additives and other preferred or other surfactant auxiliaries and optionally other detergent adjuvants may be used to illustrate the invention in more detail, but not to limit the following examples.

DETAILED DESCRIPTION OF THE INVENTION

The N-Methyl-1,1-deoxyglucity-lauramide surfactant, which is used according to the following embodiments, is prepared as follows:

Although any person skilled in the art may vary the configuration of the apparatus, it comprises a suitable three-liter four-neck flask equipped with a motor-driven paddle stirrer and a thermometer of sufficient length to contact the reaction mixture. The other two flasks are equipped with a nitrogen purge side arm and a large orifice side arm (note: a large orifice side arm is important for 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 a variable temperature control transformer (Variac) used to heat the reaction mixture 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, 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 was heated with stirring and flushing with nitrogen to form a melt (approximately 125 minutes). When the melt temperature reached 145 ° C, a catalyst (anhydrous powdered sodium carbonate, 10.5 g, 0.1 mol, J.T. Baker) was added. 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 show up on the meniscus of the reaction mixture. The 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 the time given in inches): 33.86 kPa for 3 minutes, 67.72 kPa for 7 minutes, 84.65 for 10 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 but do not limit it in any way.

Examples 1 to 6

These examples illustrate detergent compositions containing alkylbenzene sulfonates and polyhydroxy fatty acid amides for washing at temperatures above 50 ° C.

Basic granules 1 2 3 linear C12 alkylbenzenesulfonate 5.9 3.0 4.5 F N-mety1-N-L-deoxyglucity1lauramid - 7.0 - CI6 ~ 18alkylsulfát 2.5 2.5 2.5 zeolite 20.9 20.0 20.5 polyacrylate (molecular weight 4500) 3.9 3.9 3.9 sodium carbonate 12.7 16.0 12.7 water and a mixture of ingredients 8.1 8.2 8.7 admixture and spray N-methyl-N-1-deoxyglucitylcocoamide 5.6 - - N-methyl-N-1-deoxyglucitylamide tallow fatty acids - - 4.0

mixture of ingredients (filler salts, enzymes,

brighteners, buffers, zeolite, or other builders) 40.4 39.4 43.2 pretty 100.0 100.0 100.0 Cleaning agents according to Example 1 to 3 SÚ:

granular detergents for high demands on the temperature of the washing bath, preferably about 50 to about 95 ° C at a concentration of about 8000 ppm, based on the weight of the washing bath. These cleaners are prepared by suspending the ingredients for the base granules and spray drying them to a final moisture content of 10-13%. The remaining dry powder components, such as bleaches, activators and other excipients, are admixed and sprayed with the liquid components.

like perfume.

nonionic surfactants and suds suppressors.

Basic granules 4 5 6 C16-18 alkyl sulfate 2.4 2.4 2.4 linear C12 alkylbenzenesulfonate 4.6 4.6 7.6 C16-18 alkyl ethoxylate (11 mol) 1.1 1.1 1.1 zeolite 22.0 24.0 21.3 acrylate / maleate copolymer (molecular weight 6000 4.3 5.6 4.3 water and a mixture of ingredients 9.4 9.2 10.1 admixture N-methyl-N-1-deoxyglucylcycloamide d - 7.0 - N-methyl-N-1-deoxygutyl amide loka fatty acids 7.0 - 4.0 sodium citrate 8.0 - 8.0 sodium carbonate 17.5 17.3 17.5 sodium silicate (1.6 ratio) mixture of ingredients (filler salts, enzymes, brightener, buffer, zeolite or other builders) 19.3 24.8 19.4 spraying Perfumes) 0.4 0.4 0.4 si 1 icon liquid 0.5 0.5 0.5 pretty 100.0 100.0 100.0

The compositions of Examples 4 to 6 are preferably used for washing bath temperatures of about 50 to about 95 ° C at a concentration of 6000 ppm, based on the weight of the washing bath. These detergent compositions are prepared by suspending the ingredients for the base granules and spray drying them to a final moisture content of about 9%. The remaining dry powder components are mixed and the liquid components are sprayed.

Examples 7 to 9

These examples illustrate liquid cleaning compositions containing polyhydroxy fatty acid alkylbenzene sulfonates.

Basic granules 7 8 9 linear C12a alkylbenzenesulfonate 12.8 12.8 10.0 C12-14alkylsulfát 1.8 1.8 - C12-14 alkyl ethoxylate (7 mol) - - 1.6 N-methyl-N-1-deoxyglucyl-4-cycloamide; - 8.4 6.5 N-methyl-N-1-deoxyglucityl oleamide 8.4 - - oleic acid 1.8 1.8 4.0 citric acid 4.1 4.1 9.0 dodecylsuccinic acid 11.1 11.1 5.0 1 icon oil 0.5 0.5 0.3 mixture of ingredients (filler salts, enzymes, brightener, buffer, zeolite or other builders) 14.6 14.6 15.8 Water 45.0 45.0 47.8 pretty 100.0 100.0 100.0 Detergents according to Example 7 to 10 are being prepared by mixing non-aqueous solvents, water graze or solutions

surfactants, molten fatty acids, aqueous solutions of polycarboxylate builders and other salts, aqueous ethoxylated tetraethylenepentamine, buffers, soda and residual water. The pH of the detergent is adjusted to about 8.5 with aqueous citric acid or sodium hydroxide. After adjusting the pH, final ingredients such as soil release agents, enzymes, dyes and perfumes are added thereto, and the mixture is mixed to achieve a single phase.

Example 10

According to an alternative method of preparing polyhydroxyamides _: fatty acid, the following procedure is followed. · Í

A reaction mixture containing 84.87 g of fatty acid methyl ester (supplier Procter + Gambia, methyl ester CE1270), 75.00 g of N-methyl-D-glucamine (supplier Aldrich Chemical) was used.

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 based on 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 in an argon atmosphere and heating is started with good stirring (stirring bar, reflux). After 15-20 minutes, the solution is at the desired temperature and sodium ester and methoxide are added as a catalyst. Samples are taken periodically to monitor the progress of the reaction and the solution is completely cleared in 63.5 minutes. It is believed that at this point the reaction is virtually complete. The reaction mixture is maintained at reflux for 4 hours. The reaction mixture obtained weighs 156.16 g. After vacuum drying, the overall 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 to obtain 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 consideration by one skilled in the art in the manufacture of a variety of cleaning compositions using polyhydroxy fatty acid amides.

It is clear that polyhydroxy fatty acid amides, due to their amide bond, are unstable under highly alkaline or highly acidic conditions. Although some decomposition may be tolerated, it is preferred that these materials are not exposed to pH values above 11, 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.

Generally, at least polyhydroxy fatty acid amides are required; partially neutralize the basic catalyst used; for the formed amide bonds. However 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 an acid whose ion is otherwise useful and desirable in the finished detergent composition. For example, citric acid and the resulting citrate ion (approximately left in suspension with approximately 40% polyhydroxy acid amides) can be used for neutralization and can be pumped into the next production of the finished detergent. Similarly, new forms of nitrile acetate, chemicals such as ethylene i ametetraacetate grade

Oxydisuccinate, tartrate / succinate system can be used in the fatty process.

Amides of polyhydroxy fatty acids. 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). Therefore, the C 12 -C 14 materials are easier to formulate in liquid compositions and are more soluble in cold water scrubbers. However, materials having 16 to 18 carbon atoms are so good, especially in circumstances where hot to hot water is legally used. Therefore, C16-18 materials can be better detergent compositions than their C12-14 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 the polyhydroxy fatty acid amides may be increased depending on the unsaturation and / or branching of the fatty acid moiety. Materials such as oleic and isostearic acid polyhydroxy fatty acid amides are much more soluble than their n-alkyl counterparts. Similarly, the solubility of polyhydroxy fatty acid amides in the prepared disaccharides. trisaccharides, etc. it is generally greater than the solubility of their monosaccharide derived counterparts. This higher solubility can particularly assist in the formulation of liquid compositions. In addition, polyhydroxy fatty acid amides, whose polyhydroxy groups are derived from maltose, also appear to be particularly detergent. when used in admixture with conventional alkylbenzene sulfonate (LAS) surfactants. However, it is not intended to be limited to a particular theory.

it appears to be a mixture of LAS with polyhydroxy fatty acid amides.

derived from higher carbohydrates, e.g. maltose, exhibits a substantial and unexpected decrease in interfacial tension 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. from potato starch or other suitable 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 delignified hydrolyzed pulp.

As mentioned above, polyhydroxy fatty acid amides.

derived from higher carbohydrates, such as maltose and lactose, are much more soluble than they appear that the more soluble polyhydroxyamides appear to assist in varying degrees of solubilization of the counterpart. In addition, fatty acids may have less soluble counterparts. A person skilled in the art can therefore choose, for example, as a raw material instead of a high glucose corn syrup, a syrup containing a small amount of maltose (e.g. 1% or more by weight).

The polyhydroxy fatty acid mixture obtained generally has more advantageous solubility characteristics in the six years of temperature and concentration than glucose-derived polyhydroxy fatty acid amide. In addition to the economic advantages of using sugar blends over pure sugar, the polyhydroxy fatty acid amides prepared from the sugar blend still have the advantages of easy dish washing) during handling during manufacture. In some, there is a decrease in fat removal (at a fatty acid maltamide concentration above certain foaming losses at a concentration above about 10% of maltamide-derived fatty acids, as opposed to about 25% and about 33% (polyhydroxyamides of glucose-derived polyhydroxyamides). Certain darknesses are possible depending on the chain length of the fatty acid moiety The person skilled in the art may choose mixtures which he considers preferred for polyhydroxy fatty acid amides having a ratio of monosaccharides (e.g. glucose) to disaccharides and higher carbohydrates (e.g. to maltose) of about 4 : 1 to about 99 1.

Preparation of preferred non-cyclized. polyhydroxyamides of fatty acids from fatty acid esters and N-alkyl polyols can be converted in alcoholic solvents at a temperature of about 30 to about 90 ° C and preferably about 50 to 60 ° C. It has now been found that it may be convenient for a person skilled in the art to prepare e.g. The liquid detergents may be operated in a 1,2-propylene glycol solvent, as 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 convenient for a person 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, for example ethoxylated (E 3-8) alcohols having 2 to 14 carbon atoms, which are a commercial product NEODOL 23 E06.5 (Shell). When ethoxylates are used, it is preferred that they do not contain a substantial amount of the monoethoxylated alcohol (designation T).

In any case, methods for preparing polyhydroxy fatty acid amides per se are not within the scope of the present invention, yet other possibilities for preparing polyhydroxy fatty acid amides are recalled and are described below.

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

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

Preparation of N-alkylpolyhydroxyamine derived from plants.

sugar syrup.

1. Adduct preparation

According to a standard method, the reaction is allowed to proceed

420 g of approximately 55% glucose solution

- about 231 g glucose - about 1.28 (corn syrup mol) of Gardner color less than 1 with about 119 g of about 50% aqueous methylamine solution (59.5

1.92 mol)

Methylammonium (MMA) solution is purged with g of methylamine with nitrogen and cooled to approximately 10 °

C or still and a lower temperature nitrogen is introduced. Pour at a temperature of about 10 to corn syrup

20 ° C.

Corn syrup is added slowly to the methylamine solution at the above reaction temperature. The Gardner color number is measured at the following time intervals, in minutes.

Table I

Time in minutes 10 30 60 120 180 240 Reaction temperature ° C Gardner color (About) 0 1 1 1 1 1 1 20 1 1 1 1 1 30 1 1 2 2 4 5 50 4 6 10 - - - From the above values is a Obviously. that 1 Gardner color for

the adduct is much worse when the temperature rises above 30 ° C and at about 50 ° C the time for which the Gardner adduct is below 7 is only 30 minutes. For the next reaction and / or the hold time the temperature should be less than about 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 equilibrium adduct concentration is reduced by using a higher amine to sugar ratio. At a molar ratio of 1.5 ^: 1 amine to sugar, equilibrium is reached in about two hours at a reaction temperature of about 30 ° C.

1.2 · 1 under the same conditions is at least about three hours. For good color, a combination of amine to sugar ratios, reaction temperature and reaction time to achieve a substantially equilibrium conversion, for example greater than about 90%, preferably greater than about 95%, and even greater than about 99%, based on sugar and color is chosen. an adduct that is less than about 7, preferably less than about 4, and most preferably less than about 1.

In the above process, the reaction temperature is less than about 20 ° C, and corn syrup with different Gardner color and MMA adduct color (after reaching essentially equilibrium in 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

As can be seen from the table, the starting sugar may be almost colorless to form an acceptable adduct. If the sugar has a Gardner number of about 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

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

About 539 g of adduct in water and about 23.1 g of G49B nickel catalyst (United Catalysts) are charged to a 1 liter autoclave and purged twice with hydrogen at a pressure of 1380 kPa at 20 ° C. The hydrogen pressure is increased to 9660 kPa and The temperature is raised to 50 ° C. The overpressure is raised to 110 mm Hg and the temperature is maintained at 50-55 ° C for three hours. At this point the product is hydrogenated to 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 Reney 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 overpressure of 1380 kPa, after which the hydrogen pressure in the autoclave is adjusted to 11040 kPa for two hours, relieved in one hour. kPa. The adduct is then pumped to a reactor at a hydrogen pressure of 1380 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 product obtained is more than 95% of N-methylglucamine, which contains less than 10 ppm of nickel, based on the globulin, and which 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 a 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 shaded with nitrogen at about 10 to 20 ° C. Approximately 330 g of about 70 corn syrup (off-white) 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 to obtain about 95% adduct, which is a very slightly yellow solution.

About 190 g of this adduct in water and about 9 g of the GE9B nickel catalyst (United Catalyst) is charged to a 200 ml autoclave and purged three times with hydrogen at about 20 C. The hydrogen pressure is increased to about 1380 kPa and the temperature is raised to 50 ° C. The pressure is increased to 1715 kPa and the temperature is maintained at about 50-55 ° C for three hours. The temperature of the product which is hydrogenated from about 95 is raised to about 85 ° C for about 30 minutes and the product after removal of water and evaporation is about 95%

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 the N-methylglucamine in this reaction is approximately 100 ppm compared to less than 10 ppm in the previous reaction.

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

An 200 ml autoclave 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 ΜΜΆ, 1.92 mol) (from Air Products).

The reaction is carried out as follows

(1) Charge about 119 g of a 50% methylamine solution to 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) adding the corn syrup solution slowly to the methylamine solution and maintaining the temperature below about 20 ° C;

4) when all the corn syrup solution is added, stir 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 its degradation,

The reaction of the glucamine adduct is carried out as follows ^:

(1) About 134 g of adduct (Gardner Color Number less than 1) $ about 5.8 g of nickel catalyst G 49B is charged into a 200 ml autoclave,

2) purging the reaction mixture with hydrogen at a pressure of about 1380 kPa twice at 20-30 ° C.

(3) The hydrogen pressure is increased to approximately 2760 kPa and the temperature is increased to approximately 50 ° C.

4) The pressure is increased to approximately 3.45 MPa. the reaction is allowed to proceed for three hours while maintaining the temperature at about 50-55 ° C and taking a sample of 1,

5) the temperature is raised to about 85 ° C for about 30 minutes,

6) decant and filter the catalyst. a sample is taken

Second

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 a 200 ml autoclave,

(2) purging the reaction mixture with hydrogen at a pressure of about 1380 kPa twice at low temperature;

(3) The hydrogen pressure is increased to approximately 2760 kPa and the temperature is increased to approximately 50 ° C.

4) The pressure is increased to approximately 3.45 MPa. the reaction is allowed to proceed for three and a half hours while maintaining the temperature as described above,

5j is decanted and the catalyst is filtered off. Sample 3 corresponds to approximately 50-55 ° C, sample 4 approximately 75 ° C, and sample 5 approximately 85 ° C (reaction time for approximately 85 ° C is approximately 45 minutes).

All processes yield 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 11 <_;

The tallow fatty acid amide (hardened) of N-methylmaltamine for use in detergent compositions is prepared as follows;

Stage 1; Reactants; maltose monohydrate (Aldrich, lot

01318 KV), methylamine (40% by weight in water) (Aldrich lot 03325TM), Raney nickel. 50% suspension (UAD 52-73D, Aldrich lot 12921LV).

The reactants were introduced into a glass cartridge (250 g of maltose, 428 g of methylammonium solution, 1200 g of catalyst suspension - 50 g of Raney nickel) and the cartridge was placed in a 3 liter fluctuating autoclave which was purged with nitrogen (3, 45 MPa. three times) and hydrogen (gauge pressure of 3.45 MPa, twice) and rocked under hydrogen at 28 to 50 ^{0 C} over the weekend. The crude reaction mixture is filtered under vacuum twice through a glass microfiber filter with a 1 µg layer.

The filtrate was concentrated to give a viscous material. The final traces of water are removed azeotropically by dissolving the material in methanol 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 crystallize, filtered, and the filter cake was dried under vacuum at 35 ° C. This is section # 1. The filtrate was concentrated to precipitate formation and stored in a refrigerator. during the night. The solid was filtered off and dried in vacuo. This is section # 2. The filtrate 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 the N-methylmethanine used in Step 2.

Step 2.- Reagents: N-methylmaltamine (from step 1), hardened tallow methyl esters, sodium methoxide (25% in methanol), absolute methanol (solvent) 1: 1 amine: ester molar ratio, initial catalyst concentration 10% mol% (based on the weight of maltamine) is increased to 20 mol%, the solvent concentration by weight 50% in a sealed flask is 20.36 g; of the tallow methyl ester is heated to its melting point (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 prevent ester solidification. Separately, 25.0 g of N-matylamine is mixed with 45.36 g of methanol, and the resulting suspension is added to the tallow fatty acid ester with good stirring. 1.51 g of 25% sodium methoxide in methanol is added. After four hours, the reaction mixture did not clear, so an additional 10 mol% catalysts (to a total of 20 mol%) were added 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 is raised to 110 ° C. Distillation at ambient pressure is continued for 60 minutes. High-vacuum distillation is then started, which is carried out 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 100% methanol) was loaded onto silica gel and eluted several times under vacuum and washed several times with methanol. The collected eluent was evaporated to dryness (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 the restricted process of Step 1, the above reaction process can be carried out using a commercial corn syrup containing glucose or a mixture of glucose 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 NEODOLE. 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 operator, the methoxide catalyst may 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 wishes of one skilled in the art, the cleaning compositions of the invention may contain more or less different suds reducing agents. As a rule, high sudsing is desirable for dishwashing detergents so that no suds suppressors are used. For washing in top-loaded washing machines, some foam suppression may be desirable for washing in front-loaded washing machines, a significant reduction in foaming may be advantageous. A variety of suds control agents are known and can be selected as desired.

The choice of suds suppressor 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 silicone-based suds suppressors appear to be much more effective (i.e., less can be used) than various other types of suds suppressors.

The icon reagents are particularly preferred.

Trademark AE, X2-3419, Q2-3302 Foam Restriction and DC-544 (Companies

Dov Corni ng).

Those skilled in the art of laundry detergent compositions containing soil release additives can choose from a wide variety of agents (described, for example, in U.S. Patent Nos. 3,962,152, 4,116,885, 4, 5, 6, 7, 8, 9).

238532, 4

702857, 4 release

721580 and 4,877896). Additional soil-promoting agents include a nonionic oligomeric esterification product of the reaction of a mixture containing a C 1 -C 4 alkoxy-terminated carbon source, e.g.

CH3 [OCH2 CH2 116 0H source of terephthaloyl units (e.g. dimethyl terephthalate), source of poly (oxyethylene) oxyunits (e.g. polyethylene glycol), \

1500), source

1,2-propylene glycol) ethylene glycol), oxyisopropyleneoxy units, and a source of oxyethyleneoxy units especially at molar (e.g.

ratio of oxyethyleneoxy units = oxyisopropyleneoxy units at least approximately

0.5 ^: 1. Such nonionic soil release agents have the general formula

R * O- (CH ₂ CH ₂ O) x to -O-CH-CH ₂ O to -CO (CH ₂ CH ₂ O) y ^J Ŕ » m

about

C 1 -C ₆ -CH ₂ O (CH ₂ CH ₂ O) x R ^x where R ^{1 is a} lower alkyl group (e.g., C 1 -C 4), especially methyl, x and y are each an integer of about 6 to about 100. n an integer n is about 0.75 to about 30; n is 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 · 1.

Another preferred type of soil release agent is the anionic reagent generally described in U.S. Patent 4,877,896, provided that such agents are substantially free of HOROH monomers wherein R is propylene or higher alkyl. Examples of soil release agents according to U.S. Patent 4,877,896 are the reaction product of dimethyl terephthalate, ethylene glycol, 1.2 propylene glycol and 3-sodium sulfogenzoic acid, and the soil release additive may include, for example, the dimethyl terephthalate reaction product. ethylene glycol. 5-sodium sulfoixophthalate; and 3-sodium sulfobenzoic acid. Such agents are preferably used in granular detergent compositions.

One skilled in the art can also determine that the use of non-perborate bleaching additives is preferred. especially in high-duty granular laundry detergents. Various peroxy bleach additives are commercially available and can be used

However, peroxy carbonates are common and economical. The compositions according to the invention may contain solid percarbonate additives, generally in the form of sodium salt and in an amount of 3 to 20% by weight. preferably 5 to 18% and especially 8 to 15%.

Sodium percarbonate is an additive and corresponds to the formula 2NazCO3-3H2O2 and is commercially available as a crystalline solid. The most common material includes a small amount of heavy metal sesquestrants such as ethylenediaminetetraacetic acid (EDTA), 1-hydroxyethylidene-1,1-didphosphonic acid (HEDP) or aminophosphonate. which are introduced during production. According to the invention, the percarbonate is introduced into the cleaning composition without further protection, but preferably it is used in coated form. Although a wide variety of coatings can be used, sodium silicate is most economical with a ratio of silica = sodium oxide of 1.6 = 1 to 1.8 = 1. preferably 2.0 = 1. used as an aqueous solution and dried to a weight of 2 to 10%, typically 3 to 5% of silicate dry matter per weight of percarbonate. Magnesium silicate and a chelating agent, such as those mentioned above, may 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 coating, the crystals are 400 to 600 microns in size.

However, the heavy metals contained in the sodium carbonate used for the percarbonate production can be reduced by incorporating sequestering agents into the reaction mixture. the percarbonate must always be protected from heavy metals contained as impurities in other detergent components. 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 the percarbonate stability.

Example 12

This example illustrates a condensed detergent in the form of granules. It is a perborate detergent composition according to the invention with a bleach activator which is prepared by mixing the following ingredients in a mixing drum. J

In this example, Zeolite A refers to 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 a linear sodium alkylbenzene sulfonate having an average of 12.3 carbon atoms in the alkyl moiety. AS means 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 diethyltetraamine pentaacetate.

Weight parts

finished device % granules Basic granule ¹ 51.97 100.00 AS 9.44 18:16 LAS 2.92 5.62 humidity 4.47 8.60 sodium silicate (ratio 1.6 1:35 2.60 sodium sulfate 6.47 12.45 sodium polyacrylate 2.61 2.5 PEG 8000 1.18 2.27 non - ionic surface 0.46 0.89 active agents sodium carbonate 13.29 25.57 brightener 0.20 00:38 sodium aluminosilicate 9.11 17:53 DTPA 00:27 00:52 perfume 0.20 0.38 NAPAA granules 6.09 100.00 NAPM 2.86 46.93 LAS 0.30 4.93 sulfate and mixture 2.93 48.11 NOBS granules 3.88 100.00 NOBS 3.15 81.19 LAS ' 0.12 3.09 PÉG 8000 0.19 4.90 Differently 00:42 10.82 Zeolite granules ⁴ 12,00 100.00

sodium aluminosilicate 7.39 61.58 PEG 8000 1.50 12.47 non - ionic surface 1.16 9.70 active agents humidity 1.60 13.63 Differently '0.29 2:42 admixture sodium SKS-6 layered 15.84 si 1ikát protease 00:52 (0.078 mg / g potency) natriumperbonate monohydrate 1:33 citric acid 6.79 C 12-14 N -methylglucamide 1:58 whole 100.00

The base granules are prepared by spray drying mixtures of the above ingredients

A freshly prepared NAPAA wet cake is prepared.

which typically contains about 60% water by weight, about 2% available oxygen (AvO) peroxyacid (corresponding to about 36% NAPAA) and the remainder (about 4%) unreacted material.

The wet cake is adipic acid), followed by addition of the crude reaction product NAPAA (sulfuric acid mononylamide and hydrogen peroxide), filtration, washing with distilled water.

phosphate buffer and final suction filtration to yield a wet cake. A portion of the wet cake is air dried at room temperature to give a dry sample, which typically contains 5% AvO (corresponding to 90% NAPAA) and approximately 10¾ unreacted material. After drying, the sample has a pHi value ^; near 4.5.

NAPAA granules are prepared by mixing about 51.7 parts of dry NAPAA cake (containing 10 unreacted material), about 11.1 parts of a linear alkylbenzene sulfonate (LAS) paste having an average number of atoms in the alkylated portion of 12.3 (45% active ingredient), about 43 , 3 parts sodium sulfate and about 30 parts water in a CUISINART mixer. After drying, the granules (which contain approximately 47% NAPAA) are passed through a No. 14 Tyler mesh screen and all particles that have not passed through the No. 65 Tyler mesh screen are retained. The mean particle size of the peroxyacid amide (agglomerate) is about 5 to 40 microns and the mean particle size is about 10 to 20 microns according to particle size analysis of the Malvern ³ NOBS (nonanoylcycloxybenzenesulfonate) granules are prepared according to the method of U.S. Pat. No. 4,997596 to Bowling et al. March 5, 1991).

^The zeolite granules have the following composition and are prepared by mixing Zeolite A with PEG 8000 and CnAE6.5T in an Eirich high energy mixer.

Parts by weight before drying after drying

Zeolite A (including bound water

70.00

76,99

PEG 8000

10.80

12.49

CnAE6.5T

8.40

9.72 free water

10.80

0.80

PEG 8000 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 approximately 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 5000 mPa s. The weight ratio of PEG 8000 to CnAE *, 5T in a static mixer is approximately 72 = 28.

The Eirich 80 high-energy mixer works in a batch mode. First, weigh 34.1 kg of the powder into the bowl of the blender

Zeolite A. The mixer is started first by rotating the bowl counterclockwise at a speed of approximately 75 rpm and then moving the scraper blades in a clockwise rotation at 1800 rpm. The binder is then pumped from the static mixer directly into the Eirich R08 high energy mixer containing Zeolite Ä. The binder loading rate 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 is obtained. The product is then dried in a fluorodised layer at 116-132 ° C. Drying removes most of the free water and yields the finished product. The total energy introduced into the mixer is approximately 1.31 x ¹ P ¹ erg / kg at a rate of approximately 2, 18 x 10 ⁹ erg / kg s.

The final free-flowing agglomerates have a mean particle size of about 450-500 microns.

Example 13

In all of the preceding examples, the fatty acid glucamide surfactant may be replaced by an equivalent amount of maltamide surfactant or surfactant glucamide / maltamide surfactant 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 exhibits increased penenle.

For detergent compositions where high sudsing is desired (e.g. in the preparation of dishwashing compositions), it is preferred that they contain no suds suppressors. When fatty acids containing 14 or more carbon atoms can act as suds suppressors, it is preferred that the dishwashing compositions contain less than about 3 wt.

5%, preferably less than about 2%, of fatty acids having 14 or more carbon atoms, and in particular to contain no fatty acids with or more carbon atoms. Therefore, those skilled in the art, in the case of high suds cleaners, avoid avoiding suppressing agents or introducing amounts of such high suds cleansing suds into polyhydroxy amide containing compositions; fatty acids avoid the formation of C 14 and more fatty acids upon storage of the finished detergent compositions of the invention. A simple method is to use 12-carbon ester reagents to prepare polyhydroxy fatty acid amides. Fortunately, the use of amine oxide or sulfobetaine surfactants can prevent the 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 masterbatch with water and polyhydroxyamide. % of the fatty acid, and then introducing the premix into the finished detergent composition.

In the case of detergents containing zeolite builders, polyglutamic acid or polyaspartic acid can be used as a dispersant.

Examples of suds suppressors include AE liquid or flakes and DC-544 (from Dov Corning).

Those skilled in the art will appreciate 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 polyhydroxy ring structure. Such materials are fully within the scope of the invention and therefore do not depart from the scope of the invention.

Industrial usability

A liquid or solid detergent composition comprising a polyhydroxy fatty acid amide and an alkylbenzene sulfonate optionally together with a suds suppressor and surfactant auxiliary is suitable for laundry washing and, without limitation, sudsing for dishwashing and the like.

Claims (5)

PATENT CLAIMS 1. Liquid or solid and low-foaming cleaning agent, characterized in that it contains a non-phosphate builder selected from the group consisting of cicrate, gelatin or layered silicate | builder and, as surfactants, at least 3¾t by weight of alkylbenzenesulfonate and at least 3¾t of polyhydroxy fatty acid amide; of formula I and l OR ^1? II I ^R2 - C - N - Z (I) wherein R ^{@ 1} is hydrogen, C1 -C4 hydrocarbyl, A 2-hydroxyethyl group, a 2-hydroxypropyl group or a mixture thereof; R ² hydrocarbyl group having 5-31 carbon atoms, and A linear hydrocarbon chain polyhydroxy hydrocarbon group having at least three hydroxyl groups directly bonded to the chain or an alkoxylated derivative thereof, and a suds suppressor in a suds suppressor amount of a polyhydroxy fatty acid amide to an alkylbenzene sulfonate of 15 to 5-1. The cleaning composition of claim 1, wherein f further comprises from 1% to 25% by weight of surfactant aids. selected from the group consisting of alkyl ethoxylated sulfate surfactants, alkyl sulfate surfactants, alkyl ester sulfonate surfactants, alkyl ethoxylate surfactants, alkylene phenoxyalkoxy surfactants. alkyl polyglycoside surfactants. paraffin sulphonate surfactants and mixtures thereof. A cleaning composition according to claim 1, characterized in that it comprises suds suppressing agents F 'selected from the group consisting of 1 iconic, hydrocarbon, monosteraryl phosphate suds suppressors and mixtures thereof. A method of washing fabrics, characterized in that the washed fabrics are contacted with a water bath comprising a cleaning composition according to claim 1. í! The method according to claim 4, characterized in that, in general, it is a &quot; The formula (I) represents a R ² alkyl or alkenyl group having 15 to 17 carbon atoms or a mixture thereof. |