CN1193994A - Non-aqueous granular detergent composition - Google Patents

Abstract

Nonaqueous detergent compositions in liquid, paste or gel form are disclosed, which compositions comprise a bleach activator in the presence of a divalent and/or trivalent metal salt.

Description

Non-aqueous granular detergent composition

Field of Invention

The present invention relates to non-aqueous laundry detergent products in liquid, gel or paste form and in the form of stable dispersions of particulate materials such as bleaches and bleach activators.

Background of the Invention

Detergent products in liquid, gel or paste form are often considered more convenient to use than dry powder or granular detergent products. Said detergents are therefore very popular with consumers. This detergent product is easy to measure, dissolves quickly in the wash water, and can be easily applied as a concentrated solution or dispersion on soiled areas of washed clothes without dusting. They also generally take up less storage space than granular products. In addition, such detergents can be incorporated into formulation materials which deteriorate when subjected to drying operations commonly used in the manufacture of granular or granular detergent products.

Although said detergents have many advantages over granular detergent products, they also inherently suffer from some disadvantages. In particular, mutually compatible detergent composition components in granular products may interact or react with each other. Thus, such components as enzymes, surfactants, perfumes, brighteners, solvents and especially bleaches and bleach activators are particularly difficult to incorporate into liquid detergent products with an acceptable degree of chemical stability.

One approach to increasing the chemical stability of detergent composition components in detergent products is to formulate non-aqueous (or anhydrous) detergent compositions. In such non-aqueous products, at least some of the normally solid detergent composition components tend to remain undissolved in the liquid product and are therefore less reactive with each other than if they had been dissolved in the liquid matrix. For example, US4,615,820 issued October 17, 1986 to Hepworth et al, US4,929,380 issued May 29, 1990 to Schultz et al, US5,008,031 issued April 16, 1991 , EP-A-030,096, Elder et al., published June 10, 1981, WO92/09678, Hall et al., published June 11, 1992, and EP-A, published October 13, 1993, by Sanderson et al. -565,017 have disclosed non-aqueous liquid detergent compositions including those containing reactive materials such as peroxygen bleach.

Difficulties observed with incorporating bleach activators in non-aqueous detergents include the chemical and/or physical stability of the bleach activators. EP 339 995 describes a non-aqueous liquid detergent composition comprising an oversalt bleach and thus a precursor, which composition contains blocked alkoxylated nonionic surfactants. EP540 090 proposes the use of a bleach precursor which is relatively insoluble in the non-aqueous liquid phase of liquid detergent compositions.

A difficulty associated with the stability of bleach activators is that, upon dilution in the wash liquor, the bleach activator still needs to have some solubility high enough to be effective as a bleaching species in the wash liquor.

Given the foregoing, there is a clearly continuing need to identify and provide non-aqueous bleach activator-containing detergent compositions in liquid, gel or paste form which are highly chemically stable in concentrates and in wash liquors. Has effective bleaching properties.

It is therefore an object of the present invention to provide a non-aqueous detergent composition wherein the bleach activator is chemically stable in the concentrate while at the same time remaining effective as a bleaching species in the wash liquor.

According to the present invention there is provided a non-aqueous detergent composition in liquid, gel or paste form comprising a bleaching agent and a bleach activator in the form of divalent metal salts, trivalent metal salts, mixed metal salts, consisting of Here, at least one salt is a divalent or trivalent metal salt or a mixture thereof.

Invention Summary

The present invention provides a non-aqueous heavy-duty detergent composition in liquid, gel or paste form, said composition comprising a bleaching agent and a bleach activator, characterized in that said bleach activator is a divalent metal salt, Trivalent metal salts, mixed salts exist, whereby at least one salt is a divalent or trivalent metal salt or a mixture thereof.

                    Invention Details

1. Bleach and bleach activators

The bleaching agent used in the present invention can be any bleaching agent useful in detergents or bleaching compositions in textile cleaning, hard surface cleaning, or other cleaning purposes now known or to be known, and when used in the present invention to treat fabrics are useful for bleaching compositions. These include oxygen bleach as well as other bleaching agents. Perborate bleaches such as sodium perborate (eg mono or tetrahydrate) may be used in the present invention.

Peroxygen bleach is preferred for use in the composition. Suitable peroxygen bleaching compounds include perborate, sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide. Persulfate bleach (eg OXONE by Dupont Industries) may also be used.

The bleach activators of the present invention are present as divalent and/or trivalent metal salts. Bleach activator salts can be added as a powder dispersed in a non-aqueous base. It is also possible to premix the bleach activator salt with liquid non-aqueous ingredients such as nonionic surfactants, organic solvents and/or mixtures thereof. Bleach activator salts may be obtained by any known method of preparing divalent metal salts of anionic surfactant solutions.

The bleach activator salts of the present invention may comprise mixed salts whereby at least one of the salts is a divalent or trivalent salt. Mixed salts are obtained by co-crystallization of bleach activator salts. Mixed salts may include monovalent salts. Examples of such salts are _Na3Mg4- [N-nonanoyl-6-aminocaproyloxybenzenesulfonate] ₅ .

Preferred salts of the invention are Ca, Mg and Al salts. Ca and Mg salts or mixtures thereof are very preferred.

Bleach activators suitable for use in the present invention are the anionic bleach activators described in, for example, British Patents GB836,988, 864,798, 907,356, 1,003,310 and 1,519,351; German Patent 3,337,921; EP-A-0185522, EP-A-0174132 , EP-A-0120591; and US Pat.

One class of anionic bleach activators are the bleach activators disclosed in US 4,751,015 and 4,397,757, EP-A-284292, EP-A-331,229 and EP-A-03520. Examples of anionic peroxyacid bleach activators include sodium 4-benzoyloxybenzenesulfonate, sodium 1-methyl-2-benzoyloxybenzene-4-sulfonate, sodium nonanoyloxybenzenesulfonate , Sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate.

Additionally, bleach activators useful in the present invention are amide substituted compounds of the general formula or mixtures thereof: wherein ^R is an alkyl, aryl, or alkaryl group containing about 1 to about 14 carbon atoms, and ^R is an alkylene, arylene, or alkarylene group containing about 1 to about 14 carbon atoms R is ^H or an alkyl, aryl or alkaryl group containing from about 1 to about 10 carbon atoms, and L can be essentially any suitable leaving group. A leaving group is any group which is detached from the bleach activator as a result of nucleophilic attack of the bleach activator by the perhydroxide anion. This perhydrolysis reaction results in the formation of peroxycarboxylic acids. Generally, for a group to be a suitable leaving group, the group must exhibit an electron withdrawing effect. It should also form a stable ensemble such that the rate of the reverse reaction is negligible, which facilitates the nucleophilic attack of the perhydroxide anion.

The L group must be sufficiently reactive for the reaction to occur within an optimal time frame (eg one wash cycle). However, if L is too reactive, the activator will be difficult to stabilize for use in bleaching compositions. These characteristics generally parallel the pK _a of the conjugate acid of the leaving group, although exceptions to this routine are known. In general, leaving groups exhibiting this property are those wherein the pKa of their conjugate acid _is from about 4 to about 13, preferably from about 6 to about 11, and most preferably from about 8 to about 11.

其中R¹是含有约1-约14个碳原子的烷基、芳基或烷芳基基团，R³是含有1-约8个碳原子的烷基链，R⁴是H或R³，和Y是增溶阴离子基团。Preferred bleach activators are those of the above formula wherein ^R1 , ^R2 and ^R5 are as defined for peroxyacids and L is selected from the following groups and mixtures thereof:

wherein ^R is an alkyl, aryl or alkaryl group containing from about 1 to about 14 carbon atoms ^{, R} is an alkyl chain containing from 1 to about 8 carbon atoms, R is H or ^R , and Y are solubilizing anionic groups.

Solubilizing groups are _-SO3- ^, _CO2- ^, _-SO4- and ^most preferably _-SO3- and _-CO2- , where ^R3 is an alkyl chain ^containing from about 1 to about 4 ^carbon atoms.

其中R³如上所定义，和Y是-SO₃ ^-或-CO₂ ^-。Preferred anionic bleach activators are those of the above formula wherein L is selected from the group consisting of:

wherein R ³ is as defined above, and Y is -SO ₃ ^- or -CO ₂ ^- .

Preferred examples of bleach activators of the above formula include 4-[N-octanoyl-6-aminocaproyloxy]benzenesulfonate, 4-[N-nonanoyl-6-aminocaproyloxy]benzenesulfonate , 4-[N-Decanoyl-6-aminocaproyloxy]benzenesulfonate and mixtures thereof. Such activators are described in US 4,634,551 and US 4,852,989.

Another important class of anionic bleach activators provides the organic peracids described herein by ring opening due to nucleophilic attack of the carbonyl carbon of the cyclic ring by the perhydroxide anion. For example, in some activators the ring opening reaction involves attack of the lactam ring carbonyl by hydrogen peroxide or its anion. Since the attack of the acyl lactam by hydrogen peroxide or its anion preferably occurs at the exocyclic carbonyl, a catalyst may be required to achieve significant ring opening. Another example of ring-opening bleach activators may be other activators such as those disclosed in US Patent No. 4,966,723, issued October 30,1990 to Hodge et al.

It has now surprisingly been found that, in contrast to monovalent bleach activator salts, the bleach activators according to the invention are chemically stable in concentrates and at the same time effective as bleach substances in wash liquors.

In addition, bleach activators have been found to be more chemically stable when agglomerated with certain acids, such as citric acid.

The non-aqueous detergent compositions of the present invention may also comprise a liquid gel phase comprising a surfactant and a less polar solvent comprising a bleach activator salt dispersed therein. The liquid phase and solid phase components of the detergent composition of the present invention, as well as the composition form, preparation and use are described in more detail below: Unless otherwise stated, all concentrations and ratios are based on weight. Surfactant

The amount of the surfactant mixture component of the detergent compositions of the present invention can vary with the nature and amount of the other composition components, and with the desired rheological properties of the final formed composition. Generally, such surfactant mixtures are used at levels of from about 10% to about 90% by weight of the present compositions. More preferably, the surfactant mixture comprises from about 15% to 50% by weight of the present compositions.

US Patent 3,664,961 issued May 23, 1972 to Norris gives a list of typical classes of anionic, nonionic, amphoteric and zwitterionic surfactants, and the species of these surfactants.

Preferred anionic surfactants include alkyl sulfate surfactants which are water soluble salts or acids of the formula ROSO ₃ M, wherein R is preferably a C ₁₀ -C ₂₄ hydrocarbyl, preferably having a C ₁₀ -C ₁₈ alkyl moiety Alkyl or hydroxyalkyl, more preferably C ₁₂ -C ₁₅ alkyl or hydroxyalkyl, and M is H or a cation, such as an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium (quaternary ammonium cation such as tetramethylammonium and dimethylpiperidinium cations).

Highly preferred anionic surfactants include alkyl alkoxylated sulfate surfactants which are water soluble salts or acids of the formula RO(A)mSO ₃ M where R is a C ₁₀ -C ₂₄ alkyl moiety Unsubstituted C ₁₀ -C ₂₄ alkyl or hydroxyalkyl groups, preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl groups, more preferably C ₁₂ -C ₁₅ alkyl or hydroxyalkyl groups, A is ethoxy or Propoxy units, m greater than zero, generally from about 0.5 to about 6, more preferably from about 0.5 to about 3, and M is H or can be, for example, a metal cation (such as sodium, potassium, lithium, calcium, magnesium, etc.), ammonium Or a cation that replaces the ammonium cation. The present invention contemplates alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates. Specific examples of substituted ammonium cations include quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations. Exemplary surfactants are C ₁₂ -C ₁₅ alkyl polyethoxylate (1.0) sulfate (C ₁₂ -C ₁₅ E(1.0)M), C ₁₂ -C ₁₅ alkyl polyethoxylate (2.25 ) sulfate (C ₁₂ -C ₁₅ E(2.25)M), C ₁₂ -C ₁₅ alkyl polyethoxylate (3.0) sulfate (C ₁₂ -C ₁₅ E(3.0)M), and C ₁₂ - C ₁₅ alkyl polyethoxylate (4.0) sulfate (C ₁₂ -C ₁₅ E(4.0)M), wherein M is conveniently selected from sodium and potassium.

Other suitable anionic surfactants used are alkyl ester sulfonate surfactants including linear esters of _C8 - _C20 carboxylic acids (i.e. fatty acids), according to "Journal of the American Oil Chemists'Society", 52 (1975) , pp323-329, Sulfonation of the _C8 - _C20 carboxylic acids with gaseous _SO3 . Suitable materials include natural fatty materials derived from tallow, palm oil, and the like.

Preferred alkyl acid sulfonate surfactants, especially for laundry applications, include alkyl ester sulfonate surfactants of the formula: wherein ^R3 is a _C8 - _C20 hydrocarbyl group, preferably an alkyl group or a combination thereof, ^R4 is a _C1 - _C6 hydrocarbyl group, preferably an alkyl group or a combination thereof, and M is a water-soluble salt formed with an alkyl ester sulfonate cation. Suitable salt-forming cations include metals such as sodium, potassium and lithium, and substituted or unsubstituted ammonium cations. Preferably, R ³ is C ₁₀ -C ₁₆ alkyl, and R ⁴ is methyl, ethyl or isopropyl. Particular preference is given to methyl ester sulfonates in which R ³ is C ₁₀ -C ₁₆ alkyl.

Other anionic surfactants useful for detersive purposes may also be included in the laundry detergent compositions of the present invention. These may include soap salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts), C ₉ -C ₂₀ linear alkyl sulfonates, C ₈ -C ₂₂ primary or secondary alkyl Sulfonates, C ₈ -C ₂₄ olefin sulfonates, sulfonated polycarboxylic acids prepared by sulfonation of pyrolysis products of alkaline earth metal citrates, e.g. as described in British Patent Specification No. 1,082,179, C ₈ - _C24 Alkyl polyglycol ether sulfates (contains up to 10 moles of ethylene oxide), alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oil based glycerol sulfates, alkylphenol epoxy Ethyl ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, Sulfosuccinic acid monoesters (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters) and sulfosuccinic acid diesters (especially saturated and unsaturated C ₆ -C ₁₂ diesters), sulfate esters of alkylpolysaccharides Such as sulfate esters of alkyl polyglycosides (nonionic non-sulfated compounds described below ₎ , and alkyl polyethoxy carboxylates such as those of the formula RO( _CH2CH2O ) _k - _CH2COO ^- M ⁺ Those wherein R is a C ₈ -C ₂₂ alkyl group, k is an integer of 1-10, and M is a water-soluble salt-forming cation. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are described in "Surface Active Agents and Detergents" (Volumes I and II, Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in US Patent 3,929,678, issued December 30, 1975 to Laughlin et al., at column 23, line 58 through column 29, line 23 (incorporated herein by reference).

When included therein, the detergent compositions of the present invention will generally comprise from about 1% to about 40%, preferably from about 5% to about 25%, by weight, of such anionic surfactants.

One class of nonionic surfactants useful in the present invention is the condensation product of ethylene oxide with a hydrophobic moiety, resulting in an average hydrophilic-lipophilic balance (HLB) value of 8-17, preferably 9.5-14, more preferably 12-14 surfactants. The hydrophobic (lipophilic) moiety can be aliphatic or aromatic in nature, and the length of the polyoxyethylene group condensed with any particular hydrophobic group can be readily adjusted to have the desired balance between hydrophilic and hydrophobic moieties degree of water-soluble compounds.

Particularly preferred nonionic surfactants of this type are _C9 - _C15 primary alcohol ethoxylates containing 3-12 moles of ethylene oxide per mole of alcohol, especially 5-8 moles of ethylene oxide per mole of alcohol C ₁₂ -C ₁₅ primary alcohols.

Another class of nonionic surfactants includes alkyl polyglycoside compounds of the general formula RO(C _n H _2n O) _t Z _x , where Z is a moiety derived from glucose; R is a saturated Hydrophobic alkyl; t is 0-10 and n is 2 or 3; x is 1.3-4, the compound includes less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglycoside. Compounds of this type and their use in detergents are disclosed in EP-B0070077, 0075996 and 0094118.

其中R¹是H，或R¹是C_1-4烃基、2-羟基乙基、2-羟基丙基或其混合物，R²是C_5-31烃基，和Z是具有含至少3个直接连到链上的羟基的直链烃基链的多羟基烃基，或其烷氧基化的衍生物。优选R¹是甲基，R²是直链C_11-15烷基或链烯基链如椰子烷基或其混合物，和Z在还原胺化反应中衍生自还原糖如葡萄糖、果糖、麦芽糖、乳糖。非水液体稀释剂。Also suitable as nonionic surfactants are polyhydroxy fatty acid amide surfactants of the formula:

wherein R ¹ is H, or R ¹ is C _1-4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R ² is C _5-31 hydrocarbyl, and Z is a A polyhydroxyl hydrocarbyl chain of a linear hydrocarbyl chain to an on-chain hydroxyl group, or an alkoxylated derivative thereof. Preferably R is ^methyl , ^R is a straight C _11-15 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived in a reductive amination reaction from a reducing sugar such as glucose, fructose, maltose, lactose. Non-aqueous liquid diluent.

To form the liquid gel of the cream phase of the detergent composition, the above surfactant (mixture) may be combined with a non-aqueous liquid diluent such as a liquid alcohol alkoxylate material or a non-aqueous weakly polar organic solvent. alcohol alkoxylate

One liquid diluent component suitable for forming the compositions of the present invention includes alkoxylated fatty alcohol materials. This material itself is also a nonionic surfactant. This material corresponds to the general formula:

R ¹ (C _m H _2m O) _n OH wherein R ¹ is a C ₈ -C ₁₆ alkyl group, m is 2-4, and n is about 2-12. Preferably ^R1 is a primary or secondary alkyl group comprising about 9-15 carbon atoms, more preferably about 10-14 carbon atoms. Preferred alkoxylated fatty alcohols are also ethoxylated materials containing about 2 to 12 ethylene oxide moieties per molecule, more preferably about 3 to 10 ethylene oxide moieties per molecule.

The alkoxylated fatty alcohol component of the liquid diluent often has a hydrophilic-lipophilic balance (HLB) value of about 3-17. More preferably the material has an HLB value of about 6-15, most preferably about 8-15.

Examples of fatty alcohol alkoxylates useful as an essential component of the non-aqueous liquid diluent in the compositions of the present invention include those derived from alcohols having 12 to 15 carbon atoms and containing about 7 moles of ethylene oxide. Such materials have been marketed by the Shell Chemical Company under the tradenames Neodol 25-7 and Neodol 23-6.5. Other useful Neodols include Neodol 1-5 - an ethoxylated fatty alcohol having an average of 11 carbon atoms in its alkyl chain having about 5 moles of ethylene oxide, Neodol 23-9 - having about 9 moles of ethylene oxide ethoxylated primary C ₁₂ -C ₁₃ alcohols of alkanes, and Neodol 91-10 - ethoxylated primary C ₉ -C ₁₁ alcohols with about 10 moles of ethylene oxide. Alcohol ethoxylates of this type have also been sold commercially by the Shell Chemical Company under the trade name Dobanol. Dobanol 91-5 is an ethoxylated C ₉ -C ₁₁ fatty alcohol with an average of 5 moles of ethylene oxide, while Dodanol 25-7 is an ethoxylated C ₁₂ -C ₁₅ fatty alcohol.

Other examples of suitable ethoxylated alcohols include Tergitol 15-S-7 and Tergitol 15-S-9, both of which are linear secondary alcohol ethoxylates commercially sold by Union Carbide Corporation. The former is a mixed ethoxylation product of C ₁₁ -C ₁₅ linear secondary alkanols with 7 moles of ethylene oxide, while the latter is a similar product with 9 moles of ethylene oxide reacted.

Other types of alcohol ethoxylates useful in the compositions of the present invention are higher molecular weight nonionic surfactants such as Neodol 45-11, which are ethylene oxide-like condensation products of higher fatty alcohols with 14-15 carbon atoms, about 11 oxirane groups per mole. This product has been sold commercially by Shell Chemical Company.

When used as part of the liquid diluent in the non-aqueous compositions of the present invention, the alcohol alkoxylate component is generally present in an amount from about 1% to 60% by weight of the composition. More preferably, the alcohol alkoxylate component comprises from about 5% to about 40% by weight of the compositions herein. Most preferably the alcohol alkoxylate component comprises from about 10% to about 25% by weight of the detergent compositions herein. Non-aqueous weak polar organic solvent.

Another component of the liquid diluent which may form part of the detergent compositions of the present invention includes non-aqueous weakly polar organic solvents. The term "solvent" as used herein means the non-surface-active carrier or diluent portion of the liquid phase of the composition. While some of the required and/or optional components of the compositions of the present invention may actually be dissolved in the "solvent" containing phase, other components will be present as particulate material dispersed in the "solvent" containing phase. Thus, the term "solvent" does not refer to a solvent material which is required to dissolve virtually all of the detergent composition components added thereto.

The non-aqueous organic materials used as solvents here are those weakly polar liquid materials. For the purposes of the present invention, "weak polar" liquids are those which, if at all, dissolve only one of the preferred types of particulate material used in the compositions of the present invention, i.e. peroxygen bleach, sodium perborate or sodium percarbonate tendency of the liquid. Therefore relatively polar solvents such as ethanol should not be used. Suitable types of mildly polar solvents useful in the nonaqueous liquid detergent compositions of the present invention include alkylene glycol mono-lower alkyl ethers, low molecular weight polyethylene glycols, low molecular weight methyl esters and amides, and the like.

A preferred type of non-aqueous weakly polar solvent for use in the present invention includes mono-, di-, tri- or tetra-C ₂ -C ₃ alkylene glycol mono C ₂ -C ₆ alkyl ethers. Specific examples of such compounds include diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, dipropylene glycol monoethyl ether and dipropylene glycol monobutyl ether. Particular preference is given to diethylene glycol monobutyl ether and dipropylene glycol monobutyl ether. Compounds of this type have been sold commercially under the tradenames Dowanol, Carbitol and Cellosolve.

Another preferred class of non-aqueous weakly polar organic solvents useful in the present invention includes low molecular weight polyethylene glycol (PEG). Such materials are those having a molecular weight of at least about 150. PEG with a molecular weight in the range of about 200-600 is most preferred.

Yet another preferred type of non-polar, non-aqueous solvent includes low molecular weight methyl esters. Such materials are those of the general formula R ¹ -C(O)-OCH ₃ , where R ¹ is from 1 to about 18. Examples of suitable low molecular weight methyl esters include methyl acetate, methyl propionate, methyl octanoate and methyl dodecanoate.

Of course, the non-aqueous weakly polar organic solvents used should be compatible and non-reactive with other composition ingredients such as bleaches and/or activators used in the liquid detergent compositions of the present invention. Such solvent components are generally used in amounts of from about 1% to 60% by weight of the composition. More preferably, the non-aqueous weakly polar organic solvent generally accounts for about 5%-40% by weight of the composition, and most preferably accounts for about 10%-25% by weight of the composition. liquid diluent concentration

As with the concentration of the surfactant mixture, the total amount of liquid diluent in the compositions of the present invention is determined by the type and amount of other composition components and by the desired properties of the composition. Typically, liquid diluents comprise from about 20% to about 80% by weight of the compositions of the present invention. More preferably, the liquid diluent comprises from about 40% to 60% by weight of the composition. Solid Phase

The non-aqueous detergent compositions of the present invention may also comprise a solid phase of particulate material dispersed and suspended in the liquid phase. Such particulate material generally has a size of about 0.1-1500 microns. More preferably, such materials have a size of about 5-200 microns.

The particulate material used herein may comprise one or more types of detergent composition components which are in particulate form substantially insoluble in the non-aqueous liquid phase of the composition. The particulate materials that can be used for this type are detailed below: Surfactants

Another possible type of particulate material which can be suspended in the non-aqueous liquid detergent compositions of the present invention comprises auxiliary anionic surfactants which are wholly or partially insoluble in the non-aqueous liquid phase. The most common classes of anionic surfactants having such solubility properties include primary or secondary alkyl sulfate anionic surfactants. Such surfactants are those prepared by sulfation of higher C ₈ -C ₂₀ fatty alcohols.

Conventional primary alkyl sulfate surfactants have the general formula:

ROSO ₃ ^- M ⁺ where R is generally a linear C ₈ -C ₂₀ hydrocarbyl group, which may be straight or branched, and M is a water-solubilizing cation. Preferably R is C ₁₀ -C ₁₄ alkyl and M is alkali metal. Most preferably R is about _C12 and M is sodium.

Conventional secondary alkyl sulfates can also be used as the essential anionic surfactant component of the solid phase of the compositions herein. Conventional secondary alkyl sulfate surfactants are those materials that have sulfate moieties randomly distributed along the hydrocarbyl "backbone" of the molecule. This material can be described by the following structure:

CH ₃ (CH ₂ ) _n (CHOSO ₃ M ⁺ )(CH ₂ ) _m CH ₃ wherein m and n are integers of 2 or greater, and the sum of m+n is generally about 9-15, and M is water Soluble cations.

If used as all or part of the necessary particulate material, auxiliary anionic surfactants such as alkyl sulfates will generally comprise from about 1% to 10% by weight of the composition, more preferably from about 1% to 5% by weight of the composition. The alkyl sulfates used as all or part of the particulate material are prepared from unalkoxylated alkyl sulfate materials which form part of the alkyl ether sulfate surfactant component used primarily as part of the liquid phase of the present invention, And added separately in the composition of the present invention. Organic Detergent Builder Materials

Another possible type of particulate material that can be suspended in the non-aqueous liquid detergent compositions of the present invention includes organic detergents for counteracting the effects of calcium or other ions, water hardness encountered in washing/bleaching applications of the compositions of the present invention. detergent builder materials. Examples of such materials include alkali metal citrates, succinates, malonates, fatty acids, carboxymethylsuccinates, carboxylates, polycarboxylates and polyacetyl carboxylates. Specific examples include sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acid and citric acid. Examples of other organic phosphonate-type chelating agents are substances such as those already sold under the trade name Dequest by Monsanto and alkanehydroxyphosphonates. Citrate is very preferred.

Other suitable organic builders include high molecular weight polymers and copolymers known to have builder properties. Examples of such materials include suitable polyacrylic acid, polymaleic acid and polyacrylic acid/polymaleic acid copolymers and salts thereof, such as those sold under the trademark Sokalan by BASF.

Another suitable class of organic detergency builders includes water-soluble salts of higher fatty acids, ie "soaps". These materials include alkali metal soaps such as the sodium, potassium, ammonium and alkanolammonium salts of higher fatty acids having from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms. Soap can be made by direct saponification of fats and oils or by neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of fatty acid mixtures derived from coconut oil and tallow, ie tallow and coconut sodium or potassium soap.

If used as all or part of the requisite particulate material, insoluble organic detergent builders will generally comprise from about 2% to 20% of the compositions herein. More preferably, such builder materials will comprise from about 4% to about 10% by weight of the compositions. Inorganic alkaline source

Another possible type of particulate material which may be suspended in the non-aqueous liquid detergent compositions of the present invention may comprise materials which are used to render the aqueous wash solutions formed from such compositions generally alkaline in nature. Such materials may or may not function as detergent builders, ie, materials that counteract the adverse effects of water hardness on detergency performance.

Examples of suitable alkalinity sources include water soluble alkali metal carbonates, bicarbonates, borates, silicates and metasilicates. Although not preferred for ecological reasons, water-soluble phosphates can also be used as the source of alkalinity. These materials include alkali metal pyrophosphates, orthophosphates, polyphosphates and phosphonates. Of all these alkalinity sources, alkali metal carbonates such as sodium carbonate are most preferred.

The source of alkalinity, if in the form of a hydratable salt, can also be used as a drying agent in the non-aqueous liquid detergent compositions of the present invention. The presence of an alkalinity source, which is also a desiccant, can provide benefits in chemically stabilizing those composition components that are susceptible to deactivation by water, such as peroxygen bleaches.

If used as all or part of the particulate material component, the source of alkalinity will generally comprise from about 1% to about 15% by weight of the compositions herein. More preferably, the source of alkalinity comprises from about 2% to about 10% by weight of the composition. Such materials, although water soluble, are generally insoluble in the nonaqueous detergent compositions of the present invention. Thus, such materials are generally dispersed in the non-aqueous liquid phase as individual particles. optional composition components

In addition to the liquid and solid phase components of the compositions previously described, the detergent compositions of the present invention can and preferably contain a variety of optional ingredients. Such optional components may be in either liquid or solid form. Optional components are either dissolved in the liquid phase or dispersed in the liquid phase as fine particles or droplets. Some of the materials which may optionally be used in the compositions of the present invention are detailed below: Optional Inorganic Detergent Builders

The detergent compositions herein may also optionally contain one or more types of inorganic detergent builders other than those listed above which also function as a source of alkalinity. For example, such optional inorganic builders can include aluminosilicates such as zeolites. Aluminosilicate zeolites and their use as detergent builders are discussed more fully in US Patent No. 4,605,509, Corkill et al., issued August 12, 1986, the disclosure of which is incorporated herein by reference. Additionally, crystalline layered silicates such as those discussed in the '509 US patent are suitable for use in the detergent compositions of the present invention. If utilized, optional inorganic detergent builders can comprise from about 2% to about 15% by weight of the compositions herein. optional enzyme

The detergent compositions of the present invention may also optionally comprise one or more types of detergent enzymes. Such enzymes may include proteases, amylases, cellulases and lipases. Such materials are known in the art and are commercially available. They may be incorporated into the non-aqueous liquid detergent compositions of the present invention in the form of suspensions, "marumes" or "prills". Another suitable class of enzymes includes those in the form of enzyme slurries in nonionic surfactants. This form of the enzyme has been sold commercially by, for example, Novo Nordisk under the trade name "LDP".

Enzymes incorporated into the compositions of the present invention in the form of conventional enzyme granules are particularly preferred for use in the present invention. Such particles generally have a size of about 100-1,000 microns, more preferably about 200-800 microns, and are suspended throughout the non-aqueous liquid phase of the composition. Compared to other enzyme types, it has been found that the granules in the compositions of the present invention exhibit particularly desirable enzyme stability in maintaining enzyme activity over time. Thus, compositions using enzyme granules need not contain conventional enzyme stabilizers such as those which must often be used when enzymes are added to aqueous liquid detergents.

If enzyme activity is used, it will generally be incorporated into the non-aqueous liquid compositions of the present invention in an amount sufficient to provide up to about 10 mg (by weight), more typically about 0.01 mg to about 5 mg of active enzyme per gram of composition. In other words, the non-aqueous liquid detergent compositions of the present invention generally comprise from about 0.001% to 5%, preferably from about 0.01% to 1%, by weight, of commercial enzyme preparations. For example, proteases are typically present in such commercial formulations in an amount sufficient to provide 0.005-0.1 Anson Units (AU) of activity per gram of composition. optional chelating agent

The detergent compositions of the present invention may also optionally comprise chelating agents for sequestering metal ions such as iron and/or manganese in the non-aqueous detergent compositions of the present invention. Thus, such chelating agents serve to form complexes with metal impurities in the composition which would otherwise tend to deactivate composition components such as peroxygen bleach. Useful chelating agents may include amino carboxylates, phosphonates, amino phosphonates, polyfunctionally substituted aromatic chelating agents, and mixtures thereof.

Aminocarboxylates effective as optional chelating agents include ethylenediaminetetraacetate, N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, Ethylenetetraaminehexaacetate, diethylenetriaminepentaacetate, ethylenediamine disuccinate, and ethanol diglycine. Alkali metal salts of these materials are preferred.

Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least a small amount of total phosphorus is allowed in the detergent composition and include ethylenediaminetetrakis (methylene phosphonates) as DEQUEST . Preferably these amino phosphonates do not contain alkyl or alkenyl groups having more than about 6 carbon atoms.

Preferred chelating agents include hydroxyethyldiphosphonic acid (HEDP), diethylenetriaminepentaacetic acid (DTPA), ethylenediaminedisuccinic acid (EDDS) and dipicolinic acid (DPA) and salts thereof. Chelating agents can, of course, also function as detergent builders in the use of the compositions herein in fabric laundering/bleaching processes. If utilized, chelating agents may comprise from about 0.1% to about 4% by weight of the compositions herein. More preferably, chelating agents comprise from about 0.2% to 2% by weight of the detergent compositions herein. Optionally thickening, viscosity controlling and/or dispersing agents.

The detergent compositions of the present invention may also optionally contain polymeric materials which serve to enhance the ability of the composition to keep its solid particulate components suspended. Such materials may thus function as thickeners, viscosity control agents and/or dispersants. Such materials are often polymeric polycarboxylates, but may include other polymeric materials such as polyvinylpyrrolidone (PVP) and polymeric amine derivatives such as quaternized ethoxylated hexamethylenediamine.

Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylene malonic acid. The presence in the polymeric polycarboxylates of the present invention of monomeric segments that do not contain carboxylate groups such as vinyl methyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40%.

Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers useful in the present invention are water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form is preferably about 2,000-10,000, more preferably about 4,000-7,000, and most preferably about 4,000-5,000. Water-soluble salts of such acrylic acid polymers may include, for example, alkali metal salts. Water-soluble polymers of this type are known materials. The use of polyacrylates of this type in detergent compositions has been disclosed, for example, in US Patent 3,308,067, issued March 7,1967 to Diehl. This material can also act as a builder.

Optional thickeners, viscosity control agents and/or dispersants, if employed, should be present in the compositions of the present invention in an amount from about 0.1% to about 4% by weight. More preferably, such materials will comprise from about 0.5% to 2% by weight of the detergent compositions herein. Optional brighteners, suds suppressors and/or fragrances

The detergent compositions according to the invention may optionally also contain conventional brighteners, suds suppressors, silicone oils, bleach catalysts and/or perfume substances. Of course, such brighteners, suds suppressors, silicone oils, bleach catalysts and perfumes must be compatible and nonreactive with the other composition components in the non-aqueous environment. If present, whiteners, suds suppressors and/or perfumes will generally comprise from about 0.1% to 2% by weight of the compositions herein.

Suitable bleach catalysts include the manganese-based complexes disclosed in US 5,246,621, US 5,244,594, US 5,114,006 and US 5,114,611. composition form

The particulate-containing liquid detergent compositions of the present invention are substantially non-aqueous (or anhydrous) in nature. Although very small amounts of water can be incorporated into such compositions as an impurity in required or optional ingredients, the amount of water should never exceed about 5% by weight of the compositions of the present invention. More preferably, the water content of the nonaqueous detergent compositions herein is less than about 1% by weight.

The particulate-containing non-aqueous detergent compositions of the present invention are in liquid, gel or paste form. Composition Preparation and Application

The nonaqueous detergent compositions of the present invention can be prepared by combining the bleach activator salt and its optional components in any convenient order and by mixing, eg stirring, the resulting mixture of components to form the phase stable compositions of the present invention.

Compositions of the present invention prepared as hereinbefore described may be used to form aqueous wash solutions for fabric laundering and bleaching. An effective amount of such compositions is generally added to water, preferably in a conventional fabric washing automatic washing machine, to form such aqueous wash/bleach solutions. The aqueous wash/bleach solution thus formed is then contacted with the fabrics to be washed and bleached, preferably under agitation.

An effective amount of the liquid detergent compositions herein which is added to water to form an aqueous wash/bleach solution may comprise an amount sufficient to form about 500-7,000 ppm of the composition in water. More preferably, the detergent compositions herein are present at about 1,000-3,000 ppm in the aqueous wash/bleach solution.

Example

The following examples illustrate the compositions of the invention but are not meant to limit or, in other words, define the scope of the invention.

Prepare a bleach-containing non-aqueous laundry detergent having the composition described in Table I.

Table I Components wt% liquid base C _12-15 alkyl ether (EO=3) sulfate sodium salt 17C _12-14 N-methylglucamide 9C _12-14 EO=5 alcohol ethoxylate 17N-butoxy Propoxypropanol (BPP) 24 Fragrance 0.7 Solid Topped Palm Kernel Fatty Acid Sodium Salt 5.7 Trisodium Citrate 1.9 Sodium Percarbonate 9.4 Sodium Carbonate 7.5 Sodium Hydroxyethyldiphosphonate (HEDP), Na Salt 1.7 [4- [N-Nonanoyl-6-aminocaproyloxy4.7yl]benzenesulfonate] ₂ , Ca salt brightener 0.2 silicone oil DB-100 0.5 enzyme and a small amount of components until 100%

The compositions are stable anhydrous liquid laundry detergents wherein the bleach activator is stable in the concentrate and wherein the bleach activator is effective in the wash liquor.

Claims (9)

1. A non-aqueous detergent composition in liquid, paste or gel form, said non-aqueous detergent composition comprising a bleaching agent and a bleach activator, characterized in that said bleach activator is a divalent metal salt, Trivalent metal salts, mixed metal salts are present whereby at least one of the salts is a divalent or trivalent metal salt or a mixture thereof. 2. A non-aqueous detergent composition according to claim 1, wherein said divalent salt is selected from Ca and/or Mg. 3. A non-aqueous detergent composition according to claim 1, wherein the mixed metal salt comprises a monovalent metal. 4. A non-aqueous detergent composition according to claims 1-3, wherein the bleach activator is 4-benzoyloxybenzenesulfonate, 1-methyl-2-benzoyloxybenzene-4 - Sulfonate, nonanoyloxybenzenesulfonate, 3,5,5-trimethylhexanoyloxybenzenesulfonate. 5. A non-aqueous detergent composition according to claims 1-3, wherein the bleach activator is 4-[N-octanoyl-6-aminocaproyloxy]benzenesulfonate, 4-[N-nonyl Acyl-6-aminocaproyloxy]benzenesulfonate, 4-[N-decanoyl-6-aminocaproyloxy]benzenesulfonate and mixtures thereof. 6. A non-aqueous detergent composition according to claims 1-5 wherein the bleaching agent is percarbonate. 7. A non-aqueous detergent composition according to claims 1-6, further comprising a polyol-based surfactant. 8. A non-aqueous detergent composition according to claim 7, wherein the polyol-based surfactant is selected from polyhydroxy fatty acid amides. 9. A non-aqueous detergent composition according to claims 1-8, further comprising 5-25% by weight of an anionic surfactant.