PT101013B - DETERGENT COMPOSITIONS CONTAINING GLICERIL ETERES - 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

DETERGE1ITES COMPOSITIONS THAT CUT GLYCERILE ETERES

Invention field

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

Background of

Heavy-duty detergents in either granular or liquid form commonly contain an anionic detersive surfactant, for example sodium benzene (linear alkyl) sulfonate in which the alkyl group preferably has 11-13 carbon atoms, or alkyl sodium sulfate, e.g. ex ·, what is obtained by sulfata15

Mod. 71 -10000 ex. - 89/07 tion of a Gg-G-jg alkanol · To improve the performance of such detergent compositions against grease and dirt stains, it is conventional to include non-ionic surfactant, typically of a phenol (ethylene Gg-C ^ alkyl) ____________ _ε _________________________

-12 moles of ethylene oxide per mole of alkylphenol or 4 surfactant (condensation product) or a 0 ₈ “0 ₂ 2 alkanol with oxide The preferred condensates are those containing 3um one

-8 moles of ethylene oxide per mole of alkanol ·

A particularly preferred non-ionic condensate is an alkanol condensate with 7 moles of ethylene oxide per mole of alkanol.

Ethylene oxide used in the preparation of the non-ionics discussed above is, however, derived from petroleum and is, in addition, a reagent that needs to be carefully handled30 to minimize the risk of explosion. Therefore, taking into account both economic, safety and environmental considerations, it would be desirable to find an alternative nonionic detersive surfactant.

Summary of the Invention

-2This invention relates to the use as a nonionic detersive surfactant in a detergent composition

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Mod. 71 -10 000 ex. - 89/07 te of one or more glyceryl ethers of the general formula

RO - (O ₃ -H ₆ -O ₂ ) _n H (1) where

R represents an alkyl or alkenyl group of 12 to 18 carbon atoms, represents a divalent radical formed by removing one hydroxyl group from glycerol and hydrogen from another hydroxyl group, and n is an integer, in particular glyceryl ethers of which 50-100 mole percent is made up of diglyceryl ether (n = 2) and 0-25 percent mole is made up of monoglyceryl ether (n = 1), the rest, if any, made up of triglyceryl ethers (n = 3) and / or higher counterparts (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 Achievements

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 glyceryl ethers of the formula (1) present in the detergent composition of this invention must consist of diglycyl ether and not more than 25 mole percent, preferably not more than 20 mole percent must be made up of monoglyceryl ether. The remainder, if any, of the glyceryl ether component (a) consists of triglyceryl ethers and / or homologous components.

It was found that, generally, the higher the content of diglyceryl ether in the glyceryl ether-310 component

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Mod. 71-10000 ex. -89/07 go (a), the better. It is preferred that the diglyceryl ether constitutes 80 percent or more of the glyceryl ether component; it is particularly preferred that the glyceryl ether component of the present compositions is almost entirely composed of diglyceryl ether. Diglyceryl ethers can be prepared by a process known initially through the article by H. Sagitani et al., Entitled Solution properties of homogenious polyglycerol dodecyl ether nonionic surfactants, JAOCS, Vol »66, No. 1 (January 1989) pages 146- 152. Sagitani et al. Specifically mentions the preparation of dodecyldiglyceryl ether by a process whereby sodium is added to anhydrous glycolol under an atmosphere of nitrogen, the solution is heated to 13020 ° C for 1 hour, dodecyl ether is added. glycidyl dropwise to the resulting sodium glycerate over 1 hour at 180 ° C, the mixture is stirred for 8 hours and the product is purified on a silica gel column using chloroform / methanol (98: 2) as solvent . Sagitani and others represented the preparatory process through the following reaction scheme:

R ₁₂ 0CH ₂ CH ----- GH ₂

H0CH ₂ CHGH ₂ 01Ta / H0GH ₂ CHGH ₂ 0H

\) H OH

V r ₁₂ o (ch ₂ ghch ₂ o) ₂ h \ h

R ₁₂ represents the dodecyl radical.

the present applicant has discovered that the preparative process can be applied not only to the compound B-jg » ^{raas but} also to compounds with any radical within the signifi410

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Mod. 71-10000 ex. -89/07 specified for R in the general formula (1) presented above. R is usually derived from a primary or secondary alcohol.

Furthermore, while the method taught by Sagitani and others depends on chromatographic purification, it has now been found that the cyclic dimer of glycerol, the main by-product, and also the free fatty alcohol present in epoxide can be satisfactorily removed in a way that is thought innovative in this context, this is by simple distillation.

Thus, it has been proven that it is possible to obtain, using simple vacuum distillation, for example at a container temperature of about 2002G, about 95% of alkyl glyceryl ethers containing less than 2% cyclic by-product and less than 2 % free fatty alcohol, without significant discoloration and degradation. This is particularly surprising, because Takaishi and others in US-A-4 465 866 (column 3 »lines 10-14) discredit distillation in polyol ethers preparation processes as it is stressful and incapable of industrial application ·

In the case of the glyceryl ether product obtained by this process having less diglyceryl ether than the required molar percentage and / or more monoglyceryl ether than the maximum specified, the diglyceryl ether content can be developed by conventional isolation and purification techniques.

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

R - 0CH ₂ CH0HCH ₂ .0CH ₂ CH0HCH ₂ .0H (2), the diglyceryl ether of the formula r - och ₂ chohch ₂ .och-ch ₂ oh (3) \ h ₉ oh is also generally formed

Typically, about one mole of diglyceryl ether (3) is formed for every four moles of diglyceryl ether (2)

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Mod. 71 -10000 ex. - 89/07 that are produced.

Mixtures of or comprising the positional isomers of formulas (2) and (3) are believed to be new. Sagitani et al., In the work cited, refers only to the possibility of diastereomers, an aspect of optical isomerisms that is due to the fact that glycerol is proquiral. When preparing mixtures containing the isomer (3), it is thought that silica gel chromatography should be avoided, since a higher content of primary alcohol groups can be predicted to make the isomer substantive to silica gel and therefore more susceptible the removal. Mixtures of the position isomers (2) and (3) can also give better cleaning characteristics than the single isolated isomer.

In general, the group R binds to the first glycerol portion at the first location of that portion. The second glycerol can, in principle, connect to the second location of the first glycerol; in practice, however, it has generally been found that less than 10 mole percent of diglyceride ethers have such a link to said secondary site.

R can represent a mixture of alkyl and / or alkenyl radicals, as will be the case, for example, when glyceryl ethers are obtained from naturally occurring ROH fatty alcohols. An example is coconut alcohol, which primarily contains saturated C-jg »θΐ4 ^and θ16 alkyl radicals, with lesser amounts of enθ, θ10 ^and θ18 * ^s alkenyl radicals preferred for R is cocoyl, in particular the so-called cocoyl top and end ”and narrow-gamma, which is predominantly» n-dodecyl (g) and n-tetradecyl (G ^).

Alkyl (or alkenyl) -glycidyl ethers are known compounds, some of which may be commercially obtained, or prepared by generally known methods. Thus, for example, a useful starting substance is glycidyl-alkyl ether available under the trade name ”Epoxide Ro. 8 by Procter & Gamble, the alkyl groups being

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Mod. 71 -10000 ex. - 89/07 in this narrow-range cocoyl epoxide.

Diglieeryl ethers can also be prepared by a method known in principle through US-A-4 465 866 (Takaishi et al.). This US Patent teaches that a diglyceryl ether of the formula (2) presented above can be prepared by reacting, in the presence of an acid or base catalyst, a glycidyl-alkyl (or alkenyl) ether with an acetal or ketal derivative of glycerol in order to obtain 1,3-dioxolane, which is then subjected to hydrolysis. Takaishi et al. Also mentions earlier proposals for the preparation of such diglieeryl ethers, in particular (i) the reaction of the linear glycerol dimer with an alkali to form an alkali metal alcoholate, which is then reacted with alkyl halide, and ( ii) the reaction of an alcohol with a cyclic compound of the type 1,3-dioxolane with hydrolysis of the resulting addition product (with reference to Journal f. Prakt, Ghemie, Band 316 (1974), 325-336).

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

The detergent compositions of this invention, which can be in liquid or granular form, will also contain at least one anionic detersive surfactant. Optionally, the composition may also contain at least one other detersive surfactant, preferably selected from cationic, ampholytic and zwitterionic detersive surfactants, as well as other components conventional in the art, for example a bulking agent, an enzyme, a bleach , a bleach activator, polymeric dirt release agent, chelating agent, clay dirt removal / anti-redeposition agent, polymeric dispersion agent, rinse aid, foam suppression agent, ager30

«

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Mod. 71 -10 000 ex. - 89/07 te of buffering of powder, a dye or a pigment. It will be appreciated that any of the aforementioned components, whether essential or optional, can consist, if desired, of a mixture of two or more compounds of suitable description.

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

Although the invention is especially useful in heavy-duty or general-purpose laundry detergent compositions, the term detergent compositions in the present description also includes dishwashing compositions, cleaning products for difficult surfaces and for other household cleaning and household cleaning products. personal treatment such as shampoos.

The following are examples of anionic detersive surfactants and several other optional components that are taken into account.

Anionic Surfactant Agents

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

Ester Alkyl Sulfonate Surfactant

The alkyl ester sulfonate surfactants of the present invention include linear esters of Cg-G ₂₀ carboxylic acids (i.e., fatty acids) which are sulphonated with SO4 according to The Journal of the American Oil Ghemists Society, 52 (1975), pp. 323-329 · Suitable starting substances include natural fatty substances such as tallow derivatives, palm oil, etc.

Preferred alkyl ester sulfonate surfactant, especially for laundry washing applications, comprises sulfonate ester surfactants

65,418 alkyl with the structural formula:

in which kilo, ^c 1 ^g 6 »mo and M fonato

R ³ - GH I

SO ₃ M ^r

Er and a hydrocarbyl or a combination of

Mod. 71-10000 ex. - 8 89/07 ^{L "G} 20" P ^{re LV} f ^er i ^I l UTE almesmo one R ^ is a hydrocarbyl preferably an alkyl, or combination of the month is a cation which forms a water soluble salt with alkyl ester southern . Suitable salt-forming cations include metal cations such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine and triethanolamine. Preferably, R ³ is θιθ-C-ig alkyl and R 3 is methyl, ethyl or isopropyl. Especially preferred are methyl ester sulfonates where R ³ is alkyl

Alkyl Sulfonate Surfactant

The surfactants of alkyl sulfates of the present invention are water soluble salts or acids of formula water ROSO ^ M wherein R and preferably a hydrocarbyl ^L 10 ^'L 24' is preferably an alkyl alkyl component C-jQ-CGO * ^ma i ^s kyl or hydroxyalkyl C- | 2 “ ^G 18 ^and an alkali metal citric (eg, or substituted ammonium or ammonium (e.g.

dimethyl-, rio, such as tetramethyl-ammonium and dimethylpiperidium cations, and quaternary ammonium cations derived from alkylamines, such as ethylamine, diethylamine, triethylamine, and mixtures thereof and the like).

Alkyl chains with 12-16 carbon atoms are preferred, more preferably with 14-15 carbon atoms.

or hydroxyalkyl with preferably a aό H or a cation, eg sodium, potassium, lithium) eg, methyl-, and trimethyl-ammonium cations, and quaternary ammonium cations

Alkoxylated

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The surfactants of alkyl of alkoxylated sulfates of the present invention are water soluble salts or acids of water R0 formula (A) ^ 30 ^ 1 wherein R is an alkyl or hydroxyalkyl group C-IQ-C₄ substituted with one alkyl moiety ^g - | q " ^G 24" preferably an alkyl or hydroxyalkyl ^G 12 ~ ^G 2 O ' ^but preferably an alkyl group having 12 to 18 carbon atoms, especially 12 to 15 carbon atoms.

A is an ethoxy or propoxy unit, greater than zero, typically between about 0.5 and 6, more preferably between about 0.5 and about 3 and M is H or a cation which can be, for example , a metal cation (eg sodium, potassium, lithium, magnesium calcium, etc.), ammonium cation or substituted ammonium. Alkyl ethoxyl sulfates15

Mod. 71-10000 ex.-89/07 dos as well as the propoxylated alkyl sulfates are contemplated here. Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethylpiperidium cations, and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures of the same and similar.

A preferred surfactant is a polyethoxylated θ- | 2θ15 alkyl sulfate (3.0) (C 2 - C 2 E (3.0) M). Other examples of surfactants include ^G -] 2 " ^G 18 polyethoxylated (1.0) alkyl sulfate (0 ^ 2-0 ^ θΕ (1> 0) M), ^G- j2" ^G is polyethoxylated alkyl sulfate (2.25) (C12 ~ ^G igE (2.25) M), ^G i2 "° 18 P ° li alkyl sulfate ^and toxylated (3.0) (C12-C18E (3.0) M) and sulfate alkyl C- | 2 “ ^C 18 P ^olie toxiladc (4» 0) (012-C ^ gE (4> 0) M), where M is conveniently selected from sodium and potassium.

Other Anionic Surfactants

Other anionic surfactants useful for detersive purposes may also be included in the detergent compositions of the present invention. These may include salts (including, for example, sodium, potassium, ammonium salts — 10—

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NiO and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C ^ alkyl sulfonates -G li- _2Q 'neares -benzenes sulfonates, primary or secondary _C8-C22 alkane sulfonates, C _Q -G olefins, sulfonated polycarboxylic acids prepared by sulfonation of the alkaline earth metal citrate pyrolyzed product, e.g., as described in the British Patent specification Ho. 1,082,179, Cg-Ggzj alkyl. “Polyglycero-sulfates (containing up to 10 moles of ethylene oxide); alkylglycerol sulfonates, glycerol sulfonates and fatty acyls, glycerol sulfates and fatty oils, ethylene ether phenyl alkyl sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinamate monosulphides of sulfosuccininamate (especially monoestereg

Mod. 71 -10000 ex. - θ12 89/07 "18 ° ^sa ^ ^ ^ura unsaturated θ) and diesters of sulfossuccinamato (especially diesters 0g 0 ~ 2 ^ s ^^ AAOS and unsaturated), acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside ( non-ionic non-sulphated compounds) are described below as branched primary alkyl sulphates, polyethoxy-alkyl carboxylates such as those of the formula R0 (GH2GH20) GOO-M ⁺ where R is a Gg-G22 alkyl, k is an integer of 0 to 10 and M is a soluble salt-forming cation. Resin acids and hydrogenated resin acids, such as resin, hydrogenated resin and resin acids and hydrogenated resin acids present or high oil derivatives, are also suitable. More examples are shown on Surface

Active Agents and Detergents ”(Vol.

Schwartz I and II,

Per30 ry and Berch). several of these surfactants are also generally disclosed in US Patent 3,929,667,

-11 granted on December 30, 1975 to Laughlin et al., From column 23, line 29 to column 29, line 23 (incorporated herein by reference).

Anionic surfactant systems

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Preferred employed in the detergent compositions of the invention are free of alkyl benzene sulfonates salts. An extraordinarily preferred system comprises a mixture with a higher proportion of primary alkyl sulfate θ14 ~ θ15 ^{and a} lower P ^r ° P ° ^r 9 ^ ° of ethoxyl alkyl sulfate containing an average of 3 ethoxy groups per mole of sulphate of ethoxylated alkyl. The detergent compositions of the present invention typically comprise between about 1% to about 20%, preferably between about 3% to about 15% and even more preferably between about 5% to 10% by weight of anionic surfactants .

Other Surfactant Agents

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The detergent compositions of the present invention can also contain eationic, ampholytic, zwitterionic and semi-polar surfactants, and even other nonionic surfactants.

The ionic detersive surfactants suitable for use in the detergent compositions of the present invention are those having a lay-chain hydrocarbyl group. Examples of such ionic surfactants include ammonium surfactants such as alkyldimethyl ammonium halides, and surfactants of the formula [> ² (0R ³ ) y 1 LR ⁴ (OH ³ ) / | gRW ^z where R is an alkyl or alkylbenzyl group containing between about 8 to about 18 carbon atoms in the alkyl chain, each R is selected from the group consisting of -GH ₂ CH ₂ -, -CH ₂ GH (CH ₃ ) -, GH ₂ CH (GH ₂ 0H) -, -CH ₂ CH ₂ CH ₂ -, and mixtures thereof; each R ^ is selected from the group consisting of CjG ^ alkyl, hydroxyalkyl benzyl ring structures formed by the union of two groups r \-GH ₂ GH0H-GH0HC0R ⁶ GH0HCH ₂ 0H where R ⁶ is any hexose or hexose polymer with a molecular weight less than about

-1210

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Mod. 71-10000 ex.-89/07 of 1000, and hydrogen when y is not 0; R ⁵ is the same as Ar fr

R or is an alkyl chain where the total number of atoms

5 * carbon of R plus R is not greater than about 18; each Y is 0 to about 10 and the sum of the values of Ϊ is 0 to about 15; and X is any compatible anion.

Other cationic surfactants useful in the present invention are also described in Cambre North American Patent 4,228,044, issued October 14, 1980, incorporated herein by reference.

The detergent compositions of the present invention typically comprise between about 0% to about 25%, preferably between about 3% to about 15% by weight of such cationic surfactants, when included in such compositions.

The ampholytic surfactants are also suitable for use in the detergent compositions of the present invention. These surfactants can be widely described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines where the aliphatic radical can be straight or branched. One of the aliphatic substitutes contains at least about 8 carbon atoms, typically between about 8 to about 18 carbon atoms, and at least one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate . See U.S. Patent No. 3,929,678 to Laughli.i et al., Issued December 30, 1975 in column 19, lines 18-35 (incorporated herein by reference) for examples of ampholytic surfactants.

The detergent compositions of the present invention typically comprise between about 0% to about 15%, preferably between about 1% to about 10% by weight of such ampholytic surfactants, when included therein.

Zwitterionic surfactants are

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Mod. 71-10000 ex.-89/07 also suitable for use in detergent compositions. These surfactants can be widely described as derived from secondary and tertiary amines, derived from heterocyclic secondary and tertiary amines, or derived from quaternary ammonium, quaternary phosphonium or tertiary sulphenium compounds. See U.S. Patent No. 3,929,678 to Laughlin et al., Issued December 30, 1975 from column 19, line 38 through column 22, line 48 (incorporated herein by reference) for examples of zwitterionic surfactants .

The detergent compositions of the present invention typically comprise between about 0% to about 15%, preferably between about 1% to about 10% by weight of such zwitterionic surfactants, when included therein.

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

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

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ΐ

R ³ (0R ⁴ ) zK (R ⁵ ) 2 ^z where 'B. and an alkyl, hydroxyalkyl, alkylphenyl group or mixtures thereof containing between about 8 to about 22 carbon atoms; R ^{4 is} an alkylene or hydroxyalkylene group containing between about 2 to about 3 carbon atoms or mixtures thereof; x is 0 to about 3; and each R ³ is an alkyl or hydroxyalkyl group containing between about 1 to about 3 carbon atoms or an oxide group of polyethylene containing between about 1 to about 3 ^z * 5 polyethylene oxide groups. The R groups can be linked to each other, e.g. through an oxygen or nitrogen atom, to form an annular structure.

Mod. 71-10000 ex. - 89/07

These oxide surfactants include, in particular, alkyl dimethylamine oxides and alkoxyethyl dihydroxyethylamine oxides θ ₈ “θ- | 2 *

The detergent compositions of the present invention typically comprise from 0% to about 15%, preferably ^C 10 ' ^C 1 amine, ranging from about 1% to about 10% by weight of such semi-polar nonionic surfactants, when included in them.

Non-ionic surfactant agents

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

Suitable nonionic surfactants include alkylphenol condensed polyethylene oxides, e.g. condensation products of alkylphenols with an alkyl group containing from 6 to 8 carbon atoms, in a straight or branched chain configuration, with 1 to 12 moles of ethylene oxide per mole of alkylphenol.

Suitable nonionic surfactants also include condensation products of aliphatic alcohols.

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compounds containing from 8 to 22, preferably from 12 to 18, carbon atoms, in a straight chain or ramified configuration, with 2 to 12, preferably 3 to 7, moles of ethylene oxide per mole of alcohol.

Suitable nonionic surfactants also include fatty acyls or alkyl products of the density of oarbohydrates and their derivatives such as glycosides, aminodeoxy forms and polyols. Examples include coco-alkylpolyglucosides and tallow-acyl-N-methyl-glucamines.

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

es Full-bodied

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The detergent compositions of the present invention can contain organic or inorganic detergent builders to help control mineral hardness.

level of bulking agent can vary widely depending on the end use of the composition and the physical form desired for it. Liquid formulations typically comprise at least about 1%, more typically between about 5% to about 50%, preferably between about 5% to about 30% by weight of detergent bulking agent. Granular formulations typically comprise at least about 1%, more typically between about 10% to about 80%, preferably between about 15% to about 50% by weight of detergent bulking agent. However, the possibility of lower or higher levels is not excluded.

Inorganic detergent bulking agents include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by tripolyphosphates, pyrophosphates and glassy polymeric metaphosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarts ), south-16

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Mod. 71-10000 ex. - 89/07 facts and aluminosilicates. Borate bulking agents, as well as bulking agents containing borate-forming substances that can produce borate under detergent storage or washing conditions can also be used, but are not preferred in washing conditions of less than about 50 ° C, especially less than about 4020. Preferred bulking agent systems are also free of phosphates.

Examples of silicate builders are alkali metal silicates, particularly those with a Si0 ₂ : Na ₂ 0 ratio in the range of 1.6: 1 to 3.2: 1 and layered silicates, such as sodium silicates in layers described in U.S. Patent 4,664,839, issued May 12, 1987 to Η. P. Rieck, incorporated herein by reference. However, other silicates such as for example magnesium silicate can also be used, which can serve as a stabilizing agent for oxygen bleaching and as a component of foam control systems.

Examples of carbonate bulking agents are alkaline earth and 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, a revelation that is incorporated here as a reference.

Aluminosilicate bulking agents are useful in the present invention. The aluminosilicate bulking agents are of great importance in most of the heavy-duty granular detergent compositions currently on the market, and can also be a significant bulking agent ingredient in liquid detergent formulations. The aluminosilicate bulking agents include those that have the empirical formula:

M _z (zA10 ₂ * ySi0 ₂ )

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where M is sodium, potassium, ammonium or substituted ammonium, z is between about 0.5 to about 2; and y is 1; this material having a magnesium ion exchange capacity of at least about 50 milligrams of hardness equivalents per gram of anhydrous aluminosilicate. Preferred aluminosilicates are zeolite bulking agents with a force!

very:

mj: uio ₂ ) _z (sio ₂ ) _y J .xh ₂ o where z and y are integers of at least 6, the molar ratio of z to y is in the range of 1.0 to about 0.5, ex is a integer between about 15 to about 264.

Useful aluminosilicate ion exchange materials are commercially available. These aluminum can have a crystalline or amorphous structure and can be naturally occurring or synthetically derived.

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U.S. Patent 3,985,669, to Krummel et al., Issued October 12, 1976, hereby incorporated by reference, discloses a method for producing aluminosilicate ion exchange materials. The preferred synthetic crystalline aluminosilicate ion exchange materials useful in the present invention are available under the designations Zeolite A, Zeolite Ρ (B) and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:

Na ₁₂ L (A1O ₂ ) ₁₂ (SiO ₂ ) ₁₂ n * xH ₂ 0 where x is between about 20 to about 30, especially about 27 · This material is known as Zeolite A. Preferably, aluminosilicate has a particle size of about 0.1-10 microns in diameter.

Specific examples of polyphosphates are alkali metal tripolyphosphates, sodium pyrophosphate, sodium and potassium potassium, sodium and potassium orthophosphate, sodium polymetaphosphate in which the degree of polymerization ranges from about 6 to about 21, and phytic acid salts. Examples of salts of phosphonate bulking agents are salts

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Mod. 71-10000 ex. -89/07 water-soluble ethane 1-hydroxy-1,1-diphosphonate particularly sodium and potassium salts, water-soluble salts of methylene diphosphonic acid e.g. ex. trisodium · triadium and tripotassium salts and water-soluble salts of substituted methylene-diphosphofunic acids, such as ethylidene phosphonates, benzylmethylidene isopropylidene and trisodium and tripotassium methyl halide. The salts of phosphonate bulking agents of the types mentioned above are disclosed in U.S. Patent Nos. 3 159 581 and 3 213 030, issued on December 1, 1964 and October 19, 1965 to Diehl; United States Patent No. 3,242,021 issued on January 14, 1969 to Roy; and in US Patent Nos. 3,400,148 and 3,442,137 issued on September 3, 1968 and January 14, 1969 to Quimby, the disclosures of which are hereby incorporated by reference.

polycarboxylate bulking agent can generally be added to the composition in acid form, but it can also be added in the form of a neutralized salt. When used in the form of salts, alkali metals such as sodium, potassium and lithium salts are preferred, especially sodium salts or ammonium and substituted ammonium salts (eg alkanolammonium) ·

Several categories of useful materials are included among the polycarboxylate bulking agents. An important category of polycarboxylate bulking agents includes polycarboxylate ethers. Numerous carboxylate ethers have been disclosed for use as bulking agents. Examples of useful polycarboxylate ethers include oxisuccinate, as disclosed in U.S. Patent 3,128,287, to Berg, issued April 7, 1964 and U.S. Patent 3,635,830, to Lamberti et al., Con-19 January 18, 1972, both of which are incorporated herein by reference.

A specific type of polycarboxyl ethers useful as bulking agents in the present invention includes

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Mod. 71 -10000 ex. - 7/9 those who have the general formula:

CH (A) (COOX) -CH (GOOX) -O-CH (GOOX) -CH (COOX) (B) where A is H or OH; B is H or -0-GH (G00X) -GH ₂ (GG0X); and X and H or a salt-forming cation. If, for example, in the previous general formula A and B are both H, then the compound is oxidisuccinic acid and its water-soluble salts. If A is OH and B is H, then the compound is tartrate-monosuccinic acid tartrate (TMS) and its water-soluble salts. If A is H and B is -0-GH (G00X) -CH ₂ (G00X), then the compound is tartarate-disuccinic acid (TDS) and its water-soluble salts. Mixtures of these bulking agents are especially preferred for use in the present invention. Mixtures of TMS and TDS in a weight ratio of TMS to TDS between about 97: 3 to about 20:80 are particularly preferred.

These bulking agents are referred to in US Patent 4 663 071, granted to Bush. and others, on May 5, 1987.

Suitable polycarboxylate ethers also include cyclic compounds, particularly allied compounds, such as those 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 detergent bulking agents include the hydroxypolycarboxylate ethers represented by the structure:

H0- £ c (R) (C00M) -C (R) (G00M) -0j _n -H where M is hydrogen or a cation in which the resulting salt is soluble in water, preferably an alkali metal, ammonium or ammonium cation substituted, n is between about 2 to about 15 (preferably n is between about 2 to about 10, more preferably n mediates between about 2 and about 4) and each R is the same or different and selected from hydrogen, C1-4 alkyl or C1-4 substituted alkyl (preferably R is hydrogen) ·

Other polycarboxylate ethers still include

-2010

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Mod. 71-10000 ex. - 89/07 maleic anhydride copolymers with ethylene or methyl vinyl ether, 1, 3 »5-trihydroxybenzene-2, 4, 6-trisulfonic acid and carboxymethyloxysuccinic acid.

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

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

Citrus bulking agents, e.g. eg, citric acid and soluble salts thereof, are bulking agents of particular importance for heavy-duty liquid detergent formulations, but can also be used in granular compositions. Suitable salts include metal salts such as sodium, lithium and potassium salts, as well as ammonium and substituted ammonium salts.

Other carboxylating bulking agents include the carboxylated carbohydrates disclosed in U.S. Patent 3 723 322, to Diehl, issued March 28, 1973, incorporated herein by reference.

Also suitable in the detergent compositions of the present invention are 3 »3-dicarboxy-4-oxa-1,6-hexanedioates and related compounds disclosed in U.S. Patent 4 566 984» to Bush, issued January 28, 1986, incorporated herein by reference. The bulking agents useful alquilsuccínicos acids include succinic acid θ5 ^"sa ^ ^{s and} θ20 thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Alkylsuccinic acids typically have the general formula R-0H (C00H) CH ₂ (C00H) that is, derivatives of succinic acid, where R is hydrocarbon, e.g. e.g., C ₁₀ -C ₂ alkyl or alkenyl ₍₎ ,

-2110

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Mod. 71-10000 ex. -89/07 preferably 0-} ₂ θ16 or where R can be substituted with hydroxyl, sulfo, sulfoxy or sulfone substitutes, all as described in the aforementioned patents.

The succinate bulking agents are preferably used in the form of their soluble salts, including the sodium, potassium, ammonium and alkanolammonium salts.

Specific examples of succinate bulking agents include: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecyl succinate (preferred), 2-pentadecenyl succinate and the like. Lauryl succinates are the preferred bulking agents of this group and are described in European Patent Application 86200690.5 / 0 200 263 'published on 5 November 1986.

Examples of useful bulking agents also include sodium and potassium carboxymethyloxylate, carboxymethyloxysuccinate, cis-cyclohexane-hexacarboxylate, cis-cyclopentane-tetracarboxylate, water-soluble polyacrylates (these polyacrylates with molecular weights above about 2,000 can also be effective as well). dispersing agents) and copolymers of maleic anhydride with methyl vinyl ether or ethylene.

Other suitable polycarboxylates are the polyacetal carboxylates disclosed in U.S. Patent 4,144,226, to Crutchfield et al., Issued March 13, 1979, incorporated herein by reference. These polyacetal carboxylates can be prepared by putting together, under polymerization conditions, a glyoxylic acid ester and a polymerization initiator * The resulting polyacetal carboxylate ester is then attached to chemically stable terminal groups to protect the polyacetal carboxylate against rapidity. depolymerization in alkaline solution, converted to the corresponding salt and added to a surfactant.

Carboxylate bulking agents are also disclosed in U.S. Patent 3,308 O67> to Diehl,

2210

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Mod. 71-10000 ex. - 89/07 granted on 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, citraconian acid and methylenomalonic acid.

Other organic bulking agents known in the art can also be used. For example, monocarboxylic acids, and soluble salts thereof, which have long-chain hydrocarbyls can be used. These generally include materials called soaps. They are used typically chain lengths of C ^20-C ~ JQ * ^paragraphs hydrocarbyls can be saturated or unsaturated.

Enzymes

Detersive enzymes can be included in the detergent compositions of the present invention for several reasons including, for example, removing stains based on proteins, carbohydrates or triglycerides and preventing the transfer of refugee dye. The enzymes to be incorporated include proteases, amylases, lipases, cellulases and peroxidases, as well as mixtures thereof. They can be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast. However, their choice is regulated by several factors such as pH activity and / or optimum stability, thermostability, stability in relation to active detergents, bulking agents and others. In this regard, fungal or bacterial enzymes are preferred, such as amylases and bacterial proteases and fungal cellulases.

Examples of suitable proteases are subtilisins obtained from specific B. subtilis and B. licheniforms strains. Another suitable protease is obtained from a strain of Bacillus, which has maximum activity across the pH range 8-12, developed and sold by Novo Industries A / S under the registered trademark Esperase®. The preparation of this enzyme and enzymes is described

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Mod. 71-10000 ex. - 89/07 analogues in the specification of British Patent N2. 1,243,784 of Novo. The proteolytic enzymes suitable for removing protein-based stains, commercially available, include those sold under the trademarks ALGALASE ® and SAVINASE by Novo Industries A / S (Denmark) and MAXAMATASE by International Bio-Synthetics, Inc. (Netherlands) *

In the category of proteolytic enzymes, enzymes referred to in the present invention as Protease A and Protease B are of interest, especially for liquid detergent compositions. Protease A and methods for its preparation are described in European Patent Application 130 756, published in January 9, 1985, hereby incorporated by reference. Protease B is a proteolytic enzyme that differs from Protease A in that at position 217 of its amino acid sequence, leucine is replaced by tyrosine. Protease B is described in European Patent Application Serial No. 87303761.8, filed April 28, 1987, incorporated herein by reference. Protease B preparation methods are also described in European Patent Application 130 756, by Bott et al., Published on January 9, 1985, incorporated herein by reference.

Amylases include, for example, a-amylases obtained from a special strain of B. licheniforms, described in more detail in the specification of Patent Br:. Tannic No. 1 269 839 (Novo), previously incorporated herein by reference . Amylolytic proteins include, for example, RAPIDASE®, from International Bio-Synthetics, Inc. and TERMAMIL®, from Novo Industries.

Cellulases usable in the present invention include both bacterial and fungal cellulases. Preferably, they will have an optimal pH between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307,

-24de Barbesgoard et al., Granted on March 6, 1984, hereby incorporated by reference, namely funnel cellulase10

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produced from Humieola insolens. Suitable cellulases are also shown in GB-A-2,075 028; GB-A2 095 275 and DE-OS-2 247 832.

Mod. 71-10000 ex.-89/07

Examples of such cellulases are cellulases produced by a strain of Humieola insolens (Humieola grisea var. Thermoidea), particularly the strain Humieola DSM 1800, and cellulases produced by a fungus or Bacillus N or a cellulase produced by fungus 212 belonging to the genus Aeromonas and cellulase extracted from hepatopancreas of a marine mollusk (Dolabella Auricula Solander).

Lipase enzymes suitable for detergent use include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCG 19 154, as disclosed in British Patent 1,372,034, incorporated herein by reference. Suitable lipases include those that show a positive immunological cross-reaction with the lipase antibody produced by the microorganism Pseudomonas fluorescens IAM 1057. This lipase and a method for its purification are described in Japanese Patent Application 53-20487, disclosed in 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 must cross-react. positive immunological with the Amano-P antibody, using the standard, 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, to Thom et al., Issued on November 17, 1987, incorporated herein by reference. Typical examples of these are lipas

-25Amano-P, lipase ex Pseudomonas fragi FERM P 1339 (available under the trademark Amano-B), lipase ex Pseudomonas nitroreducens var. lipolyticum FERM P 1338 (available with

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Mod. 71-10000 ex. - 89/07 the trademark Amano-CES), lipases ex Chromobacter viscosu.m, p. ex. Chromobacter target the one, p. Chromobacter viscosum var. lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and also Chromobacter viscosum lipases from U.S. Biochemical Corp., USA and Disoynth Co., Netherlands, and lipases ex Pseudomonas gladioli.

Peroxidase enzymes are used in combination with oxygen sources, e.g. eg, percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used as a bleaching solution, that is, to prevent the transfer of dyes or pigments removed from the substrates during washing operations to other substrates in the washing solution. Peroxidase enzymes are known in the art, and include, for example, horseradish, peroxidase, lignin and haloperoxidase such as chlorine and bromo-peroxidase. Detergent compositions containing peroxidase are disclosed, for example, in International PCT Application Wo 89/099813, published on October 19, 1989, by O. Kirk, assigned to Novo Industries A / S, incorporated herein by reference.

A wide range of enzymatic substances and means for their incorporation into synthetic detergent granules is also disclosed in U.S. Patent 3,553,139, issued on January 5, 1971 to McCarty and others (incorporated herein by reference). Enzymes are further disclosed in U.S. Patent No. 4,101,557, to Place et al., Issued on July 18, 1978, and U.S. Patent 4,507,219, to Hughes, issued on March 26, 1985 »both incorporated herein by reference. Useful enzyme substances for liquid detergent formulations are disclosed, and their incorporation in such formulations, in U.S. Patent 4,261,868, to Hora et al., Issued on April 14, 1981, also incorporated herein by reference.

Enzymes normally incorporate at levels sufficient to provide up to about 5 mg by weight, plus

-26—

I

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Mod. 71-10000 ex. - 89/07 typically about 0.5 mg to about 3 mg, of active enzyme per gram of composition.

The enzymes for granular detergents are preferably coated or "prilled" with inert additives in relation to the enzymes to minimize dust formation and improve storage stability. The operations for doing this are well known in the art. In liquid formulations, an enzyme stabilization system is preferably used. Enzyme stabilization techniques for aqueous detergent compositions are well known in the art. A technique for stabilizing enzymes in aqueous detergent compositions involves, for example, the use of calcium ions free from sources such as calcium acetate, calcium formate and calcium propionate. Calcium ions can be used in combination with salts of short chain carboxylic acids, preferably formats. See, for example, U.S. Patent 4,318,818, to Letton et al., Issued March 9, 1982, hereby incorporated by reference. The use of polyols such as glycerol and sorbitol has also been proposed. Dialkyl glycoether alcohols alcohols, mixtures of polyvalent alcohols with polyfunctional aliphatic amines (eg, alkanolamines such as diethanolamine, triethanolamine, diisopropanolamine, etc.) and boric acid or alkali metal borate. Enzyme stabilization techniques are further revealed and exemplified in US Patent 4,261,868, issued on April 14, 1981 to Horn et al., US Patent -

600 319 'issued on August 17, 1971 to Gedge and others, both of which are incorporated herein by reference, and in European Patent Application Publication, No. 0 199 405, Application No. 86200586.5, published on October 29, 1986, by Venegas. Stabilizers other than boric acid and borate are preferred. Enzyme stabilization systems are also described, for example, in US Patents

261 868, 3,600,391 and 3,519,570.

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Mod. 71-10000 ex. 07/07

Bleaching Compounds - Bleaching Agents and Bleaching Activators

The detergent compositions of the present invention can contain bleaching agents or bleaching compositions, which contain bleaching agent or one or more bleaching activators. When included, the bleaching compounds present will typically comprise between about 1% to about 20%, more typically between about 1% to about 10%, of such a 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 between about 0.5% to about 40% of the bleaching composition.

The bleaching agents used in the present invention can be any of the bleaching agents useful for textile cleaning detergent compositions, difficult surface cleaning or other cleaning purposes known today or known to be known. These include oxygen bleaches as well as other bleaching agents. For water conditions below about 5020, especially below about 4020, it is preferable that the compositions of the present invention do not contain borate or borate-forming material (i.e., borate-forming material) under conditions detergent storage or washing. In these conditions, it is preferred, since using a bleaching agent that is neither borate nor borate-forming. Preferably, the detergents to be used at these temperatures are substantially free of borate or borate-forming materials. As used herein, substantially free of borate or borate-forming material means that the composition contains no more than about 2% by weight of borate-containing material or borate-forming material of any kind, preferably not more than what

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Mod. 71 -10000 ex. - 89/07

1%, more preferably 0%.

A category of bleaching agent that can be used includes bleaching agents for percarboxylic acids 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 United States Patent 4,483,781, to Hartman, issued on November 20, 1984, United States Patent Application 740 446, by Burns et al., Filed on June 3, 1985, Application European Patent 0 133 354, by Banks et al., published on February 20, 1985 and United States Patent 4,412,934, by Chung et al., issued on November 1, 1983, all incorporated herein by reference. Extremely preferred bleaching agents also include 6-nonylamino-6-oxoperoxicaproic 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 limitation of the previously mentioned water condition, sodium perborate monohydrate and tetrahydrate ·

The peroxygen bleaching agents are preferably combined with bleach activators, which result in the production in the 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 U.S. Patent 4,179,390, to Spadini and others. Activators

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Preferred bleaching agents include tetraacetylalkylene diamines, particularly tetraacetyl ethylene diamine (TAED) and tetraacetyl glycolour (TAGU).

Mod. 71-10000 ex. - 89/07 where R is the alkyl group containing between about 1 to about 18 carbon atoms where the longest linear alkyl chain extending from carbonyl carbon, including it, contains between about 6 to about 10 carbon atoms and L is a separation group, whose conjugated acid has a pK in the range between about 4 to 13. These bleaching activators are described in U.S. Patent 4,915,854, issued to April 10, 1990 to Mao et al., Incorporated herein by reference, and in US Patent 4 412 934, previously incorporated herein by reference.

There are other bleaching agents, in addition to oxygen bleaching agents, also known in the art and that can be used in the present invention. A type of oxygen-free bleaching agent of particular interest includes photoactivated bleaching agents such as zinc phthalocyanines and / or aluminum sulfones. These materials can be deposited on the substrate during the washing process. When irradiated with light in the presence of oxygen, as when hanging clothes to be air dried in daylight, zinc sulphone ·· phthalocyanine is activated and, consequently, the substrate is bleached.

A preferred zinc phthalocyanine and a photoactivation bleaching process are described in Korte-American Patent 4,033,718, issued July 5, 1977, to Hoh combe et al., Incorporated herein by reference. Typically, detergent compositions will contain between about

-3065.4W

/

Mod. 71 -10000 ex. - 89/07

0.025% to about 1.25% was by weight, of the sulfonated zinc phthalocyanine.

Polymeric Dirt Release Agent

The detergent compositions of the present invention can contain any polymeric dirt releasing agent known to those skilled in the art. Polymeric dirt release agents are characterized by having either hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester or nylon, or hydrophobic segments, which are deposited on the hydrophobic fibers and remain adherent to them until the washing is complete and the rinse cycles, thus serving as an anchor for hydrophilic segments. This can allow stains that occur after treatment with the dirt release agent to be cleaned more easily in the last washing procedures.

Polymeric dirt releasing agents include cellulosic derivatives such as hydroxyether cellulosic polymers, copolymer blocks of ethylene terephthalate or polypropylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like.

Cellulosic derivatives that function as release agents are commercially available and include cellulose hydroxyethers such as Methocel® (Dow).

Cellulosic soil release agents also include those that are selected from the group consisting of C1 -C4 alkyl ^and hydroxyalkyl cellulose such as methylcellulose, ethylcellulose, hydroxypropylmethylcellulose and hydroxybutylmethylcellulose. In US Patent 4 000 093 »issued on December 28, 1976 to Nicol and others, included herein by reference, several cellulose derivatives useful as polymers for releasing dirt are disclosed.

The dirt release agents feature 3110

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Mod. 71 -10000 ex. - 89/07 using hydrophobic poly (vinyl ester) segments, p. e.g., G ^-C ^ vinyl esters, preferably poly (vinyl acetate) grafted onto polyalkylene oxide structures, such as polyethylene oxide structures. Such materials, known in the art, are described in European Patent Application 0 219 048, published on April 22, 1987, by Kuda et al. Suitable commercially available dirt-releasing agents include Sokalan® material, e.g. e.g., Sokalan ^ HP-22, available from BASP (Germany).

A preferred type of soil release agent is a copolymer that has random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. More specifically, these polymers consist of the repetition of ethylene terephthalate and PEO terephthalate units in a molar ratio of ethylene terephthalate units to PEO terephthalate units between about 25:75 to about 35:65, containing the said units of PEO terephthalate polyethylene oxides with molecular weights between about 300 to about 2000. The molecular weight of this polymeric dirt releasing agent is in the range between about 25,000 to about 55,000. See the patent North American 3 959 230, de Hays, granted on May 25, 1976, which is incorporated herein by reference. See also, US Patent 3,893,929, to Basudur, issued on July 8, 1975 (incorporated by reference) which discloses similar copolymers.

Another preferred polymeric dirt release agent is a polyester with repeating ethylene terephthalate units containing 10-15% by weight ethylene terephthalate units together with 80-90% by weight of polyoxyethylene terephthalate units, derived of an average molecular weight polyoxyethylene glycol 300-5000, and where the molar ratio of ethylene terephthalate units to polyoxyethylene terephthalate units in

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Mod. 71 -10000 ex. - 89/07 polymeric compound is between 2: 1 and 6: 1. Examples of this polymer include the commercially available materials Zelcon 5126 (from Dupont) and Milease (from ICI). These polymers and their methods of preparation are described in more detail in U.S. Patent 4,702,857, issued October 27, 1987, to Gosselink, which is incorporated herein by reference.

Another preferred polymeric dirt release agent is a sulfonated product of a substantially linear oligomeric ester consisting of an oligomeric ester structure of repeated units of terephthaloyl and oxyaleneoxy and terminal portions covalently linked to the structure, said dirt release agent being derived of an ethoxylated allyl alcohol, dimethyltereftalate and 1,2-propylene-diol, characterized in that the end portions of each oligomer have, on average, a total between about 1 to about 4 sulfonate groups. These dirt-releasing agents are fully described in U.S. Patent 4,968,451 'issued on November 6, 1990 to JJ Scheibel and Ε. P. Gosselink, in U.S. Patent Application Serial No. 07/474 709, filed January 29, 1990, hereby incorporated by reference. Other suitable polymeric dirt releasing agents include the ethyl or methyl-coated ethylene 1,2-propylene terephthalate polyesters of U.S. Patent 4,711,730, issued December 8, 1987 to Gossolink and others , the terminally covered anionic oligomeric esters of U.S. Patent 4,721,580, issued on January 26, 1988, to Gosselink, characterized in that the anionic end caps comprise polyethylene glycol-derived sulfopolietoxy groups (PEG), polyester oligomeric compounds in blocks of US Patent 4 702 857 'issued on October 27, 1987 to Gosselink, which have polyethylene end caps of formula X- (0CH ₂ CH ₂ ) _n - where n is en-3310

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Mod. 71 -10000 ex. 89/07 tre 12 to about 43 and X is a G ^-G ^ alkyl, or preferably methyl, all of which are incorporated herein by reference.

Additional dirt release polymers include dirt release polymers of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al., Which discloses anionic end-cover terephthalate esters, especially sulfoaroil, whose patent is hereby incorporated by reference. Terephthalate esters contain unsymmetrical substituted oxy-1,2-alkyleneoxy units.

If used, dirt release agents will generally comprise between about 0.01% to about 10.0%, preferably between about 0.1% to about 5.0%, more preferably between 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 magnesium chelating agents as a bulking agent auxiliary material. Such chelating agents can be selected from the group consisting of amine phosphonate amine carboxylates, polyfunctional substituted aromatic chelating agents and mixtures thereof, all as defined hereinafter. Without wishing 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 through the formation of soluble chelates.

Amine carboxylates useful as optional chelating agents in compositions of the invention can have one or more units, preferably at least two, of the substructure

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Mod. 71-10000 ex. - 89/07

-ch ₂ \

- (0Η ₂ ) _χ “ ^G00M ” where M is hydrogen, alkali metal, ammonium or substituted ammonium (eg, ethanolamine) exe between 1 to about 3 ”preferably 1. Preferably, these amine carboxylates do not contain groups alkyl or alkenyl with more than about 6 carbon atoms. Operational amine carboxylates include ethylene diamine tetraacetates, N-hydroxyethyl ethylene diamine triacetates, nitrilotriacetates, ethylene diamine tetrapropionates, triethylene tetraamine hexaacetates, diethylene triamine pentaacetates and ethanoldiglycines, amine salts and metals. replaced and mixtures thereof.

Amine phosphonates are also suitable for use as chelating agents in the detergent compositions of the invention when at least low levels of total phosphorus are allowed in the detergent compositions. Compounds with one or more units, preferably at least two, of the substructure ch ₂ / N (0Η ₂ ) _χ P0 ₃ M ₂ , where M is hydrogen, alkali metal, ammonium or substituted ammonium are used, and ex is between 1 to about of 3, preferably 1, and include ethylene-diamine-tetrakis (methylene phosphonates), nitrilotris (methylene phosphonates) and diethylene-triamine-pentaquis (methylene phosphonates). Preferably, these amine phosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms. Alkylene groups can be shared by the substructures.

Polyfunctional substituted aromatic chelating agents are also useful in the compositions of the present invention. These materials may comprise compounds

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who have the general formula;

Mod. 71-10000 ex.-89/07 where at least one R is -SO ^ H or -COOH or soluble salts thereof and mixtures thereof. The US Patent

812 044, issued on May 21, 1974, to Connor et al., Incorporated herein by reference, discloses polyfunctional substituted and sequestering aromatic chelating agents. Preferred compounds of this type in acid form are dihydroxy disulfobenzenes such as 1,2-dihydroxy-3,5-disulfo-benzene. Alkaline detergent compositions may contain these materials in the form of alkali metal, ammonium or substituted ammonium salts (eg, mono or triethanolamine) ·

If used, these chelating agents will generally comprise between about 0.1% to about 10% by weight of the laundry detergent compositions of the present invention. Most preferably the chelating agents will comprise between about 0.1% to about 3.0% by weight of such compositions.

Clay Stain Removal / Anti-Redeposition Agents

Clay stain / anti-redeposition agents useful in the detergent compositions of the present invention include polyethylene glycols and water-soluble ethoxylated amines that have clay stain / anti-redeposition properties. The polyethylene glycol compounds useful in the detergent compositions of the present invention typically have a molecular weight in the range between about 400 to about 100,000, preferably between about 1,000 to

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about 20,000, more preferably between about 2,000 to about 12,000 and most preferably between about 4,000 and about 8,000. Such compounds are commercially available and are sold as Carbowax®, which is available from Union Garbide, located in Danbury, Gonn.

The water-soluble ethoxylated amines are preferably selected from the group consisting of: ethoxylated monoamines with the formula (xl) -n_r (r ² ) 2 ethoxylated diamines with the formulas R ² -NR ¹ -NR ² (R ² ) 2- HR ¹ -N- (R ² ) ₂ f

L t

X (D (2)

Mod. 71-10000 ex. - 89/07 or (3) (4) and

(5) (xl) ₂ -nr ¹ -n- (r ² ) ₂ ethoxylated polyamines

R ³ - (a ¹ ) q- (R ⁴ ) tMLz) _p polymers of ethoxylated amines with the formula: _n with the formula mixtures of

Themselves;

1!

where A is:

-NG-, f

R

-NGO-, I

R

-NGN-,

I

R R tt —GO—,

-hollow-,

-0G-,

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Mod. 71 -10000 ex. - 89/07 or -0-; R and H or CjC ^alkyl or hydroxyalkyl R ^and alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene θ2 “θ12 ' ^or utaa P ° ^r S ^ ⁰ oxyalkylene C ₂ -C ^ ^COKI -' ^{í and} between 2 to about 20 oxyalkylene units as long as 0-N bonds are not formed; each R ² is alkyl or hydroxyalkyl GpG ^, the -L-Σ portion, or two R ² together form the - (CH.,) portion.

Q Ο _zz Λ *

-A - (GH ₂ ) _s “» where A is -0- or -CHg-, r is 1 or 2, if 1 or 2 ₍ er + if 3 or 4; Σ and a non-ionic group, an anion group, co or a mixture thereof; R and an alkyl, hydroxyalkyl, alkenyl, aryl or C 1 -C 4 alkyl substituted with substitution sites; R 2 is alkylene, hydroxyalkylene, alkenylene, arylene or C 4 -C ₂ alkylene, or an oxyalkylene G ₂ -C ^ moiety containing from 2 to about 20 oxyalkylene moieties provided that no 0-0 or 0-N bonds are formed; L is a hydrophilic chain containing the polyoxyalkyl · no - ((R ^ O ^ GHgGHgO) ^) -, where R ^ is alkylene or hydroxyalkylene C ^ -G ^ and m are numbers such that the - (CHgCHgO) - portion comprises at least about 50% by weight of said polyoxyalkylene portion; monoami ··nas, m from 0 to about 3, and at least about 6 quan * 1 z of R and alkylene, hydroxyalkylene, or C _O -G _Q alkenylene, and & j at least about 3 when R is not alkylene, hydroxyalkylene or alkenyl C ₃ -C ene; for said polyamines and amine polymers, m is from 0 to about 10 and n is at least about 3; foot between 3 to 8; q is 1 or O; t is 1 or O, provided that t is 1 when q is 1; w is 1 or O; x + y + z pe ··lo minus 2; ey + z is at least 2.

stain-releasing agent and anti-redepo ·· sition most preferred is ethoxylated tetraethylene-pentaamine. Examples of ethoxylated amines are also described in U.S. Patent 4,597,898 to VanderMeer, issued July 1, 1986, hereby incorporated by reference. Another preferred group of clay stain / anti-redness agents are the cationic compounds disclosed in European Patent Application 111 965, by Oh and Gosse-3810

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Mod. 71-10000 ex. - 89/07 link, published on 27 June 1984, hereby incorporated by reference. Other clay stain / anti-redeposition agents that can be used include the ethoxylated amine polymers disclosed in European Patent Application 111 984, by Gosselink, published on June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112 592, by Gosselink, published on July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744, to Connor, issued October 22, 1985, which are all incorporated herein by reference.

The most preferred stain release and anti-deposition agents are ethoxylated tetraethylene-pentamine and polyethylene glycols with a molecular weight in the range between about 4,000 to about 8,000.

Granular detergent compositions containing such compounds typically have between about 0.01% to about 10.0% by weight of the clay removing agent; liquid detergent compositions typically contain between about 0.01% to about 5.0% by weight.

Polymeric Dispersing Agent

Polymeric polycarboxylate dispersing agents can advantageously be used in the detergent compositions of the present invention. These materials can help control the hardness of calcium and magnesium. In addition to acting as an auxiliary bulking agent analogously to the polycarboxylate mentioned earlier in the description of the Bulking Agent, it is believed, although not intended to be limited by theory, that these higher molecular weight dispersing agents may still intensify the overall performance of the detergent's bulking agent by inhibiting the growth of inorganic crystals, by forming peptide stain particles and by anti-redeposition, when used in combination with other bulking agents including lower molecular weight polycarboxylates.

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The polycarboxylate materials that can be employed as the polymeric polycarbarboxylate dispersing agents are polymers or copolymers that contain at least about 60% by weight of segments of the general formula:

ΣZ

CC

YCOOM n

wherein Σ, Y, and Z are individually selected from the group consisting of hydrogen, methyl, carboxy, carboxymethyl, hydroxy and hydroxymethyl; M is a salt-forming cation and n is between about 30 to about 400. Preferably, X is hydrogen or hydroxy, Y is hydrogen or carboxy, Z is hydrogen and M is hydrogen, alkali, ammonium or substituted ammonium.

Polymeric polycarboxylate materials of this type can be prepared by polymerization or copolymerization of suitable unsaturated monomers, preferably in their acidic forms. Unsaturated monomeric acids that can be polymerized to form suitable polymeric carboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenomalonic acid. The presence in the present polymeric polycarboxylates of monomeric segments not containing carboxylate radicals such as methyl vinyl ether, styrene, ethylene, etc. it is suitable as long as such segments make up no more than about 40% by weight.

Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers which are useful in the present invention z z z z are the water-soluble salts of polymerized acrylic acid »

4010

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/

Mod. 71-10000 ex. -89/07 The average molecular weight of such polymers in acid form ranges from about 2,000 to 10,000, more preferably between about 4,000 to 7,000 and even more preferably between about 4,000 to 5,000. The soluble salts in water 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. The use of polyacrylates of this type in detergent compositions has been disclosed, for example, in U.S. Patent No.

308 067, from Diehl, issued March 7, 1967. This patent is incorporated herein by reference.

As a preferred component of the dispersing agent, acrylic / maleic acid based copolymers can also be used. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic ^z. The average molecular weight of such copolymers in 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 about 60,000. The ratio of the acrylate segments for maleate in such copolymers it will generally range from about 30: 1 to about 1: 1, more preferably between 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 known materials described in European Patent Application No. 66 915, published on December 15, 1982, the publication of which is hereby incorporated by reference.

If used, polymeric dispersing agents will generally comprise between about 0.2% to about 10%, preferably between about 1% to about 5% by weight of the detergent compositions.

Avivador

Optical brighteners or other brightening or brightening agents known to those skilled in the art

-> 41 -

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Mod. 71 -10000 ex. 89/07 can be incorporated into the laundry detergent compositions of the present invention. However, the choice of the revivator will depend on several factors, such as the type of detergent, the nature of other components present in the detergent composition, the washing temperatures, the degree of agitation and the ratio of the washed material to the size of the tube.

The selection of the revivator is also dependent on the type of material to be cleaned, p. eg cottons, synthetics, etc. Since most laundry detergent products are used to clean various fabrics, detergent compositions must contain a mixture of brighteners that is effective for various fabrics. Of course, it is necessary that the individual components of such a reviving mixture are compatible.

Commercial optical brighteners can be classified into subgroups that include, but are not limited to, derivatives of stilbene, pyrazoline, eumarine, carboxylic acid, methinocyanines, dibenzotifene-5,5-dioxide, azoles, 5- and 6-membered heterocyclic rings and other miscellaneous agents. Examples of such revivals are revealed in The Prodution and Application of Fluorescent Brightening Agents ”, M. Zahradnik, Published by John Wiley & Sons, Rova York (1982), the revelation of which is incorporated here as a reference ·

Stybene derivatives include, but are not limited to, stylbene derivatives; triazoles derived from stilbene; oxadiazoles derived from stilbene; and stilbene sterile.

Certain bis (triazinyl) aminostilbene derivatives can be prepared from 4,4'-diamine-stilbene-2,2'-disulphenic acid.

Eumarino derivatives include, but are not limited to, substituted derivatives in position-3, position-7 and positions -3 and -7 ·

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Mod. 71 -10000 ex. - 89/07

Carboxylic acid derivatives include, but are not limited to, fumaric acid derivatives; benzoic acid derivatives; p-phenylene-bis-acrylic acid derivatives; naphthalene-dicarboxylic acid derivatives; heterocyclic acid derivatives; and derivatives of cinnamic acid.

Derivatives of cinnamic acid can further be subclassified into groups that include, but are not limited to, derivatives of cinnamic acid, styrylazoles, styryl benzofurans, styryloxadiazoles, styryl triazoles and styryl polyphenyls, as revealed on page 77 of the Zahradnik reference.

Styrenazoles can further be subclassified into styryl benzoxazoles, styrylimidazoles and styltiazoles, as revealed on page 78 of the Zahradnik reference. It will be understood that these three identified subclasses may not necessarily reflect an exhaustive list of subgroups in which stretchers can be subclassified.

Other optical brighteners are the dibenzothiophene-5,5-dioxide derivatives disclosed on pages 741-749 of The Kirk-Othmer Encyclopedia of Ghemical Technology, Volume 3, pages 737-750 (John Wiley & Son, Inc., 1962), a disclosure of which is incorporated herein by reference, and includes 3,7-diaminodibenzothiophene-5,5-dioxide, 8-disulfonic acid.

Other optical brighteners are azoles, which are derived from 6-membered heterocyclic rings. These can still be subcategorized in mono-zones and bisazoles. Examples of monoazoles and bisazoles are revealed in the Kirk-Othmer reference. Other optical brighteners are still those derived from 6-membered heterocyclic rings disclosed in the Kirk-Othmer reference. Examples of such compounds include pyrazine derived brighteners and 4-aminonaphthalamide-based brighteners.

In addition to the avivadores already described,

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Mod. 71-10000 ex. - 89/07 miscellaneous can also be useful as revivals. Examples of such miscellaneous agents are disclosed on pages 93-95 of the Zahradnik reference and include 1-hydroxy-3,6,8-pyrenotrisulfonic acid; 2,4-dimethoxy-1,3,5-triazine-6-yl-pyrene; 4,5- * diphenylimidazolonedisulfonic acid; and pyrazollnaquinoline derivatives.

Other specific examples of optical brighteners are those identified in the United States Patent

790 856, issued to Wixon on December 13, 1988, the disclosure of which is incorporated herein by reference. These brighteners include the Phorwhite ^ series of brighteners from Verona. Other revivals revealed in this reference include: Tinotipal UNPA, Tinotipal CBS and Tinotipal 5BM, available through Ciba-Geigy; Artic Wh.it and CC and Artic White OWD, available through Hilton-Davis, located in Italy; 2- (4-styrylphenyl) -2H-naphthol (1,2-d) triazoles; 4-4 ’~ bis- (1,2,3-triazol-2-yl) -stilbene; 4,4'-bis (styryl) bisphenyls; and y-amino-coumarins. Specific examples of these revivifiers include coumarin 4-methyl-7-diethylamine; 1,2-bis (-benzimidazole-2-yl) -ethylene; 1,3-diphenylpyrazolines; 2,5-bis (benzoxazol-2-yl) -thiophene: 2-styryl-naphtho- (1,2-d) -oxazole; and 2- (stylbene-4-yl) -2H-naphtho (1,2-d) triazole ·

Still other optical brighteners include those disclosed in U.S. Patent 3,646,015, issued on February 29, 1972 to Hamilton, whose disclosure is hereby incorporated by reference.

If used, optical brighteners will generally comprise between about 0.05% to about 2.0%, preferably between about 0.1% to about 1.0% by weight of laundry detergent compositions.

Foam Suppression Agents

Known or known compounds may be incorporated into the detergent compositions of the present invention to reduce or suppress foaming. The incorporation of such materials, hereinafter desi-4410

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Mod. 71-10000 ex. - 89/07 foam suppression agents may be desirable because the polyhydroxy fatty acid amide surfactants of the present invention can increase the foam stability of detergent compositions. Foam suppression can be particularly important when detergent compositions include a relatively very foamy surfactant in combination with the polyhydroxy fatty acid amide surfactant. Foam suppression is particularly desirable in compositions intended for use in front loadable washing machines. These machines are typically characterized by having drums, to contain laundry and washing water, which has a horizontal axis and rotating action around this axis. This type of agitation can result in a high foaming and, consequently, a reduction in cleaning performance. The use of foam suppressing agents can also be particularly important in hot water washing conditions and in conditions of high surfactant concentration. A wide variety of materials can be used as foam suppression agents. Foam suppression agents are well known to those skilled in the art. They are described in general, for example, in the Kirk Othmer Encyclopedia of Chemical Technology, 3rd Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979) · A category of foam suppression agents of particular interest includes monocarboxylic fatty acids and their soluble salts. These materials are discussed in United States Patent 2,954,347, issued on September 27, 1960 to JohnWayne St., said patent being incorporated herein by reference. Monocarboxylic fatty acids, and salts thereof, for use as foam suppressants typically have hydrocarbyl chains between 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include alkali metal salts such as sodium, potassium, and li-4510 salts

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Mod. 71-10000 ex. - 89/07 uncle, and ammonium and aleanolammonium salts. These materials are a preferred category of foam suppressors for detergent compositions.

The detergent compositions of the present invention can also contain non-foam suppressants that are not surfactants. These include, for example, hydrocarbons of high molecular weight such as paraffin, fatty acid esters (p. Ex "triglyceride fatty attaches), fatty acid esters of monovalent alcohols, ketones ⁰ lifáticas (p · g., Stearone) , etc. Other foam inhibitors include N-alkylated aminotriazines such as tri- to hexaalkylamine chlorotriazines or di-tetraalkyl diamine formed as cyanuric chloride products with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, oxide of propylene, and monostearyl phosphates such as monostearyl alcohol phosphate ester and alkali di metal metal phosphates (e.g., sodium, potassium, lithium) monostearyl and phosphate esters. Hydrocarbons, such as paraffin and haloparaffin, can be used in liquid form. Liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range between about -4020 to about 520, and a minimum boiling point of not less than about 10020 (atmospheric pressure). It is also known to use brain hydrocarbons preferably having a melting point below about 100 ° C. Hydrocarbons are a preferred category of foam suppressants for detergent compositions. Hydrocarbon foam suppressants are described, for example, in U.S. Patent 4,265,779, issued on May 5, 1981 to Gondolfo et al., Incorporated herein by reference. The hydrocarbons thus include saturated or unsaturated aliphatic, alicyclic, aromatic and heterocyclic hydrocarbons having between about 12 to about 70 carbon atoms. The term paraffin ',

-4FEVJ993

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Mod. 71-10000 ex. -89/07 as used in this discussion of foam suppression agents, presupposes the inclusion of mixtures of true paraffins and cyclic hydrocarbons.

One or another preferred category of foam suppressants other than surfactants comprises silicone foam suppressants. This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxanes oils or resins, and combinations of polyorganosiloxanes with silica particles where the polyorganosiloxane is chemically absorbed or melted on silica. Silicone foam suppressors are well known in the art and are disclosed, for example, in U.S. Patent 4,265,779, issued on May 5, 1981 to Gandolfo et al. And in European Patent Application No. 89307851.9, published in February 7, 1990, by MS Starch, both of which are incorporated herein by reference.

Other silicone foam suppressors are disclosed in U.S. Patent 3,455,839, which deals with compositions and processes for defoaming aqueous solutions by incorporating small amounts of polydimethyl siloxane fluids into them.

Mixtures of silicone and silane silica are described, for example, in German Patent Application DOS 2 124 526. Silicone defoamers and foam control agents in granular detergent compositions are disclosed in U.S. Patent 3,933,672, to Bartolotta and others, and U.S. Patent 4,652,392, to Baginski et al., issued March 24, 1987.

An exemplary silicone-based foam suppressor for use in the present invention is a foam suppressant amount of a foam control agent consisting essentially of:

(i) polydimethyl siloxane fluid with a viscosity between about 2.10 ³ m / s (20 cs) to about —47

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parts for 100 units in a range of 1.5.1 ~ ³ m ² / s (1500 cs) at 2520;

between about 5 to about 50 parts by weight of:

of siloxane resin composed (Cf ₃ ) ₃ SiO ₂ / g and Si ₀ units ₂ units (CH ₂ ) ₄ SiO ₂ g for Si 0 ₂ units between about 0.6: 1 to about 1.2: 1; and between about 1 to about 20 parts to 100 parts by weight of:

of a solid silica gel.

Foam suppressors, when used, are

Mod. 71 -10000 ex. - 89/07 (ii) (i) (iii) (i) so present in a number of foam suppressors. By the amount of foam suppressors, it is stated that the composer of the composition can select an amount of this foam control agent that will control the foams in the desired size. The amount of foam control will vary with the selected detergent surfactant. For example, with highly foamy surfactants, relatively more foam control agent is used to achieve the desired foam control than with low foamy surfactants.

The detergent compositions of the present invention will generally comprise between 0% to about 5% foam suppressant. When used as foam suppressants, monocarboxylic acids, and salts thereof, will typically be present in amounts up to about 5%, in weight, of the detergent composition. Preferably, between about 0.5% to about 3% fat monocarboxylate foam suppressant is used. Silicon foam suppressors are typically used in amounts up to about 2.0% by weight of the detergent composition, although higher amounts can be used. This upper limit is of a practical nature, due in the first place to the concern to keep costs minimized and efficiency of lower amounts for effective foam control. Preferably,

-48 ·

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Mod. 71-10000 ex. - 89/07 between about 0.01% to about 1% of silicone foam suppressant, more preferably between about 0.25% to about 0.5% · As used here, these values Weight percentages include any silica that can be used in conjunction with polyorganosiloxane, as well as any auxiliary materials that can be used. Monostearyl phosphates are generally used in amounts ranging from about 0.1% to about 2% by weight of the compositions.

Hydrocarbon foam suppressing agents are typically used in amounts ranging from about 0.01% to about 5%, although higher levels can be used.

Other Ingredients

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

Liquid detergent compositions can contain water and other solvents as vehicles. Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol and isopropanol are suitable. Monohydric alcohols are preferred for solubilizing the surfactant, and polyols such as those containing between about 2 to about 6 carbon atoms and between about 2 to about 6 hydroxy groups (p propylene glycol, ethylene glycol, glycerin and 1,3-propanediol)

The detergent compositions of the present invention will preferably be formulated in such a way that during use in aqueous cleaning operations, the washing water will have a pH 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 »

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Mod. 71-10000 ex. - 89/07 more preferably between about 7.5 and about 9.0. The pH control techniques at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those of skill in the art *

This invention further provides a method for cleaning substrates, such as fibers, fabrics, difficult surfaces, skin, etc., by contacting said substrate with a detergent composition containing the glyceryl ether component (a) and the surfactant component. -anionic detersive active (b), in the presence of a solvent such as water or a water-miscible solvent (eg, a primary or secondary alcohol). Stirring is preferably provided to intensify cleaning. Suitable means for providing agitation include scrubbing by hand, preferably with the aid of a brush, or other cleaning device, automatic washing machine, automatic dishwasher or the like.

Although, as indicated above, it is possible to include conventional polyethoxylated nonionic surfactants in the present compositions, it is commonly preferred not to do so. In fact, it is an advantage of the glyceryl ethers used as a component (a) that they allow the substitution of non-ionic polyethoxylated surfactants, thus obviating the need for the use of ethylene oxide, while obtaining excellent cleaning performance characteristics. Thus, the glyceryl ethers of formula (1) are very effective against fat stains, although they do not show significant weakening against other stains, e.g. particulate matter: in addition, glyceryl ethers are satisfactory in terms of redeposition of stains. In addition, glycerol ethers exhibit other advantages, such as, for example, stabilizing the enzyme in liquid detergents for hard work. Glyceryl ethers also have comparatively low melting points and their use as binding agents is considered.

-50W-Í9 '

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The present invention is illustrated in the course of, and through, 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. 1 (January 1989) page 146, using the following reagents:

30g (0.124 mole) of Distilled Dodecyl Epoxide No. 8 (from Procter & Gamble)

0.14g (6.2 x 1 (T ³ mole) of sodium

57g (0.62 mole) of anhydrous glycerol

Sodium and glyceryl were reacted together at 13O2C for one hour under nitrogen. The epoxide was then added dropwise over one hour to the reaction mixture at 180 ° C, the reaction mixture was stirred at that temperature for 8 hours.

Mod. 71-10000 ex. - 7/7 hours. The reaction mixture was dissolved in ethanol and treated with carbon dioxide pellets in order to neutralize the sodium. The mixture was released from ethanol in a rotary evaporator and then distilled (1.75 mmHg (233 Pa); head temperature 14020) to remove a previous fraction of the glycerol dimer (identified as such using gas-liquid chromatography) · ether dodecyl diglyceryl produced in this way was a low melting solid (44-4620) comprising 92% diglyceryl ethers, 1.5% monoglyceryl ethers and 2% triglyceryl ethers.

diglyceryl ether contained approximately 4 moles of linear ether ”of the general formula (2) per mole of the branched ether of the general formula (3) ·

The previous synthesis can also be carried out using Epoxide No. 8 to which a small amount of sodium borohydrate is added, in order to obtain the final product with better color.

Example 2

Cocoyl-diglyceryl ether was prepared by the method

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Mod. 71-10000 ex.-89/07 of Takaishi et al., US-A-4 465 866, using the following reagents:

74.5g (0.5625 mole) of ketal glycerol acetone (available under the trade name ”Solketal” from Aldrich Chemical Company)

3.2g (0.018 mole) of tetramethyl-diaminohexane 45g (0.18 mole) of Bpoxide STo. 8 (by Procter & Gamble)

The ketal glycerol acetone and tetramethyldiaminohexane were mixed together and heated to 100 ° C. The epoxide was then added dropwise over a period of 30 minutes, maintaining the temperature between 100 and 11020. The resulting mixture was then heated at that temperature for 6 hours. The product was distilled (1 ramHg (133 Pa) at 5220 head temperature) to remove excess ketal glycerol acetone and further distilled with vacuum (4.5 mmHg (600 Pa) at a head temperature of 23020) to collect the product (dioxolane intermediate).

34.8g (0.09 mole) of the dioxolane intermediate was then added in 75 ml of ethanol to 4.6 g (0.046 mole) of concentrated sulfuric acid in 100 ml of water and the resulting mixture was heated to reflux for 4 hours. hours. When the solution cooled, it was neutralized with 3.6 g (0.09 mole) of sodium hydroxide. The product was extracted using diethyl ether, dried over sodium sulfate and then evaporated to dry on a rotary evaporator to give a golden paste.

Example 3

A series of liquid detergent compositions for hard work, A-C, were prepared, these compositions having the surfactant components shown in the following Table, in which the amount of each component is shown as a percentage of the weight of the composition.

52A

12.9

8.4

B

12.9

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Table 1

Tensio-Active Agent

NaCnAS

Nat. NI

Nat. NI

CnDGE

Ç

12.9

E07

E05

8.4

The surfactants classified as follows: NaCnAS Nat. NI do Quadro

8.4 are idencoco and sodium

E07

Nat. NI E05 = alkyl sulfate = fatty alcohol condensate of natural origin with 7 moles of ethylene oxide per mole.

= condensate of fatty alcohol of natural origin with 5 moles of ethylene oxide per moMod. 71-10000 ex. - 89/07

GhDGE le.

= coconut alkyldiglyceryl ether (prepared as in Example 1).

The compositions were tested against a variety of stains, and the dirty loads were washed in a 6020 mini-washing machine using tap water (total hardness of 5 moles), at 1 percent usage. Dirty loads are prepared by staining cotton or polyester / cotton (PA) samples in a conventional manner.

performance of removing dirt was judged by a panel of experts in a known way, with the results recorded in psu (panei score units), the score units panel, on the Scheffe scale, taking the results as standard (0.0) obtained using composition A. The results are shown in the following Table:

Table 2

Stain Removal (Cotton / PA)

Fat:

Make-up

Baton

Spaghetti

-53B + 0.4 / + 0.7 + 0.6 / + 0.5 + 0.5 / + 1.2 + 0.2 / + 0.4

C + 1.4 / + 1.0 + 1.8 / + 0.9 + 2.3 / + 1.7 + 0.5 / + 0.3

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DM0 + 0.7 / + 0.6 + 1.0 / + 0.9 Blanking -0.2 / + 0.2 + 1.1 / + 0.9 Enzyme -0.1 / 0.0 + 0.3 / -0.0 of Particles -0.1 / -0.6 + 0.2 / + 1.1

Mod. 71 -10000 ex. - 89/07

Grades; enzymatic refers to removable stains with proteasse;

ΏΜΟ »dirty motor oil.

As can be seen from Table 2, composition C, which is in accordance with the present invention, exhibits excellent cleaning performance, especially against grease stains and particle stains.

Example 4

A reference composition was prepared in the form of heavy-duty liquid detergent containing 7.25 percent by weight linear alkyl sulfonate-benzene, 1.75 percent coconut alkyl sulfate, 9% citrusy bulking agent, 5 percent of another bulking agent and 10 percent of fatty alcohol condensate with 7 moles of ethylene oxide per mole.

A test composition was then prepared, which is essentially similar to the reference composition, but only with 6 percent of the said fatty alcohol condensate / ethylene oxide and with 4 percent of the coconut alkyldiglyl ether ether (prepared as in Example 1).

The compositions were tested against a variety of stains, the test method and the evaluation method being as described in Example 3. The psu results for the test composition, in relation to the 0.0 results of the reference compositions for stained cotton loads and stained polyester / cotton loads are shown in the following table:

Table 3

Stain Cotton Polyester / Cotton

Fat +0.7 +0.8

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z

Bleached -0.1 -0.1 Enzyme -0.2 +0.1 From Particles +0.3 -0.3 BMI empa +0.1 +0.1

Mod. 71 -10000 ex. - 89/07

Note BMI empa is a standardized stain consisting of blood, milk and ink (Blood, Milk and Ink = BMI) on a polyester-cotton substrate sold by the EMPA Institute, St. Gallen, Switzerland.

Regarding the reference composition (which typifies conventional liquid formulations of detergents for hard work), the test composition, which was formulated according to the present invention, showed better performance against grease stains with comparable performance against other stains.

It will be understood, of course, that the present invention has been described purely by way of example and that modifications of details can be made within the spirit of the invention.

Lisbon, -4.FEV.W

By THE PROCTER & GAMBLE COMPANY

wee MARQ0ES IHW

Ageme Opcial

d. P-.r ·

CfJióúT · - ‘« j. · <4ί ·; β9. 3 · 1 *** 11W tíSHHI

-5535

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Mod. 71 -10000 ex. - 89/07

Claims (9)

= CLAIMS = 1â.- Detergent composition characterized by comprising (a) one or more glyceryl ethers of general formula; RO - (C ₃ H ₆ O ₂ ) _n H where R represents an alkyl or alkenyl group having 12 to 18 carbon atoms, ^C 3 ^H 6 ° 2 ^{re Pr} ® ^sen ta ^a divalent radical formed by removal from glycerol of a hydroxyl group and the hydrogen atom of the hydroxyl rest en the group is an integer, with at least 50 mol% of component (a) consisting of diglyceryl ether and not more than 25 mol% of component (a) consisting of monoglyceryl ether and (b) an anionic detersive surfactant. 2. A composition according to claim 1, characterized in that at least 60 mol% of component (a) consists of diglyceryl ether and not more than 20 mol% of component (a) consisting of monoglyceryl ether. 3. A composition according to claim 1 or 2, characterized in that the diglyceryl ether of the component (1) is a mixture comprising diglyceryl ethers of the general formulas: r - och ₂ chohch ₂ .och ₂ chohch ₂ .oh (2) e R - 0CH ₂ CH0HCH ₂ .0CH - CH ₂ 0H (3) \ íh ₂ oh 4.- Composition according to claim 3, characterized in that the ethers of formulas (2) and (3) are 65,418 Mod. 71-10000 ex. - 89/07 present in a molar ratio of about 4: 1. 5. A composition according to any one of claims 1 to 4, characterized in that component (a) is substantially and totally diglyceryl ether. 6. A composition according to any one of claims 1 to 5, characterized in that R is an alkyl alkyl group. 7. A composition according to any one of claims 1 to 6, characterized in that it also comprises at least one other component selected from cationic, ampholytic, dipolar and semi-polar detersive surfactants, detergent-building agents, enzymes, bleaches and agents chelation. 8. A composition according to any one of claims 1 to 7, characterized in that it is in the form of an effective liquid detergent or an effective granular detergent. 9. A process for the preparation of a diglyceryl ether of the general formula (1) according to claim 1 or a mixture of such ethers, characterized in that a compound of the general formula is reacted: R - 0 - CH ₂ CH - CH ₂ wherein R has the meaning given in claim 1 with glycerol in the presence of a base and / or with a glycerate and the impurities in the product are removed by distillation.