CZ135499A3 - Detergents - Google Patents

Abstract

Detergent compositions or components thereof at least 20% by weight of an inorganic filler; one or more cationic surfactants of formula (I), wherein R 1 is hydroxyalkyl consisting of no more than 6 atoms carbon, each of R 2 and R 3 is independently selected from C 1 to C 4 alkyl or alkenyl, R 4 is C 5 to C 8 alkyl or alkenyl and X 1 is counter ion.

Description

Technical field

The present invention relates to detergent compositions or components thereof containing large amounts of builder component and cationic quaternary ammonium compounds. Detergent compositions are generally intended for use in the washing and dishwashing process, providing improved grease removal and cleaning.

BACKGROUND OF THE INVENTION

The use of cationic surfactants in detergent compositions is known. For example, GB 2040990A discloses a granular detergent composition comprising cationic surfactants.

If the cationic bivalent ions causing hardness, magnesium and calcium are not properly controlled by the appropriate amount of filler, they may be detrimental to the laundering effect. The surface activity and thus stain removal can be influenced and, in addition to the precipitation of hardness ions with, for example, fatty acids, the coating on the fabric and the graying of the fabric can occur. Therefore, the builder is an essential ingredient in detergent compositions. Conversely, the presence of a low concentration of divalent metal ions is beneficial in stain removal in the presence of large amounts of fillers by reducing the interfacial tension, particularly at the oil / water interface, and achieving better stain removal results.

In the present invention, the aim was to provide the benefit of the presence of small amounts of hardness ions, but without adverse results. Applicants have found that this can be achieved by incorporating a cationic surfactant having a particular short alkyl chain into detergent compositions containing large amounts of builders. Applicants have found a group of · 4 · 4 · 4 · 4

Compounds that act as hardness ions without organic matter. Moreover, since the cationic surfactants are well soluble, even as complexes with fatty acids, the compositions of the present invention will also reduce coating formation and provide improved whiteness maintenance as well as improved stain removal.

The invention has been found to be particularly useful in detergent compositions which further comprise anionic surfactants. Without wishing to be bound by any particular theory, the present inventors assume that the particular cationic surfactants used in the detergent compositions of the present invention have surprisingly good solubility and optionally also form an associate in the presence of anionic components, resulting in surprisingly soluble anionic / cationic complexes leading to unexpected improvement. The cationic surfactant rapidly contacts and dissolves greasy stains. In addition, it is believed that upon dissolution of the oily soil, the cationic surfactants used in the present invention also form soluble complexes with fatty acids and other negatively charged dissolution products thereby increasing their solubility and increasing the efficiency of removing oily oily soil and increasing overall cleaning efficiency. .

All documents cited in the present specification are incorporated herein by reference.

SUMMARY OF THE INVENTION

Summary of the invention

The present invention relates to a detergent composition or component thereof comprising (a) at least 20% by weight of an inorganic builder component and (b) a cationic surfactant of formula (I):

·· · · · · ·

R ^{4 is} R ⁴ N ⁺ X (I) wherein R ¹ is hydroxyalkyl, which consists of no more than 6 carbon atoms, each of R ² and R ³ is independently selected from C 1 to C 4 alkyl or alkenyl, R ⁴ is C 5 to C C _n alkyl or alkenyl and X 'is the counterion.

Unless otherwise indicated, alkyl or alkenyl as used herein is branched, linear or substituted. The substituents are, for example, aromatic groups, heterocyclic groups containing one or more N, S or O atoms, or halogen substituents.

DETAILED DESCRIPTION OF THE INVENTION

Cationic surfactant

The cationic surfactant is generally present in the composition or component thereof in an amount of not more than 60% by weight, preferably not more than 10% by weight, most preferably not more than 4.5% or even 3% by weight. The benefits of the invention have been found even with very small amounts of the cationic surfactants of formula (I). In general, the detergent compositions of the present invention will contain at least 0.01% by weight, preferably 0.05% by weight, or at least 0.1% by weight of cationic surfactants.

Preferably, R ¹ in formula (I) hydroxyalkyl, which consists of not more than 6 carbon atoms, and preferably having an -OH group is separated from the quaternary ammonium nitrogen atom by no more than 3 carbon atoms. Preferred R ¹ groups are -CH ₂ CH ₂ OH, -CH ₂ CH ₂ CH ₂ OH, -CH ₂ CH (CH ₃ ) OH and -CH (CH ₃ ) CH ₂ OH.

-CH ₂ CH ₂ OH and -CH ₂ CH ₂ CH ₂ OH are most preferred, and -CH ₂ CH ₂ OH is particularly preferred. Preferably R ² and R ³ are selected from ethyl and methyl and most preferably both R ² and R ³ are methyl. Preferred R ⁴ groups consist of at least 6 carbon atoms or even at least 7 carbon atoms. R ^{4 does} not consist of more than • ftft • · ft · carbon atoms or even consists of more than 8 or 7 carbon atoms. Preferred R ⁴ groups are linear alkyl groups. Preferred are linear R ⁴ groups consisting of 8 to 11 carbon atoms or consisting of 8 to 10 carbon atoms. Preferably each of R ² and R ³ is selected from -C 4 alkyl and R ⁴ is a C 6 to C _n alkyl or alkenyl.

While pure or substantially pure cationic compounds are within the scope of the present invention, it has been found that, in particular, formula (I) is effective. One of which at least mixtures of cationic surfactants of general examples of suitable mixtures are those in 10% by weight or preferably at least 20% by weight of cationic surfactants of formula (I) has R ⁴ C ₅ to C ₉ alkyl or alkenyl. Other examples include surfactant compositions wherein R ⁴ is a combination of C ₈ and C (n-2:

generally comprise linear alkyl or C ₉ and C _n alkyl. According to one aspect of the present invention, a mixture of cationic surfactants of formula (I) is present in the composition, wherein the mixture comprises a surfactant of formula (I) with a shorter alkyl and a surfactant of formula (I) with a longer alkyl. The longer chain cationic surfactant is preferably selected from surfactants of formula (I) wherein R ⁴ is alkyl consisting of n carbon atoms, wherein n is from 8 to 11, the shorter alkyl surfactant is preferably selected from surfactants of formula (I), wherein R ⁴ is alkyl consisting of carbon atoms. Such mixtures of cationic surfactants 5% by weight to 95% by weight of the total cationic surfactants of the general formula (I) with longer alkyl, preferably 30% to 90% by weight and most preferably at least 50% by weight of the mixture. In general, the compositions will contain from 5% to 95% by weight, preferably from 5% to 70% by weight, even more preferably from 35% to 65% by weight, and most preferably at least 40% by weight of the cationic short-alkyl surfactants.

X in formula (I) is any counter-charged ion providing electroneutrality, but is preferably selected from the group consisting of halide, methyl sulfate, sulfate and nitrate, more preferably selected from methyl sulfate, chloride, bromide and iodide. Most preferred are halides, especially chloride.

Inorganic filler

The detergent compositions of the present invention comprise at least 20% by weight of an inorganic builder. The inorganic filler component consists of one or a mixture of more than one inorganic filler.

Suitable inorganic filler materials include carbonates, bicarbonates, borates, silicates, aluminosilicates, and phosphates.

Examples of carbonates are the alkaline earth and alkali metal carbonates, including bicarbonate and any mixtures thereof with very fine calcium carbonate, as described in German Patent Application No. 2,321,001, issued November 15, 1973.

Suitable silicates include water-soluble sodium silicates with a SiO ₂ : Na ₂ O ratio of 1.0 to 2.8, with ratios of 1.6 to 2.0 being preferred, and a ratio of 2.0 is most preferred. The silicates are either in the form of the anhydrous salt or the hydrated salt. Sodium silicate with a SiO ₂ : Na ₂ O 2.0 ratio is the most preferred silicate.

Preferred crystalline silicates to be used in the present invention are compounds of formula (II):

NaMSi _x O _{2x + 1} -yH ₂ O (II) wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered silicates of this type are described in EP-A-0164514 and methods their preparations are described in DE-A-3417649 and DE-A-3742043. In the present invention, x in formula (II) is 2, 3 or 4 and is preferably 2.

The most preferred material is 5-Na ₂ Si ₂ O _s , available from Hoechst AG as NaSKS-6.

Borate builders as well as fillers containing borate-forming materials from which borate is formed during storage or under wash conditions are water-soluble builders useful in the present invention.

Suitable examples of water-soluble phosphate builders are alkali metal, sodium, potassium and ammonium pyrophosphate, sodium and potassium phosphate, sodium polymer / phosphate, in which the degree of polymerization is 6 to 21, and the phytic acid salt.

Suitable aluminosilicate zeolites have a unit cell of formula (III):

Na _z [(A10 ₂ ) _z (SiO ₂ ) _y ] · χΗ ₂ Ο (III) where z and y are at least 6, the molar ratio of z to y is 1.0 to 0.5 and x is at least 5, preferably 7.5 The aluminosilicate materials are in hydrated form and are preferably crystalline, containing 10% to 28% by weight, even more preferably 18% to 22% by weight of water in bound form.

Aluminosilicate zeolites are naturally occurring materials, but are preferably synthetically treated. Synthetic crystal aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A is a compound of formula (IV):

Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] · χΗ ₂ 0 (IV) where x is 20 to 30, especially 27. Zeolite X is a compound of formula (V):

Na ₈₆ [(A1O ₂ ) ₈₆ (SiO ₂ ) _10Ě ] · 276Η ₂ Ο (V).

99

999

9 9 9 9 9 0 · 0 ry ··············

Another preferred aluminosilicate zeolite is zeolite MAP builder.

The zeolite MAP is present in an amount of 1 wt% to 80 wt%, more preferably 15 wt% to 40 wt% of the total weight of the compositions. Zeolite MAP is described in EP 384070 A (Unilever). It is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminum ratio of less than 1.33, preferably 0.9 to 1.33, and most preferably 0.9 to 1.2. Of particular interest is zeolite MAP having a silicon to aluminum ratio of less than 1.15 and more particularly less than 1.07. In a preferred aspect, the zeolite MAP detergent builder has a particle size, expressed as d _{50, of} 1.0 gm to 10.0 gm, more preferably 2.0 gm to 7.0 gm, most preferably 2.5 gm to 5.0 gm. The d ₅₀ value indicates that 50% by weight of the particles have a diameter less than that value. The particle size can be determined by conventional analytical techniques, such as electron scanning microscope or laser granulometer. Other methods of establishing d ₅₀ values are disclosed in EP 384070 A.

The amount of builder in the detergent compositions of the present invention is preferably at least 25% by weight or 30% by weight, and is generally up to 85% by weight. Preferably, from about 25% to about 75%, most preferably from about 30% to about 60%, by weight of the detergent composition will be.

In one preferred builder component, at least 10% by weight of the detergent composition is a carbonate or bicarbonate, preferably at least 15% by weight or even 20% by weight or 25% by weight of the detergent composition, and up to 40% by weight, preferably up to 35% by weight.

• ·

Generally, such carbonates will be present in the form of alkali metal or alkaline earth metal salts. Potassium and sodium salts are particularly preferred.

The builder component optionally comprises high amounts of phosphates such that the detergent composition comprises at least 20% by weight of phosphate, preferably at least 25% by weight, and up to 60% by weight of phosphate, preferably up to 50% by weight.

In another preferred composition of the present invention, at least 10% by weight, preferably 15% by weight, most preferably at least 20% by weight of zeolite, will generally be no more than 45% by weight, preferably no more than 40% by weight.

A preferred detergent composition of the present invention comprises zeolite and silicate, especially layered silicate and carbonate component. Preferably, the detergent composition comprises from 2% to 30% by weight of carbonate or bicarbonate, from 0% to 15% by weight of silicates, from 0% to 30% by weight, preferably from 2% to 20% by weight of crystalline layered silicates, 45% zeolite by weight. Even more preferably, such a detergent composition comprises 5% to 25% by weight of carbonate or bicarbonate, 5% to 20% by weight of crystalline layered silicates, and 10% to 40% by weight of zeolite.

Additional detergent ingredients

Optionally, the detergent compositions or components thereof of the present invention also comprise additional detergent ingredients. The exact nature of these additional ingredients and the amounts in which they are added will depend on the physical form of the composition or its ingredients and the exact nature of the cleaning operation for which it will be used.

The compositions or components thereof of the present invention preferably comprise one or more detergent ingredients selected from additional surfactants, fillers, masking agents, bleach, bleach precursors, bleach catalysts, organic polymeric compounds, additional enzymes, suds suppressors, soap dispersants, suspending additives impurities and soil release agents and anti-redeposition agents, fragrances and corrosion inhibitors.

Additional surfactant

The detergent compositions or components thereof of the present invention preferably comprise an additional surfactant selected from anionic, nonionic, cationic, ampholytic, amphoteric or zwitterionic surfactant and mixtures thereof.

A typical list of anionic, nonionic, ampholytic and zwitterionic surfactants is given in U.S. Pat. No. 3,929,678, Lauglin and Heuring, issued Dec. 30, 1975. Further examples are given in Surface Active Agents and Detergents (Vol. I and III, Schwartz, Perry and Berch). A list of suitable additional cationic surfactants is given in U.S. Pat. No. 4,259,217, Murphy, issued Mar. 31, 1981.

If present, ampholytic, amphoteric and zwitterionic surfactants are generally used in combination with one or more anionic and / or nonionic surfactants.

Anionic surfactant

In a particularly preferred embodiment of the present invention, the detergent compositions comprise an additional anionic surfactant. Any anionic surfactant useful for detergent purposes is suitable. These include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di-, and triethanolammonium salts) of the anionic surfactants of the sulfate, sulfonate, carboxylate and sarcosinate surfactants. . Anionic sulfate surfactants are preferred.

Other suitable anionic surfactants include isethionates such as acyl isethionates, N-acyltaurates, methyltauride fatty acid amides, alkyl succinates and sulfosuccinates, sulfosuccinate monoesters (particularly saturated and unsaturated C ₁₂ to C ₁₉ monoesters) sulfosuccinate diesters (especially saturated and unsaturated C ₁₄ to ₁₄₎ ), N-acyl sarcosinates. Also suitable are resin acids and hydrogenated resin acids such as rosin hydrogenated rosin and resin acids and hydrogenated resin acids present in or derived from tallow.

Anionic sulfate surfactant

Anionic sulfate surfactants suitable for use in the compositions of the present invention include linear and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, glycerol sulfates derived from fatty oleic acids, alkyl phenol ethylene oxide ether sulfates, C ₅ -C ₁₇ acyl-N- (C ₁ -C ₄ alkyl) and - N- _{(C-X-C 2} hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).

The alkyl ethoxy sulfate surfactants are preferably selected from the group consisting of C ₉ to C ₂₂ alkyl sulfates which have been ethoxylated with 0.5 moles to 20 moles of ethylene oxide per molecule. More preferably the alkyl ethoxysulfate surfactant is C _n to C _18, preferably C _n to C ₁₅ alkyl sulfate which has been ethoxylated with from 0.5 moles to 7 moles, preferably 1 mole to 5 moles of ethylene oxide per molecule.

A particularly preferred aspect of the invention includes mixtures of preferred alkyl sulfate and alkyl ethoxy sulfate surfactants. Such mixtures have been described in PCT Patent Application No. WO 93/18124.

· · · · · ·

0 ··································

Anionic sulfate surfactant

Anionic sulfate surfactants suitable for use in the present invention include salts of C ₅ to C ₂₀ linear alkylbenzene sulfonates, alkyl ester sulfonates, C ₆ -C ₂₂ primary or secondary alkane sulfonates, C ₆ -C ₂₄ olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acylglycerol sulfonates, fatty acylglycerol sulfonates of any mixtures thereof.

Particularly preferred compositions of the present invention further comprise an anionic surfactant selected from the alkyl sulfate and / or alkyl benzene sulfonate surfactants of formulas (VI) and (VII):

R ^b 0 S 0,

R S 0 (VI)

M ' ⁺ (VII) wherein R ⁵ is a linear or branched alkyl or alkenyl of 9 to 22 carbon atoms, preferably C 12 to C 18 alkyl or as found in secondary alkyl sulfates, R ⁶ is C 10 to C ₁₆ alkylbenzene preferably C _{n-C 13} alkylbenzene M ⁺ and M ^'+ independently vary and is an alkali metal, alkaline earth metals, alkanol ammonium and ammonium.

Particularly preferred compositions of the present invention include an alkyl sulfate surfactant and an alkylbenzene surfactant preferably in ratios of a compound of formula (VI) to a compound of formula (VII) of 15: 1 to 1: 2, most preferably 12: 1 to 2: 1.

The amounts of one or a mixture of more than one anionic surfactant in the preferred composition are 1% to 50% by weight, but preferably the anionic surfactant is present in amounts of 5% to 40% by weight of the composition. Preferred amounts of alkyl sulfate surfactants are generally up to 40% by weight of the detergent composition. Preferred amounts of the alkylbenzene sulfonate surfactants of formula (VII) in the detergent formula (VI) are even more preferably 6% by weight or the composition is at least 1% by weight, preferably at least 2% by weight or even at least 4% by weight. Preferred amounts of the alkylbenzene sulfonate surfactant are up to 23% by weight, more preferably not more than 20% by weight and most preferably up to 15% by weight or even 10% by weight.

Advantages of using an anionic surfactant in the compositions of the present invention are particularly achieved when using anionic surfactants with a longer hydrocarbon chain, such as those having a hydrocarbon chain of C ₁₂ or longer, especially hydrocarbon chains of C ₁₄ to C ₁₅ or even up to C ₁₆ to C ₁₈ .

In preferred embodiments of the detergent compositions of the present invention containing an anionic surfactant, the anionic surfactants will have a noticeable excess, preferably at a weight ratio of anionic to cationic surfactant of 50: 1 to 2: 1, most preferably 30: 1 to 8: 1. However, the advantages of the present invention are also achieved when the ratio of cationic surfactant to anionic surfactant is substantially stoichiometric, for example 3: 2 to 4: 3.

In a preferred embodiment of the present invention, the necessary cationic surfactant of formula (I) is thoroughly mixed with one or more anionic surfactants before addition of the other detergent ingredients.

Anionic carboxylate surfactant

Suitable anionic carboxylate surfactants include alkyl ethoxycarboxylates, alkylpolyethoxypolycarboxylate surfactants, and soaps (alkylcarboxylates), in particular certain secondary soaps are described herein.

Suitable alkyl ethoxycarboxylates include compounds of formula (VIII):

RO (CH ₂ CH ₂ O) _x CH ₂ COCT M ⁺ (VIII) · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · Where R is a C ₆ to C ₁₈ alkyl, x is in the range of 0 to 10 and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less %, and M is a cation. Suitable alkylpolyethoxypolycarboxylate surfactants include compounds of formula (IX):

RO- (CHR ₁ -CHR ₂ -O) -R ₃ (IX) wherein R is C ₆ -C ₁₈ alkyl, x is 1 to 25, R ₂ and R ₂ are selected from the group consisting of hydrogen, methyl, amber residue and the R ₃ is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having 1 to 8 carbon atoms, and mixtures thereof.

Suitable soap surfactants include secondary soap surfactants which contain a carboxyl unit attached to the secondary carbon. Preferred secondary soap surfactants for use in the present invention are water-soluble members selected from the group consisting of water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid , 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps can also be used to suppress the formation of soaps.

Alkali metal sarcosinate surfactant

Other suitable anionic surfactants are the alkali metal sarcosinates of formula (X):

R-CON (R ¹ ) CH ₂ COOM (X) wherein R is linear or branched C ₅ -C ₁₇ alkyl or alkenyl, R ¹ is C ₃ -C ₄ alkyl and M is an alkali metal ion. Preferred examples are myristyl and oleoylmethylsacrosinates in the form of their sodium salts.

• • •

Alkoxylated nonionic surfactant

In principle, any alkoxylated nonionic surfactants are suitable in the present invention. Ethoxylated and propoxylated surfactants are preferred. Linear or branched alkoxylated groups are suitable.

Preferred alkoxylated surfactants can be selected from the group of nonionic condensates of alkylphenols, nonionic ethoxylated alcohols, nonionic ethoxylated / propoxylated fatty alcohols, nonionic ethoxylated / propoxylated condensates with propylene glycol, and nonionic ethoxylate condensation products with propylene oxide / propylene oxide / propylene oxide.

Nonionic alkoxylated alcohol surfactant

The condensation products of aliphatic alcohols with 1 to 25 moles of alkylene oxide, in particular ethylene oxide and / or propylene oxide, are suitable for use in the present invention. The alkyl chain of the aliphatic alcohol is either straight or branched, primary or secondary, and generally consists of 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group of 8 to 20 carbon atoms with 2 moles to 10 moles of ethylene oxide per mole of alcohol.

Non-ionic surfactant amide polyhydroxy fatty acid

The polyhydroxy fatty acid amides suitable for use in the present invention are compounds of formula (XI):

E ^ CONI ^ Z (XI) wherein R ¹ is H, a C ₁ to C ₄ hydrocarbon, 2-hydroxyethyl, 2-hydroxypropyl, ethoxy, propoxyl or a mixture thereof, preferably C 1 to C ₄ alkyl, even more preferably up to C ₂ alkyl, most preferably C ₉ alkyl (i.e. methyl) and R ₂ is a C ₅ to C ₃₁ hydrocarbon, preferably a C ₅ to C ₁₉ straight chain alkyl or alkenyl, even more preferably C ₉ to β • 00 • 0 • 000

0000000 0 · ···· * · * · * · ** **

C ₁₇ alkyl or alkenyl, straight chain, most preferred and C _u and C ₁₇ alkyl or alkenyl chain or mixtures thereof, and Z is a polyhydroxyhydrocarbyl comprises a hydrocarbon chain having at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative ( preferably ethoxylated or propoxylated). Z is preferably derived from a reducing sugar in a reductive amination reaction, even more preferably Z is glycityl.

Nonionic surfactant fatty acid amide

Suitable fatty acid amide surfactants include compounds of formula (XII):

R ⁶ CON (R ⁷ ) ₂ (xii) wherein R ⁶ is alkyl of 7 to 21 carbon atoms, preferably 9 to 17 carbon atoms, and each R ⁷ is selected from the group consisting of hydrogen, C ₇ to C ₄ alkyl , C ₇ -C ₄ hydroxyalkyl and (C ₂ H ₄ O) _x , wherein x is in the range of 1 to 3.

Nonionic alkylpolysaccharide surfactant

Suitable alkyl polysaccharides for use in the present invention are described in U.S. Pat. No. 4,565,647, Llenado, issued Jan. 21, 1986, which comprises a hydrophobic group consisting of 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, wherein the hydrophilic group contains 1.3 to 10 carbohydrate units.

Preferred alkyl polyglycosides are compounds of formula (XIII):

R ² O (C _n H 2 _n O) t (glycosyl) _x (XIII) wherein R ² is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, wherein the alkyl groups consist of 10 to 18 carbon atoms, n is 2

ΦΦΦ ΦΦΦ »» ♦ »» »» »» »» »» »

Or 3, t is 0 to 10 and χ is 1.3 to 8. Glycosyl is preferably derived from glucose

Amphoteric surfactant

Suitable amphoteric surfactants for use in the present invention include amine oxide surfactants and alkylamphocarboxylic acids.

Suitable amine oxides include compounds of formula (XIV): R ³ (OR ⁴ ) X N ° (R ⁵ ) 2 (XIV) wherein R ³ is selected from alkyl, hydroxyalkyl, acylamidopropoyl and alkylphenyl or mixtures thereof of 8 to 26 atoms R ⁴ is an alkylene or hydroxyalkylene of 2 to 3 carbon atoms or mixtures thereof, x is 0 to 5, preferably 0 to 3, and each R ⁵ is an alkyl or hydroxyalkyl of 1 to 3 ethylene oxide groups or a polyethylene oxide of 1 to 3 ethylene oxide groups. Preferred are C ₁₀ -C ₁₈ alkyldimethylamine oxide and C ₁₀ -C ₁₈ acylamidoalkyldimethylamine oxide.

A suitable example of an alkylaphodicarboxylic acid is Miranol ™ C2M Conc. manufactured by Miranol, Inc., Dayton, NJ.

Zwitteriontový surfactant

Zwitterionic surfactants may also be included in the detergent compositions or components thereof of the present invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Examples of zwitterionic surfactants to be used in the present invention are betaines and sultains.

Suitable betaines are compounds of formula (XV):

R (R ') ₂ N ⁺ R ² COO- (XV) wherein R is a C ₆ to C ₁₈ hydrocarbon, each R ¹ is typically a C 1 -C 3 alkyl and R ² is a C 3 -C ₅ hydrocarbon. Preferred betaines are C ₁₂ to C ₁₈

99

9 • ·> ··· 44

9 · 99

9 9 9

9 999

4 4 9 4

4

And C ₁₀ to C ₁₈ acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use in the present invention.

Additional cationic surfactants

Compositions of the present invention preferably are substantially free of quaternary ammonium compounds of formula (I) in which one of R ^1, R ^2, R ³ or R ⁴ alkyl group longer than C _n. Preferably, the compositions should contain less than 1% by weight, preferably less than 0.1% by weight, or even less than 0.05% by weight, and most preferably less than 0.01% by weight of the compounds of formula (I) containing linear (or even branched) alkyl consisting of 12 or more carbon atoms.

Another suitable class of cationic surfactants that can be used in the detergent compositions of the present invention are cationic ester surfactants. A cationic ester surfactant is a compound that has surfactant properties and contains at least one ester (i.e., -COO-) linker and at least one cationic charged group. Preferred cationic ester surfactants are water dispersible.

Suitable cationic ester surfactants, including cholinester surfactants, have been described, for example, in U.S. Pat. Nos. 4228042, 4239660 and 4260529.

In preferred cationic ester surfactants, the ester linker and the cationic charged group are separated from each other in the surfactant molecule by a linker group consisting of a chain of at least three atoms (i.e. a chain of three atoms length), preferably of three to eight atoms, more preferably of three to five atoms, and most preferably of three atoms. The linking group atoms are selected from the group consisting of carbon, nitrogen and oxygen, and any mixtures thereof, provided that any nitrogen or oxygen atom in the chain is attached only to the carbon atom of that chain. This excludes linking groups containing, for example, -O-O- (i.e. peroxide), -NN- and -N-O- linkages, while linking groups containing, for example, -CH ₂ -O-CH ₂ - and -CH ₂ - NH-CH ₂ - belongs to this group. In a preferred aspect, the linker chain comprises only carbon atoms, the most preferred chain being a hydrocarbon chain.

Basicity

Advantageously, a basic system is present in the detergent compositions of the present invention to achieve an optimum cationic surfactant effect. The basic system is formed at least in part from the builders in the detergent composition. The basic system comprises components capable of providing basic particles in solution. Examples of basic particles include carbonate, hydroxide, various silicate anions, peroxyborates, perphosphates, and peroxy silicates. Such basic particles are formed, for example, by dissolving in water alkali salts selected from alkali metal and alkaline earth metal salts of carbonate, bicarbonate, hydroxide or silicate, including crystalline layered silicate, percarbonate, perborate, peroxyphosphate, persulfate and peroxy silicate, and any mixtures thereof .

bicarbonate, peroxycarbonates,

Water-Soluble Organic Builder Compound The detergent compositions of the present invention optionally additionally comprise a water-soluble builder compound typically present in detergent compositions in an amount of 1% to 80% by weight, preferably 10% to 70% by weight, most preferably 20% to 20% by weight. 60% by weight of the composition.

• · · · · · · · · · ·

Suitable water-soluble filler compounds include water-soluble monomeric polycarboxylates or acid forms thereof, homo or copolymeric polycarboxylic acids or salts thereof, wherein the polycarboxylic acid consists of at least two carboxyl residues separated from each other by no more than two carbon atoms, borates, phosphates and any mixtures thereof.

Carboxylate or polycarboxylate builders are of monomeric or oligomeric type although monomeric polycarboxylates are generally preferred because of their cost and efficiency.

Suitable carboxylates containing one carboxyl group include the water-soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxyl groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid as well as ether carboxylates and sulfinyl carboxylates. Polycarboxylates containing three carboxyl groups include, in particular, water-soluble substrates, aconitates and citraconates, as well as succinic acid derivatives such as the carboxymethyloxysuccinate disclosed in British Patent No. 1,389,732 and the aminosuccinates disclosed in Dutch application 7205873 and oxypolycarboxylate materials such as 1-2-carboxylate; 3-propanetricarboxylates disclosed in British Patent No. 1,387,447.

Polycarboxylates containing four carboxyl groups include the oxydisuccinates described in British Patent 1,261,829, 1,1,2,2-ethanethetracarboxylates, 1,1,3,3-propantetracarboxylates and 1,1,2,3-propantetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,421 and U.S. Pat. No. 3,936,448 and the sulfonated pyrolyzed citrates disclosed in British Patent No. 1,439,000. Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxyl groups per molecule, more particularly citrates.

The starting acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate / citric acid mixtures are also considered to be useful filler components.

Masking agent for heavy metal ions

The detergent compositions or components thereof of the present invention preferably comprise a heavy metal ion masking agent as an optional component. Heavy metal ion sequestrant refers to components which act to mask heavy metal ions. These components optionally have the capacity to chelate calcium and magnesium, but preferably exhibit selectivity for binding heavy metal ions such as iron, manganese, and copper.

Heavy metal masking agents are generally present in an amount of 0.005 wt% to 20 wt%, preferably 0.1 wt% to 10 wt%, even more preferably 0.25 wt% to 7.5 wt%, and most preferably 0.5 wt% up to 5% by weight of the compositions.

Suitable heavy metal masking agents for use in the present invention include organic phosphonates such as aminoalkylene poly (alkylene) phosphonates, alkali metal salts of ethane 1-hydroxy diphosphonates, and nitrilotrimethylene phosphonate.

Among these, diethylenetriamine penta (methylene phosphonate), ethylenediamine tri (methylene phosphonate), hexamethylenediaminetetra (methylene phosphonate) and hydroxyethylene 1,1-diphosphonate are preferred.

Other suitable heavy metal masking agents for use in the present invention include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetraacetic acid, ethylenetriaminepentaacetic acid, ethylenediamine disuccinic acid, ethylenediamine disiglutaric acid, 2-hydroxypropylenediamine disuccinic acid, or any salt thereof. Particularly preferred is ethylenediamine-Ν, Ν'-disuccinic acid (EDDS) or its alkali metal, alkaline earth metal, ammonia or substituted ammonia salts or mixtures thereof.

Other suitable heavy metal masking agents for use in the present invention are iminodiacetic acid derivatives such as 2-hydroxyethyldiacetic acid or glyceryliminodiacetic acid described in EP-A-317,542 and EP-A-399,133. Iminodiacetic acid-N-2-hydroxypropylsulfonic acid-aspartic acid-N-carboxymethyl-N-2-hydroxypropyl-3-sulfonic acid masking agents described in EP-A-516,102 are also suitable for use in the present invention. Also suitable are heavy metal masking agents based on β-alanine-N, N'-diacetic acid, aspartic acid-N, Ν'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid described in EP-A-509,382 .

EP-A-476,257 discloses suitable aminobasic masking agents for heavy metals. EP-A-510,331 describes suitable heavy metal masking agents derived from collagen, keratin or casein. EP-A-528,859 discloses suitable heavy metal masking agents based on alkyldiiminoacetic acid. Also suitable are dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid. Also suitable are glycinamide-N, N'-disuccinic acid (GADS), ethylenediamine-N, N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N, N'-disuccinic acid (HPDDS).

Organic peroxyacid bleach system

A preferred feature of the detergent compositions or components thereof of the present invention is a bleach-based system

............

organic peroxyacids. In a preferred embodiment, the bleach system consists of a hydrogen peroxide source and an organic peroxyacid bleach precursor compound. Organic peroxyacids are produced in situ by reacting the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic peroxide bleaches. In an alternative preferred embodiment, the preformed organic peroxyacid is mixed directly into the composition. Compositions comprising mixtures of a hydrogen peroxide source and an organic peroxyacid precursor in conjunction with an organic peroxyacid are also contemplated.

% by weight of peroxysulfane and peroxide salts

Inorganic peroxide bleaches

Inorganic peroxide salts are preferred sources of hydrogen peroxide. These salts are normally used in the form of alkali metal salts, preferably sodium, in an amount of 1% to 40% by weight, more preferably 2% to 30% by weight, and most preferably 5% to 25% by weight of the composition.

Examples of inorganic peroxide salts include the perborate, percarbonate, perphosphate, peroxy silicate salts. Inorganic salts are normally alkali metal salts.

Inorganic peroxide salts can be used as crystalline solids without further protection. However, for some peroxide salts, preferred embodiments of granular compositions that utilize a coated form of material that provides improved storage stability of the peroxide salts in the granular product and / or sustained release of the peroxide salt upon contact of the granular product with water. Suitable coatings include inorganic salts such as alkali metal salts of silicate, carbonate or borate or inorganic materials such as waxes, oils or fatty soaps.

Sodium perborate is a preferred perhydrate salt and is in the monohydrate form NaBO ₂ H ₂ O ₂ or the tetrahydrate NaBO ₂ H ₂ O ₂ «3 H ₂ 0th

Alkali metal percarbonates, especially sodium percarbonate, are preferred peroxides in the present invention. Sodium percarbonate is an addition compound of 2 Na ₂ CO ₃ * 3 H ₂ O and is commercially available as a crystalline solid.

Potassium peroxymonoperoxysulfate is another inorganic peroxide salt used in the detergent compositions of the present invention.

Peroxyacid bleach precursor

Peroxyacid bleach precursors are compounds that react with hydrogen peroxide in a peroxyhydrolytic reaction to form a peroxyacid. In general, peroxyacid bleach precursors are compounds of formula (XVI):

II

X - C - L (XVI) wherein L is a leaving group and X is necessarily any functional group such that upon perhydrhydrolysis a peroxyacid structure of formula (XVII) is formed:

II

X-C-00H

The peroxyacid bleach precursor compounds are preferably used in amounts of from 0.5% to 20% by weight of the detergent compositions herein.

Suitable bleach precursor peroxyacid compounds typically contain one or more N- or O-acyl groups, meaning that the precursors may be selected from a wide variety of groups. Suitable groups include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these groups are described in GB-A-1586789.

• • • •

Suitable esters are described in GB-A-836988, 864789, 1147871,

2143231 and EP-A-0170386.

Outgoing groups

The leaving groups, hereinafter referred to as L groups, must be sufficiently reactive to cause peroxyhydrolysis in an optimal time frame (eg, during a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.

Preferred L groups are selected from the group consisting of:

R3 OY-O-E = CHR4 _and -N-S-CH-R4

R 3 O and mixtures thereof, wherein R ¹ is alkyl, aryl or aralkyl of 1 to 14 carbon atoms, R ³ is alkyl of 1 to 8 carbon atoms, R ⁴ is H or R ³ , R ⁵ is alkenyl of 1 and Y is H or a solubilizing group. Any of R ¹ , R ^3, and R ⁴ is optionally substituted with essentially any functional group including, for example, alkyl, hydroxyl, alkoxy, halogen, amine, nitrosyl, amide, and ammonia or alkylammonium.

The preferred solubilizing groups are -SO ₃ -M ^+, COY ', -SO / M ^+, -N ^{+ (R3)} 4X and O <- N (R3) ³ and most particularly preferable as -SOýM ⁺ and -COY ⁺ ,

4

4 4 ·

4

4 ·· ’· ........

wherein R ³ is C 1 -C 4 alkyl, M is a cation which provides solubility to the bleach activator. Preferably M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methyl sulfate or acetate anion.

Bleaching precursors of alkylperoxycarboxylic acids

Bleach precursors of alkyl peroxycarboxylic acids form peroxyhydrolysis of peroxycarboxylic acids. Preferred precursors of this type provide peracetic acid after peroxyhydrolysis.

Preferred imide-type alkylperoxycarboxylic acid precursor compounds include Ν, Ν, Ν ', N'-tetraacetylated alkylenediamines in which the alkylene group consists of 1 to 6 carbon atoms, especially those compounds in which the alkylene group consists of 1, 2 and 6 carbon atoms. Tetraacetyl ethylenediamine (TAED) is particularly preferred.

Other preferred alkyl peroxycarboxylic acid precursors include sodium 3,5,5-trimethylhexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS), and pentaacetylglucose.

Amide substituted alkylperoxyacid precursors

Amide substituted alkylperoxyacid precursor compounds are useful in the present invention, including compounds of formula (XVIII) and (XIX):

R ¹ -CNR ² -CL R ¹ -NCR ² -CL

II

R ⁵ O R ⁵ 0 O (XVIII) (XIX) wherein R ¹ is alkyl of 1 to 14 carbon atoms, R ² is alkylene of 1 to 14 carbon atoms and R ⁵ is H or alkyl of 1 to 10 atoms carbon and L is necessarily any leaving group. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.

• ·

Peroxybenzoic acid precursor

Peroxybenzoic acid precursor compounds provide peroxybenzoic acid in peroxyhydrolysis. Suitable O-acylated peroxybenzoic acid precursor compounds include substituted and unsubstituted benzoyloxybenzenesulfonates and benzoylation products of sorbitol, glucose and all carbohydrates with benzoylating agents and those of the imide type including N-benzoylsuccinimide, tetrabenzoylethylenediamine and N-benzoyl substituted ureas. Suitable imidazole-type peroxybenzoic acid precursors include N-benzoylbenzimidazole. Other useful N-acyl-containing peroxybenzoic acid precursors include N-benzoylpyrrolidone, dibenzoyltaurine and benzoylpyroglutamic acid.

Cationic peroxyacid precursors

The cationic peroxyacid precursor compounds after peroxyhydrolysis provide cationic peroxyacids.

Typically, cationic peroxyacid precursors are formed by replacing the peroxyacid portion of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkylammonium group, preferably ethyl or methylammonium. Cationic peroxyacid precursors are typically present in solid detergent compositions in the form of a salt with a suitable anion, such as a halide ion.

Peroxyacid precursor compounds thus cationically substituted are peroxybenzoic acid or substituted derivatives thereof, precursor compounds which have already been described. Alternatively, the peroxyacid precursor compound is an alkylperoxycarboxylic precursor compound of the acid or precursor compound. amide substituted alkylperoxycarboxylic acids.

Cationic peroxyacid precursors are described in U.S. Pat. U.S. Patent Nos. 4,904,406, 4,751,015, 4,988,451, 4,397,757, 5,269,962, 5,127,852, 5,093,022, 5,106,528, U.K. 1,382,594, EP 475,512, 458,396 and 284,292 and in JP 87-318,332.

Examples of preferred cationic peroxyacid precursors are described in UK Patent Application No. 9407944.9 and U.S. Pat. Nos. 08/29903, 08/298650, 08/298904 and 08/298906.

Suitable cationic peroxyacid precursors include any ammonium or alkylammonium substituted alkyl or benzoyloxybenzenesulfonates, N-acylated caprolactams and monobenzoyltetraacetylglucosabenzoyl peroxides. Preferred cationic peroxyacid precursors from the group of N-acylated caprolactams include trialkylammoniummethylenebenzoylcaprolactams and trialkylammoniummethylenealkylcaprolactams.

Benzoxazine organic peroxyacid precursors

Also suitable are benzoxazine-type precursor compounds as described, for example, in EP-A-332,294 and EP-A-482,807, in particular compounds of formula (XX):

(XX) wherein R _x is H, alkyl, alkaryl, aryl or arylalkyl.

Pre-prepared organic peroxyacid

The organic peroxyacid bleach system contains, in addition to, or as an alternative to, the organic peroxyacid bleach precursor compound, a preformed organic peroxyacid, typically in an amount of 1% to 15% by weight. «Β · Β»

Β ΒΒ Β Β ΒΒΒ Β Β Β Β

ΒΒΒΒΒΒΒ · Β

..... · ........

%, more preferably from 1% to 10% by weight of the composition.

A preferred group of organic peroxyacid compounds are amide substituted compounds of formulas (XXI) and (XXII):

R ¹ -CNR ² -C III II - OOH R ¹ - N - C - R ² AND - C - OOH III II 0 R ⁵ 0 1 R ⁵ 1 1 0 0 (XXI) (XXII) wherein R ¹ is alkyl, aryl or aralkyl consisting of 1 to 14 atoms carbon, R ² is alkylene, arylene and alkarylene consisting of 1 to 14 and R ⁵ is H or alkyl, aryl or alkaryl Consisting of 1 to 10 carbon atoms. Amidem substituted

organic peroxyacid compounds of this type are described in EP-A-0170386.

Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanoic acid, diperoxytetradecanedioic acid and diperoxyhexadecanedioic acid. Mono- and diperazelaic acid, mono- and diperbrassylic acid, and N-phthaloylaminoperoxycaproic acid are also useful in the present invention.

Bleach catalyst

The compositions of the present invention optionally comprise a bleach catalyst comprising a transition metal. One suitable type of bleach catalyst is a catalyst system comprising a heavy metal cation of defined bleach catalyst activity, such as a cation of copper, iron, or manganese, an auxiliary metal cation having little or no bleach catalyst activity, such as a zinc or aluminum cation, and a masking agent that has a defined stability constant for catalytic and auxiliary metal cations, especially ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) and its water-soluble salts. Such catalysts are described in U.S. Pat. No. 4,430,243.

··············································

............

Other types of bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. No. 5,246,621 and U.S. Pat. patent

5,244,594. Preferred examples of such catalysts include

Mn ^IV 2 (µ-O) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane) _2- (PF ₆ ) ₂ ,

Mn ^IIT 2 (u-0)! (u-OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (C10 ₄ ) ₂ , Mn ^IV 4 (u-0) ₆ (1,4,7-triazacyclononane) _4- (C10 ₄ ) ₂ , Mn ^and Mn ^IV 4 (u-0)! (µ-OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) _2- (C _{10 4} ) ₃ and mixtures thereof. Others are described in European Patent Application Publication No. 549,272. Other ligands suitable for use in the present invention include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane,

1,2,4,7-tetramethyl-1,4,7-triazacyclononane and mixtures thereof.

For examples of suitable bleach catalysts, see US Patent 4,246,612 and US Patent 5,227,084. See also U.S. Patent 5,194,416, which discloses mononuclear manganese complexes such as η (1,4,7-trimethyl-1,4,7-triazacyclononane) (OCH ₃ ) ₃ -PF ₆ . Yet another type of bleach catalyst disclosed in US Patent 5,114,606 is a water-soluble manganese and / or manganese complex with a ligand which is a non-carboxylate polyhydroxyl compound having at least three consecutive C-OH groups. Other examples include binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including N ₄ Mn ^ITI (u-0) 2Mn ^IV N4) ⁺ and [Bipy2Mn ¹¹¹ (u-0) 2Mn ^Iv bipy ₂ ] - (C1O _{4) 3rd}

Other suitable bleach catalysts are described, for example, in European Patent Application No. 408,131 (cobalt complex catalysts), European Patent Applications, Publication Nos. 384,503 and 306,089 (metalloporphyrin catalysts), U.S. Pat. No. 4,728,455 (manganese / multidentate ligand catalyst), U.S. Pat. No. 4,711,748 and European Patent Application Publication No. 224,952 (absorbed manganese or aluminosilicate catalyst); No. 4,601,845 (aluminosilicate carrier with manganese and zinc or magnesium salts), U.S. Pat. No. 4,626,373 (manganese / ligand catalyst); No. 4,116,558 (Ferric Complex Catalyst), German Patent Specification.

2,054,019 (cobalt chelant catalyst), Canadian patent

No. 866,191 (salts include transition metal); No. 4,430,243 (chelator with manganese cations and non-catalytic metal cations) and U.S. Pat. No. 4,728,455 (manganese gluconate catalysts).

Additional enzymes

The compositions of the present invention optionally comprise one or more additional enzymes.

Preferred additional enzyme materials include commercially available enzymes. These enzymes include enzymes selected from lipases, cellulases, hemicelulases, peroxidases, proteases, glucoamylases, amylases, xylanases, phospholipases, esterases, cutanes, pectinas, keratanas, reductases, oxidases, phenoloxidases, lipoxygenases, ligninas, pululanases, tannas, pentosanas, malans β-glucanase, arabinosidase, hyaluronidase, chondroitinas, lackas or mixtures thereof.

A preferred combination of additional enzymes is a cleaning composition which is a mixture of commonly used enzymes such as lipase, protease, amylase, cutinase and / or cellulase in conjunction with one or more plant cell wall degrading enzymes. Suitable enzymes are disclosed in U.S. Pat. Nos. 3,519,570 and 3,533,139.

Suitable proteases are subtilisins that can be obtained from particular strains of B. subtilis and B. licheniformis (subtilisin BPN and BPN '). A suitable protease can be obtained from a Bacillus strain having a maximum activity in the pH range of 8-12, which was developed and marketed as ESPERASE® by Novo Industries A / S Denmark, hereinafter referred to as Novo. The preparation of this enzyme and analogous enzymes is described in GB 1,243,784, Novo. Other suitable proteases include ALCALASE®, DURAZYM® and SAVINASE® from Novo and MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® (protein-treated Maxacal) from Gist-Brocades. Proteolytic enzymes also include modified bacterial serine proteases, such as those described in European Patent Application Serial Number 87303761.8, filed Apr. 28, 1987 (specifically pages 17, 24 and 98), herein referred to as Protease B, and in U.S. Pat. European Patent Application 199,404, Venegas, issued Oct. 29, 1986, which relates to a modified bacterial serine. proteolytic enzyme, which in the present invention is referred to as Protease A. Also suitable is an enzyme called Protease C, which is a variant of the alkaline serine protease from Bacillus in which at position 27 arginine is replaced by lysine, at position 104 valine is replaced by tyrosine, at position 123 arginine replaced by serine and at position 274 threonine replaced by alanine. Protease C is described in EP 90915958: 4, corresponding to WO 91/06637, published May 16, 1991. Genetically modified variants, particularly Protease C, also belong to the present invention.

A preferred protease referred to as Protease D is a carbonyl hydrolase variant having an amino acid sequence not found in nature and derived from a carbonyl hydrolase precursor by replacing different amino acids with other amino acid residues at a position corresponding to +76 in the carbonylhydrolase, preferably also in combination with one or more amino acid residues at positions corresponding to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128 , +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and / or +274 in accordance with by numbering Bacillus amylolinquefaciens substilisin as described in WO95 / 10591 and in C. Ghosh, et al. Bleaching Compositions Comprising Protease Enzymes, which has U.S. Pat. Serial No. 08 / 322,677, filed October 13, 1994.

Also suitable for the present invention are the proteases described in patent application EP 251 446 and WO91 / 06637, the BLAP® protease described in WO91 / 02792 and variants thereof described in WO95 / 23221.

• • •

See also high pH protease from BaciUus sp. NCIMB 40338, described in WO 93/18140 A, Novo. Enzymatic detergents comprising a protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A, Novo. If desired, a protease having reduced adsorption and increased hydrolysis capacity is available as described in WO 95/07791 to Procter & Gamble. A recombinant protease such as trypsin for detergents suitable for the present invention is described in WO 94/25583, Novo. Other suitable proteases are described in EP 516 200, Unilever.

One or a mixture of proteolytic enzymes may be included in the detergent compositions of the present invention, generally in an amount of 0.0001% to 2% by weight, preferably 0.001% to 0.2% by weight, even more preferably 0.005% to 0.1% by weight. pure enzyme in the composition.

When present in the detergent compositions of the present invention, the lipolytic enzyme component is generally present in amounts of 0.00005% to 2% by weight of the active enzyme in the detergent composition, preferably in an amount of 0.001% to 1% by weight, most preferably 0.0002% % to 0.05% by weight of the active enzyme in the detergent composition.

Suitable lipolytic enzymes for use in the present invention include those produced by microorganisms of the Pseudomonas family, such as Pseudomonas stutzeri ATCC 19.154, as described in British Patent 1,372,034. Suitable lipases include those that exhibit a positive immunological cross-section with a lipase antibody produced by Pseudomonas Hisorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P Amano ', hereinafter referred to as Amano-P. Other suitable commercial lipases include Amano-CES, a lipase from Chromobacter viscosum, eg Chromobacter viscosum var.

• · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

.......... ** lipolytic NRRLB 3673, commercially available from Toyo Jozo Co. Tagata, Japan, Chromobacter viscosum lipases from U.S. Pat. Biochemical Corp. U.S.A. and Disoynth Co., The Netherlands and lipases from Pseudomonas gladioli. Particularly suitable lipases are lipases such as M1 Lipase® and Lipomax® (Gist-Brocades) and Lipolase® and Lipolase Ultra® (Novo), which have been found to be very effective when used in conjunction with the compositions of the present invention. Also suitable are the lipolytic enzymes described in EP 258 068, WO 92/05249 and WO 95/22615, Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 Unilever.

Also suitable are cutinases [EC 3.1.1.50], which can be considered a special kind of lipase, namely a lipase that does not require interphase activation. The addition of cutin to detergent compositions has been described, for example, in WO-A-88/09367 (Genencor),

WO 90/09446 (Plant Genetic System) and WO 94/14963 and WO 94/14964 (Unilever). The LIPOLASA enzyme derived from Humicola lanuginosa and commercially available from Novo (see also EPO 341, 947) is a preferred lipase for use in the present invention.

Another preferred lipase to be used in the present invention is the D96L lypolitic enzyme variant of natural lipase derived from Humicola lanuginosa. Most preferably, the strain Humicola lanuginosa used is DSM 4106.

The D96L lipolytic enzyme variant refers to the Upase variant as described in patent application WO 92/05249, in which the natural lipase from Humicola lanuginosa has an aspartic acid residue (D) at position 96 changed to leucine (L). According to this nomenclature, the replacement of aspartic acid with leucine in Op. 96 is given as: D96L. A standard LU test (Analytical Method, Novo Nordisk AF No. AF 95/6-GB 1991.02.07) was used to determine D96L enzyme activity. The substrate for D96L was prepared by emulsifying glycerin tributyate (Merck) with gum arabic as emulsifier. Lipase activity was measured at pH 7 using a static pH method.

• ·

The detergent compositions of the present invention also optionally comprise one or a mixture of more than one amylase enzyme (and and / or β). WO94 / 02597, Novo Nordisk A / S, published

February 3, 1994 discloses cleaning compositions containing mutant amylases. See also WO95 / 10603, Novo Nordisk A / S, issued April 20, 1995. Other amylases known for use in detergent compositions include α and β amylases, α-amylases are known in the art and include those described in U.S. Pat. No. 5,003,257, EP 252,666, WO / 91/00353. FR

2,676,456, EP 285,123, EP 525,610, EP 368,341 and British Patent Application No. 1,296,839 (Novo). Other suitable amylases are the improved stability amylases described in WO94 / 18314, published August 18, 1994 and WO96 / 05295, Genencor, issued February 22, 1996, and amylase variants having further modifications over the original type available from Novo Nordisk A / The amylases described in EP 277 216, WO95 / 26397 and WO96 / 23873 (all Novo Nordisk) are also suitable.

Examples of commercial α-amylase products are Purafect Ox Am® from Genencor and Termamyl®, Ban®, Fungamyl® and Duramyl®, all of which are available from Novo Nordisk A / S, Denmark. WO95 / 26397 describes other suitable amylases, α-amylases, characterized in that they have a specific activity at least 25% higher than the specific activity of Termamyl® in the temperature range of 25 ° C to 55 ° C and at a pH of 8 to 10 as measured by activity assay. Padebas® amylases. Variants of said enzymes described in WO96 / 23873 (Novo Nordisk) are suitable. Other preferred amylolytic enzymes with improved properties with respect to activity level and a combination of thermostability and higher activity are described in WO95 / 35382.

Amylolytic enzymes, if present, are generally used in the detergent compositions of the present invention in an amount of 0.0001% by weight to 2% by weight, with preferably 0.00018% by weight. % to 0.06% by weight, even more preferably 0.000024% to 0.048% by weight of the pure enzyme in the composition.

Optionally, the detergent compositions of the present invention additionally comprise one or more cellulase enzymes. Suitable cellulases include both bacterial and fungal cellulases. Preferably, they have a pH optimum of 5 to 12 and an activity of greater than 50 CELL (Cellulose Viscosity Unit). Suitable cellulases are described in U.S. Pat. No. 4,435,307 to Barbesgoard et al., J61078384 and WO96 / 02653, which disclose fungal cellulases produced from Humicola insolens, trichoderma, Thielavia and Sporotrichum. EP 739 982 describes cellulases isolated from a novel Bacillus species. Suitable cellulases are also disclosed in GB-A-2.075.028, GB-A-2.095.275, DE-OS-2.247.832 and WO95 / 26398.

Celluzyme

WO91 / 21801

Examples of such cellulases are cellulases produced by Humicola insolens (Humicola grisea var. Thermoidea), particularly Humicola DSM 1800. Other suitable cellulases are those derived from Humicola insolens having a molecular weight of 50 kDa, an isoelectric point of 5.5, containing 415 amino acids and 43 kDa. endoglucanase derived from Humicola insolens, DSM 1800, exhibiting cellulase activity, the preferred endoglucanase component has the amino acid sequence described in PCT Patent Application No. WO 91/17243. Also suitable are cellulases of EGIII from Trichoderma longibrachiatum described in WO94 / 21801, Genencor, issued September 29, 1994. Particularly suitable cellulases are cellulases that benefit from color care. Examples of such cellulases are cellulases described in European Patent Application No. 91202879.2, filed Nov. 6, 1991. Carezyme and (Novo Nordisk A / S) are particularly useful. See also WO91 / 17244 and Other suitable cellulases for fabric care and / or cleaning are described in WO96 / 34092, WO96 / 17994 and WO9524471.

Peroxidase enzymes can also be used in the compositions of the present invention, useful in combination with a detergent source

Peroxidases are oxygen, e.g.

• • •

..........

peroxycarbonate, peroxyborate, persulfate, hydrogen peroxide, etc. They are used for bleaching a solution, i.e. to prevent the transfer of dyes or pigments removed from the substrate during the wash process to other substrates in the wash solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase and haloperoxidase such as chloro- and bromoperoxidase. Peroxidase-containing detergent compositions are described, for example, in PCT International Application WO89 / 099813, WO89 / 09813 and European Patent Application No. 91202882.6, filed November 6, 1991 and EP No. 96870013.8, filed February 20, 1996. Also suitable is a laccase enzyme.

Preferred enhancers are substituted phenthiazine and phenoxazine. 10-phenothiazinepropionic acid (PPT),. 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP) and 10-methylphenoxazine (described in WO 94/12621) and substituted syringates (C3 to C5 substituted alkylsyringates) and phenols. Preferred sources of hydrogen peroxide are sodium percarbonate or sodium perborate.

Cellulases and / or peroxidases, if present, are normally used in the detergent composition in amounts of 0.0001% to 2% by weight of the active enzyme in the detergent composition.

Additional enzymes, if present, are normally used in the detergent composition in amounts of 0.0001% to 2% by weight of the active enzyme in the detergent composition. Additional enzymes may be added as a separate individual component (granules, stabilized fluids, etc. containing one enzyme) or as mixtures of two or more enzymes (eg cogranulates).

· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

37 • ftft · ftft • · ftft • · ftft Enzyme oxidation trap Other suitable detergent folders, that can add are Enzyme oxidation scavengers which they are described in parallel

European Patent Application 92870018.6, filed Jan. 31, 1992. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.

Enzyme materials

A range of enzyme materials and compositions for incorporating them into synthetic detergent compositions are also described in WO 9307263 A and WO 9307260 A, Genencor International, WO 8908694 A, Novo and U.S. Pat. No. 3,553,139, Jan. 5, 1971 to McCarty et al. Enzymes are further described in U.S. Pat. No. 4,101,457, Plače et al., Jul 18, 1978, and U.S. Pat. No. 4,507,219, Hughes, Mar. 26, 1985. Enzyme materials useful in, and incorporation into, liquid detergent compositions are disclosed in U.S. Pat. No. 4,261,868, Mountain et al., Apr. 14, 1981. Enzymes intended for use in detergents can be stabilized by various techniques. Enzyme-stabilizing techniques are described with examples in U.S. Pat. No. 3,600,319, Aug. 17, 1971, Gedge et al., EP 199,405 and EP 200,586, Oct. 29, 1986, Venegas. Enzyme stabilizing systems are also described, for example, in U.S. Pat. No. 3,519,570. Useful Bacillus, sp. AC13 providing proteases, xylanases and cellulases is described in WO 9401532 A to Novo.

Organic polymer compound

The organic polymeric compounds are the preferred detergent builder components or components thereof of the present invention and are preferably present as components of any particular detergent builder component where it optionally acts to bind the individual components together. By organic polymeric compound is meant any polymeric organic compound generally used as a dispersant, agent

0 0 0

0

000000 «·

............

an anti-redeposition agent or an impurity suspending agent in detergent compositions including any of the higher molecular weight organic polymeric compounds described in the present invention as impurity precipitating agents.

Such an organic polymeric compound is generally present in the detergent compositions of the present invention in an amount of 0.1% to 30% by weight, preferably 0.5% to 15% by weight, most preferably 1% to 10% by weight of the compositions.

Examples of organic polymeric compounds include water-soluble organic homo- or copolymeric polycarboxylic acids or salts thereof, wherein the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by no more than two carbon atoms. Polymers of the latter type are described in GB-A-1,596,759. Examples of such salts are polyacrylic acid or polyacrylates having a molecular weight of 1000 to 5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of 2000 to 100 000, in particular 40 000 to 80 000. Suitable examples are also polymaleates or polymaleic acid polymers and salts thereof.

Polyamino compounds useful in the present invention include those derived from aspartic acid including polyaspartic acid and those described in EP-A-305282, EP-A-305283 and EP-A-351629.

Also suitable for use in the compositions of the present invention are terpolymers comprising monomer units selected from maleic acid, acrylic acid, aspartic acid and vinyl alcohol or acetate, especially those having an average molecular weight of 1000 to 30,000, preferably 3000 to 10,000.

Other organic polymeric compounds suitable for use in the detergent compositions of the present invention include cellulose derivatives such as methylcellulose, carboxy.

Methylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose and hydroxyethylcellulose.

Other useful organic polymeric compounds are polyethylene glycols, especially those having a molecular weight of 1000 to 10,000, more preferably 2000 to 8,000, and even more preferably 4000.

Cationic anti-redeposition / soil release compounds

Optionally, the detergent compositions or components thereof of the present invention comprise water-soluble cationic ethoxylated amine compounds which act to release impurities and / or to resist impurities. These cationic compounds are described in more detail in EP-B-111965, U.S. Pat. No. 4,659,802 and U.S. Pat. Particularly preferred of these cationic compounds are ethoxylated cationic monoamines, diamines or triamines. Particularly preferred are cationic monoamines, diamines and triamines of formula (XXIV):

ch ₃

N- (CH ₂ CH ₂ O) n X ^Jb (CH ₂ CH ₂ O) _n -X ch ₃ I

X - (OCH ₂ CH ₂ ) _n - (- N - CH _{2 -} CH ₂ - (CH ₂ ) _and (CH ₂ CH ₂ O) x X (XXIV) wherein X is a nonionic group selected from the group consisting of H, C / a to C ₄ alkyl or hydroxyalkyl ester or ether and mixtures thereof, a is 0 to 20, preferably 0 to 4 (e.g. ethylene, propylene, hexamethylene), b is 2, 1 or 0, for cationic monoamines (b = 0), n is preferably at least 16 with a typical range of 20 to 35, for cationic diamines or triamines, n is preferably at least 12 with a typical range of 12 to 42.

These compounds, when present in the composition, are generally present in an amount of 0.01% to 30% by weight, preferably 0.05% to 10% by weight.

• Β

Β ΒΒΒ

ΒΒ Β Β ΒΒ

ΒΒΒΒ Β · · · · · · · · · · · ·

Foam suppressing system

The detergent compositions of the present invention, when intended for use in laundry detergent compositions, preferably comprise a suds suppressor system in an amount of 0.01% to 15% by weight, preferably 0.05% to 10% by weight, most preferably 0.1% to 5% by weight of the composition.

Suitable suds suppressor systems intended for use in the present invention necessarily comprise any known antifoam compound, including, for example, silicone antifoam compounds and 2-alkyl alkanol antifoam compounds.

An antifoam compound in the present invention refers to any compound or mixture of compounds which acts to suppress foaming or soap formation from a detergent solution solution, particularly when shaking the solution.

Particularly preferred antifoam compounds for use herein are the silicone antifoam compounds defined in the present invention as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain silica as a component. The term silicone as used in the present invention and generally throughout the industry includes relatively high molecular weight polymers containing siloxane units and hydrocarbon groups of various types. Preferred silicone antifoam compounds are siloxanes, especially polydimethylsiloxanes having trimethylsilyl end groups.

Other suitable antifoam compounds include monocarboxylic fatty acids and soluble salts thereof. Such materials are described in U.S. Pat. No. 2,954,347, issued Sep. 27, 1960 to Wayne St.; John. The monocarboxylic fatty acids and their salts intended for use as suds suppressors typically have a hydrocarbon chain of 10 to 24 carbon atoms, preferably 12 to 100 > 0 &quot;

I 0 000

00 r 0 4 4 t 0 0

Stearone) N-alkylated up to 18 carbon atoms. Suitable salts include alkali metal salts such as sodium, potassium and lithium salts and ammonium and alkanolammonium salts.

Other suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g.

triglycerides of fatty acids), fatty acid esters of aliphatic C ₁₈ to C ₄₀ ketones (eg aminotriazines such as tri- to hexaalkylmelamines or di- to tetraalkyldiamine chlorotriazines formed as cyanuric acid chloride products with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, stearic acid bisamide and monostearyl di-alkali metal (e.g., sodium, potassium, lithium) phosphates and phosphate esters.

A preferred suds suppressor system comprises (a) an antifoam compound, preferably a silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination (i) a polydimethylsiloxane in an amount of 50 wt% to 99 wt%, preferably 75 wt% to 95 wt% silicone antifoam compound and (ii) a silica in an amount of 1% to 50% by weight, preferably 5% to 25% by weight of the silicone / silica antifoam compound, wherein the silica / silicone antifoam compound is used in an amount of 5% to 50% by weight. (b) a dispersion compound, most preferably comprising a silicone glycol copolymer having a polyoxyalkylene content of 72% to 78% by weight and an ethylene oxide to propylene oxide ratio of 1: 0.9 to 1: 1.1 in an amount of 0 5% to 1% by weight 0% by weight, preferably 1% to 10% by weight, a particularly preferred silicone glycol copolymer of this type is DCO544, commercially available from DOW Corning under the trade name DCO544, (c) an inert carrier liquid compound, most preferably consisting of a C ₁₆ to C ₁₈ ethoxylated alcohol with a degree of ethoxylation of 5 to 50, preferably 8 to 15, in an amount of 5% to 80% by weight, preferably 10% to 70% by weight.

A highly preferred particular suds suppressor system is disclosed in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range of 50 ° C to 80 ° C, wherein the organic carrier material comprises a glycerol monoester and a fatty acid which it has a hydrocarbon chain of 12 to 20 carbon atoms. EP-A-0210721 discloses other preferred particular suds suppressor systems in which the organic carrier material is a fatty acid or alcohol having a hydrocarbon chain of 12 to 20 carbon atoms, or a mixture thereof, with a melting point of 45 ° C to 80 ° C .

Polymeric dye transfer inhibiting agents

The detergent compositions of the present invention also optionally contain from 0.01% to 10% by weight, preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents.

The polymeric dye transfer inhibiting agents are preferably selected from polyamine-N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, or combinations thereof, wherein the polymers are optionally crosslinked polymers.

a) Polyamine-N-oxide polymers

The polyamine-N-oxide polymers suitable for use in the present invention comprise units of formula (XXV):

• · • ···

43 ···· ·· ·· ·· ·· P

Αχ

where P is 0 1 I R polymerisable R ¹ R ¹ 0 1 III (XXV) unit a 0 I 1 0 I 1 R ¹ I 1 I A is - C i III - Ν -, - N - C 1 1 - CO, - 1 1 C -, -O-, -S-, 1 - Ν -, x is 0 or 1, R ¹ is H or C ₁ to C ₆ linear or branched

alkyl or optionally forms a heterocycle with R 1, R 2 is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group or any combination thereof to which the nitrogen of the N-O group is attached or wherein the N-O group forms part of this group.

The N-0 group can be represented by the following general formulas (XXVI) and (XXVII):

OO tt (R) X n- _(R2) y = N- (R) x (R 3) Z (XXVI) (XXVII) wherein R, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof , x or / and y or / az is 0 or 1 and wherein the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group forms part of these groups. The N-O group is optionally part of a polymerizable unit (P) or is attached to the polymer backbone or a combination of both.

Suitable polyamine N-oxides in which the N-O group forms part of the polymerizable unit include polyamine N-oxides in which R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. One group of polyamine-N-oxides contains a group of polyamine-N-oxides in which the nitrogen of the N-O group forms part of the group R. Preferred polyamine-N-oxides are

44

4 4

4 444

44

4 4 4

44

4444 44 • 4 44

I 4 4 4

44 unit.

includes those wherein R is a heterocyclic group such as pyridine, N-substituted pyrrole, imidazole, N-substituted pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.

Other suitable polyamine N-oxides are polyamine oxides in which the N-O group is attached to the polymerizable group. A preferred group of these polyamine N-oxides is the polyamine N-oxides of formula (XXV) wherein R is an aromatic, heterocyclic or alicyclic group in which nitrogen of the N-O function is part of the R group. Examples of these groups are polyamine oxides in which R is a heterocyclic compound such as pyridine, N-substituted pyrrole, imidazole and derivatives thereof.

Polyamine N-oxides can be obtained at almost all stages of polymerization. The degree of polymerization is not critical provided the material has the desired water solubility and dye suspending power. Typically, the average molecular weight is in the range of 500 to 1,000,000.

b) N-vinylpyrrolidone and N-vinylimidazole copolymers

Suitable copolymers of the present invention are copolymers of N-vinylimidazole and N-vinylpyrrolidone having a preferred average molecular weight of 5000 to 100,000 or 5000 to 50,000. Preferred copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone of 1 to 0.2.

c) Polyvinylpyrrolidone

The detergent compositions of the present invention also optionally utilize a polyvinylpyrrolidone (PVP) of 400,000 medium.

molecular weight

2500 and polyvinylpyrrolidones are commercially available from

Suitable ISP companies

Corporation, New York, NY and Montreal, Canada under the names PVP K-15 (viscosity molecular weight 10,000), PVP K-30 (average molecular weight 40,000), PVP K-60 (average molecular weight 160,000), PVP K -90 (average molecular weight 360,000). PVP K-15 is also available from ISP Corporation. Other suitable polyvinylpyrrolidones which are: &quot; 9 &quot;

Commercially available from BASF Corporation include Sokalan

HP 165 and Sokalan HP 12.

d) Polyvinyloxazolidone

The detergent compositions of the present invention also optionally utilize polyvinyloxazolidones as dye transfer inhibiting polymeric agents. These polyvinyloxazolidones have an average molecular weight of 2500 to 400,000.

(e) Polyvinylimidazole

The detergent compositions of the present invention also optionally utilize polyvinylimidazole as polymeric dye transfer inhibiting agents. These polyvinylimidazoles have an average molecular weight of 2500 to 400,000.

Optical brighteners

The detergent compositions of the present invention also optionally contain from about 0.005% to about 5% by weight of some types of hydrophilic optical brighteners.

Hydrophilic optical brighteners useful in the present invention include compounds of structural formula (XXVIII):

wherein R is selected from aniline, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl, R ₂ is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morpholino, chloro and amino and M is a salt-forming cation such as sodium or potassium.

When in structural formula (XXVIII), R _{x is} aniline, R ₂ is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4'-bis [(4-aniline-6- (N- 2-bis-hydroxyethyl) -5-triazin-2-yl) amine] 2,2'-stilbenedisulfonic acid and its disodium salt. This particular brightener is commercially marketed under the trade name Tinopal-UNRA-GX by Ciba-Geigy

00 00 00 * 0 00 ·· 0 00 «00 ··· 0 ···· · ·· • •••• 0 · 0

Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions of the present invention.

When aniline is present in structural formula (XXVIII), R ₂ is

N-2-hydroxyethyl-N-2-methylamine and M is a cation such as sodium, the brightener is 4,4'-bis [(4-aniline-6- (N-2-hydroxyethyl-N-methylamine) disodium) -s- triazin-2-yl) amine] 2,2'-stilbenedisulfonic acid. This particular brightener is commercially marketed under the tradename Tinopal-5BM-GX by Ciba-Geigy Corporation.

When in the structural formula (XXVIII), R _{4 is} aniline, R ₂ is morpholine and M is a cation such as sodium, the brightener is the sodium salt of 4,4'-bis [(4-aniline-6-morpholine) -s-triazine- 2-yl) amine] 2,2 ' stilbenedisulfonic acid. This particular brightener is commercially marketed under the tradename Tinopal-AMS-GX by Ciba-Geigy Corporation.

Polymeric soil release agent

The known polymeric soil release agents, hereinafter referred to as SRAs, can optionally be used in the detergent compositions of the present invention. When used, SRAs will generally be present in an amount of 0.01% to 10.0% by weight, typically 0.1% to 5% by weight, preferably 0.2% to 3.0% by weight of the compositions.

Preferred SRAs typically have a hydrophilic portion that hydrophilizes the surface of hydrophobic fibers such as polyester and nylon, and hydrophilic portions that deposit on the hydrophobic fibers and remain adhered until the wash and rinse cycle is completed, thereby serving as an anchor for the hydrophilic portions. This makes it easier to remove stains in the next wash cycle process as it is released by the SRA.

Preferred SRAs include oligomeric terephthalate esters, typically prepared by processes involving at least one ftft transesterification / oligomerization, often with a metal catalyst such as titanium alkoxide. Such esters can be prepared by the addition of monomers capable of being incorporated into the ester structure via one, two, three, four or even more positions without, of course, forming a dense overall crosslinked structure.

Suitable SRAs include a sulfonated product of a substantially linear ester oligomer consisting of an oligomeric or polymeric ester backbone or terephthaloyl and oxyalkyleneoxy repeating units and allyl derived sulfonated end groups covalently attached to the backbone, for example as described in U.S. Pat. No. 4,968,451, Nov. 6, 1990, J. J. Scheibel and E.P. Gosselink. Such ester oligomers can be prepared by (a) ethoxylating allyl alcohol, (b) reacting product (a) with dimethyl terephthalate (DMT) and 1,2-propylene glycol (PG) in a two step transesterification / oligomerization procedure, and (c) reacting product (b) with metabisulfite sodium in water. Other SRAs include the nonionic terminated 1,2-propylene / polyoxyethylene terephthalate polyesters of U.S. Pat. No. 4,711,730, Dec. 8, 1987, to Gosselink et al., For example, those resulting from transesterification / oligomerization of poly (ethylene glycol) methyl ether, DMT, PG, and poly (ethylene glycol) (PEG). Other examples of SRAs include: partially and fully anionic terminated oligomeric esters of U.S. Pat. No. 4,721,580, Jan. 26, 1988, Gosselink, such as ethylene glycol (EG), PG, DMT, and Na-3,6-dioxa-8-hydroxyoctane sulfonate oligomers, non-ionically terminated block polyester oligomer compounds of U.S. Pat. No. 4,702,857, Oct. 27, 1987, Gosselink, e.g., made of DMT, methyl (Me)-terminated PEG and EG and / or PG or a combination of DMT, EG and / or PG, Me terminated PEG and Na-dimethyl-5-sulfoisophthalate and anionic, especially sulfoaryl-terminated terephthalate esters of US No. 4,877,896, Oct. 31, 1989, Maldonado, Gosselink et al., where the latter is a typical SRA for use in both laundry and laundry products.

I 0 * «* · 0

0 • 0 0 «0 1

0 see U.S. Pat. methyl cellulose as a conditioning agent, an example being an ester composition made from the monosodium salt of m.-sulfobenzoic acid, PG and DMT, optionally but preferably further comprising added PEG, e.g. PEG 3400.

SRAs also include single copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see US Patent 3,959,230, Hays, May 25, 1976 and US 3,893,929, Basadur, June 8, 1975, cellulose derivatives such as hydroxyether cellulose polymers available as METHOCEL from Dow , C _x to C ₄ alkyl celluloses and C ₄ hydroxyalkyl celluloses, patent 4000093, 28. 12. 1976, to Nicol et al., and ethers with an average degree of substitution (methyl) per anhydroglucose unit from 1.6 to 2.3 and a solution viscosity of 80 cP up to 120 cP measured at 20 ° C as a 2% aqueous solution. Such materials are available as METOLOSE SM100 and METOLOSE SM200, which are trade names of methylcellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.

Additional SRA groups include (i) non-ionic terephthalates linked by a diisocyanate coupling agent to polymeric ester structures, see U.S. Pat. No. 4,201,824 to Violland et al., and U.S. Pat. No. 4,240,918 to Lagasse et al., (ii) SRAs with carboxyl end groups produced by adding trimellitic anhydride to known SRAs, thereby converting the terminal hydroxyl groups to trimellitic acid esters. With suitable selection of the catalyst, trimellitic anhydrides form the linkages to the ends of the polymer through the isolated carboxylic acid ester of trimellitic anhydride rather than by opening the anhydride bond. Non-ionic or anionic SRAs can be used as starting materials if they have terminal cydroxyl groups that can be esterified. See U.S. Pat. No. 4,525,524 to Tung et al. Another group includes (iii) an anionic terephthalate-based SRA with a urethane linker, see U.S. Pat. No. 4,201,824 to Violland et al.

99

9 9

9 999

Other optional ingredients

Other optional ingredients suitable for use in the compositions of the present invention include fragrances, colorants, and builder salts, with sodium sulfate being the preferred builder.

9 9 9

99 9 9 9

9

99 salt

Detergent with near neutral washing pH

Although the detergent compositions of the present invention are useful in a wide range of laundry pHs (e.g., 5-12), they are particularly useful when used at near neutral wash pH, i.e., starting pH 7.0 to 10.5 at a concentration of 0.1% % to 2% by weight in water at 20 ° C. Almost neutral wash pH compositions are superior for enzyme stability and to prevent staining caused by environmental exposure. In such compositions, the wash pH is preferably 7.0 to 10.5, even more preferably 8.0 to 10.5, most preferably 8.0 to 9.0.

Preferred detergent compositions having near neutral wash pH are described in European Patent Application 83.200688.6, filed May 16, 1983, J.H.M. Wertz and P.C.C. Goffinet.

Highly preferred compositions of this type also preferably comprise from 2% to 10% by weight of citric acid and small amounts (e.g., less than 20%) of neutralizing agents, buffering agents, phase regulators, hydrotropes, enzymes, enzyme stabilizing agents, polyacids, regulators foaming agents, opacifiers, anti-oxidants, bactericides, dyes, fragrances and brighteners, such as those described in US No. 4,285,841, Barrat et al., issued Aug. 25, 1981 (incorporated herein by reference).

Form of resources

The compositions of the present invention are in a variety of physical forms including granules, tablets, flakes, lozenges and sticks and liquid forms. The liquids are aqueous or non-aqueous and optionally in the form of a gel. The means are mainly so-called.

concentrated granular detergent compositions adapted to be added to the washing machine by means of a distribution device located in the drum of the washing machine with a load of soiled fabrics.

Such granular detergent compositions or components thereof of the present invention can be made by a variety of methods including spray drying, dry blending, extrusion, agglomeration and granulation. The cationic quaternized surfactant is added to the other detergent ingredients by mixing, agglomeration (preferably in conjunction with a carrier material), granulation or as a spray drying component.

The compositions of the present invention may also be used in conjunction with other bleaching compositions, for example, containing chlorine bleach.

In one aspect of the present invention, the average particle size of the components of the granular compositions of the present invention should preferably be such that no more than 15% by weight of the particles are larger than 1.8 mm in diameter and no more than 15% by weight of the particles are less than 0%. , 25 mm in diameter. Preferably, the average particle size is such that 10 wt% to 50 wt% of the particles have a size of 0.2 mm to 0.7 mm in diameter.

The term mean particle size as defined in the present invention is calculated by sieving a formulation sample into several fractions (typically 5 fractions) on a series of sieves, preferably on Tyler sieves. The fraction weight thus obtained is plotted against the size of the sieve opening. The average particle size is taken as the size of the aperture through which passes 50% by weight of the sample.

In another aspect of the present invention, at least 80% by weight, preferably 90% by weight of the composition is comprised of particles having a mean particle size of at least 0.8 mm, more preferably at least 1.0 mm and most preferably 1.0 mm or 1.5 mm to 1.5 mm. 2.5 mm. Most preferably, the mean particle size will have at least 95% by weight of the particles. Such particles are preferably prepared by extrusion.

The bulk density of the granular detergent composition of the present invention is typically at least 400 g / L, preferably at least 600 g / L, and even more preferably 650 g / L to 1200 g / L. The bulk density is measured using a simple hopper / container device in which a conical hopper formed firmly on the base and provided with a check valve at the lowest point, thereby allowing the hopper contents to be emptied into an axially fixed cylindrical container located below the hopper. The hopper is 130 mm high and has inner diameters of 130 mm and 40 mm at the highest and lowest points. It is fixed so that the lowest point is 140 mm above the upper surface of the foundation. The container has an overall height of 90 mm and an inner height of 87 mm and an inner diameter of 84 mm. Its nominal volume is 500 ml.

When taking measurements, the hopper is manually filled with powder, the pop-up valve opens and the powder is allowed to overfill the container. The filled container is removed from the frame and the excess powder is removed from the container with a flat-blade tool, eg a knife, by swiping over the top edge. The filled container is then weighed and the powder value obtained is multiplied by two to give a bulk density in g / l. Repeat the measurement as necessary.

The compacted solids can be produced by any suitable compacting process, such as tabletting, briquetting or extrusion, preferably tabletting. Preferably, the dishwashing tablets are manufactured using a standard rotary tablet press at a compression force of 5 kN / cm ² to 13 kN / cm ² , more preferably 5 kN / cm ² to 11 kN / cm ² such that the compacted solid has a minimum a hardness of 176 N to 275 N, preferably 195 N to 245 N, as measured by the C100 hardness test as supplied by I. Holland. This procedure can be used to prepare homogeneous or layered tablets of any size or shape. Preferred tablets are symmetrical to ensure uniform dissolution of the tablet in the wash solution.

for example from spray on

Washing method

Washing methods in a washing machine of the present invention typically comprise treating an impure laundry with an aqueous washing solution in which an effective amount of a detrimental laundry detergent composition of the present invention has been dissolved or dispersed in the washing machine. An effective amount of detergent composition is from about 10 g to about 300 g of product dissolved or dispersed in a wash solution of about 5 liters to about 65 liters, which are typical product doses and volumes of wash solution generally used in conventional washing machines. The dosage depends on specific conditions such as water hardness and the degree of soiling of the laundry.

The detergent can be dispersed in the drawer dispenser or can be soiled in the washing machine.

In one aspect of the use, a dispensing device is used in the washing method. The dosing device is filled with a detrgent product and used to introduce the product directly into the drum of the washing machine before starting the washing cycle. Its volume should be such that it is able to accommodate a sufficient amount of the detergent product that should normally be used in the laundry process.

The dispensing device containing the detergent product is placed in the drum before washing, before or simultaneously with or after the washing machine has been loaded with laundry. At the start of the wash cycle, water enters the drum and the drum rotates regularly. The design of the dispensing device should be such that it allows placement of the dry detergent product, but then allows release of the product during the wash cycle in response to shaking as the drum rotates and also as a result of contact with the wash water.

······· · ·

Γ- _ο ······ ·· ·· · ♦ ··

Alternatively, the dispensing device is a flexible container such as a sachet or bag. Optionally, the pouch is a fibrous structure coated with a water impermeable protective material to retain the contents as described in European Published Patent Application No. 0018678. Alternatively, it is formed of a water insoluble synthetic polymeric material provided with an edge lock or closure designed to rupture in an aqueous medium as described in European Published Patent Applications Nos. 0011500, 0011501, 0011502 and

A conventional form of water-soluble closure comprises a water-soluble adhesive disposed along one end of a bag formed of a water impermeable polymer film such as polyethylene or polypropylene.

Method of washing dishes

Any suitable method of washing dishes or cleaning of soiled tableware, especially soiled silverware, can be envisaged.

A preferred method of dishwashing comprises treating an aqueous liquid in which an effective amount of a dishwashing composition in the dishwasher of the present invention has been dissolved or dispersed on solid members selected from porcelain, glassware, kitchenware, silverware and cutlery, and mixtures thereof. An effective amount of dishwashing detergent composition is from about 8 g to about 60 g of product dissolved or dispersed in a 3 liter to 10 liter cleaning solution, which are typical product doses and cleaning solution volumes generally used in conventional dishwashing methods.

Packaging of funds

Commercially available bleach formulations can be packaged in any suitable container including those made of paper, cardboard, plastic materials and any suitable laminates. A preferred embodiment of the package is described in European Application No. 94921505.7.

DETAILED DESCRIPTION OF THE INVENTION

Abbreviations used in the examples

In detergent compositions, the abbreviations of the ingredients have the following meanings:

LAS: sodium salt of linear _C12 alkylbenzene sulfonate

TAS: sodium salt of alkyl sulphate derived from tallow

C _xy AS: C to C _{lx ly} sodium alkylsulfate

C46SAS: C ₁₄ to C ₁₆ secondary (2,3) sodium alkyl sulphate

C _xy ESS: C to C _{lx ly} sodium alkyl sulfate condensed with z moles of ethylene

C _xy Ez: C to C _{lx ly} mainly linear primary alcohol condensed with an average of Z moles of ethylene oxide

QAS1: R ₂ N ⁺ (CH _{3) 2} (C ₂ H ₄ OH) with R ₂ = C ₉ to C _n linear alkyl chloride

QAS2: R ₂ N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH) chloride with approximately 50 mole% R ₂ = C ₈ linear alkyl, approximately 50 mole% R ₂ = C ₁₀

QAS3: R ₂ N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH) chloride with approximately 40 mol% R ₂ = C _n linear alkyl, approximately 60 mol% R ₂ = C ₉

QAS4: R ₂ N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH) sulfate with R ₂ = C ₆ linear alkyl

QAS5: R ₂ N ⁺ (CH _{3) 2} (C ₂ H ₄ OH) sulfate _R2 = linear alkyl C _lo

Soap: sodium linear alkyl carboxylate derived from a mixture of tallow and coconut oil 80/20

CFAA: C ₁₂ to C ₁₄ (coco) alkyl-N-methylglucamide

TFAA: C ₁₆ to C ₁₈ alkyl-N-methylglucamide

TPKFA: C ₁₂ to C ₁₄ fatty acids

STPP: anhydrous sodium tripolyphosphate

TSPP: tetrasodium pyrophosphate

Zeolite A: hydrated sodium aluminosilicate

Na ₁₂ (AlO ₂ SiO ₂ ) ₁₂ · 27 H ₂ 0 with primary particle size

0.1 micrometers to 10 micrometers

Zeolite MAP: hydrated aluminosilicate zeolite MAP NaSKS-6: sodium with a silicon to aluminum ratio of 1.07 crystalline δ-Na ₂ Si ₂ O ₅ layered silicate Acid citrónová: anhydrous citric acid Boritan: sodium borate ί Carbonate: anhydrous sodium carbonate particle size Hydrogen- 200 μιη to 900 μτη

carbonate: anhydrous sodium bicarbonate with a particle size distribution of 400 μτη to 1200 μτη

Silicate: amorphous sodium silicate (SiO ₂ : Na ₂ 0 = 2,0: 1) Sodium sulphate: anhydrous sodium sulphate

Citrate: trisodium citrate dihydrate with an activity of particle size distribution 425 μιη to 850 μιη MA / AA: 1: 4 maleic acid / acid copolymer acrylic with an average molecular weight of 70 000 AA: sodium polyacrylate polymer of medium molecular weight 4,500 CMC: sodium carboxymethylcellulose Ether cellulose: cellulose methyl ether having a degree of polymerization of 650 Protease: available from Shin Etsu Chemicals proteolytic enzyme with an activity of 4 KNPU / g sold by NOVO Industries A / S under under the trade name Savinase Alkalasa: proteolytic enzyme having an activity of 3 AU / g sold by NOVO Industries A / S Cellulasa: cellulytic enzyme of 1000 CEVU / g activity

sold by NOVO Industries A / S under • ·

brand name Carenzym Amylasa: amylolytic enzyme with an activity of 120 KNU / g sold by NOVO Industries A / S under Lipase: brand name Termamyl 120T lipolytic enzyme having an activity of 100 KLU / g sold by NOVO Industries A / S under . Endolasa: under the trade name Lipolasa endoglucanase enzyme of 3000 CEVU / g activity sold by NOVO Industries A / S ‘PB4: sodium perborate tetrahydrate NaBO ₂ · H ₂ O ₂ PB1: anhydrous sodium perborate bleach of the hub ₂ »H ₂ O Peroxy- carbonate: sodium percarbonate 2Na ₂ CO ₃ * 3H ₂ O ₂ NOBS: nonanoyloxybenzenesulfonate in the form of the sodium salt TAED: tetraacetylethylenediamine Mn kataly- zátor: Mn ^IV 2 (mO) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (PF ₆ ) ₂ , which is described in US Patent Nos. 5,246,621 and 5,244,594 DTPA: diethylenetriaminepentaacetic acid DTPMP: diethylenetriaminpenta (methylenephosphonate) sold by Monsanto under the trade name Dequest 2060

Photoactivated

bleach: sulfonated zinc phthalocyanine embedded in bleaching the dextrin soluble polymer

Brightener 1: 4,4'-bis (2-sulfostyryl) biphenyl disodium Brightener 2: 4,4'-bis (4-anilino-6-morpholino-1,3,5-triazine

2-yl) aminostilbene-2: 2'-disulfonate HEDP: 1,1-hydroxyethane diphosphonic acid EDDS: ethylenediamine-N, N-disuccinic acid QEA: bis ((C ₂ H ₅ O) (C ₂ H ₄ O _n ) (CH ₃ ) -N ⁺ -C ₆ H ₁₂ -N ⁺ - (CH 3) bis ((C ₂ H ₅ O) (C ₂ H ₄ O) _n ), where n = 20 to 30 PEGX: polyethylene glycol of molecular weight x

• · • ··

PEO: polyethylene oxide ο 50,000 molecular weight

:ΕΡΑΕ: tetraethylenepentaminethoxylate

PVP: polyvinylpyrrolidone polymer

PVNO: polyvinyl pyridine N-oxide

PVPVI: copolymer of polyvinylpyrrolidone and vinylimidazole

SRP 1: Sulfobenzoylated and terminated esters with oxyethyleneoxy and terephthaloyl chains

SRP 2: diethoxylated poles (1,2-propylene terephthalate) short block copolymer

Silicone anti-foaming agent: polydimethylsiloxane foaming controller with a siloxane-oxyalkylene copolymer dispersing agent having a foaming controller to dispersant ratio of 10: 1 to 100: 1

Wax: paraffin wax

In the following examples, all amounts are expressed as% by weight of the composition.

Example 1

The following granular laundry detergent compositions of high density A to F for specific use under European washing conditions are examples of the present invention:

AND (B) C D E F LAS 8.0 8.0 8.0 WHAT O 8.0 8.0 C25E3 3.4 3.4 3.4 3.4 3.4 3.4 C4 6AS 1.0 2,0 2.5 - 3.0 4.0 C68AS 3.0 2,0 5, 0 7.0 1.0 0, 5 QAS 1 0, 05 - - - - WHAT O QAS 2 - 0.05 0, 8 - - - QAS 3 - - - 1.4 1.0 - Zeolite A 18.1 18.1 16.1 18.1 18.1 18.1 Zeolite MAP - 4.0 3.5 - - -

0

00

0 0000 00

Carbonate 12.0 12.0 13.0 26.0 26.0 26.0 Silicate 1.4 1.4 1.4 3.0 3.0 3.0 NaSKS-6 (citric acid 79: 21) 11.0 6.0 6, 0 - - 12.5 Sodium sulfate 26.1 26.1 25.0 17.1 24.1 9.1 MA / AA 0.3 0.3 0.3 0.3 0.3 0.3 CMC 0.2 0.2 0.2 0.2 0.2 0.2 PB4 9.0 9.0 9.0 9.0 9.0 9.0 TAED 1.5 1.5 1.0 1.5 - 1.5 Mn catalyst - 0.03 0.07 - - - DTPMP 0.25 0.25 - 0.25 0.25 0.25 HEDP 0.3 0.3 0.2 0.2 0.3 0.3 EDDS - - 0.4 0.2 - - QEA 1.0 0.8 0.7 1,2 - 0.5 Proteasa 0.85 0, 85 0, 85 0, 85 0.85 0.85 Amylasa 0.1 0.1 0.4 0.3 0.1 0.1 Lipasa 0, 05 0, 6 0.7 0.1 0.07 0.1 Photoactivated bleach (ppm) 15 pp 15 pp 15 pp 15 pp 15 pp 15 pp Brightener 1 0.09 0.09 - 0.09 0.09 0.09 Fragrance 0.3 0.3 0.3 0.3 0.3 0.3 Silicone antifoam 0.5 0.5 0.5 0, 5 0.5 0.5 Various minor components rest up to 100% by weight Density in g / l 850 850 850 850 850 850

Example 2

The following granular laundry detergent compositions G to I for specific use under European washing conditions are examples of the present invention:

G H AND LAS 5.3 5.61 4.76 TAS 1.3 1.86 1.57 C45AS - 2.24 3.89 C25E3S - 0.76 1.18 C45E7 3.3 - 5.0 C25E3 - 5.5 - QAS 1 WHAT O 3.0 2.5

• φφ · · · φφφφ φ φ

STPP 19.7 - - Zeolite A - 19.5 19.5 Zeolite MAP 2,0 - - NaSKS-6 / citric acid (79: 21) - 13.0 10.6 Carbonate 5.1 18.4 21.4 Hydrogen carbonate - 2, 0 2,0 Silicate 6.8 - - Sodium sulfate 37.8 - 7.0 MA / AA 0.8 1.6 1.6 CMC 0.2 0.4 0.4 PB4 5.0 12.7 - Peroxycarbonate 5.0 - 12.7 TAED 0.5 3.1 - Mn catalyst 0.04 - - DTPMP 0.25 0.2 0.2 HEDP - 0.3 0.3 QEA 0.9 - - Proteasa 0.85 2.8 0.85 Lipasa 0.15 0.25 0.15 Cellulasa 0.28 0.28 0.28 Amylasa 0.4 0.1 0.1 PVP 0.9 1.3 0.8 Photoactivated bleach (ppm) 15ppm 27 ppm 27 ppm Brightener 1 0.08 0.19 0.19 Brightener 2 - 0.04 0, 04 Fragrance 0.3 0.3 0.3 Silicone antifoam 0, 5 2.4 2.4 Various minor components rest up to 100% by weight 1.3 1.1 0.3

Example 3

The following detergent compositions for specific use under European washing conditions are examples of the present invention:

J TO L M Blown powder LAS 6.0 5.0 11.0 6.0 TAS 2,0 - - 2,0

• 444 • 44 • 44

4 4 4 4 4 5

4444 44 44 44

QAS 2 0.8 1.0 - - QAS 3 - - 1.5 0.6 Zeolite A - 27.0 - 20.0 STPP 24.0 - 24.0 - Sulfate 6.0 6.0 9.0 - MA / AA 2,0 4.0 6.0 4.0 Silicate 7.0 3.0 3.0 3.0 CMC 1.0 1.0 0.5 0, 6 QEA - - 1.4 0, 5 Brightener 0.2 0.2 0.2 0.2 Silicone antifoam 1.0 1.0 1.0 1.0 DTPMP 0.4 0.4 0.2 0.4 Sprayed C45E7 - - - 5.0 C45E5 2.5 2.5 2,0 - C45E3 2, 6 2.5 2,0 - Fragrance 0.3 0.3 0.3 0.2 Silicone antifoam 0.3 0.3 0.3 Dry additives Sulfate 3.0 3.0 5.0 10.0 Carbonate 6, 0 13.0 15.0 11.0 PBI - - - 1.5 PB4 18.0 18.0 10.0 18.5 TAED 3, 0 2,0 - 2,0 EDDS - 2,0 2.4 - Proteasa 3.25 1.0 3.25 3.25 Lipasa 0, 4 0, 5 0.4 0.2 Amylasa 0.2 0.2 0.2 0.4 Photoactivated bleach - - - 0.15 Various minor components rest up to 100% by weight

Example 4

The following granular detergent compositions are examples of the present invention. The composition N is particularly suitable for use under Japanese washing machine washing conditions. Compositions 0 to S are particularly suitable for use under American wash conditions.

• 9 · 9 9 9 9 9

9

N O P Q R WITH Blown powder LAS 22.0 5.0 4.0 9.0 8.0 7.0 C45AS 7.0 7.0 6.0 - - C4 6AS - 4.0 3, 0 - - - C45E35 - 3.0 2,0 8.0 5, 0 4.0 QAS 1 0.5 - - - - - QAS 2 - 0, 5 - 2, 0 - 3, 5 QAS 3 - - 0.8 - 3.0 - Zeolite A 6.0 16.0 14.0 19.0 16.0 14.0 MA / AA 6.0 3.0 3.0 - - - AA - 3.0 3.0 2,0 3.0 3.0 Sodium sulfate 6.0 3.3 2.3 24.0 13.3 19.3 Silicate 5, 0 1.0 1.0 2,0 1.0 1.0 Carbonate 28.3 9.0 3.0 25.7 8.0 6.0 QEA 0.4 0.4 - - 0.5 1.1 PEG 4000 0.5 - 1.5 1.0 1.5 1.0 Sodium oleate 2,0 - - - - - DTPA 0.4 - 0, 5 - - 0.5 Brightener 0.2 0.3 0.3 0.3 0.3 0.3 Sprayed C25E5 1.0 - - - - - C45E7 - 2,0 2,0 0.5 2,0 2,0 Fragrance 1.0 0.3 0.3 1.0 0, 3 0.3 Agglomerates C4 5AS - 5.0 5, 0 - 5.0 5.0 LAS - 2,0 2,0 - 2,0 2,0 Zeolite A - 7.5 7.5 - 7.5 7.5 HEDP - 1.0 - - 2, 0 - Carbonate - 4.0 4.0 - 4.0 4.0 PEG 4000 - 0.5 0.5 - 0.5 0.5 Miscellaneous (water, etc.) - 2,0 2,0 - 2,0 2,0 Dry additives TAED 1.0 2,0 3.0 1.0 3.0 2,0 PB1 - 1.0 4.0 - 5.0 0.5 PB4 6.0 - - - - - Peroxycarbonate - 5.0 12.5 - - - Carbonate - 5.3 0.8 - 2.5 4.0

Φ · ♦ · * φ φ φ • φ φ φ φ φ • • • • • • φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ

NOBS 4,5 - 6.0 - - 0.6 Cumene sulfonic acid - 2,0 2, 0 - 2,0 2,0 Lipasa 1.6 0.4 0.4 0.1 0.05 0.2 Cellulasa - 0.2 0.2 - 0.2 0.2 Amylasa - 0.3 0.3 - - - Proteasa - 1, 6 1.6 - 1.6 1.6 PVPVI - 0.5 - - - - PVP 0.5 - - - - - PVNO - 0.5 0.5 - - - SRPI - 0.5 0.5 - - - Silicone antifoam - 0.2 0.2 - 0.2 0.2 Various minor components rest up to 100% by weight

Example 5

The following granular detergent compositions are examples of the present invention. Compositions W and X are particularly suitable for use under American wash conditions. Y is a composition particularly suitable for use under Japanese washing machine washing conditions.

T at IN Blown powder Zeolite A 30.0 22.0 6, 0 Sodium sulfate 19.0 5.0 7.0 MA / AA 3.0 2,0 6.0 LAS 14.0 12.0 22.0 C4 5AS 8.0 7.0 7.0 QAS 1 0.7 - - QAS 2 - 2.2 - QAS 5 - - 1.5 Silicate - 1.0 5.0 Soap - - 2, 0 Brightener 1 0.2 0.2 0.2 Carbonate 7.0 16.0 20.0 DTPMP - 0.4 0.4 Sprayed C45E7 1.0 1.0 1.0

• 9

999

99 »9 ·« ···

9 9

Dry additives HEDP 1.0 - - PVPVI / PVNO 0.5 0.5 0, 5 Proteasa 3.25 3.25 3.25 Lipasa 0.4 0.1 0.2 Amylasa 1 — 1 Ό 0.1 0.1 Cellulasa 0.1 0.1 0.1 TAED - 6.1 4,5 PB1 11.0 5.0 6.0 Sodium sulfate - 6.0 - Rest (humidity and various)

Example 6

The following granular detergent compositions particularly suitable for use under European machine washing conditions are examples of the present invention.

W X Blown powder Zeolite A 20.0 - STPP - 20, 0 LAS 6.0 6.0 C68AS 2,0 2,0 QAS 1 0.01 - QAS 4 - 0, 6 Silicate 3.0 8.0 MA / AA 4.0 2,0 CMC 0, 6 0, 6 Brightener 1 0.2 0.2 DTPMP 0.4 0.4 Sprayed C45E7 5, 0 5.0 Silicone antifoam 0, 3 0.3 Fragrance 0.2 0.2 Dry additives Carbonate 14.0 9.0 PB1 1.5 2, 0 PB4 18.5 13.0 TAED 2,0 2,0

·· ·· 44 · * - ·· ·

9 9 9 · 4 446 «

99 4 4,444 4 4 4 4

4444444 · <

4444 »44 44 44 44

Photoactivated bleach 15 ppm 15 ppm Proteasa 1.0 1.0 Lipasa 0.2 0.08 Amylasa 0.4 0.4 Cellulasa 0.1 0.1 Sulfate 10.0 20.0 Rest (humidity and various) 10.6 5.12 Density (g / liter) 700 700

Example Ί

The following detergent compositions are examples of the present invention:

Y of AA Blown powder Zeolite A 15.0 15.0 15.0 Sodium sulfate 19.0 5.0 7.0 LAS 3.0 3.0 3, 0 QAS 2 1.0 - - QAS 5 - 3.0 2,0 DTPMP 0.4 0.2 0.4 CMC 0.4 0.4 0.4 MA / AA 4.0 2,0 2, 0 Agglomerates LAS 5.0 5.0 5, 0 TAS 2,0 2,0 1.0 Silicate 3.0 3, 0 4.0 QEA - 1.0 0, 6 Mn catalyst 0.03 - - Zeolite A 8.0 8.0 O what Carbonate 8.0 8.0 4.0 Sprayed Fragrance 0.3 0.3 0, 3 C45E7 2,0 2,0 2,0 C25E3 2,0 - - Dry additives Citrate 5, 0 - 2,0 Hydrogen carbonate - 3, 0 - Carbonate OO O 12.5 5.5

Peroxycarbonate - 7.0 10.0 TAED 6.0 2,0 5.0 PB1 14.0 7.0 10.0 EDDS - 2,0 - Polyethylene oxide of molecular weight 5 000 000 - - 0.2 Bentonite clay - - 0.2 Proteasa 1.0 3.25 3.25 Lipasa 0.4 0.1 1.0 Amylasa 0, 6 0, 6 - Cellulasa 0, 6 0, 6 - Silicone antifoam 5.0 5.0 5.0 Dry additives Sodium sulfate 0.0 3.0 0.0 The rest (humidity and various) up to 100% by weight Density (g / liter) 850 850 850

Example 8

The following detergent compositions are examples of the present invention:

BB cc DD EE LAS 20.0 14.0 24.0 22.0 QAS 1 0.7 1.0 0 0 QAS 2 - - 0.08 - QAS 4 - - - 1.0 TFAA - 1.0 - - C25E5 / C45E7 - 2,0 - 0, 5 C45E3S - 2.5 - - STPP 30, 0 18.0 30, 0 22.0 Silicate 9.0 5.0 10.0 8.0 Carbonate 13, 0 7.5 - 5.0 Hydrogen carbonate - 7.5 - - Peroxycarbonate - 5.0 9.0 15, 0 DTPMP 0.7 1.0 - - QEA 1 0.4 1,2 0.5 2,0 QEA 2 0.4 - - - CFP 1 0.3 0.2 - 0.1

• • •

MA / AA 2,0 1.5 2,0 1.0 CMC O 00 0.4 0.4 0.2 Proteasa 2.6 3.25 1.6 1.6 Amylasa 0.8 0.4 - - Lipasa 0.2 0.06 0.25 0.1 Cellulasa 0.15 0, 05 - - Photoactivated bleach (ppm) 70ppm 45ppm - 10ppm Brightener 1 0.2 0.2 0.08 0.2 PB1 6.0 2,0 - - HEDP - - 2.3 - TAED 2,0 1.0 - - The rest (humidity and various) up to 100% by weight

Example. 9

The following laundry bar formulations are examples of the present invention.

FF GG HH II JJ KK LL MM LAS - - 19.0 15.0 21.0 6.75 8.8 - C28AS 30.0 13.5 - - - 15.75 11.2 22.5 Laurat sodium 2.5 9.0 - - - - - - QAS 1 - - - 0.08 - - 2,0 - QAS 2 1.5 - 0.8 - - - - - QAS 3 - 5 - - - - - 0.1 QAS 4 - - - - 1.5 0.04 - - QAS 5 - - - - - 0.04 - - Zeolite A 2,0 1,25 - - - 1,25 1,25 1,25 Carbonate 20.0 3.0 13.0 8.0 10.0 15.0 15.0 10.0 Carbonate Calcium 21.5 - - - - - - - Sulfate 5.0 - - - - - - - TSPP 5.0 - 5.0 - 5.0 5.0 2.5 5, 0 STPP 5.0 15.0 - - - 5.0 WHAT : ** O 10.0 Bentoni- tová clay 10, 0 5.0 DTPMP - 0.7 0, 6 - 0, 6 0.7 0.7 0.7 MA / AA 0.4 1.0 - - 0.2 0.4 0.5 0.4

• · · ··· ··· · · · ···· · · ·

SRPl 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Proteasa - 0.39 - - 0.26 - - - Lipasa 0.07 0.1 0.15 0.1 0.2 0, 5 0.1 0.1 Amylasa - - - - - - 0.1 - Cellulasa - 0.15 - - 0.15 - - - PEO - 0.2 - 0.2 0.3 - - 0.3 Fragrant substance 1.6 - - - - - - -

Industrial applicability

The compositions of the present invention are industrially useful for the manufacture of detergent compositions or components thereof.

Claims (15)

PATENT CLAIMS A detergent composition comprising: (a) at least 20% by weight of an inorganic filler; and (b) a cationic surfactant of formula (I): R ¹ R ² R ³ R ⁴ N ⁺ X '(I) wherein R ¹ is hydroxyalkyl which consists of no more than 6 carbon atoms, each of R ² and R ³ is independently selected from C 3 -C 4 alkyl or alkenyl, R 2 ⁴ is C5- _C11 alkyl or alkenyl and X 'is a counterion. 2. A detergent composition according to claim 1 wherein the cationic surfactant is present in an amount of 0.01% to 20% by weight of the composition. 3. A detergent composition according to claim 2 wherein the cationic surfactant is present in an amount of 0.05% to 5% by weight of the composition. 4. A composition according to any of the preceding claims, characterized in that the cationic compound of formula (I), ^R1 is -CH2CH2OH or -CH2CH2CH2OH, R ² and R ³ are each methyl, R ⁴ is a C 6 to C _n alkyl. 5 A detergent composition according to any one of the preceding claims, characterized in that in the cationic compound of formula (I), R ⁴ is a C ₆ to C _n linear alkyl. Detergent composition according to any one of the preceding claims, characterized in that the cationic surfactant comprises a compound of formula (I) in which R ⁴ is a higher alkyl group consisting of n carbon atoms, wherein: n is 8 to 11 and a compound of formula (I) wherein R ⁴ is lower alkyl consisting of (n-2) carbon atoms. 7. A detergent composition according to claim 6 wherein the cationic surfactant comprises from 5% to 95% by weight of the compound of formula (I) with higher alkyl and from 5% to 95% by weight of the compound of formula (I) with lower alkyl. 8. Detergent means according to any of of the preceding claims , marked u se t í m, that it contains 25% % by weight to 85 % by weight an inorganic filler. 9. Detergent means according to claim 8, characterized is three m that contains 20% weight to 35% by weight carbonate, hydrogen carbonates and / or sesquicarbonates. 10. Detergent means according to claim 8, v y z learning is three m that contains 20% up to 40% % zeolite. 11. Detergent means according to claim 8, v y z learning is three m that contains 2% up to 30% by weight of carbonate, bicarbonate and / or sesquicarbonate, 0% to 15% by weight of silicate, 0% to 30% by weight of crystalline layered silicate, and 2% to 45% by weight of zeolite. Detergent composition according to any one of the preceding claims, characterized in that it comprises an anionic surfactant selected from anionic surfactants of the general formulas (VI) and (VII): R ⁵ OSO ₃ - M ⁺ R ⁶ S Of M ' ⁺ (VI) (VII) wherein R ⁵ is a linear or branched alkyl consisting of 9 to 22 carbon atoms, R ⁶ is a C ₁₀ to C ₁₆ alkylbenzene, M ⁺ and M ^{, +} are selected from the alkali metals, alkaline earth metals, alkanolammonium and ammonia. A detergent composition according to claim 12, wherein the anionic surfactant comprises an anionic surfactant of formula (VI) and an anionic surfactant of formula (VII) in a weight ratio of compound of formula (VI) to compound of formula (VII) of 15: 1 to 1: 2. A detergent composition according to claim 12 or claim 13, wherein the anionic end-capped surfactant of formula (VI) is C ₁₆ to C ₁₈ primary or secondary linear or branched alkyl sulfate and the anionic end-capped surfactant of formula (VII) is C _n to C ₁₃ alkyl benzene sulphonate. A detergent composition according to any preceding claim, further comprising a nonionic surfactant selected from the group consisting of alcohol ethoxylates, alkyl phenol ethoxylates, polyhydroxy fatty acid amides, alkyl polyglucosides, and mixtures thereof. Composition according to any one of claims 10 to 13, characterized in that it comprises: (a) 0.25% by weight to 3% by weight of a cationic surfactant of formula (I): R ¹ R ² R ³ _N + _X (I) wherein R ¹ is an optionally substituted phenol or hydroxyalkyl consisting of no more than 6 carbon atoms, each of R ² and R ³ is independently selected from C 1 -C 4 alkyl or alkenyl, R 1 ⁴ is a C6 to C _u alkyl or alkenyl and X- is a counterion, (b) 3% to 40% by weight of a straight chain or branched, primary or secondary alkyl sulfate as surfactant of the formula (VI), (c) 6% % to 23% by weight of an alkylbenzene sulfonate surfactant of formula (VII); 3393 - 335½ (d) 0.5% to 20% by weight of nonionic surfactants. Composition according to any one of the preceding claims, characterized in that it is essentially free of bleach. Detergent composition, characterized in that it is formed by mixing at least 20% by weight of an inorganic filler and a cationic surfactant of formula (I): _R 1r ² r ³ R ⁴ _{N + χ} (I) wherein R ¹ is an optionally substituted phenol or hydroxyalkyl consisting of no more than 6 carbon atoms, each of R ² and R ³ is independently selected from up to C 4 alkyl or alkenyl, R ⁴ is C 6 to C _u alkyl or alkenyl and X- is a counterion with one or more optional detergent components. A method of washing laundry in a domestic washing machine, comprising dispensing a dispensing device comprising an effective amount of a solid detergent composition according to any one of the preceding claims into the washing machine prior to commencing washing, wherein the dispensing device allows the detergent composition to be released gradually into the wash solution during washing.