WO1993009214A1 - Detergent compositions comprising glyceryl ethers - Google Patents

Abstract

A detergent composition comprises (a) one or more glyceryl ethers of a C12-C18 alkyl or alkenyl primary or secondary alcohol, at least 50 mole percent of the glyceryl ether being diglyceryl ether and not more than 25 mole percent of the glyceryl being monoglyceryl ether, and (b) an anionic detersive surfactant. The compositions, which may be in granular or liquid form, may also contain other conventional ingredients, e.g. other detersive surfactants, detergency building compounds, enzymes and bleaches.

Description

DETERGENT COMPOSITIONS COMPRISING GYLCERYL ETHERS

Field of the invention

The present invention relates to detergent compositio especially heavy duty compositions, that contain one more glyceryl ethers as a nonionic detersive surfactant.

Background to the invention

Heavy duty detergents, whether in granular or liquid fo commonly comprise an anionic detersive surfactant, example sodium (linear alkyl) benzene sulfonate in wh the alkyl group preferably has 11-13 carbon atoms, sodium alkyl sulfate, e.g that obtained by sulfating a

Ci₈ alkanol. To improve the performance of such deterg compositions against greasy stains and soils, it conventional to include a nonionic detersive surfacta typically a condensation product of a (C₆-C₁₅ alkyl) phe or a C₈-C22 alkanol with ethylene oxide. Prefer condensates are those containing 3-12 moles of ethyl oxide per mole of alkylphenol or 4-8 moles of ethyl oxide per mole of alkanol. A particular preferred nonio is a condensate of C₁₄-C₁₅ alkanol with 7 moles of ethyl oxide per mole of alkanol.

The ethylene oxide used in the preparation of the ab discussed nonionics is, however, derived from oil a furthermore, is a reagent that needs careful handling order to minimise the risk of explosion. Thus, on acco both of economics and of saftey and other environmen considerations, it would be desirable to find alternative nonionic surfactant. Summary of the invention

The present invention relates to the use as a nonio detersive surfactant in a detergent composition of one more glyceryl ethers of the general formula

RO - (C₃-H₆-0₂)_nH (1) wherein

R represents an alkyl or alkenyl group of from 12 to

18 carbon atoms,

C₃H6O2 represents a divalent radical formed by removal from glycerol of an hydroxyl group and of the hydrogen from another hydroxyl group, and _n is an integer, in particular glyceryl ethers of which 50-100 mole percent is constituted by diglyceryl ether ( n = 2 ) and 0-25 mole percent is constituted by monoglyceryl ether ( n = 1 ) , the remainder, if any, being constituted by triglyceryl ethers ( n = 3 ) and/or higher ho ologues (n>3) .

In one aspect , the present invention provides a detergent composition comprising (a) one or more glyceryl ethers of the general formula (1) as defined above and (b) an anionic detersive surfactant. Description of exemplary embodiments.

The glyceryl ethers of the general formula (1) defined above are effective as nonionic detersive surfactants. At least 50 mole percent and preferably at least 60 mole percent of the glyceryl ethers of the formula (1) present in the detergent composition of this invention should be constituted by diglyceryl ether and not more than 25 mole percent, preferably not more than 20 mole percent should be constituted by monoglyceryl ether. The remainder, if any, of the glyceryl ether component (a) is constituted by triglyceryl ethers and/or higher homologues.

Generally, it has been found that the higher the content of diglyceryl ether in the glyceryl ether component (a) , the better. It is preferred that diglyceryl ether should constitute 80 mole percent or more of the glyceryl ether component; it is particularly preferred that the glyceryl ether component of the present compositions should be substantially entirely composed of diglyceryl ether.

Diglyceryl ethers may be prepared by a process known in principle from the article by H.Sagitani et al , entitled

"Solution properties of homogenious polyglycerol dodecyl ether nonionic surfactants", J.A.O.C.S., Vol. 66, No.l January 1989 ) pages 146-152. Specifically, Sagitani et disclose the preparation of diglyceryl dodecyl ether by process in which sodium is added to anhydrous glycer under a nitrogen atmosphere, the solution is heated 130°C for 1 hour, glycidyl dodecyl ether is added dropwi to the resultant sodium glycerate over 1 hour at 180°C, t mixture is stirred for 8 hours and the product is purifi on a silica gel column using chloroform/methanol (98:2) a solvent. Sagitani et al depicted the preparative proce by means of the following reaction scheme:

R₁₂0(CH₂CHCH₂0)₂H OH

wherein

R^₂ represents the dodecyl radical.

The present applicant has found that the preparati process can be applied not just to the R₁₂ compound but compounds with any radical within the meaning specified f R in general formula (1) above. R is usually derived fr a primary or secondary alcohol.

Furthermore, whereas the method taught by Sagitani et depends upon a chromatographic purification, it has n been found that the principal by-product, glycerol cycl dimer and also free fatty alcohol present in the epoxi can be removed to a satisfactory extent in a manner thoug to be novel in this context, i.e by simple distillation. Thus it has been proved possible to obtain, using simple vacuum distillation, for example at a pot temperature of about 200°C, about 95% alkyl glyceryl ethers containing less than 2% cyclic by-product and less than 2% free fatty alcohol, without significant discoloration and degradation. This is surprising, particularly as Takaishi et al in US-A- 4,465,866 (column 3, line 10-14) disparage distillation in processes for the preparation of polyol ethers as being irksome and incapable of industrial application. Where the glyceryl ether product obtained by this process has less than the required molar percentage of diglyceryl ether and/or more than the specified maximum of monoglyceryl ether, the diglyceryl ether content can be worked up by conventional purification and isolation techniques.

It has also been found that, in addition to the diglyceryl ether of the formula

R - OCH₂CHOHCH₂.0CH₂CHOHCH₂.OH (2) ,

the diglyceryl ether of the formula

R - OCH₂CHOHCH₂.OCH-CH₂OH (3)

\

CH₂OH

is also generally formed. Typically, about one mole of diglyceryl ether (3) is formed for every four moles of diglyceryl ether (2) that are produced.

Mixtures of or comprising the positional isomers of the formulae (2) and (3) are thought to be novel. Sagitani et al, Op.cit. , disclose only the possibility of diastereomers, an aspect of optical isomerisms due to the fact that glycerol is prochiral. When preparing mixtures containing the isomer (3) it is thought that silica-gel chromatgraphy should be avoided since the higher content of primary alcohol groups may be predicted to render the isomer more substantive to silica gel and hence susceptible to remova Mixtures of the position isomers (2) and (3) may well gi rise to the better cleaning characteristics than the sing isomer alone.

In general, the group R bonds to the first glycerol moie at the primary site of the latter. The second glycer could, in principle, bond to the secondary site of t first glycerol; in practise, however, it has generally be found that less than 10 mole percent of the diglyceri ethers have such bonding at the said secondary site. R may represent a mixture of alkyl and/or alkenyl radical as will be the case, for example, when the glyceryl ethe are obtained from naturally occurring fatty alcohols RO An example is coconut alcohol, which contains primari ^c12» ^c14 ^{and c}16 saturated alkyl radicals, with small amounts of C₈, C₁₀ and C₁₈ alkenyl radicals. A preferr meaning for R is cocoyl, in particular so-called "topp and tailed" and "narrow-range" cocoyl, which predominantly n-dodecyl (C₁₂) and n-tetradecyl (C14) .

The glycidyl alkyl (or alkenyl) ethers are known compound some of which may be obtained commercially, or may prepared by methods known in principle. Thus, for exampl a useful starting material is the alkyl glycidyl eth available under the trade name "Epoxide No. 8" from Proct & Gamble, the alkyl groups in this epoxide being narro range cocoyl.

The diglyceryl ethers may also be prepared by a meth known in principle from US-A-4,465,866 (Takaishi et al This U.S. Patent teaches that a diglyceryl ether of t formula (2) given above can be prepared by reacting, in t presence of an acid or basic catalyst, an alkyl ( alkenyl) glycidyl ether with an acetal or ketal derivati of glycerol in order to obtain a l, 3-dioxolane, which then subjected to hydrolysis. Takaishi et al also menti earlier proposals for the preparation of such diglyce ethers, in particular (i) the reaction of the linear di of glycerol with an alkali to form an alkali me alcoholate, which is then reacted with alkyl halide, and (ii) the reaction of an alcohol with a cyclic compound of the l, 3-dioxolane type with hydrolysis of the resultant addition product ( reference being made to Journal f. Prakt.Chemie, Band 316 (1974), 325-336).

The glyceryl ether components (a) will be present in the compositions of this invention in an amount usually of the form 0.5 to 30%, preferably from 3 to 15% and more preferably from 5 to 10 %, by weight.

The detergent compositions of this invention, which may be in liquid or granular form, will also contain at least one anionic detersive surfactant. Optionally, the composition may also comprise at least one other detersive surfactant, preferably selected from cationic, ampholytic and zwitterionic detersive surfactants, as well as other component conventional in the art, for example a builder, an enzyme, a bleach, a bleach activator, a polymeric soil- release agent, a chelating agent, a clay soil removal/anti- redeposition agent, a polymeric dispersing agent, a brightener, a suds suppressor, a pH-buffering agent, a dye or a pigment. It will be understood that any of the above mentioned components, whether essential or optional, may be constituted, if desired, by a mixture of two or more compounds of the appropriate description.

The detersive surfactant(s) will typically be used in a total amount of from 0 to 50, preferably 1 to 30 and more preferably 5 to 20 percent by weight.

Although the invention is especially useful in heavy duty or general purpose, laundry detergent compositions, the expression "detergent compositions" herin also includes dishwashing compostions, hard-surface and other household cleaners and personal care products such as shampoos. Examples of anionic detersive surfactants and of the various optional components that come into consideration are as follows. Anionic Surfactants

The detergent compositions of the present invention c contain, in addition to the nonionic surfactant system the present invention, one or more anionic surfactants described below.

Alkyl Ester Sulfonate Surfactant

Alkyl ester sulfonate surfactants hereof include line esters of C₈-C_2Q carboxylic acids (i.e. , fatty acid which are sulfonated with gaseous SO₃ according to "T Journal of the American Oil Chemists Society", 52 (1975 pp 323-329. Suitable starting materials would inclu natural fatty substances as derived from tallow, palm oi etc.

The preferred alkyl ester sulfonate surfactant, especial for laundry applications, comprise alkyl ester sulfona surfactants of the structural formula:

O R³ - CH - C - OR⁴

S0₃M

wherein R³ is a C₈-C₂₀ hydrocarbyl, preferably an alky or combination thereof, R₄ is a C^-Cg hydrocarby preferably an alkyl, or combination thereof, and M is cation which forms a water soluble salt with alkyl est sulfonate. Suitable salt-forming cations include meta such as sodium, potassium, and lithium, and substituted unsubstituted ammonium cations, such as monoethanolamin diethanolamine, and triethanola ine. Preferably, R^{3 c}1₀~^c1₆ alkyl and R⁴ is methyl, ethyl or isopropy

Especially preferred are the methyl ester sulfonat wherein R³ is C₁₀~^c1₆ alkyl.

Alkyl Sulfonate Surfactant

Alkyl sulfate surfactants hereof are water soluble sal or acids of the formula ROSO3M wherein R preferably is ^c10"^c24 hydrocarbyl, preferably an alkyl or hydroxyal having a C₁₀-C₂o alkyl component, more preferably a C₁₂- c₁₈ alkyl or hydroxyalkyl, and M is H or a cation, e.g. an alkali metal cation (e.g., sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethly- , and trimethyl ammonium cations and quaternary ammonium cations such as tetramethly-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like) . Alkyl chains 12-16 carbon atoms, more preferably 14-15 carbon atoms are preferred. Alkyl Alkoxylated Sulfate Surfactants

Alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A)_mS0₃ ^M wherein R is an unsubstituted C₁₀-C₂ alkyl or hydroxyalkyl group having a C_1Q~C₂4 alkyl component, preferably a C^₂-C₂o alkyl or hydroxyalkyl, more preferably an alkyl group having from 12 to 18 carbon atoms, especially from 12 to 15 carbon atoms.

A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted ammonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium cations and σuaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like. A preferred surfactant is C₁₂~^c15 alkyl polyethoxylate (3.0) sulfate (C₁₂-C₁5E(3.0)M) . Other exemplary surfactants include C₁ -C₁₈ alkyl polyethoxylate (1.0) sulfate (Ci2~^c1₈ ^E(¹-°)^M» ^c12"^c18 alkyl polyethoxylate (2.25) sulfate (C₁₂-C₁₈E(2.25)M) , C₁₂-C₁₈ alkyl polyethoxylate (3.0) sulfate (C₁₂-C₁₈E(3.0)M) , and C₁₂-C alkyl polyethoxylate (4.0) sulfate

(^C12~^C ₁₈ ^E( •°)^M) wherein M is conveniently selected fro sodium and potassium.

Other Anionic Surfactants

Other anionic surfactants useful for detersive purpos can also be included in the detergent compositions of t present invention. These can include salts (includin for example, sodium, potassium, ammonium, and substitut ammonium salts such as mono-, di- and triethanolami salts) of soap, ^c _o ^-G ₂n li^near alkylbenzenesulfonates, C

C__ primary or secondary alkanesulfonates, C_-C olefinsulfonates, sulfonated polycarboxylic acids prepar by sulfonation of the pyrolyzed product of alkaline ear metal citrates, e.g., as described in British Pate specification No. 1,082,179, ^c ₈"^c alkylpolyglycethersulfates ( containing up to 10 moles ethylene oxide); alkyl glycerol sulfonates, fatty ac glycerol sulfonates, fatty oleyl glycerol sulfates, alk phenol ethylene oxide ether sulfates, paraffin sulfonate alkyl phosphates, isethionates such as the ac isethionates, N-acyl taurates, alkyl succinamates a sulfosuccinates, monoesters of sulfosuccinate (especial saturated and unsaturated C. -C monoesters) and dieste of sulfosuccinate (especially saturated and unsaturat C --C12 diesters) , acyl sarcosinates, sulfates alkylpolysaccharides such as the sulfates alkylpolyglucoside (the nonionic nonsulfated compoun being described below) , branched primary alkyl sulfate alkyl polyethoxy carboxylates such as those of the formu RO(CH₂CH₂0)_kCH₂COO-M⁺ wherein R is a C₈-C₂₂ alkyl, k is integer from 0 to 10, and M is a soluble salt-formi cation. Resin acids and hydrogenated resin acids are al suitable, such as rosin, hydrogenated rosin, and res acids and hydrogenated resin acids present in or deriv from tall oil. Further examples are given in "Surfa Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch) . A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference) .

Prefered anionic surfactants systems employed in -the detergent compositions of the invention are free fo alkyl benzene sulfonate salts. A highly preferred system comprises a mixture of a major proportion of a 0^4-0^5 primary alkyl sulfate and a minor proportion of a C₁₂-Ci5 alkyl ethoxysulfate containing an average of three ethoxy groups per mole of alkyl ethoxy sulfate. The detergent compositions of the present invention typically comprise from about 1% to about 20 %, preferably from about 3% to about 15% and most preferably from 5% to 10% by weight of anionic surfactants. Other Surfactants

The detergent compositions of the present invention may also contain cationic, ampholytic, zwitterionic, and semi- polar surfactants, and even further nonionic surfactants. Cationic detersive surfactants suitable for use in the detergent compositions of the present invention are those having one long-chain hydrocarbyl group. Examples of such cationic surfactants include the ammonium surfactants such as alk ldimethylammomium halogenides, and those surfactants having the formula:

[R²(OR³) _γ ] [R (OR³)_y]₂R⁵N+X-

wherein R² is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R³ is selected from the group consisting of -CH2CH₂-,

CH₂CH(CH₃)-, -CH₂CH(CH₂OH)-, - CH₂CH₂CH₂-, and mixtures thereof; each R⁴ is selected from the group consisting of ^cl"^c4 alkyl, ^-04 hydroxyalkyl, benzyl ring structures formed by joining the two R⁴ groups, - CH₂CH0H- CHOHCOR⁶CHOHCH2θH wherein R⁶ is any hexose or hexo polymer having a molecular weight less than about 100 and hydrogen when y is not 0; R⁵ is the same as R⁴ or an alkyl chain wherein the total number of carbon atoms R² plus R⁵ is not more than about 18 ; each y is from 0. about 10 and the sum of the y values is from 0 to abo 15; and X is any compatible anion.

Other cationic surfactants useful herein are al described in the U.S. Patent 4,228,044, Cambre, issu October 14, 1980, incorporated herein by reference. When included therein, the detergent compositions of t present invention typically comprise from 0% to about 25 preferably from about 3% to about 15% by weight of su cationic surfactants.

Ampholytic surfactants are also suitable for use in t detergent compositions of the present invention. The surfactants can be broadly described as aliphat derivatives of secondary or tertiary amines, or aliphat derivatives of heterocyclic secondary and tertiary amin in which the aliphatic radical can be straight chain branched. One of the aliphatic substituents contains least about 8 carbon atoms, typically from about 8 about 18 carbon atoms, and at least one contains anionic water-solubilizing group, e.g., carbox sulfonate, sulfate. See U.S. Patent No. 3,929,678 Laughlin et al. , issued December 30, 1975 at column 1 lines 18-35 (herein incorporated by reference) f examples of ampholytic surfactants.

When included therein, the detergent compositions of t present invention typically comprise from 0% to about 15 preferably from about 1% to about 10% by weight of su ampholytic surfactants.

Zwitterionic surfactants are also suitable for use detergent compositions . These surfactants can be broad described as derivatives of secondary and tertiary amine derivatives of heterocyclic secondary and tertiary amine or derivatives of quaternary ammonium, quaterna phosphonium or tertiary sulfonium compounds. See U.S. Patent No. 3,929,678 to Laughlin et al. , issued December 30, 1975 at column 19, line 38 through column 22, line 48 (herein incorporated by reference) for examples of zwitterionic surfactants.

When included therein, the detergent compositions of the present invention typically comprise from 0% to about 15%, preferably from about 1% to about 10% by weight of such zwittarionic surfactants.

Semi-polar nonionic surfactants are a special category of nonionic surfactants which include water-soluble amine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; water- soluble phosphine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.

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

wherein R is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms; R is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3; and each R is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups.

5 The R groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure. These amine oxide surfactants in particular include C -

C alkyl dimethyl amine oxides and ^c ₈~^c ₁₂ alkoxy ethyl dihydroxy ethyl amine oxides.

When included therein, the detergent compositions of the present invention typically comprise from 0% to about 15%, preferably from about 1% to about 10% by weight of such semi-polar nonionic surfactants.

Nonionic surfactants

The detergent compositions of this invention may contain a nonionic surfactant in addition to the glyceryl ether component discussed above.

Suitable nonionic surfactants include the polyethylene oxide condensates of alkly phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from 6 to 8 carbon atoms, in either a straight-chain or branched-chain configuration, with from 1 to 12 moles of ethylene oxide per mole of alkyl phenol.

Suitable nonionics also include the condensation products of aliphatic alcohols containing from 8 to 22, preferably

12 to 18, carbon atoms, in either straight-chain or branched-chain configuration, with from 2 to 12, preferably 3 to 7, moles of ethylene oxide per mole of alcohol.

Suitable nonionic surfactants also include the fatty acyl or alkyl condensation products of carbohydrates and their derivatives such as glycosides, aminodeoxy forms, and polyols. Examples include coco-alkyl polyglucosides and tallow-acyl-N-methyl-glucamides.

The additional nonionic surfactants, if used, will generally be present at a level of up to 15 percent, usually from 1 to 6 precent, by weight of the composition. Builders

The detergent compositions of the present invention can comprise inorganic or organic detergent builders to assist in mineral hardness control.

The level of builder can vary widely depending upon the end use of the composition and its desired physical form. Liquid formulations typically comprise at least about 1%, more typically from about 5% to about 50%, preferably from about 5% to about 30% by weight of the detergent builder. Granular formulations typically comprise at least about 1%, more typically from about 10% to about 80%, preferably from about 15% to about 50% by weight of the detergent builder. Lower or higher levies of builder, however, are not meant to be excluded.

Inorganic detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates) , phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates) , sulphates, and aluminosilicates. Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions can also be used but are not preferred at wash conditions less than about 50°C, especially less than about 40°C. Preferred builder systems are also free of phosphates.

Examples of silicate builders are the alkali metal silicates, particularly those having a Siθ2:Na₂0 ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck, incorporated herein by reference. However, other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems. Examples of carbonate builders are the alkaline earth an alkali metal carbonates, including sodium carbonate and sesquicarbonate and mixtures thereof with ultra-fine calcium carbonate as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973, the disclosure of which is incorporated herein by reference.

Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula:

M₂(zAl0₂'ySi0₂)

wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2; and y is 1; this material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaCO hardness per gram of anhydrous aluminosilicate. Preferred alumino¬ silicates are zeolite builders which have the formula:

Na_z[(A10₂)_z (Si0₂)_y].xH₂0

wherein z and y are integers of at least 6, the mola ratio of z to y is in the range from 1.0 to about 0.5, an x is an integer from about 15 to about 264. Useful aluminosilicate ion exchange materials ar commercially available. These aluminosilicates can b crystalline, or amorphous in structure and can b naturally-occurring aluminosilicates or syntheticall derived. A method for producing aluminosilicate io exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, el at , issued October 12, 1976, incorporated herei by reference. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B) , and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:

Na₁₂[( l0₂)₁₂(Si0₂)₁₂]-xH₂0

wherein x is from about 20 to about 30, especially about 27. This material is known as Zeolite A. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter.

Specific examples of polyphosphates are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassiuA orthophosphate, sodium polymeta phosphate in which the degree of polymerization ranges from about 6 to about 21, and salts of phytic acid. Examples of phosphonate builder salts are the water- soluble salts of ethane 1-hydroxy-l, 1-diphosphonate particularly the sodium and potassium salts, the water- soluble salts of methylene diphosphonic acid e.g. the trisodium and tripotassium salts and the water-soluble salts of substituted methylene diphosphonic acids, such as the trisodium and tripotassium ethylidene, isopyropylidene benzylmethylidene and halo methylidene phosphonates. Phosphonate builder salts of the aforementioned types are disclosed in U.S. Patent Nos. 3,159,581 and 3,213,030 issued December 1, 1964 and October 19, 1965, to Diehl; U.S. Patent No. 3,422,021 issued January 14, 1969, to Roy; and U.S. Patent Nos. 3,400,148 and 3,422,137 issued September 3, 1968, and January 14, 1969 to uimby, said disclosures being incorporated herein by reference. Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form alkali metals, such as sodium, potassium, and lithiu salts, especially sodium salts, or ammonium an substituted ammonium ( e.g., alkanolammonium ) salts ar preferred.

Included among the polycarboxylate builders are a variet of categories of useful materials. One important categor of polycarboxylate builders encompasses the ethe polycarboxylates. A number of ether polycarboxylates hav been disclosed for use as detergent builders. Examples o useful ether polycarboxylates include oxydisuccinate, a disclosed in Berg, U.S. Patent 3,128,287, issued April 7 1964, and Lamberti et al. , U.S. Patent 3,635,830, issue January 18, 1972, both of which are incorporated herein b reference.

A specific type of ether polycarboxylates useful a builders in the present invention also include thos having the general formula:

CH(A) (COOX)-CH(COOX)-0-CH(COOX)-CH(COOX) (B)

wherein A is H or OH; B is H or -O-CH(COOX)-CH₂(COOX) ; an

X is H or a salt-forming cation. For example, if in th above general formula A and B are both H, then th compound is oxydissuccinic acid and its water-solubl salts. If A is OH and B is H, then the compound i tartrate monosuccinic acid (TMS) and its water-solubl salts. If A is H and B is -O-CH(COOX)-CH₂ (COOX) , then th compound is tartrate disuccinic acid (TDS) and its water soluble salts. Mixtures of these builders are especiall preferred for use herein. Particularly preferred ar mixtures of TMS and TDS in a weight ratio of TMS to TD of from about 97:3 to about 20:80. These builders ar disclosed in U.S. Patent 4,663,071, issued to Bush et al. on May 5, 1987.

Suitable ether polycarboxylates also include cycli compounds, particularly alicyclic compounds, such as thos described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903, all of which are incorporated herein by reference.

Other useful detergency builders include the ether hydroxypolycarboxylates represented by the structure:

HO-[C(R) (COOM)-C(R) (COOM)-0]_n~H wherein M is hydrogen or a cation wherein the resultant salt is water-soluble, preferably an alkali metal, ammonium or substituted ammonium cation, n is from about 2 to about 15 (preferably n is from about 2 to about 10, more preferably n averages from about 2 to about 4) and each R is the same or different and selected from hydrogen, C, . alkyl or C, . substituted alkyl (preferably

R is hydrogen) .

Still other ether polycarboxylates include copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid.

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

Also included are polycarboxylates such as mellitic acid, succinic acid, polymaleic acid, benzene 1,3,5- tricarboxylic acid, benezene pentacarboxylic acid, and carboxymethyloxysuccinic acid, and soluble salts thereof. Citric builders, e.g., citric acid and soluble salts thereof, is a polycarboxylate builders of particular importance for heavy duty liquid detergent formulations, but can also be used in granular compositions. Suitable salts include the metal salts such as sodium, lithium, and potassium salts, as well as ammonium and substituted ammonium salts. Other carboxylate builders include the carboxylat carbohydrates disclosed in U.S. Patent 3,723,322, Dieh issued March 28, 1973, incorporated herein by reference.

Also suitable in the detergent compositions of the prese invention are the 3,3-dicarboxy-4-oxa-l,6-hexanedioat and the related compounds disclosed in U.S.. Pate

4,566,984, Bush, issued January 28, 1986, incorporat herein by reference. Useful succinic acid builde include the C-.-C- alkyl succinic acids and salts thereo

A particularly preferred compound of this type dodecenylsuccinic acid. Alkyl succinic acids typical are of the general formula

R-CH(COOH)CH₂ (COOH) i.e., derivatives of succinic aci wherein R is hydrocarbon, e.g., C -C alkyl or alkeny preferably C,2_-C1,_c6 or wherein R may be substituted wi hydroxyl, sulfo, sulfoxy or sulfone substituents, all described in the above-mentioned patents.

The succinate builders are preferably used in the form their water-soluble salts, including the sodiu potassium, ammonium and alkanolammonium salts. Specific examples of succinate builders includ laurylsuccinate, myristylsuccinate, palmitylsuccinate, dodecenylsuccinate (preferred) , 2-pentadecenylsuccinat and the like. Laurylsuccinates are the preferred builde of this group, and are described in European Pate Application 86200690.5/0,200,263, published November 1986.

Examples of useful builders also include sodium a potassium carboxymethyloxymalonat carboxymethyloxysuccinate, cis-cyclo-hexan hexacarboxylate,cis-cyclopentane-tetracarboxylate, wate soluble polyacrylates (these polyacrylates havi molecular weights to above about 2,000 can also effectively utilized as dispersants) , and the copolyme of maleic anhydride with vinyl methyl ether or ethylene. Other suitable polycarboxylates are the polyacet carboxylates disclosed in U.S. Patent 4,144,22 Crutchfield et al, issued March 13, 1979, incorporated herein by reference. These polyacetal carboxylates can be prepared by bringing together, under polymerization conditions, an ester of glyoxylic acid and a polymerization initiator. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, converted to the corresponding salt, and added to a surfactant. Polycarboxylate builders are also disclosed in U.S. Patent 3,308,067, Diehl, issued March 7, 1967, incorporated herein by reference. Such materials include the water- soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.

Other organic builders known in the art can also be used. For example, monocarboxylic acids, and soluble salts thereof, having long chain hydrocarbyls can be utilized.

These would include materials generally referred to as "soaps." Chain lengths of C-.-C-- are typically utilized.

The hydrocarbyls can be saturated or unsaturated. Enzymes

Detersive enzymes can be included in the detergent compositions of the present invention for a variety of reasons including removal of protein-based, carbohydrate- based, or triglyceride-based stains, for example, and prevention of refugee dye transfer. The enzymes to be incorporated include proteases, amylases, lipases, cellulases, and peroxidases, as well as mixtures thereof. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH- activity and/or stability optima, thermostability, stability versus active detergents, builders and so on. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and funga cellulases.

Suitable examples of proteases are the subtilisins whic are obtained from particular strains of B.subtilis an B.licheniforms. Another suitable protease is obtaine from a strain of Bacillus, having maximum activit throughout the pH range of 8-12, developed and sold b Novo Industries A/S under the registered trade nam Esperase^@. The preparation of this enzyme and analogou enzymes is described in British patent specification No. 1,243,784 of Novo. Proteolytic enzymes suitable fo removing protein-based stains that are commerciall available include those sold under the tradename ALCALASE™ and SAVINASE™ by Novo Industries A/S (Denmark) and MAXATASE™ by International Bio-Synthetics, Inc. (Th Netherlands) .

Of interest in the category of proteolytic enzymes, especially for liquid detergent compositions, are enzyme referred to herein as Protease A and Protease B. Proteas A and methods for its preparation are described i European Patent Application 130,756, published January 9, 1985, incorporated herein by reference. Protease B is proteolytic enzyme which differs from Protease A in tha it has a leucine substituted for tyrosine in position 21 in its amino acid sequence. Protease B is described i European Patent Application Serial No. 87303761.8, file April 28, 1987, incorporated herein by reference. Method for preparation of Protease B are also disclosed i European Patent Application 130,756, Bott et al. , publishe January 9, 1985, incorporated herein by reference. Amylases include, for example, a-amylases obtained from special strain of B.licheniforms, described in more detai in British patent specification No. 1,296,839 (Novo) previously incorporated herein by reference. Amylolyti proteins include, for example RAPIDASE™, Internationa Bio-Synthetics, Inc. and TERMAMYL™, Novo Industries. The cellulases usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4, 435, 307, Barbesgoard et al. , issued March 6, 1984, incorporated herein by reference, which discloses fungal cellulase produced from Humicola insolens. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE- OS-2.247.832.

Examples of such cellulases are cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea) , particularly the Humicola strain DSM 1800, and cellulases produced by a fungas of Bacillus N or a cellulase 212-producing fungas belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusc (Dolabeila Auricula Solander) . Suitable lipase enzymes for detergent usage include those produced by micro-organisms of the of the Pseudomonas groups, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034, incorporated herein by reference. Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase produced by the microorganism Pseudomonas fluorescens IAM 1057. This lipase and a method for its purification have been described in Japanese Patent Application 53-20487, laid open on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd. , Nagoya, Japan, under the trade name Lipase P "Amano," hereinafter referred to as "Amano-P." Such lipases of the present invention should show a positive immunological cross reaction with the Amano-P antibody, using the standard and well-known immunodiffusion procedure according to Ouchterlony (Acta. Med. Scan., 133, pages 76-79 (1950)). These lipases, and a method for their immunological cross-reaction with Amano-P, are also described in U.S. Patent 4,707,291, Thorn et al. , issued November 17, 1987, incorporated herein by reference. Typical examples thereof are the Amano-P lipase, t lipase ex Pseudomonas fracri FERM P 1339 (available und the trade name Amano-B) , lipase ex Pseudomon nitroreducens var. lipolyticum FERM P 1338 (availabl under the trade name Amano-CES) , lipases ex Chromobact viscosum, e.g. Chromobacter viscosum var. lipolytic

NRRLB 3673, commercially available from Toyo Jozo Co.

Tagata, Japan; and further Chromobacter viscosum lipas from U.S. Biochemical Corp., U.S.A. and Disoynth Co., T

Netherlands, and lipases ex Pseudomonas gladioli.

Peroxidase enzymes are used in combination with oxyg sources, e.g., percarbonate, perbonate, persulfate hydrogen peroxide, etc. They are used for "solutio bleaching", i.e. to prevent transfer of dyes or pigment removed from substrates during wash operations to othe substrates in the wash solution. Peroxidase enzymes ar known in the art, and include, for example, horseradis peroxidase, ligninase, and haloperoxidase such as chloro and bromo-peroxidase. Peroxidase-containing detergen compositions are disclosed, for example, in PC

International Application Wo 89/099813, published Octobe

19, 1989, by O.Kirk, assigned to Novo Industries A/S incorporated herein by reference.

A wide range of enzyme materials and means for thei incorporation into synthetic detergent granules is als disclosed in U.S. Patent 3,553,139, issued Jaunary 5, 197 to McCarty et al. (incorporated herein by reference) Enzymes are further disclosed in U.S. Patent No. 4, 10 457, Place et al. , issued July 18, 1978, and in U.S. Pate 4,507,219, Hughes, issued March 26, 1985, bo incorporated herein by reference. Enzyme materials usef for liquid detergent formulations, and their incorporati into such formulations, are disclosed in U.S. Pate 4,261,868, Hora et al . , issued April 14, 1981, al incorporated herein by reference.

Enzymes are normally incorporated at levels sufficient provide up to about 5 mg by weight, more typically abo 0.5 mg to about 3 mg, of active enzyme per gram of the composition.

For granular detergents, the enzymes are preferably coated or prilled with additives inert toward the enzymes to minimize dust formation and improve storage stability. Techniques for accomplishing this are well known in the art. In liquidformulations, an enzyme stabilisation system is preferably utilized. nzyme stabilization techniques for aqueous detergent compositions are well known in the art. For example, one technique for enzyme stabilization in aqueous 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 combination with short chain carboxylic acid salts, preferably formates. See. for example, U.S. Patent 4,318,818, Letton et al. , issued March 9, 1982, incorporated herein by reference. It has also been proposed to use polyols like glycerol and sorbitol. Alkoxy-alcohols, dialkylgycoethers, mixtures of polyvalent alcohols with polyfunctional aliphatic amines ( e.g., alkanolamines such as diethanolamine, triethanolamine, di-isoropanolamine,etc ) , and boric acid or alkali metal borate. Enzyme stabilization techniques are additionally disclosed and exemplified in U.S. Patent 4,261,868, issued April 14, 1981 to Horn et al. ,U.S. Patent 3,600,319, issued August 17, 1971 to Gedge, et al. , both incorporated herein by reference, and European Patent Application Publication No. 0 199 405, Application No.86200586.5, published October 29, 1986, Venegas. Non-boric acid and borate stabilizers are preferred. Enzyme stabilization systems are also described, for example, in U.S Patents 4,261,868, 3,600,391, and 3,519,570.

Bleaching Compounds - Bleaching Agents and Bleaching Activators

The detergent composition of the present invention may contain bleaching agents or bleaching compositions, containing bleaching agent or one or more bleach activators. When included, present bleaching compounds will typically comprise from about 1% to about 20%, more typically from about 1% to about 10%, of such laundry detergent composition. In general, bleaching compounds are optional components in non-liquid formulations, e.g., granular detergents. If present, the amount of bleach activators will typically be from about 0.1% to about 60%, more typically from about 0.5% to about 40% of the bleaching composition.

The bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known. These include oxygen bleaches as well as other bleaching agents. For wash conditions below about 50°C, especially below about 40°C, it is preferred that the compositions hereof not contain borate or material which can form borate in situ (i.e. borate-forming material) under detergent storage or wash conditions. Thus it is preferred under these conditions that a non-borate, non-borate forming bleaching agent is used. Preferably, detergents to be used at these temperatures are substantially free of borate or borate- forming material. As used herein, "substantially free or borate or borate-forming material" shall mean that the composition contains not more than about 2% by weight of borate-containing and borate-forming material of any type, preferably, no more than 1%, more preferably 0%. One category of bleaching agent which can be used encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloroperbenzoic acid, 4-nonylamino-4- oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent Application 740,446, Burns et al. ,filed June 3, 1985, European Patent Application 0,133,354, Banks et al. ,published February 20, 1985, and U.S. Patent 4,412,934, Chung et al. , issued November 1, 1983, all of which are incorporated by reference herein. Highly preferred bleaching agents also include 6-nonlyamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6.1987 to Burns et al., incorporated herein by reference.

Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide, and subject to the wash condition limitation perviously mentioned, sodium perborate onohydrate and tetrahydrate.

Peroxygen bleaching agents are preferably combined with bleach activators, which lead to the in situ production in aqueous solution ( i.e., during the washing process ) of the peroxy acid corresponding to the bleach activator. A wide range of bleach activators can be used, examples being disclosed in Spadini et al USP 4179390. Preferred bleach activators include the tetraacetyl alkylene dia ines, particularly tetraacetyl ethylene diamine (TAED) and tetraacetyl glycouril (TAGU) .

R - C - L

wherein R is the alkyl group containing from about 1 to about 18 carbon atoms wherein the longest linear alkyl chain extending from and including the carbonyl carbon contains from about 6 to about 10 carbon atoms and L is a leaving group, the conjugate acid of which has a pK_a in the range from about 4 to 13. These bleach activators are described in U.S. Patent 4,915,854, issued April 10, 1990 to Mao etal. , incorporated herein by reference, and the U.S. Patent 4,412,934, which was previously incorporated herein by reference. Bleaching agents other than oxygen bleaching agents ar also known in the art and can be utilized herein. One typ of non-oxygen bleaching agent of particular interes includes photo-activated bleaching agents such as th sulfonated zinc and/or aluminimu phthalocyanines. Thes materials can be deposited upon the substrate during th washing process. Upon irradiation with light, in th presence of oxygen, such as by hanging clothes out to dr in the daylight, the sulfonated zinc phthalocyanine i activated and, consequently, the substrate is bleached

Preferred zinc phthalocyanine and a photoactivate bleaching process are described in U.S. Patent 4,033,718 issued July 5, 1977 to Holcombe et al. ,incorporated herein b reference. Typically, detergent compositions will contai about 0.025% to about 1.25% by weight, of sulfonated zin phthalocyanine.

Polymeric Soil Release Agent

Any polymeric soil release agents known to those skilled in the art can be employed in the detergent compositions of the present invention. Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.

Polymeric soil release agents include cellulosic derivatives such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polyrropylene oxide terephthalate, and the like.

Cellulosic derivatives that are functional as soil release agents are commercially available and include hydroxyethers of cellulose such as Methocel^R (Dow) . Cellulosic soil release agents also include those selected from the group consisting of 0^-04 alkyl and c₄ hydroxyalkyl cellulose such as methylcellulose, ethylcellulose, hydroxypropyl methycellulose, and hydroxybutyl methylcellulose. A variety of cellulose derivatives useful as soil release polymers are disclosed in U.S. Patent 4,000,093, issued December 28, 1976 ^"to Nicol, etal. , incorporated herein by reference. Soil release agents characterized by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g. C^-C_Q vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylen oxide backbones. Such materials are known in the art and are described in European Patent Application 0,219,048, published April 22, 1987 by Kud, et al. Suitable commercially available soil release agents of this kind include the Sokalan™ type of material, e.g., Sokalan™ HP-22, available from BASF (West Germany) . One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. More specifically, these polymers are comprised of repeating units of ethylene terephthalate and PEO terephthalate in a mole ratio of ethylene terephthalate units to PEO terephthalate units of from about 25:75 to about 35:65, said PEO terephthalate units containing polyethylene oxide having molecular weights of from about 300 to about 2000. The molecular weight of this polymeric soil release agent is in the range of from about 25,000 to about 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976, which is incorporated by reference. See also U.S. Patent 3,893,929 to Basadur issued July 8, 1975 (incorporated by reference) which discloses similar copolymers.

Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units containing 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethlyene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-

5,000, and the mole ratio of ethylene terephthalate units to polyoxyethylene terephthalate units in the polymeric compound is between 2:1 and 6:1. Examples of this polymer include the commercially available material Zelcon^R 5126

(from Dupont) and Milease ^R T (from ICI) . These polymers and methods of their preparation are more fully described in U.S. Patent 4,702,857, issued October 27, 1987, to

Gosselink, which is incorporated herein by reference.

Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyaleneoxy repeat units and terminal moieties covalently attached to the backbone, said soil release agent being derived from a allyl alcohol ethoxylate, dimethtlterephthalate, and 1,2 propylene diol, wherein the terminal moieties of each oligomer have, on average, a total of from about 1 to about 4 sulfonate groups. These soil release agents are described fully in

U.S. Patent 4,968,451, issued 6 November, 1990 to J. J.

Scheibel and E. P. Gosselink, U.S. Serial No. 07/474,709, filed January 29, 1990, incorporated herein by reference.

Other suitable polymeric soil release agents include the ethyl- or methyl-capped 1,2-propylene terephthalate- polyoxy- ethylene terephthalate polyesters of U.S. Patent

4,711,730, issued December 8, 1987, to Gosselink et al. , the anionic end-capped oligomeric esters of U.S. Patent

4,721,580, issued January 26, 1988, to Gosselink, wherein the anionic end-caps comprise sulfo-polyethoxy groups derived from polyethylene glycol (PEG) , the block polyester oligomeric compounds of U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink, having polyethoxy end-caps of the formula X-(OCH₂CH2)_n- wherein n is from

12 to about 43 and X is a C1-C4 alkyl, or preferably methyl, all of these patents being incorporated herein by reference.

Additional soil release polymers include soil release polymers of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al. , which discloses anionic, especially sulfoaroyl, end-capped terephthalate esters, said patent being incorporated herein by reference. The terephthalate esters contain unsymmetrically substituted oxy-1,2- alkyleneoxy units.

If utilized, soil release agents will generally comprise from about 0.01% to about 10.0%, preferably from about 0.1% to about 5.0%, more preferably from about 0.2% to about 3.0% by weight of the laundry detergent compositions of the present invention. Chelating Agents

The detergent compositions of the present invention may also contain one or more iron and manganese chelating agents as a builder adjunct material. Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally- substituted aromatic chelating agents and mixtures thereof, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates. Amino carboxylates useful as optional chelating agents in compositions of the invention can have one or more, preferably at least two, units of the substructure

-CH₂

\

^{N *} (^CH?>v ^{" C00M}'

/ wherein M is hydrogen, alkali metal, ammonium or substituted ammonium (e.g. ethanolamine) and x is from 1 to about 3, preferably 1. Preferably, these amino carboxylates do not contain alkyl or alkenyl groups wit more than about 6 carbon atoms. Operable amin carboxylates include ethylenediaminetetraacetates, N hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexa-acetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salt thereof and mixtures thereof.

Amino phosphonates are also suitable for use as chelatin agents in the detergent compositions of the invention whe at least low levels of total phosphorus are permitted i detergent compositions. Compounds with one or more, preferably at least two, units of the substructure

CH,

N <^CH2>x P0₃M₂,

/ wherein M is hydrogen, alkali metal, ammonium o substituted ammonium and x is from 1 to about 3, preferably 1, are useful and includ ethylenediaminetetrakis (methylenephosphonates) , nitrilotris (methylenephosphonates) an diethylenetriaminepentakis (methylenephosphonates) . Preferably, these amino phosphonates do not contain alky or alkenyl groups with more than about 6 carbon atoms. Alkylene groups can be shared by substructures. Polyfunctionally-substituted aromatic chelating agents a also useful in the compositions herein. These materia can comprise compounds having the general formula:

wherein at least one R is -SO_H or -COOH or soluble salts thereof and mixtures thereof. U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al., incorporated herein by reference, discloses polyfunctionally-substituted aromatic chelating and sequestering agents. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy -3,5- disulfo- benzene. Alkaline detergent compositions can contain these materials in the form of alkali metal, ammonium or substituted ammonium (e.g. mono-or triethanol- a ine) salts.

If utilized, these chelating agents will generally comprise from about 0.1% to about 10% by weight of the laundry detergent compositions of the present invention. More preferably chelating agents will comprise from about 0.1% to about 3.0% by weight of such compositions. Clay Soil Removal/Anti-redeposition Agents Clay soil removal/anti-redeposition agents useful in the detergent compositions of the present invention include polyethylene glycols and water-soluble ethoxylated amines having clay soil removal and anti-redeposition properties. Polyethylene glycol compounds useful in the detergent compositions of the present invention typically have a molecular weight in the range of from about 400 to about 100,000, preferably from about 1,00 to about 20,000, more preferably from about 2,000 to about 12,000, most preferably from about 4,000 to about 8,000. Such compunds are commercially available and are sold as Carbowax^@, which is available from Union Carbide, located in Danbury

Conn.

The water soluble ethoxylated amines are preferabl selected from the group consisting of :

(1) ethoxylated monamines having the formula :

(X-L)-N_R(R²)₂

(2) ethoxylated diamines having the formula :

R²-N-R¹-N-R² (R²)₂-N-R¹-N-(R²)₂ I I I

L L L

I I I

X X X or

(X-L)₂-N-Rl-N-(R²)₂

(3) ethoxylated polyamines having the formula :

R³-(

(4) ethoxylated amine polymers having the general formula :

R² ( (R²)₂-N)_w(R^l-N)_χ(R^l-N)_y(R^l-N-L-X) _Z

L X and

(5) mixtures thereof; wherein A¹ is :

R R R R

0 Q 0 0 0 II f| II || II -CO-, -OCO-, -OC-, -CNC-, or -0-; R is H or C!-C₄ alkyl or hydroxyalkyl R¹ is C₂-c₁₂ alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C₂-C₃ oxyalkylene moiety having from 2 to about 20 oxyalkylene units provided that no O-N bonds are formed ; each R² is Cχ-04 or hydroxyalkyl, the moiety -L-

X, or two R² together form the moiety -(CH₂)_r, -A²-(CH₂)_S-

, wherein A² is -O- or -CH₂-, r is 1 or 2, s is 1 or ^"2, and r + s is 3 or 4 ; X is a nonionic group, an anionic group or mixture thereof ; R³ is a substituted C₃-C12

• alkyl, hydroxyalkyl, alkenyl, aryl, or alkaryl group having substitution sites ; R⁴ is C₁-C₁₂ alkylene, hydroxyakylene, alkenylene, arylene or alkarylene, or a C₂-C₃ oxyalkylene moiety having from 2 to about 20 oxyalkylene units provided that no 0-0 or O-N bonds are formed ; L is a hydrophilic chain which contains the polyoxyalkylene moiety -((R⁵0)_m(CH₂CH₂0)_n)-, wherin R⁵ is C3-C4 alkylene or hydroxyalkylene and m and n are numbers such that the moiety -CH2CH2θ)_n- comprises at least about 50% by weight of said polyoxyalkylene moiety ; for said monamines, m is from 0 to about 3, and n is at least about 6 when R¹ is C₂-C₃ alkylene, hydroxyalkylene, or alkenylene, and at least about 3 when R¹ is other than C₂-

C₃ alkylene, hydroyalkylene or alkenylene ; for said polyamines and amine polymers, m is from 0 to about 10 and n is at least about 3 ; p is from 3 to 8 ; q is 1 or 0 ; t is 1 or 0, provided that t is 1 when q is 1 ; w is 1 or 0 ; x + y + z at least 2 ; and y + z is at least 2.

The most preferred soil release and anti-redeposition agent are ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986, incorporated herein by reference. Another group of preferred clay soil removal/anti-redeposition agents are the cationic compounds disclosed in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984, incorporated herein by reference. Other clay soil removal/anti-redeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22, 1985, all of which are incorporated herein by reference.

The most preferred soil release and anti-deposition agents are ethoxylated tetraethylenepentamine and the polythylene glycols having a molecular weight in the range of from about 4,000 to about 8,000.

Granular detergent compositions which contain such compounds typically contain from about 0.01% to about 10.0% by weight of the clay removal agent; liquid detergent compositions typically contain from about 0.01% to about 5.0% by weight. Polymeric Dispersing Agent

Polymeric polycarboxylate dispersing agents can advantageously be utilized in the detergent compositions of the present invention. These materials can aid in calcium and magnesium hardness control. In addition to acting as a builder adjunt analogously to the poycarboxylate described above in the Builder description, it is believed, though it is not intended to be limited by theory, that these higher molecular weight dispersing agents can further enhance overall detergnet builder performance by inhibiting crystal growth of inorganics, by particulate soil peptization, and by antiredeposition, when used in combination with other builders including lower molecular weight polycarboxylates.

The polycarboxylate materials which can be employed as the polymeric polycarboxylate dispersing agent are these polymers or copolymers which contain at least about 60% by weight of segments with the general formula :

wherein X, Y, and Z are each selected from the group consisting fo hydrogen, methyl, carboxy, carboxmethyl, hydroxy and hydroxymethyl; a salt forming cationand n is from about 30 to about 400. Preferably, X si hydrogen or hydroxy, Y is hydrogent or carboxy, Z is hydrogen and M is hydrogen, alkali metal, ammonia or substituted ammonium. Polymeric polycarboxylate materials of this type can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated onomeric acids that can be polymerized to form suitable polymeric polycarxylates include acrylic acid, aleic acid (or maleic anhydride) , fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence in the polymeric polycarboxylates herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight.

Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers which are useful herein are the water soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000. Water soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions have been disclosed, for example, in Diehl, U.S. Patent No. 3,308,067, issued March 7, 1967. This patent is incorporated herein by reference. Acrylic/maleic-based copolymers may also be used as a preferred component of the dispersing agent. Such materials include the water soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form ranges from about 5,000 to 100,000, preferably from about 6,000 to 60,000, more preferably from about 7,000 to 60,000. The ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1:1, moe preferably from about 10:1 to 2:1. Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are knwon materials which are described in European Patent Application No. 66915, published December 15, 1982, which publication is incorporated herein by reference.

If utilized, the polymeric dispersing agents will generally comprise from about 0.2% to about 10%, preferably form about 1% to about 5% by weight of the detergent compositions. Brightener

Optical brighteners or other brightening or whitening age known to those skilled in the art can be incorporated i the laundry detergent compositions of the present inventi However, the choice of brightener will depend upon a num of factors, such as the type of detergnt, the nature of ot components present in the detergent composition, temperatures of wahs wash, the degree of agitation, and ratio of the material washed to tub size.

The brightener selection is also dependent upon the type of material to be cleaned, e.g. cottons, synthetics, etc. Since most laundry detergent products are used to clean a variety of fabrics, the detergent compositions should contain a mixture of brighteners which will be effective for a variety of fabrics. It is of course necessary that the individual components of such a brightener mixture be compatible.

Commercial optical brighteners can be classified into subgroups which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiphene-5,5- dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982) , the disclosure of which is incorporated herein by reference.

Stilbene derivatives include, but are not necessarily limited to, derivatives of stilbene; triazole derivatives of stilbene; oxadiazole derivatives of stilbene; oxazole derivatives fo stilbene; and stryl of stilbene. Certain derivatives of bis(triazinly) aminostilbene may be prepared from 4,4^,-diamine-stilbene-2,2*-disulfonic acid. Coumarin derivatives include, but are not necessarily limited to, derivatives substituted in the 3-position, in the 7-position, and in the 3- and 7-positions. Carboxylic acid derivatives include, but are not necessarily limited to, fumaric acid derivatives; benzoic acid derivatives; p-phenylene-bis-acrylic acid derivatives; naphthalenedicarboxylic acid derivatives; heterocyclic acid derivatives; and cinnamic acid derivatives. Cinna ic acid derivatives can be further subclassified into groups which include, but are not necessarily limited to, cinnamic acid derivatives, styrylazoles, styrylbenzofurans, styryloxadiazoles, styryltriazoles, and styrylpolyphenyls, as disclosed on page 77 of the Zahradnik reference. The styrylazoles can be further subclassified into styrylbenzoxazoles, styrylimidazoles and styrylthiazoles, as disclosed on page 78 of the Zahradnik reference. It will be understood that these three identified subclasses may not necessarily reflect an exhaustive list of subgroup into which styrylazoles may be subclassified. Other optical brighteners are the derivatives o dibenzothiophene-5,5-dioxide disclosed at page 741-749 o The Kirk-Othmer Encyclopedia of Chemical Technology. Volum 3, pages 737-750 (John Wiley & Son, Inc., 1962), th disclosure of which is incorporated herein by reference and include 3,7-daiminodibenzothiophene-2, 8-disulfoni acid5, 5 dioxide.

Other optical brighteners are azoles, which are derivative of 6-membered ring heterocycles. These can be furthe subcategorized into monoazoles and bisazoles. Examples o monazoles and bisazoles are disclosed in the Kirk-Othme reference.Still other optical brigteners are th derivatives of 6-membered-ring heterocycles disclosed i the Kirk-Othmer reference. Examples of such compound include brighteners derived from pyrazine and brightener derived from 4-aminonaphthalamide.

In addition to the brighteners already described miscellaneous agents may also be useful as brighteners Examples of such miscellaneous agents are disclosed a pages 93-95 of the Zahradnik reference, and include l hydroxy-3,6,8-pyrenetrisulfonic acid; 2,4-dimethoxy-l,3,5 triazin-6-yl-pyrene; 4 ,5-diphenylimidazolonedisulfoni acid; and derivatives of pyrazolinequinoline. Other specific examples of optical brightener are thos identified in U.S. Patent 4,790,856, issued to Wixon o December 13,1988, the disclosure of which is incorporate herein by reference. Thse brighteners include th Phorwhite™ series of brighteners from Verona. Other brighteners disclosed in this reference include : Tinopa UNPA, Tinopal CBS adn Tinopal 5BM; available from Ciba Geigy; Artie White CC and Artie White CWD, available fro Hilton-Davis, located in Italy; the 2-(4-styrylphenyl)-2H naphthol(l,2-d)triazoles; 4,4'-bis-(1,2,3-triazol-2-yl) stilbene; 4,4'-bis(styry1)bisphenyIs; and the y-amino coumarins. Specific examples of these brighteners includ 4-methyl-7-diethylamino coumarin; l,2-bis(-bensimidazol-2- yl)-ethylene; 1,3-diphenylphrazolines; 2,5-bis(benzoxazol- 2-yl)-thiophene; 2-styryl-naphth-(l,2-d)-oxazole; and 2- (stilbene-4-yl)-2H-naphtho(1,2-d)triazole.

Still other optical brighteners include those disclosed in U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton, the disclosure of which is incorporated herein by reference.

If utilized, the optical brighteners will generally comprise from about 0.05% to about 2.0%, preferably from about 0.1% to about 1.0% by weight of the laundry detergent compositions. Suds Suppressors

Compounds known, or which become known, for reducing or suppressing the formation of suds can be incorporated into the detergent compositions of the present invention. The incorporation of such materials , hereafter "suds supressor", can be desirable because the polyhydroxy fatty acid amide surfactants hereof can increase suds stability of the detergent compositions. Suds suppression can be of particular importance when the detergent compositons include a relatively high sudsing surfactant in combination with the polyhydroxy fatty acid amide surfactant. Suds suppression is particularly desirable for compositions intended for use in front loading automatic washing machines. These machines are typically characterized by having drums, for containing the laundry and wash water, which have a horizontal axis and rotary action about the axis. This type of agitation can result in high suds formation and, consquently, in reduced cleaning performance. The use of suds suppressors cna also be of particular importance under hot water wahsing conditions and under high surfactant concentration conditions.

A wide variety of materials may be used as suds suppressors. Suds suppressors are well known to those skilled in the art. They are generally described, for example, in Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (Joh Wiley & Sons, Inc., 1979). One categroy of suds suppresso of particular interest encompasses monocarboxylic fatt acids and soluble salts thereof. These materials ar discussed in U.S. Patent 2,954,347, issued September 27 1960 to Wayne St. John, said patent being incorporate herein by reference. The monocarboxylic fatty acids, an salts thereof, for use as suds suppressors typically hav hydrocarbyl chains of 10 to about 24 carbon atoms preferably 12 to 18 carbon atoms. Suitable salts includ alkali metal salts such as sodium, potassium, and lithiu salts, and ammonium and alkanolammonium salts. Thes materials are a preferred category of suds suppressor fo detergent compositions.

The detergent compositions of the present invention ma also contain non-surfactant suds suppressors. Thes include, for example, high molecular weight hydrocarbon such as paraffin, fatty acid esters (e.g. , fatty aci triglycerides) , fatty acid esters of monovalent alcohols aliphatic C^_Q-C^_Q ketones (e.g. stearone) , etc. Other sud inhititors include N-alkylated amino triazines such as tri to hexa-alkylemlamines or di- to tetra-alkyldaimin chlortriazines formed as products of cyanuric cholorid with two or three moles of a primary or secondary amin containing 1 to 24 carbon atoms, propylene oxide, an monostearyl phosphates such as monostearyl alcoho phosphate ester and monostearyl di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphat esters. The hydrocarbons, such as paraffin an haloparaffin, can be utilized in liquid form. The liqui hydrocarbons will be liquid at room temperature an atmospheric pressure, and will have a pour point in th range of about -40°C and about 5°C, and a minimum boilin point not less than about 100°C (atmospheric pressure) . I is also known to utilize waxy hydrocarbons, preferabl having a melting point below about 100°C. The hydrocarbon constitute a preferred category of suds suppressor fo detergent compositions. Hydrocarbon suds suppressors are described for example in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. , incorporated herein by reference. The hydrocarbons, thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or . unsaturated hydrocarbons having from about 12 to about 70 carbon atoms. The term "parrafin", as used in this ^"suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.

Another preferred category of non-surfactant suds comprises silicone suds suppressors. This category includes the use of polyorganosiloxane oils, such as polydimethysiloxane, dispersions or emulsions fo polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed of fused onto the silica. Silicone suds suppressors are well known in the art and are, for example disclosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al., and European Patent Application No. 89307851.9, published February 7, 1990, by Starch, M.S., both incorporated herein by reference.

Other silicone suds suppressors are disclosed in U.S. Patent 3,455,839, which relates to compositions and processes for defoaming aqueous solutions by incorporating therein small amounts of polydimethylsiloxane fluids. Mixtures of silicone and silanated silica are described, for instance, in German Patent Application DOS 2,124,526. Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et al., and in U.S. Patent 4,652,392, Baginski et al. , issued March 24, 1987. An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of :

(i) Polydimethlsiloxane fluid having a viscosity of from about 20 cs. to about 1500 cs. at 25°C; (ii) From about 5 to about 50 parts per 100 parts by weight of : (i) of siloxane resin composed of (CH₃)₃ Siθ_!/₂ units of Si0₂ units in a ratio of from CH_3j3Si0₁/₂ units and to Si0₂ units of from about 0.6:1 to about 1.2:1; and (iii) from about 1 to about 20 parts per 100 part^'s by weight of : (i) of a solid silica gel :

Suds suppressors, when utilized, are present in a "sud suppressing amoung". By "suds suppressing amount" is mean that he formulator of the composition can select an amoun of this suds controlling agent that will control the sud to the extent desired. Teh amount of suds control wil vary with the detergent surfactant selected. Fro example with high sudsing surfactants, relatively more of the sud controlling agent is used to achieve the desired sud control than with low foaming surfactants.

The detergent compositions of the present invention wil generally comprise from 0% to about 5% of suds suppressor When utilized as suds suppressors, monocarboxylic fatt acids, and salts thereof, will be present typically i amounts up to about 5%, by weight, of the deterge composition. Preferably, from about 0.5% to about 3% fatty monocarboxylate suds suppressor is utilize Silicone suds suppressors are typically utilized in amoun up to about 2.0%, by weight, of the detergent compositio although higher amounts may be used. This upper limit practical in nature, due primarily to concern with keepi costs minimized and effectiveness of lower amounts f effectively controlling sudsing. Preferably from abo 0.01% to about 1% of silicone suds suppressor is used, mo preferably from about 0.25% to about 0.5%. As used herei these weight percentage values include any silica that m be utilized in combination with polyorganosiloxane, as we as any adjunct materials that may be utilized. Monostear phosphates are generally utilized in amounts ranging from about 0.1% to about 2% by weight of the compositions. Hydrocarbon suds suppressors are typically utilized in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used. Other Ingredients

A wide variety of other ingredients which can be included in the detergent compositions of the present invention include other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulation.

Liquid detergent compositions can contain water and other solvents as carriers. Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable. Monohydric alcohols are preferred for solubilizing surfactant, and polyols such as those containing from about 2 to about 6 carbon atoms and from about 2 to about 6 hydroxy groups ( e.g. ropylene glycol, ethylene glycol, glycerine, and 1,3- propandiol ) can also be used.

The detergent composition of the present invention will preferably be formulated such that during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and 11, preferably between about 7.5 and about 10.5. Liquid product formulations preferably have a pH between about 7.5 and about 9.5, more preferably between about 7.5 and about 9.0. Techniques for controlling pH at recommended usage levels include the use of buffers, alkali,acids, etc., and are well known to those skilled in the art.

This invention further provides a method for cleaning substrates, such as fibres, fabrics, hard surfaces, skin, etc., by contacting said substrate with a detergent composition containing the glyceryl ether component (a) and the anionic detersive surfactant component (b) , in the presence of a solvent such as water or a water-misile solvent ( e.g. a primary or secondary alcohol ) . Agitation is preferably provided for enhancing cleaning. Suitable means for providing agitation include rubbing by hand, preferably with the aid of a brush, or other cleaning device, automatic laundry washing machine, automatic dish washer or the like.

Although, as indicated above, it is possible to include conventional polyethoxylate nonionic surfactants in the present compositions, it is currently preferred not to do so. In fact, it is an advantage of the glyceryl ethers employed as component (a) that they allow the replacement of polyethoxylate nonionic surfactants, thereby obviating the need to use ethylene oxide, whilst obtaining excellent cleaning characteristics. Thus, the glyceryl ethers of the formula (1) are very effective against greasy stains whilst showing no significant weaknesses against other, e.g. particulate, stains: furthermore, the glyceryl ethers are satisfactory with regard to redeposition of soils. Furthermore, the glyceryl ethers exhibit further advantages, for example the stabilization of enzyme in heavy duty detergent liquids. Also, the glyceryl ethers have comparatively low melting points and their use as agglomerating agents comes into consideration. The present invention is illustrated in and by the following Examples. Example 1

Cocoyl diglyceryl ether was prepared by a method analogous to that described by Sagitani et al. , J.O.A.C.S, Vol. 66, No.l (January 1989) page 146, using the following reagents:

30g (0.124 mole) distilled dodecyl Epoxide No.8 ( from

Proctor and Gamble)

0.14 ( 6.2 x 10~³ mole ) sodium

57g ( 0.62 mole ) anhydrous glycerol The sodium and glyceryl were reacted together at 130°C for one hour under nitrogen. The epoxide was added dropwise over one hour to the reaction mixture and 180°C, the mixture then being stirred at that temperature for 8 hours. The reaction mix was dissolved in ethanol and treated with pellets of carbon dioxide in order to neutralize the sodium. The mix was freed of ethanol on a rotary evaporator and then distilled (1.75 mmHg (233 Pa);140°C head temperature) to remove a fore-fraction of glycerol dimer ( identified as such using gas-liquid chromatography) .

The dodecyl diglyceryl ether as produced was a low-melting (44-46°C) solid comprising 92% diglyceryl ethers, 1.5% monoglyceryl ethers and 2% triglyceryl ethers. The diglyceryl ether contained approximately 4 moles of the "linear" ether of the general formula (2) per mole of the "branched" ether of the general formula (3) . The above synthesis may also be carried using Epoxide No. 8 to which a small amount of sodium borohydride has been added, in order to obtain the end product of improved color. Example 2

Cocoyl diglyceryl ether was prepared by the method of Takaishi efaA.,US-A-4,465,866, using the following reagents: 74.5g (0.5625 mole) acetone glycerol ketal ( available under the trade name "Solketal" from Aldrich Chemical Company)

3.2g (0.018 mole) tetramethyldiaminohexane 45g (0.18 mole) Epoxide No. 8 (from Proctor and Gamble)

The acetone glycerol ketal and tetramethyldiaminohexane were mixed together and heated to 100°C. The epoxide was added dropwise over a period of 30 minutes, keeping the temperature between 100 and 110°C. The resultant mixture was then heated at that temperature for 6 hours. The product was distilled (1mm Hg (133Pa) at 52°C head temperature) to remove the excess acetone glycerol ketal, and was vacuum distilled further (4.5 mmHg (600 Pa) at a head temperature of 230°C) to collect the product (dioxolane intermediate) .

34.8g (0.09 mole) of the dioxolane intermediate in 75ml of ethanol were added to 4.6g (0.046 mole) concentrated sulfuric acid in 100ml of water, and the resultant mixtur was heated to reflux for 4 hours. The solution was the neutralized with 3.6g (0.09 mole) sodium hydroxide whe cool. The product was extracted using diethyl ether dried over sodium sulfate and then evaporated to dryness o a rotary evaporator to give a golden paste. Example 3

A series of heavy duty liquid detergent compositions, A C, were prepared, these compositions having the surfactan components shown in the following Table, in which th amount of each component is shown in percent by weight o the composition.

Table l

Surfactant A B C

NaCnAS 12.9 12.9 12.9

Nat. NI E07 8.4

Nat. NI E05 - 8.4

CnDGE - - 8.4

In the above Table 1, the surfactants are identified a follows:

NaCnAS = sodium coconut-alkyl sulfate

Nat. NI E07 = condensate of naturally occurring fatty alcohol with, per mole, 7 moles of ethylen oxide. Nat. NI E05 = condensate of naturally occurring fatty alcohol with, per mole, 5 moles of ethylen oxide. CnDGE = coconut alkyl diglyceryl ether (prepared a

Example 1 above) .

The compositions were tested against a variety of stains wherein soiled loads were washed in a miniwasher at 60° using city water ( 5 moles total hardness ) , at 1 percen usage. The soiled loads were prepared by staining cotto or polyester/cotton (PC) swatches in conventional manner. The stain-removal performance was judged by an expert panel in a known manner, the results being recorded in panel score units (psu) on the Scheffe scale, taking the results obtained using composition A as the standard (0.0). The results are given in the following Table: Table 2

Stain Removal fCotton/PC) B C ^*

Greasy: +0.4/+0.7 +1.4/+1.0

Make-Up +0.6/+0.5 +1.8/+0.9

Lipstick +0.5/+1.2 +2.3/+1.7

Spaghetti +0.2/+0.4 +0.5/+0.3

DMO +0.7/+0.6 +1.0/+0.9

Bleachable -0.2/+0.2 +1.1/+0.9

Enzymatic -0.1/0.0 +0.3/0.0

Particulate -0.1/-0.6 +0.2/+1.1

Notes: "enzymatic" refers to stains removable with protease. DMO = dirty motor oil

As will be seen form Table 2, the composition C, which is according to the present invention, exhibited an excellent cleaning performance, especially against greasy stains and particulate stains. Example 4

A reference composition was prepared in the form of a heavy duty detergent liquid containing 7.25 percent by weight of linear alkyl benzene sulfonate, 1,75 percent coconut- alkyl sulfate, 9 percent of citric builder, 5 percent of other builder and 10 percent of condensate of fatty alkyl alcohol with, per mole,7 moles of ethylene oxide. A test composition was then prepared, this being essentially similar to the reference composition but with only 6 percent of the said fatty alkyl alcohol/ethylene oxide condensate but with 4 percent of coconut alkyl diglyceryl ether (prepared as in Example 1 above) . The compositions were tested against a variety of stains, the test method and the evaluation method being as described in Example 3. The results in psu for the test composition, relative to the reference compositions results as 0.0 for the stained cotton loads and the stained polyester/cotton loads, are given in the following Table. Table 3

Stain Cotton Polyester/Cotton

Greasy +0.7 +0.8

Bleachable -0.1 -0.1

Enzymatic -0.2 +0.1

Particulate +0.3 -0.3

BMI empa +0.1 +0.1

Note: BMI empa is a standardized soil comprised of blood, ilk and ink on a polyester-cotton substrate and sold by EMPA Institute, St. Gallen, Switzerland.

Relative to the reference composition ( which typifies conventional heavy duty detergent liquid formulations) , the test composition, which was formulated according to the present invention, showed improved performance against greasy stains with comparable performance against other stains.

It will of course be understood that the present invention has been described above purely by way of example and that modifications of detail can be made within the scope of the invention.

Claims

1. A detergent composition comprising (a) one or more glyceryl ethers of the general formula :

RO - (C₃H₆0₂)_nH wherein

R represents an alkyl or alkenyl group from 12 to 18 carbon atoms,

^C3^H6°2 represents a divalent radical formed by removal from glycerol of a hydroxyl group and of the hydrogen atom from the remaining hydroxyl group, and n is an integer, at least 50 mole percent of component (a) being constituted by diglyceryl ether and not more than 25 mole percent of component -

(a) being constituted of monoglyceryl ether, and

(b) an anionic detersive surfactant.

2. A composition according to claim 1., wherein at least60 mole percent of component (a) is constituted by diglyceryl ether and not more than 20 mole percent of component (a) being constituted by monoglyceryl ether.

3. A composition according to claim 1. or 2. in which the diglyceryl ether of component (1) is a mixture comprising the diglyceryl ethers of the general formulae:

R - 0CH₂CHOHCH₂.OCH₂CHOHCH2.OH (2)

and

R - OCH₂CHOHCH₂.OCH - CH₂OH (3)

^CH₂OH

4. A composition according to the claim 3., in which th ethers of the formulae (2) and (3) are present in a mola ratio of about 4:1.

5. A composition according to any of the claims 1. to 4, , in which component (a) is substantially entirely diglyceryl ether.

6 A composition according to any of the claims 1. to 5. in which R is a coconut alkyl group.

7. A composition according to any of the claims l. to 6. , which also comprises at least one further component selected from cationic, ampholytic, zwitterionic, and semi-polar detersive surfactants, detergency building agents, enzymes, bleaches and chelating agents.

8. A composition according to any of the claims 1. to 7. in the form of a heavy duty detergent liquid or a heavy duty detergent granule.

9. A process for the preparation of a diglyceryl ether of the formula (1) given in a claiml, or a mixture of such ethers, wherein a compound of the general formula :

R - O - CH₂CH - CH₂

O

wherein R has the meaning given in claim (1) , is reacted with glycerol in the presence of a base and/or with a glycerate and impurities in the product are removed by distillation.

10. The use, as above, as a detersive surfactant, of the diglyceryl ether of the formula (1) in claim 1., or a mixture of such ethers.