CZ295596A3 - Detergent containing enzyme and a bleaching system with delayed release of peroxy acid - Google Patents

Abstract

There is provided a detergent composition containing (a) an enzyme; and (b) an organic peroxyacid bleaching system, wherein a means is provided for delaying the release to a wash solution of said peroxyacid bleach relative to the release of said enzyme.

Description

Technical field

The present invention relates to a detergent composition comprising an enzyme, preferably an amylase enzyme, and an organic peroxyacid bleach system, and at the same time comprising a composition for delaying the release of said bleaching peroxyacid into the wash solution relative to the rate of release of said enzyme.

The state of the art

The satisfactory removal of colored impurities / stains of natural origin, such as blood, eggs, chocolate, juice from stained / soiled substrates, is a challenge and challenge for detergent formulators used in laundering or machine dishwashing.

Removal of such stained stains / dirt has generally allowed the use of bleaching components such as oxygen bleaching agents, including hydrogen peroxide and organic peroxyacids, as well as the use of enzyme components. Organic peroxyacids are often obtained by in situ perhydrolysis, i.e., a reaction between hydrogen peroxide and a bleach precursor of organic peroxyacids.

A problem with the use of certain peroxyacid bleaching agents in laundry washing is the tendency of these agents to impair the color fastness of the laundry being washed. The type of damage to the laundry may be fading of colored spots on the laundry or localized bleached bleaches.

A problem with using enzymes as a detergent component is that the presence of other detergent components in the wash solution may impair the activity of the enzyme. The degradation of enzymes by the bleaching component has been found to be the biggest problem. It has also been found that degradation of the enzyme substrate by the bleaching agent reduces the activity of the enzyme, particularly amylase.

When formulating the detergent formulation, the formulator of the detergent formulation has the dual task of achieving maximum dirt and stain removal, while minimizing unwanted enzyme degradation or impairing the color fastness of the fabric material with the bleaching component.

Applicants have found that the occurrence of deterioration of fabric color fastness or enzyme degradation by a bleaching organic peroxyacid in laundering is related to the release rate of the bleaching peroxyacid into the wash solution as well as to the absolute level of peroxyacid present in the wash solution.

The high rate of release of the peroxyacid bleach into the wash solution increases the likelihood that unwanted deterioration in color fastness of the laundry and enzyme degradation will occur as a result of the high absolute level of bleach in the wash solution.

Decreasing either the release rate of the peroxyacid bleach or the absolute level of the bleaching agent used in the wash results in reducing these problems, but this may be accompanied by a negative effect on the ability to remove dirt and stains.

SUMMARY OF THE INVENTION

However, the Applicants have now found that a composition comprising both an enzyme and a peroxyacid bleach source can be prepared and provided with a means to delay the release of the peroxyacid bleach into the wash solution as compared to the enzyme release, and that this composition will improve stain / dirt removal, If these natural origin. The invention is particularly advantageous in the case of compositions comprising proteases, lipases, and most preferably amylases, cellulases and peroxidases.

In addition, when used in laundries, this composition also reduces the susceptibility to color stability.

Accordingly, it is an object of the present invention to provide compositions with improved stain removal properties, namely compositions suitable for laundries and machine dishwashing.

It is also an object of the present invention to provide compositions suitable for laundry washing methods, which compositions exhibit less susceptibility to deterioration of color fastness to the laundry.

DETAILED DESCRIPTION OF THE INVENTION

According to one aspect of the present invention, there is provided a detergent composition comprising (a) an enzyme; and (b) an organic peroxyacid bleaching system, wherein a means is provided to delay release into the organic peroxyacid of the wash solution as compared to the enzyme release, such that in the T50 assay described herein, the time to reach a concentration of 50% λ

the maximum enzyme concentration is less than 120 seconds, and the time to reach a concentration equal to 50% of the maximum organic peroxyacid concentration is greater than 180 seconds.

According to another aspect of the invention, there is provided a detergent composition comprising (a) an enzyme; and (b) an organic peroxyacid bleach system in which a measure is provided to delay release of said organic peroxyacid into the wash solution as compared to the enzyme release, such that in the T50 assay described herein, the time to reach a concentration equal to 50% of the maximum concentration of said the enzyme is at least 100 seconds, more preferably at least 120 seconds, and most preferably at least 150 seconds less than the time required to reach 50% of the maximum concentration of said organic peroxyacid.

The organic peroxyacid bleach system preferably consists of a combination of (i) a hydrogen peroxide source? and (ii) an organic peroxyacid bleach precursor compound (precursor).

Enzyme

An essential component of the detergent composition is an enzyme. Suitable enzymes are the commercially available lipases, amylases, neutral and alkaline proteases, cellulases, pectinases, lactases, and peroxidases, i.e., enzymes with lipolytic, amylolytic, proteolytic, cellolytic, pectolytic, lactolytic and peroxidolytic activity, which are commonly incorporated into detergent compositions. Suitable enzymes are described in US Patents 3,519,570 and 3,533,139.

Particularly preferred enzyme components are proteases. Preferred are commercially available proteases sold under the proprietary names Alcalase, Savinase, Primase, Durazy and Esperase by Novo Industries A / S (Denmark), under the name Maxatase, Maxacal and Maxap by Gist Brocades, further sold by Genencor International, and finally by Solvay Enzymes under the trade names Opticlean and Optimase. The protease enzyme is incorporated into the compositions of the invention in an amount of 0.0001-4% active enzyme by weight of the composition.

Preferred amylases are, for example, alpha-amylases obtained from a particular strain of B. licheniformis, described in more detail in GB 1,269,839 (Novo). Preferred commercially available amylases are, for example, those sold under the tradename Rapidase by Gist-Brocades, and under the name Termamyl and BAN by Novo Indurstries A / S. The amylase enzyme is used in the composition of the invention in an amount of 0.0001-4% active enzyme by weight of the composition.

The lipolytic enzyme (lipase) is used in an amount of active lipolytic enzyme of 0.0001-4 wt%, more preferably 0.001-1 wt%, most preferably 0.001-0.5 wt%. by weight of the composition.

The lipase may be of fungal or bacterial origin, such as from a lipase-producing strain of Humicola sp., Or Pseudomonas sp., Including Pseudomonas pseudoalcaisenes or Pseudomas fluorescens. Lipases from chemically or genetically modified mutants of these strains can also be used herein.

Preferably, a lipase derived from Pseudomonas pseudoalkaliqenes is used. described in the European patent granted EP-B-0218272.

Another preferred lipase is obtained by cloning the gene from Humicola lanuqinosa and inserting (squeezing) this gene into Asperqillus orvzae as a host, as described in European patent application EP-A-0258 068, which lipase is commercially available from Novo Industries A / S, Bagsvaerd, Denmark , under the trade name Lipolase. This lipase is also described in USP 4,810,414, Huge-Jensen et al., Issued March 7, 1989.

Bleaching system with organic peroxyacid

An essential feature of the present invention is an organic peroxyacid bleach system. In one preferred embodiment, the bleach system comprises a source of hydrogen peroxide and an organic peroxyacid bleach precursor compound (precursor). The formation of organic peroxyacid occurs in situ by reaction of the precursors with a source of hydrogen peroxide. A preferred source of hydrogen peroxide is the perhydrate of the inorganic bleaching salt. Compositions comprising mixtures of a hydrogen peroxide source and organic peroxyacid precursors with a preformed organic peroxyacid are also contemplated.

Perhydrates of inorganic bleaching salts

A preferred source of hydrogen peroxide is the perhydrates (peroxohydrates) of inorganic salts. These salts are normally used as alkali metal salts, preferably as sodium salt, in an amount of 1-40% more preferably 2-30%, and most preferably

5-25% by weight of the composition.

Examples of suitable inorganic pero (oxo) hydrated salts are perborates (perborates), percarbonates, perphosphates, persulfates and persilicates, and mixtures thereof. Inorganic perhydrated salts are normally alkali metal salts. The inorganic perhydrated salts can be used as a crystalline solid without further protection. However, for some perhydrated salts, a preferred embodiment of granular compositions is to use a coating of a material providing better storage stability of the perhydrate salt in the granular product.

Sodium perborate (perborate) is in the form of the monohydrate of the formula NaBO ₂ H ₂ O ₂ or NaBO ₂ H ₂ O ₂ · 3 H ₂ O.

Alkali metal percarbonates, especially sodium percarbonate, are also perhydrates advantageously useful in the compositions of the invention. It has been found that percarbonate-containing compositions tend to gel less in the presence of surfactants and water than perborate-containing compositions. It is believed that this is because a typical percarbonate has less surface area and porosity than perborate monohydrate. This small surface area and low porosity prevent co-gelation with fine particles of surfactant agglomerates and thus do not interfere with the release.

In addition, sodium percarbonate is an addition compound of the formula corresponding to 2Na ₂ CO ₃ .3H ₂ O ₂ , which is commercially available as a crystalline substance. The percarbonate is most preferably used in such a coating composition to protect the stability of the product.

A suitable coating material to ensure the stability of the composition is a mixture of water-soluble alkali metal sulfate and carbonate salts. Such coatings, together with the coating process, have already been described in GB-1,466,799, issued to Interox on March 9, 1977. The weight ratio of the mixed coating salts to the percarbonate is in the range of 1: 200 to 1: 4, more preferably from 1:99 to 1: 9, and most preferably from 1:49 to 1:19. Preferably, the mixed salt of sodium sulfate and carbonate has the general formula Na ₂ SO ₄ , n.Na ₂ CO ₃ , wherein n is from 0.1 to 3,

More preferably from 0.3 to 1.0, and most preferably n is from 0.2 to 0.5.

Advantageously, other coatings containing silicate (alone or borates or boric acid or other inorganic substance), waxes, oils, fatty acid soaps may be used according to the invention.

Another inorganic perhydrate salt for use in the detergent composition of the invention is potassium peroxymonopersulfate.

Peroxyacid bleach precursor

Peroxyacid bleach precursors are compounds that react with hydrogen peroxide by a reaction called '‘perhydrolysis' and produce peroxyacid. Generally, peroxyacid bleach precursors are represented by the group il

X-C-L where L is a leaving group and X is essentially any functional group, so that after "perhydrolysis" the structure of the peroxyacid formed is

II

X-C-OOH

Peroxyacid bleach precursor compounds (precursors) are preferably used in an amount of 0.5-20%, more preferably 1-15%, and most preferably 1.5-10% by weight of the detergent composition.

Suitable peroxyacid bleach starting compounds typically contain one or more N- or O-acyl groups, and such precursors may be selected from a wide variety of classes of compounds. Suitable classes are anhydrides, esters, imides, lactams and acyl derivatives of imidazoles and oximes. Examples of useful materials of these classes are given in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.

Applicants have found that stain damage can be attributed in particular to peroxyacid bleach starting compounds which upon perhydrolysis provide a peroxyacid which is (i) perbenzoic acid or a non-cationic substitute derivative thereof, or (ii) a cationic peroxyacid.

Also, benzoxazine precursors have been confirmed as the cause of this problem.

Leaving groups

The leaving group, still group L, must be sufficiently reactive for the perhydrolysis reaction to proceed within an optimal time interval (e.g., one wash cycle). However, if L is too reactive, it will be difficult to stabilize this activator for use in a bleaching composition.

Preferably, the group L is selected as a group consisting of:

Y

R ^s

-O-CH = C-CH = CH 2

Y

-O-CH = C-CH = CH 2 O

¹¹ 1 -OCR ¹

II. CHyC / * \.

-NL ⁴ -NR ⁴

NR ⁴

R ³ 0 Y

I II I.

-O-C 1 HR ⁴ , and -NS-CH-R ⁴

Ø 0 ³ and mixtures thereof, wherein R ¹ represents alkyl, aryl or alkaryl group absahující 1-14 carbon 'atoms, R ³ represents an alkyl chain containing 1-8 carbon atoms, R ⁴ represents a hydrogen atom H or R ^3, and Y is H or a solubilizing group. Any of R ¹ , R ³ and R ⁴ may be substituted with substantially any functional group, including, for example, alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium, or alkyl ammonium.

Preferred solubilizing groups are -SO ₃ M ⁺ , -CO 2 -M ⁺ , -SO 4 "M ⁺ , -N ⁺ (R ³ ) 4X" and 0 <-N (R ³ ) 3, and most preferred are -SO ₃ "M ⁺ and -CO ₂ -M ⁺ , wherein R ³ is an alkyl chain of 1-4 carbon atoms, M is a bleach activator solubility cation, and X is an anion conditional on bleach activator solubility. For M, an alkali metal, ammonium or substituted ammonium cation is preferably used, with sodium and potassium being most preferred, and X is a halide, hydroxydium, methylsulfate or acetate anion.

Perbenzoic acid and its derivatives as precursors Perbenzoic acid precursors by perhydrolysis provide perbenzoic acid.

Suitable O-acylated perbenzoic acid starting compounds are optionally substituted benzoyloxybenzenesulfonates, including e.g.

Benzoyl-oxybenzenesulfonate:

⁰ i

Also suitable are benzoylation products of sorbitol, glucose and all carbohydrates with benzoylating agents, including, but not limited to:

Ac = COCH 3; Bz = Benzoy 1

Imide type perbenzoic acid precursors include succinic acid N-benzoylimide, tetrabenzoyl-ethylenediamine and N-benzoyl substituted ureas. Suitable imidazole types of perbenzoic acid precursors are N-benzoylimidazole and N-benzoyl-benzimidazole; other useful N-acyl-containing precursors are N-benzoyl-pyrrolidone, dibenzoyl-taurine and benzoyl-pyroglutamic acid.

Other benzoyl diacyl peroxide precursors, compound of formula:

perbenzoic acids are benzoyl tetraacylperoxides, and

o θ 'O ^^ COOH

Phthalic anhydride is another suitable precursor of perbenzoic acid:

A suitable N-acylated perbenzoic acid has the formula;

lactam as an acid precursor

II o c-ch ₂ —ch,

- II I ‘

R ⁶ —CH 2 --CH 2 --CH 2] _n wherein n is 0-8, preferably 0-2, and R ⁶ represents an aryl, alkoxyaryl or alkaryl group having 1-12 carbon atoms or a substituted phenyl group having 6-18 carbon atoms, preferably a benzoyl group.

Perbenzoic acid derivatives precursors

Perbenzoic acid derivatives precursors by perhydrolysis ”provide substituted perbenzoic acids.

Suitable prodrugs of perbenzoic acid derivatives are any of the perbenzoic acid prodrugs herein, wherein the benzoyl group is substituted with substantially any positively uncharged (i.e., non-cationic) functional group, including, e.g., alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl. and an amide group.

A preferred class of substituted starting compounds are amido-substituted compounds of the following formula:

wherein R ¹ is an aryl or alkaryl group having 1-14 carbon atoms, R ² is an arylene or alkarylene group having 1-14 carbon atoms, R ⁵ is H or an alkyl, aryl or alkaryl group and 1- And L represents any leaving group. Preferably R ¹ contains 6-12 carbon atoms, R ² contains 4-8 carbon atoms. R ¹ is also aryl substituted aryl or alkaryl with branching, substitution, or both, the sources of which may be both synthetic and natural, including, for example, tallow. Analogous structural variations are also possible in the case of R ^2nd By substitution is meant alkyl, aryl, halogen, nitrogen, sulfur and other typical substituent groups or organic compounds. R ⁵ is preferably H or methyl. R ¹ and R ⁵ should not contain more than 18 carbon atoms in total. Amide-substituted bleach activator compounds of this type are described in EP-A-0170386.

Cationic peroxyacid precursors

The starting compounds of cationic peroxyacids by perhydrolysis produce cationic peroxyacids.

Typical cationic peroxyacid precursors are formed by substituting the peroxyacid portion of a suitable starting compound with a positively charged functional group, such as ammonium or alkyl ammonium, preferably ethyl or methyl ammonium. Cationic peroxyacid precursors typically occur in solid detergent compositions as a salt with a suitable anion, such as a halide ion.

The peroxyacid starting compound so cationically substituted may be the perbenzoic acid starting compound or a substituted derivative thereof described above. Alternatively, the peroxyacid precursor may be an alkyl percarboxylic acid precursor or a substituted alkyl peroxyacid amide precursor, which will be described later.

Cationic peroxyacid precursors are described in US Patents 4,904,406; 4,751.015; 4,988,451; 4,397,757;

5,269,962; 5,093.022; 5,106,528; U.K. 1,382,594; EP 475.512; 458.396; 284.292; and JP 87-318.332.

Examples of preferred cationic peroxyacid precursors are described in British Patent Application No. 9407944.9 and in US Application No. 08/298903, 08/298650,

08/298904 and 08/298906.

A suitable cationic peroxyacid precursor is ammonium or alkylammonium-substituted benzxoyl-oxybenzenesulfonates, N-acylated and monobenzxoyl-tetraacetyl-glucosobenzoyl, any of the alkyl or caprolactams, peroxides.

A preferred cationically substituted benzoyloxybenzenesulfonate is 4- (trimethylammonium) methyl benzoyloxybenzenesulfonate:

A preferred cationically substituted alkyl oxybenzene sulfonate has the formula:

Preferred cationic peroxyacid precursors of the N-acyl-caprolactam class are trialkyl-ammonium-methylene-benzoyl-caprolactams, in particular trimethyl-ammonium-methylene-benzoyl-caprolactam:

Other preferred cationic peroxyacid precursors of the N-acyl-caprolactam class are trialkyl-ammonium-methylene-alkyl-caprolactams:

where n is 0-12.

Another preferred cationic peroxyacid precursor is

2- (N, N, N-trimethyl-ammonium) ethyl-N-4-sulfophenyl carbonate chloride.

Alkyl percarboxylic acid bleach precursors

Alkyl percarboxylic acid bleach precursors by "perhyrolysis" produce percarboxylic acid. Preferred precursors of this type produce peracetic acid by perhydrolysis.

Preferred imide-type alkyl percarboxylic precursors are N, N, N ¹ N ¹ -tetraacetylated alkylenediamines in which the alkylene group contains 1-6 carbon atoms, and particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetyl ethylenediamine (TAED) is particularly preferred.

Other preferred alkyl percarboxylic acid precursors are sodium 3,5,5-trimethylhexanoyloxyoxybenzenesulfonate (iso-NOBS), sodium nonanoyloxy oxybenzenesulfonate (NOBS), sodium acetoxybenzenesulfonate (ABS) and pentaacetylglucose.

Precursors of amide substituted alkyl peroxyacids

Also suitable are precursors on amide substituted alkyl peroxyacids, having the general formula:

R ¹ - C N - R ²

R ⁵ O — C — L

wherein R ¹ is C 1-4 alkyl, R ² is alkylene

And R ⁵ is a hydrogen atom (H) or an alkyl group of 1-10 carbon atoms, and L is essentially any leaving group. Preferably R ¹ contains 6-12 carbon atoms, R ² 4-8 carbon atoms. R ¹ is a straight chain or branched alkyl containing branching, substitution, or both, and the source is either synthetic or natural, including, for example, tallow fat. For R ² , structural variations are analogous. The substituent is alkyl, halogen, nitrogen, sulfur and other typical substituent groups or organic compounds. is preferably hydrogen or methyl. R ¹ and R ⁵ should not contain more than a total of 18 carbon atoms. Amide-substituted bleach activator compounds of this type are described in EP-A-0170386.

Precursors of benzoxazine organic peroxyacids

Also suitable are the benzoxazine-type starting compounds described in EP-A-332.294 and EP-A-482.807, in particular with

wherein R 11 is hydrogen, alkyl, alkaryl, aryl, arylalkyl, and wherein R ₂ , R ₃ , R ₄ and R 8 are the same or different substituents selected from: H, halogen, alkyl, alenyl, aryl, hydroxyl, alkoxy, amino, alkylamino, COOR (where R _g is H or an alkyl group) and carbonyl functions.

Particular preference is given to the benzoxazine-type precursor:

Preformed organic peroxyacid

The organic peroxyacid bleach system outside or as an alternative to the peroxyacid organic bleach precursor comprises a preformed organic peroxyacid in a typical amount of 1-15%, more preferably 1-10% by weight of the composition.

A preferred class of organic peroxyacids are amide substituted compounds of the general formula:

R ⁵ O

R ¹ - _c -

C - OOH R ¹

O or

NC-R ² -C -OOH

II o

where

R ¹ is alkyl, aryl or alkaryl of 1-14 carbon atoms, R ² is alkylene, arylene or alkarylene of 1-14 carbon atoms, and R ⁵ is H or alkyl, aryl or alkaryl of 1-10 atoms contains 6 -12 carbon atoms. R ² atoms. ^{The ol} preferably contains 4-8 or branched alkyl, branched, with a substituent, or with either a synthetic or natural one, including for R ² , analogous is acceptable. The substituent is alkyl, aryl, halogen, typical substituent groups or organic compounds. R ⁵ is preferably hydrogen or methyl. R ¹ and R ⁵ may not contain more than a total of 18 carbon atoms. Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.

R ^A preferably is carbon atoms, substituted

R ¹ is a straight chain aryl or alkaryl both, and the source is e.g. tallow fat. structure variations, nitrogen, sulfur and others

Other organic peroxyacids are diacyl and tetraacyl peroxides, in particular diperoxydodecanedioic acid, diperoxytetradecanedioic acid and diperoxyhexadecanedioic acid. Also suitable herein are mono- and diperazelaic, mono- and diperbrassylic and N-phthaloyl-amino-peroxyprinic acid.

Bleaching with chlorine

The compositions herein preferably do not use chlorine for bleaching.

Bleaching catalyst

The invention also encompasses compositions comprising a catalytically effective amount of a bleach catalyst, such as a water-soluble manganese salt.

In the compositions of the invention, a bleach catalyst is used in a catalytically effective amount. A catalytically effective amount is a mini- mum sufficient (under any conditions of the comparative test) to enhance the whitening effect and remove the stain or stains from the substrate being investigated. Thus, for the laundry operation, the substrate to be examined is a textile material with stains, eg from various foods. For automatic dishwashing, the substrate under investigation is, for example, a porcelain mug or a plate with tea stains or a polyethylene plate with tomato sauce stains. Test conditions vary depending on the washing equipment and user's habits. Thus, front-load washers of the type used in Europe use less water and a higher detergent concentration than top-load washers in the US. Some machines have a significantly longer wash cycle than others. Some users choose very hot water for washing machine operations, others choose hot or cool water. It goes without saying that these considerations affect the catalytic efficiency of the bleach catalyst, and accordingly the amount of bleach catalyst in detergent and bleach formulation formulations needs to be appropriately adjusted. In practice, and not for limitation, the compositions and processes disclosed herein can be adjusted to the order of at least 1 part of active bleach catalyst to 10 million parts of wash fluid; preferably a ratio of 1-200 ppm of catalyst in the wash liquid is used. To further illustrate this point: of the order of 3 micromoles of manganese catalyst at 40 ° C, pH 10, are effective under European conditions using a perborate and a bleach precursor (e.g. benzoylcaprolactam). In order to achieve the same results under American conditions, it is necessary to increase the concentration

3-5 times. Conversely, the use of a bleach precursor and a perborate with a manganese catalyst will allow the formulator to achieve equivalent whitening at a lower level of perborate than without a manganese catalyst.

The bleach catalyst material may be loose

acid, or may be in the form of a suitable salt.

One type of bleach catalyst is a catalytic system consisting of heavy metal cations with a defined bleaching catalytic activity, such as copper, iron or manganese cation, a cationic metal cation with little or no catalytic activity, such as zinc or aluminum, and a preservative with a defined stability of catalytic and auxiliary cations, especially ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid), and their water-soluble salts. Such catalysts are described in USP 4,430,243.

Another type of bleach catalyst is the manganese-based complexes disclosed in USP 5,246,621 and USP 5,244,594. Preferred examples of these catalysts are Mn ^IV 2 (µ-O) ₃ (1,4,7-trimethyl-1,4,7 (triazacyclononan) ₂ - (PFg) 2 · Mn ^III 2 (µ-0Ac) ₂ (1, 4,7-trimethyl-1,4,7 (triazacyclononane) (C1O ₄ ) ₂ , Mn ^IV 4 (u-0) ₆ (1,4,7-trimethyl-1,4,7 (triazacyclononane) ₄ - (C1O) ₄ ) ₂ , Mn ^III Mn ^IV 4 (µC) ₁ (µ-OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ - (ClO ₄ ) ₃ , and mixtures thereof. described in European Patent Application Publication No. 549,272. Other ligands suitable for this use are 1,5,9-trimethyl-1,5,9-triaza cyclodecane,

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. in UPS 4,246,612 and USP 5,227,084. See also USP 5,194,416 which discloses mononuclear manganese (IV) complexes such as Mn (1,4,7-trimethyl-1,4,7-triazacyclononan) (OCH ₃ ) ₃ (PFg).

Yet another type of bleach catalyst disclosed in USP 5,114,606 is a water soluble manganese (II), (III) and / or (IV) complex with a ligand which is a non-carboxylic polyhydroxy compound having at least three consecutive C-OH groups. Preferred ligands are sorbitol, idite, dulsit, mannitol, xylite, arabite, adonite, meso-erythrite, meso-inosit, lactose, and mixtures thereof.

USP 5,114,611 discloses a bleach catalyst consisting of a complex of transition metals, including Mn, Co, Fe, and Cu, with a non-(macro) -cyclic ligand. These ligands have the formula:

R ² R ³

R ¹ -N = O-8-C = NR ⁴ wherein R, R, R ^J and R ⁴ (any of which may be H, substituted with alkyl and aryl groups, such that each R ¹ -N = CR ² and R ³ -C = NR ⁴ form a five or six membered ring, which ring may be further substituted.B is a bridging group consisting of O, S, CR 4 R 6, NR ⁷ and C = O, wherein R 6,

R ⁶ a

R ⁷ can (each) be H, alkyl or aryl, including substituted or unsubstituted groups. Preferred ligands are pyridine, pyridazine, pyrimidine, pyrazine, and triazole rings. These rings are substituted with substituents such as halide and nitro2,2-bis-pyridylamine, Co, Cu, Mn,

Highly preferred pyrazole, preferably aryl, alkoxy, is an imidazole ligand, may be alkyl,

Especially preferred

Preferred bleach catalysts are Fe-bispyridylmethane and bispyridylamine.

the catalysts are

Co (2,2-bispyridylamine) Cl ₂ , di (isothiocyanato) bis-pyridylamine-cobalt (II), trisdipyridylamine-cobalt (II) perchlorate, Co (2,2-bispyridylamine) ₂ 0 ₂ C10 ₄ , bis- (2 2-bispyridylamine) measures (II) perchlorate, tris (di-2-ridylamine) iron (II) perchlorate, and mixtures thereof.

Other examples are manganese gluconate, Mn (CF ₃ SO ₃ ) ₂ , binuclear manganese complexes with bi-N-dentate ligands, including

N ₄ Mn ^III (u O) 2mn ^IV N 4) ⁺ and ^[III Bipy2Mn (UO) 2mn ^Iv bypy _2]. (C1O ₄ ) ₃ ·

Bleach catalysts are also prepared by combining a water-soluble ligand with a water-soluble manganese salt in an aqueous medium, and concentrating the resulting mixture by evaporation. Any suitable salt can be used herein

CO (NH ₃ ) ₅ Cl, and water-soluble manganese tetra-N-dentate ²⁰ . Manganese (II), (III), (IV) and / or (V) is readily available commercially. In some cases, there may be sufficient manganese in the wash liquid, but generally Mn cations may be added to the detergent composition only to provide a catalytically effective amount. Thus, the sodium ligand and a member selected from the group consisting of MnSo ₄ , Mn (C10 ₄ ) ₂ or MnCl ₂ (this is preferred) are dissolved in water in a ligand: Mn molar ratio from 1: 4 to 4: 1 at neutral or slightly alkaline pH. The water must first be deoxygenated by boiling and cooled by bubbling nitrogen. The resulting solution is evaporated (under nitrogen if desired) and the resulting residue is used in the bleaching and detergent compositions of the invention without further purification.

In another method, a water soluble manganese source, such as MnSO ₄ , is added to the bleach / scrubbing agent or to the aqueous bleach / scrubbing bath containing the ligand. Some types of complexes are formed in situ to provide better bleaching efficiency. In such an in situ process, it is convenient to use a significant molar excess of the ligand over the manganese; typical molar ligand: Mn ratios are 3: 1 to 15: 1. The excess ligand also serves to bind mixed metal ions such as iron and copper, thereby protecting the bleach component from decomposition. One such possible system is described in European Patent Application Publication No. 2001/007. 549.271.

Since the structures of some of the bleach catalysing manganese complexes described herein have not been elucidated, it can be concluded that they contain chelates or other hydrated coordination complexes resulting from the interaction of the carboxyl and nitrogen atom in the ligand with the manganese cation. Similarly, the oxidation state of the manganese cation during the catalytic process is not known, so that the valence state may be (+11), (+ III), (+ IV) or (+ V). Since there are 6 possible attachment points for the ligand to the manganese cation, one can reasonably assume that in an aqueous bleaching environment there are multi-nuclear or cage-like structures. Whatever the form of the active Mn-ligand, it actually acts in a catalytic manner to better whiten stubborn stains such as tea, ketchup, coffee, blood, etc.

Other bleach catalysts are disclosed in European Patent Application Publication No. 2001/00511. 408.131 (cobalt complex catalysts), no. 384,503 and 306,089 (metal-poryphyrin catalysts), in USP 4,728,455 (manganese / multidentate ligand), USP 4,711,748 and Europe. U.S. Pat. Application No. 224.952 (manganese absorbed on an alumino-siliceous catalyst), USP 4,601.845 (manganese-aluminosilicate support with zinc or magnesium salt), USP 4,626.373 (manganese / ligand), USP 4,119.557 (ferric complex catalyst), German (BRD) ) Patent Specification 2,054,019 (cobalt chelant), Canadian Patent 866,191 (transition metal containing salts), USP 4,430,243 (manganese cation chelate and non-catalysing metal cations), and USP 4,728,455 (manganese gluconate).

Relative release kinetics

An important aspect of the invention is to provide a means for delaying the release of the bleached organic peroxyacid into the wash solution relative to the release of the enzyme.

The composition may be a means to delay the release of the bleached organic peracid into the wash solution.

Alternatively, the composition may be a means for accelerating the release of the enzyme into solution.

The most preferred method is the release of both the peroxyacid bleach and the release of H ₂ O ₂ .

Delayed release means

Certain compositions may cause delayed release of the bleaching organic peroxyacid source itself into the wash solution. Alternatively, if the source is a peroxyacid precursor compound, the delayed release means may comprise a means to prevent or prevent the perhydrolytic reaction in situ before the organic peroxyacid is released into solution. For example, such a composition may include delayed release of the hydrogen peroxide source into solution by, e.g., delayed release of an inorganic perhydrated salt acting as the hydrogen peroxide source.

The delayed release means may be a coating of a suitable component with a coating or a mixed coating designed to provide delayed release. Thus, the coating may consist, for example, of a poorly water-soluble material, or it may be of sufficient thickness such that the dissolution kinetics guarantee a controlled release rate.

The coating material can be applied using various methods. A typical weight ratio of any coating material to the bleach component is 1:99 to 1: 2, preferably 1:49 to 1: 9.

Suitable coating materials are triglycerides (e.g., partially hydrated vegetable oil, soybean oil, cottonseed oil), mono- or diglycerides, microcrystalline waxes, gelatin, cellulose, fatty acids, or any mixture thereof.

Other suitable coating materials are alkali metal and alkaline earth metal sulphates, silicates, carbonates, including calcium carbonate.

A suitable coating material is sodium silicate with a SiO ₂ : Na ₂ O ratio of from 1.6: 1 to 3.4: 1, preferably 2.8: 1, applied as an aqueous solution containing 2-10% (normally

3-5%) silicate dry matter per weight of percarbonate. The coating may also contain magnesium silicate.

Each inorganic coating material may be combined with an organic binder to form compound inorganic salt / organic binder coatings. Suitable binders include the ^C io ^"C2o alcohol ethoxylates containing from 5 to 100 moles of ethylene oxide per mole of alcohol and more preferably the C ₁₅ -C ₂₀ primary alcohol ethoxylates containing from 20 to 100 moles of ethylene oxide per mole of alcohol.

Other preferred binders are certain polymeric materials. Examples of such polymeric materials are polyvinylpyrrolidone having an average molecular weight of 12,000 to 700,000, and polyethylene glycols (PEG) having an average molecular weight of 12,000 to 700,000. molecular weight 600-10,000. Copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid wherein the maleic anhydride is at least 20 mol-percent of the polymer are further examples of polymeric materials used as a binder. These polymeric materials can be used as such or in combination with solvents such as water, propylene glycol, and the aforementioned C ₁₀ -C ₂₀ alcohol ethoxylates containing 5-100 moles of ethylene oxide per mole of alcohol. Further examples of binders include ^C 10 ° ^C 20 ^mon - ^and di-glycerol ethers and the fatty acids _of C ₁₀ to C _20. Other examples of binders suitable for use in the present invention are cellulose derivatives such as methylcellulose, ethyl-hydroxyethylcellulose and hydroxyethylcellulose, and homoa co-polymeric polycarboxylic acids or salts thereof.

One method of applying the coating material is agglomeration. For the sintering process, it is preferable to use the organic binders described above. Any conventional agglomerator / mixer may be used, including, but not limited to, a pan, a rotary drum, or a vertical mixer. It is also possible to apply the molten coating material, either by pouring onto the bleaching agent, or by atomizing spray on its fluidized bed.

Another means of realizing delayed release is to mechanically alter the physical properties of the bleaching agent to control solubility and release rate. Compaction, mechanical injection, manual injection, and adjustment of the bleach compound solubility by selecting the particle size of the component are suitable.

The choice of particle size will depend on both the composition of the component and the delayed release kinetics required, but it is desirable that the particle size be over 500 microns, with an average diameter of 800-1200 microns being preferred.

Other methods for forming the delayed release compositions also include the appropriate selection of some other component of the detergent composition matrix so that, after the composition is introduced into the wash solution, the ionic strength environment formed therein allows the desired delayed release kinetics to be achieved.

Means of accelerated release

All suitable means for accelerating the release of the enzyme into solution are contemplated.

The accelerated release means comprises coating a suitable component with a release enhancing coating.

Thus, the coating may consist, for example, of a highly or even violently (effervescent) water-soluble material.

Other means of accelerated delay are mechanical, γ altering the physical properties of the enzyme to increase solubility and accelerate release.

A suitable procedure is to consider the particle size of the respective enzyme-containing component. The choice of particle size depends both on the composition of the component and the desire to achieve accelerated release kinetics. Desirably, the particle size is less than 1200 microns, a mean particle diameter of 1100-500 microns is preferred.

Other processes for forming the delayed release compositions also include the appropriate selection of some other component of the detergent composition matrix so that, upon introduction of the composition into the wash solution, the ionic strength environment formed therein allows the desired sustained release kinetics to be achieved.

Delayed release - kinetic parameters

The release of the organic peroxyacid component from the peroxyacid-containing bleach system relative to the release of the enzyme component must be such that in the T50 test described herein the time required to reach a concentration equal to 50 percent of the final (maximum) concentration of said enzyme is less than 120 seconds, preferably less more than 90 seconds, and preferably less than 60 seconds, and the time required to reach a concentration equal to 50 percent of the final (maximum) concentration of said peroxyacid bleach is greater than 180 seconds, preferably 180-480 seconds, and most preferably 240-360 seconds. In another aspect, the T50 for the enzyme component must be at least 100 seconds less than the T50 for the peroxyacid bleach component.

In one of the major aspects of the present invention, the bleach component release is such that, according to the T50 assay described herein, a time to reach a total accessible oxygen (AvO) level of 50 percent of the final level is greater than 180 seconds, more preferably 180-480 seconds, most preferably 240-80 seconds. 360 seconds.

The method for determining the level of AvO is described in the application

European Patent No. 93870004.4.

In another important aspect of the invention, when the peroxyacid bleach source is a precursor thereof in combination with a hydrogen peroxide source, the kinetics of release of the hydrogen peroxide into the scrubbing solution relative to the enzyme component is such that according to the T50 method described herein. the concentration of said enzyme is less than 120 seconds, more preferably 90 seconds, most preferably 60 seconds, and the time to a concentration equal to 50% of the final (maximum) concentration of hydrogen peroxide and said peroxyacid precursor is greater than 180 seconds, more preferably 180-480 seconds, and most preferably 240-360 seconds.

When the enzyme is a protease, the final (maximum) amount in a typical wash solution is about 0.1-100 KNPUs, preferably 0.5-50 KNPUs, more preferably 3-30 KNPU, and most preferably 6-30 KNPU.

When the enzyme is amylase, the final amount in a typical wash solution is 1-200 KNU, preferably 10-100 KNU, more preferably 40-80 KNU.

AND

When the enzyme is a lipase, the final amount in a typical wash solution is 1-300 KLUs, more preferably 10-200 KLU, and most preferably 10-100 KLU.

When the enzyme is a cellulase, the final amount in the wash solution is typically 10-1200 units of a Vascular, preferably 50-1000 Vascular, more preferably 80-500 Vascular.

The final (maximum) washing concentration of the bleaching inorganic perhydrate typically is 0.005-0.25% by weight, preferably more than 0.05% by weight. more preferably greater than 0.075% by weight.

The final wash concentration of any peroxyacid precursor is typically 0.001-0.08% by weight, preferably 0.005-0.05% by weight, and most preferably 0.015-0.05% by weight.

Delayed release - test method

The delayed release kinetics in the present invention are defined based on the TA test method, in which the time required to reach A% final concentration / level of the respective component is measured when the composition containing the component is dissolved under standard (normalized) conditions described below.

Standard conditions: fill a glass beaker with 100 ml of distilled water at 20 ° to which 10 g of the composition are added. The contents are mixed with a magnetic stirrer set at 100 rpm. The magnetic stirrer has a pea shape with a maximum dimension of 1.5 cm and min. size 0,5cm. The maximum concentration / level is considered to be the concentration reached 10 minutes after placing the composition in a beaker of water.

After adding the composition to a beaker of water, a suitable analytical method is chosen to reliably determine the instantaneous and final concentration of the component considered.

Such an analytical method may be continuous concentration level monitoring, such as photometry and conductometry.

Alternatively, methods of determining the titre of the solution at certain time intervals may be used, stopping the dissolution process by a suitable means, such as rapidly lowering the temperature of the solution, and then determining the component concentration by a chemical method, e.g., titration.

It is possible to use a graphic to calculate the result value.

The choice depends on the method, including plotting the TA curve from the crude analytical concentration of the composition, certain analytical methods to determine the nature of the component and the whole containing the component.

Additional detergent components

The detergent compositions herein will contain the additional detergent properties of these additional components and the amount used will depend upon the physical form of the composition and the nature of the cleaning operation for which it will be used.

The compositions according to the invention may be formulated, for example, as detergent compositions for hand and machine washing, as additional laundry compositions, and as compositions suitable for pre-cleaning laundry with stains, or for machine dishwashing.

When formulating for machine methods, eg for machine washing or dishwashing, the compositions of the invention preferably comprise one or more additional detergent components selected from the following: surfactants, heavy metal ion masking agents, organic polymeric compounds, soap suppressors, soaps, clay suspending and settling agents (anti-redeposition agents),

The laundry compositions may also comprise components of the invention. Precise lime dispersants to prevent its novel and corrosion inhibitors, as well as an additional detergent component, include softening agents.

Surfactants

The optional detergent composition of the invention comprises a surfactant, anionic, cationic, nonionic ampholytic, amphoteric and zwitterionic, and mixtures thereof.

A typical surfactant content is 0.1-60% by weight. More preferred is 1-35 wt%, most preferred

1-20% by weight.

It is preferred to formulate the surfactant as compatible with the respective enzyme component of the composition. In the case of liquid and gel (gel) compositions, it is most preferred to formulate a surfactant such that it promotes or at least does not degrade the stability of the respective enzyme in the composition.

A typical listing of anionic, nonionic, ampholytic, and zwitterionic classes and species is given in USP 3,929,678 issued to Laughlin and Heuring on December 30, 1975. Other examples are in Surface Active Agents and Detergents (Vol. I and II, Schwartz, Perry, and Berch). Suitable cationic surfactants are listed in USP 4,259,217, issued to Murphy on March 31, 1981.

When ampholytic, amphoteric and zwitterionic surfactants are used, they are generally used in combination with one or more nonionic surfactants.

Anionic surfactants

Essentially any anionic surfactant useful for cleaning purposes can be used in the detergent compositions herein. These may be salts (eg, Na, K, ammonium, substituted ammonium such as mono-, di- and triethanolamine) of anionic sulfate, sulfonates, carboxylate and sarcosinate surfactants.

Other anionic surface agents include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C ₁₂ "C ₁₈ .monoestery) diesters of sulfosuccinate (especially. Saturated and unsaturated Cg -C ₁₄ -diesters), N-acyl sarcosinates. Also suitable are optionally hydrogenated resin acids such as rosin, hydrogenated rosin, and optionally hydrogenated resin acids contained in or derived from body oil.

Anionic sulfate surfactants

Anionic sulfate surfactants for use herein include the linear and branched primary alkyl sulfates, alkyl ethoxysulfates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, C ₅ -C ₇ -a ^c yl-N- ( _Ci-C4 alkyl) and -N- (C ₁ -C ₂ hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).

The alkyl ethoxy sulfates are preferably selected from the group of C ₆ -C ₁₈ -alkyl sulfates which have been ethoxylated with 0.5-20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxy sulfate surfactant is a C 8 -C ₁₈ alkylisulfate ethoxylated with 0.5-20, more preferably 0.5-5 moles of ethylene oxide per molecule.

Anionic sulfonate surfactants

The anionic sulfonate active compounds useful herein are salts of C ₅ -C ₂₀ linear alkyl benzene sulfonates, alkyl aster sulfonates, ^C 6 -C ₂₂ primary or secondary alkane sulfonates, C 8 -C ₂₄ -olefin sulfonates, sulfonated alkyl polycarboxylic acids glycerin sulfonates, oleyl glycerin sulfonates, and any mixtures thereof.

Anionic carboxylic surfactants

Anionic carboxylic surfactants suitable for use herein include alkyl ethoxy carboxylates, alkyl polyethoxy polycarboxylates, and soaps (alkyl carboxylates), particularly some of the secondary soaps described herein.

Preferred alkyl ethoxy carboxylates for use herein include those listed with the formula RO (CH ₂ CH ₂ O) _x CH ₂ COOM ^+, wherein R is the alkyl ^C 6- ^C I8, ^x is from 0 to 10, and the ethoxylate distribution is such that the amount of material at X = 0 is less than 20 wt%, at X > 7 it is below 25 wt%? the average X is 2-4 if the average RC is ₁₃ or less, and the average X is 3-10 if the average R is greater than C ₁₃ ? and M is a cation, preferably an alkali metal, a caustic earth metal, ammonium, mono-, dia-triethanol-ammonium, most preferably sodium, potassium, ammonium, and mixtures thereof with magnesium ions. Preferred alkyl ethoxy carboxylates are those wherein R is ^C 12 ^-C 13 alkyl.

Alkyl polyethoxy polycarboxylates surfactants have the formula RO- (CHR ₁ -CHR ₂ -O) -R ₃ , wherein R is C 8 -C ₁₈ alkyl, X is 1-25, R _x and R ₂ are selected as a group containing hydrogen, a methyl acid, succinic or hydroxysuccinic acid radical and mixtures thereof, wherein at least one of R ₁ or R ₂ is a succinic or hydroxy succinic acid radical, and R ₃ is selected as a hydrogen, substituted or unsubstituted hydrocarbon group having 1- 8 carbon atoms, and mixtures thereof.

Anionic secondary soaps as surfactants

Preferred soap actives are secondary soaps containing a carboxyl unit attached to the secondary carbon. The secondary carbon may be in the ring structure, e.g., as in p-octylbenzoic acid, or in alkyl-substituted cyclohexyl carboxylates. Preferred secondary soaps should contain no ether or ester linkages, and no hydroxyl groups. Even in the parent group (in the amphiphilic part) there must be no nitrogen atoms. Secondary soaps as surfactants typically contain a total of 11-15 carbon atoms, although up to 16, e.g., β-octylbenzoic acid, can be tolerated.

The following general structures further illustrate some secondary soaps as surfactants:

A. A highly preferred class of secondary soaps comprises secondary carboxyl materials of formula

R ³ CH (R ⁴ ) COOM, wherein R ³ is CH 3 (CH 2) x and R ⁴ CH 3 (CH ₂ ) y, wherein y may be 0 or an integer from 1 to 4, x is an integer from 4 to 10 and the sum (x + y) is 6-10, preferably 7-9, most preferably 8.

B. Another preferred class of secondary soaps are carboxyl compounds wherein the carboxyl substituent is on a ring hydrocarbyl unit, i.e., they are secondary soaps of the formula R ⁵ -R ⁶ -COOM, wherein R ⁵ is C ⁷ -C ¹⁰ alkyl or alkenyl, more preferably C ⁸ -C ⁹ , and R ⁶ is a ring structure such as benzene, cyclopentane or cyclohexane. (Note: R ⁵ may be ortho, meta or para relative to the ring carboxyl.)

C. Yet another preferred class of secondary soaps consists of secondary carboxylic compounds of formula CH ₃ (CHR) _k - (CH ₂ ) _m - (CHR) _n -CH (COOM) (CHR) _Q - (CH ₂ ) _p - (CHR) _q -CH ₃ , wherein each R is alkyl-4 -04, wherein k, n, o, q are 0 to 8, provided that the total number of carbon atoms (including carboxyl) is in the range of 10-18.

In each of formulas A, B, C above, M is any suitable counterion, particularly promoting water solubility.

Highly preferred secondary soaps for use herein are water-soluble members of the group comprising the water-soluble salts of 2-methyl-1-undecanoic acid,

2-ethyl-1-decanoic, 2-propyl-1-nonanoic, 2-butyl-1-octane and 2-pentyl-1-heptane.

Alkali metal sarcosinates as surfactants

Other suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON (R - * -) CH ₂ COOM, wherein R is a linear or branched alkyl or alkenyl ^C 5 ^"C 17 · R ¹ is alkyl and M is an alkali metal. Preferred examples are myristyl and oleyl methyl sarcosinates in the form of their sodium salts

Nonionic surfactants

Essentially any nonionic surfactant can be used in the detergent compositions herein. The following are non-limiting examples of individual classes of these substances.

Nonionic polyhydroxy fatty acid amides

Nonionic polyhydroxy fatty acid suitable for use herein are those having the structural formula R ² CONR ¹ Z wherein: ^R1 is H, hydrocarbyl and ^{C "C4,} 2-hydroxyethyl,

2-hydroxypropyl or mixtures thereof, preferably an alkyl 0 - ^ - 04, more preferably Ci or _C2 alkyl, jvýhodně not be Cj alkyl (i.e., methyl); R ² is hydrocarbyl C ₅ -C ₃₁ , preferably unbranched C 8 -C 18 -alkyl or alkenyl, more preferably straight C 8 -C ₁₇ -alkyl or -alkenyl, most preferably straight C 1 -C 6 -alkyl or alkenyl, or mixtures thereof; Z is a polyhydroxy-hydrocarbyl having a linear chain and at least 3 hydroxyls attached directly to the chain, or alkoxylated derivatives thereof (preferably ethoxylated or propoxylated). Z is preferably derived from a reducing sugar by reductive amination; most preferably Z is glycityl.

Nonionic Condensates of Alkylphenols Preferred for Polypropylene Uses generally have polyethylene alkylphenols.

polyethylene oxide. These compounds of the invention are condensates and polybutylene oxide, and the preferred condensates are the condensation products of alkylphenols with an alkyl of 6-18 carbon atoms optionally in branching, and alkylene oxide.

Nonionic ethoxylated alcohols

Suitable for use herein are the alkyl ethoxylate condensation products of aliphatic alcohols with 1-25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol may optionally be branched, primary or secondary, and generally contains 6-22 carbon atoms. Most preferred are the condensation products of alcohols with an alkyl

8-20 carbons with 2-10 moles of ethylene oxide per mole of alcohol.

Nonionic ethoxylated / propoxylated fatty alcohols

Suitable for use herein are the ethoxylated fatty alcohols, C ₁₈ -C _g ^and mixed ethoxy / propoxylated fatty alcohols, in particular those soluble in water. from ethoxylated alcohols, preferred alcohols are C ₁₈ -C _1Q with a degree of ethoxylation

3-50, most preferred are C ₁₂ -C ₁₈ alcohols at a degree of ethoxylation of 3-40. Of the mixed ethoxy / propoxylated fatty alcohols, those having an alkyl of 10-18 carbon atoms at an ethoxylation degree of 3-30 and a propoxylation degree of 1-10 are preferred.

Nonionic EO / PO condensates with propylene glycol

Suitable for use herein are the condensation products of ethylene oxide with a hydrophobic base formed by condensation of propylene oxide with propylene glycol. The hydrophobic portion of these compounds has a preferred molecular weight of 1500-1800, and causes water insolubility. Examples of compounds of this type are some of the commercially available Pluronic ™ surfactants sold by BASF.

Nonionic EO condensation propylene oxide / ethylenediamine adducts

Suitable for use herein with ethylene oxide products with reaction products s are condensation propylene oxide and ethylenediamine. The hydrophobic half of these products consists of the reaction products of ethylenediamine and an excess of propylene oxide, and usually has a molecular weight of 2500-3000. Examples of nonionic surfactants of this type are some of the commercially available Tetronic ™ compounds sold by BASF.

Nonionic alkyl polysaccharide surfactants

Alkylpolysaccharides suitable for use herein are described in USP 4,565,647 (Llenado) of January 21, 1986, wherein the hydrophobic group has 6-30 carbon atoms, preferably 10-16, and the polysaccharide, e.g., polyglycoside, and the hydrophilic group has 1,3- 10, more preferably 1.3-3, and most preferably 1.3-2.7 carbohydrate units. Any reducing carbohydrate having 5 or 6 carbon atoms may be used, e.g., glucose, the galactose moiety and the galactosyl moiety may be replaced by the glucosyl moiety. (The hydrophobic moiety can optionally be attached to the 2-, 3-, 4-, etc. position, thereby bringing glucose or galactose against the glucoside or galactoside.) The intersaccharide linkages may be e.g. between one position of another carbohydrate unit and the 2-, 3-position. -,

4-, and / or 6- preceding saccharide units.

Preferred alkylpolyglycosides have the formula R ² 0 (C _n H _2n O) t (glycosyl) _χ wherein R ² is selected from alkyl, alkylphenyl, hydroxyalkyl, hydroxyalky1fenyl, and mixtures thereof in which the alkyl groups have from 10 to 18, more preferably 12- 14 carbon atoms; n is 2 or 3, t is 0-10, preferably 0, and X is 1.3-8, more preferably 1.3-3, most preferably 1.3-2.7. Glycosyl is preferably derived from glucose.

Nonionic fatty acid amides as active substances

The fatty acid amides for use herein have the formula R ⁶ CON (R ⁷ ) ₂ , wherein R ⁶ is an alkyl having 7-21, more preferably

9 to 17 carbon atoms and each R ⁷ is selected from the group consisting of hydrogen, C ^ alkyl, hydroxyalkyl, ^C i-4, and - (C ₂ H ₄ O) _x H, where x is 1-3.

Amphoteric surfactants

Suitable amphoteric active agents for use herein include amine oxides and alkyl amphocarboxylic acids.

A suitable example of an alkyl-amphocarboxylic acid for use herein is Miranol (TM) C2M Conc, manufactured by

Miranol, Inc., Dayton, N.J.

Amine oxide surfactants

Amine oxides useful herein include compounds of the formula selected alkyl, and phenyl or mixtures thereof, preferably 8-18 C atoms; R ⁴ is

R ³ (OR ⁴ ) x N ° (R ⁵ ) 2, wherein as R ³ hydroxyalkyl, acylamido-propoyl containing 8-26 carbon atoms, with alkylene or hydroxyalkylene of 2-3, more preferably 2 C atoms, or mixtures thereof; x is 0-5, more preferably 0-3; and each R ⁵ is alkyl or hydroxyalkyl of 1-3, more preferably 1-2 C atoms, or is a polyethylene oxide group containing 1-3, more preferably 1 ethylene oxide group. The R ⁵ groups can be linked to each other, e.g. via an oxygen or nitrogen atom, to form a cyclic structure.

Amine oxide actives include ^<io-C 18 alkyl dimethylamine oxide, and C ₈ _ ₁₈ -alkoxyethyl-dihydroxyethyl amine oxides. Examples of such materials are: dimethyloctylamine oxide, diethyl decylamine oxide, bis- (2-hydroxyethyl) dodecylamine oxide, dimethyldodecylamine oxide, dipropyl-tetradecylamine oxide, methylethyl hexadecylamine oxide, dodecylamidopropyl dimethylamine oxide, cetyl dimethylamine oxide, stearyl dimethylamine oxide, stearyl dimethylamine oxide, 2-hydroxy-octadecyl amine oxide. Preferred are

C 10-10 -alkyldimethylamine oxide a

C ₁₀ _ ₁₈ -acylamido-alkyldimethyl.

Surface active substances with zwitterions

The zwitterionic active ingredients can also be incorporated into the detergent compositions of the present invention. These may be briefly described as derivatives of optionally heterocyclic secondary and tertiary amines, or as derivatives of quaternary ammonium, quaternary phosphonium and tertiary sulfonium compounds. Examples of zwitterionic active agents useful herein are betaine and sultain.

Surface active betaines

Betaines useful herein are compounds having the formula R (R ¹ ) ² N ⁺ R ² COO ", wherein R is a C ₈ -C ₁₈ hydrocarbyl, preferably a C ₁₀ -C ₁₆ alkyl or a C ₁₀ -C ₁₆ acylamido-alkyl group, each R 8 ¹ is typically C 1-3 -alkyl, preferably methyl, and R ² is C1_ ₅ hydrocarbyl, preferably C ₁ _ ₃ alkylene, more preferably C ₂ alkylene. Examples of suitable betaines are: coconut acylamido-propyl-dimethyl-betaine; hexadecyl-dimethyl-betaine; C, N, N-acylamidopropyl-betaine; Cg_ ₁₄ -acylamido hexyldietyl-betaine;

4-C ₁₄ _ ₁₆ -acylmetylamido-dietylamonio / -l-carboxybetaine · Cig-Ig-acylamido-dimethyl betaine; C 1-8 -acylamido-pentanediethyl-betaine; C ₁₂ _i -acylmetylamido _6-dimethyl betaine. Preferred betaines are C ₁₂ _ _g dimethyl-ammonio-hexanediol and C ₁₀ _ ₁₈ -acylamido -propane (or ethane) dimethyl (or diethyl) betaines. Complex betaines are also suitable for use herein.

Surface-active sultains

According to the present invention are useful sultaines are compounds of the formula R (R ¹⁾ 2 N ⁺ R ² SO 3 "wherein R is a hydrocarbyl Cg_ _Ig with výhdou C ₁₀ _ ₁₆ -alkyl, preferably C ₂ _ ₁₃ alkyl, each R ¹ is typically C _1-3 -alkyl, preferably methyl, and R ² is -hydrocarbyl, preferably C _1-3 -alkylene or hydroxyalkylene.

?

Ampholytic surfactants

Ampholytic surfactants can be used in the detergent composition of the invention. These can be broadly described as aliphatic derivatives of secondary or tertiary amines, or as aliphatic derivatives of heterocyclic secondary and tertiary amines. amines in which the aliphatic radical may be a straight or branched chain.

Cationic surfactants

The detergent compositions cationic surfactants, quaternary ammonium compounds preferably C ₆ _ ₁₀ N-alkyl or compounds, wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.

can also be used of which they are suitable from mono C ₆ _ ₁₆ -, alkenyl-derived ammonium actives

Water-soluble binder (carrier) compound

The detergent compositions of the present invention comprise as a preferred optional component a water-soluble binder (parent) compound present in a typical amount of 1-80%, more preferably 10-70%, and most preferably 20-60% by weight of the composition.

Preferred water-soluble binder (base) components are water-soluble monomeric polycarboxylates or acid forms thereof, homo- or co-polymeric polycarboxylic acids or salts thereof, wherein the polycarboxylic acid consists of at least two carboxylic radicals separated by no more than two carbon atoms, carbonates, bicarbonates, borates, phosphates, silicates, and mixtures of any of the foregoing.

The carboxylate or polycarboxylate component may be of a monomeric or oligomeric type, although monomeric polycarboxylates are generally preferred for reasons of cost and efficiency.

Suitable single-carboxylate carboxylates are the water-soluble salts of lactic acid and glycolic acid, and ether derivatives thereof. Dual carboxylate polycarboxylates are the water-soluble salts of succinic, malonic, (ethylenedioxy) di-acetic, maleic, diglycolic, tartaric, tartronic and fumaric acids, as well as ether carboxylates and sulfinyl carboxylates. The three carboxylate polycarboxylates are in particular water-soluble citrates, aconitates and citraconates, as well as amber derivatives such as the carboxymethyloxy succinates disclosed in British Patent No. 1,379,241, the lactoxy succinates disclosed in BP No. 1,389,732, and the amine succinates disclosed in Dutch Application 7205873, and oxypolycarboxylates such as the 2-oxa-1,1,3-propane tricarboxylates described in BP No. 1,387,447.

Polycarboxylates containing four carboxylates are the oxydisuccinates disclosed in BP No. 1,261,829, furthermore 1,1,2,2-ethane-tetracarboxylates, 1,1,3,3-propane-tetracarboxylates, and 1,1,2,3-propane-tetracarboxylates .

Sulfosubstituted polycarboxylates are sulfosuccinic acid derivatives disclosed in BP Nos. 1,398,421 and BP 1,398,422, and in USP 3,936,448, and the sulfonated pyrolyzed citrates described in BP 1,439,000.

Alicyclic and heterocyclic polycarboxylates are cyclopentane-cis, ois, cis-tetracarboxylates, cyclopentadiene pentacarboxylates, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran-cis-dicarboxylates,

2,2,5,5-tetrahydrofuran tetracarboxylates, 1,2,3,4,5,6-hexane hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates are mellitic acid, pyromellitic acid and phthalic acid derivatives disclosed in BP 1,425,343.

Of the above polycarboxylates, hydroxycarboxylates having up to three carboxyl groups per molecule, especially citrates, are preferred.

The starting acids of the monomeric and oligomeric polycarboxylate chelating agents or mixtures thereof and mixtures of their salts, such as citric acid or mixtures thereof with citrates, are also considered to be useful binding (carrier) components.

Borate binders as well as the borate-forming binder components for detergent storage or washing are also useful, but are not preferred under washing conditions below 50 ° C, especially below 40 ° C.

Examples of carbonate binder components are the alkaline earth and alkali metal carbonates, including n- and acidic sodium carbonate, and mixtures thereof with ultrafine calcium carbonate, described in German Application No. 2,321.001, published November 15, 1973.

Specific examples of water-soluble phosphate binder components are alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymer / phosphate with a degree of polymerization

6-21, and salts of phytic acid.

Suitable silicates are water-soluble sodium silicate having a SiO ₂ : Na ₂ O ratio of 1.0-2.8, more preferably 1.6-2 / 4, and most preferably 2.0. The silicates may be in the form of an anhydride or a hydrated salt. Sodium silicate with a ratio of 2.0 is the most preferred silicate.

Silicates are included in the detergent composition of the invention in an amount of 5-50%, more preferably 10-40% by weight of the composition.

Partially soluble and insoluble binder (carrier) component

The detergent compositions of the invention may comprise a partially soluble or insoluble carrier component in a typical amount of 1-80%, more preferably 10-70%, and most preferably 20-60% by weight of the composition.

An example of a partially soluble component are crystalline layered silicates. Examples of water-insoluble components are sodium aluminosilicates.

Crystalline layered sodium silicates have the general formula NaMSi2χ + ι · Υ ^Η 2 ° 'where 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 sodium silicates of this type are described in EP-A-0164514, and methods for their preparation in DE-A-3417649 and DE-A-3742043. For the purposes of the present invention, x in the formula above has a value of 2, 3, or 4, preferably 2. The most preferred material is delta-Na ₂ Si ₂ O ₅ , supplied by Hoechst AG under the designation NaSKS-6.

The crystalline layered sodium silicate material is preferably used in granular detergent compositions as a tightly particulate particulate solid, water-soluble ionizable material for which some of the organic acid, organic and inorganic acid salts, and mixtures thereof are selected.

Suitable aluminosilicate zeolites Formula base unit ₂ C (Α1Ο _{2) ζ} (3ίΟ ₂₎ γ] H ₂ O, the emanations are at least 6; the molar ratio of z is 1.0: 0.5, and x is at least 5, preferably 7.5-276, more preferably 10-264. The aluminosilicate material is in hydrated form and preferably crystalline, containing

% 10-28, more preferably 18-22 wt. bound water.

The aluminosilicate ion exchange materials may be of natural origin, but synthetic is preferred. Synthetic crystalline aluminosilicate ion exchangers are available under the designation Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite MAP, Zeolite HS, and mixtures thereof. Zeolite A has the formula: Na ₁ 2 / ( ^A10 2 ^ 12 ^ ^s ^ ° 2 ^ 12 ^{, xH} 2 ° 'where - 3 ^e 20-30, most preferably 27. Zeolite X has the formula Na ^ g ^: [(AlO2) 86 (SiO2) 106] .2 ⁷ 6H2O. Γ

Masking of heavy metal ions

The detergent compositions of the present invention comprise as a preferred optional component a heavy metal ion masking agent. By this is meant the components used herein to form a chelate (complex) with heavy metal ions. These components also have a chelating capacity for calcium and magnesium, but preferably exhibit selectivity in binding heavy metal ions such as iron, manganese and copper.

These heavy metal ion chelators (maskers) are usually present in an amount of 0.005-20%, preferably 0.1-10%, more preferably 0.25-7.5% and most preferably 0.5-5% by weight of the composition.

These heavy metal ion chelators are acidic in nature, for example having phosphonium and carboxyl functional groups, and may be present either in their acid form or as a complex / salt with a suitable tick ion, such as an alkali or alkali metal ion, ammonium, or substituted ammonium, or any mixtures thereof. Water-soluble complex / salt is preferred. The molar ratio of said countercation to the chelate is preferably at least 1: 1.

Suitable heavy metal ion chelators for use herein are organic phosphonates such as amino-alkylene-poly- (alkylene-phosphonates), ethane-1-hydroxy-diphosphonates and alkali metal nitrilo-trimethylene-phosphonates.

Of the above, preferred are diethylene triamine penta (methylene phosphonate), ethylenediamine tri (methylene phosphonate), hexamethylenediamine tetra (methylene phosphonate) and hydroxyethylene 1,1-diphosphonate.

Other suitable chelating agents are nitrilo-triacetic acid and polyaminocarboxylic acids such as ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid, and salts thereof.

Particularly preferred is ethylenediamine-N, N-disuccinic acid (EDDS) or its alkali metal, caustic earth, ammonium or substituted ammonium salts thereof. Preferred EDDS compounds are the free acid form and the sodium or magnesium salt, or a complex thereof. Examples of preferred sodium EDDS salts are Na ₂ EDDS and Na ₃ EDDS. Examples of preferred magnesium EDDS complexes are MgEDDS and Mg ₂ EDDS.

Other preferred heavy metal ion chelators for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid described in EP-A-317.542 and EP-A-399.133.

Also preferred are the chelating agents: iminodiacetic acid-N-2-hydroxypropylsulfanoic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid, described in EP-A-516.102. Also suitable are beta-alanine-N, N-diacetic acid, asparagyl-N, N-diacetic acid, aspargyl-N-monoacetic acid and imino-disuccinic acid as described in EP-A-509.382.

EP-A-476,257 discloses amine-based chelates. EP-A-510,331 describes suitable chelants derived from collagen, keratin or casein. EP-A-528.859 discloses chelating agents with alkyl iminodiacetic acid. Dipicolinic and 2-phosphonobutane-1,2,4-tricarboxylic acid as well as glycinamide-N, N-disuccinic acid (GADS) are also suitable.

Enzyme stabilizing system

Preferred enzyme compositions also contain 0.001-10%, more preferably 0.005-8%, and most preferably 0.01-6% by weight of the enzyme stabilizer. The enzyme stabilizer may be any stabilizing system that is compatible with the purification enzyme. Such a stabilizing system may include calcium ion, boric acid, propylene glycol, short chain carbon acid, mountain acid, and mixtures thereof. It may also contain reversible enzyme inhibitors such as a reversible protease inhibitor.

The compositions of the invention further comprise 0-10%, more preferably 0.01-6% by weight of a chlorine scrubber which prevents the chlorine added frequently to the drinking water from attacking and inactivating the enzyme, especially in a basic environment.

Although the level of chlorine in the water is low, typically 0.5-1.75ppm, the amount of chlorine in the total volume of water coming into contact with the enzyme during washing is considerable and therefore the stability of the enzyme could be problematic.

Suitable anionic chlorine scavengers are widely known as salts containing ammonium cations or sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc. Antioxidants such as carbamates, ascorbates, etc., organic amines such as ethylenediaminetetraacetic acid may also be used. (EDTA) or its alkali salts, monoethanolamine (MEA), and mixtures thereof. If desired, other scavengers such as bisulfate, nitrate, chloride, hydrogen peroxide sources such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate as well as phosphate, condensed phosphate, acetate, benzoate may be used. , citrate, formate, lactate, malate, tartrate, salicytate, etc., and mixtures thereof.

Organic polymer compounds

Organic polymeric compounds are particularly preferred components of the detergent compositions herein. By this is meant essentially any polymeric organic compound commonly used in detergent compositions as a dispersant and an anti-redeposition agent (sludge re-settling) and a soil suspending agent.

The organic polymeric compound is used in a detergent composition of the invention in a typical amount of 0.1-30%, more preferably 0.5-15%, and most preferably 1-10% by weight of the composition.

Examples of organic polymeric compounds are the water-soluble organic homo- and co-polymeric polycarboxylic acids and their salts, in which the polycarboxylic acid consists of at least two carboxylic radicals separated from each other by not more than two carbon atoms. Polymers of this latter type are described in GB-A-1,596,756. Examples of salts

are polyacrylates having a molecular weight of 2000-5000, and copolymers thereof with maleic anhydride, and such copolymers have a molecular weight of from 20,000 to 100,000, more preferably 40,000-80,000.

Other acrylamides and copolymers suitable organic polymers are polymers of acrylates having a molecular weight of 3,000-100,000, acrylates and fumarate with a mol. weight

2.000-80.000.

Also useful herein are aspartic acid derivatives, polyamino compounds including those described in EP-A-305282,

EP-A-305283 and EP-A-351629.

Also suitable herein is the use of terpolymers composed of maleic, acrylic, polyaspartic and vinyl alcohol, especially those with an average molecular weight of 5,000-10,000.

Other polymeric compounds suitable for incorporation into detergent compositions are cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose.

Other useful polymeric compounds are polyethylene glycols in particular having a molecular weight of 1000-10000, more preferably 2000-8000, and most preferably about 4000.

Lime-soap dispersion compounds

The compositions of the invention may comprise a lime soap dispersion compound having a lime soap dispersion force (LSDP) as defined below up to a value of 8, more preferably a value of 7, and most preferably a value of 6. This dispersion compound is preferably present in an amount of 0. 1-40%, more preferably 1-20%, and most preferably 2-10% by weight of the composition.

The lime-soap dispersant is a material that prevents the precipitation of alkali, ammonium and amino salts, fatty acids by calcium or magnesium. The numerical value of the efficacy of the lime soap dispersant is given by the lime soap dispersion force (capacity) (LSDP), which is determined by the dispersion test described in the article by HC Borghetty and CABergman, J. Am.Oil. Chem. Soc., Vol. 27, pp. 88-90 (1950). This method is widely used by practitioners in the art, and is disclosed, for example, in the following review articles: WNLinfield, Surfacant Science Series vol. 7, pp. 3? Tenside Surf, WNLinfield. Det., Vol. 27, pp. 159-161 (1990); and Μ. K. Nagara Jan, WF Masler, Cosmetics and Toiletries, Vol. 104, pp. 71-73, (1989). LSDP is the weight ratio of dispersant to sodium oleate needed to disperse the lime soap deposits formed with 0.025 grams of sodium oleate in 30ml of water with a hardness equivalent of 333ppm CaCO ₃ (Ca: Mg = 3: 2).

Surfactants (surfactants) with good dispersing capacity include certain amine oxides, betaines, sulfobetaines, alkyl 1-ethoxy sulfates and ethoxylated alcohols.

Exemplary surfactants having a LSDP of no more values to 8 used according to the invention comprise C ₁₆ _ ₁₈ -dimetylaminoxid, _1Q _ C ₁₂ alkyl ethoxysulfates with an average degree of ethoxylation of from 1-5, particularly _C12-alkyl _i5 surfactants ethoxylated sulfates with a degree of ethoxylation of about 3 ( LSDP = 4), and C ₁₃ _ ₁₅ -etoxylované alcohols centered budf degree of ethoxylation of 12 (LSDP = 6) or; 30, sold by BASF GmbH under the trade names Lutensol A012 and Lutensol A030.

Polymeric lime-soap dispersants suitable for use herein are described in M. K. Nagarajan and W. F. Masler, Cosmetics and Toiletries, Vol. 104, pp. 71-73, (1989). Examples of such dispersants are certain water-soluble salts of copolymers of acrylic acid, methacrylic acid or mixtures thereof, and acrylamide or substituted acrylamide, wherein the typical molecular weight of such polymers is 5,000-20,000.

Soap suppression system

The detergent formulations of the invention formulated for machine washing preferably contain some suds suppressant system in an amount of 0.01-15%, more preferably 0.05-10%, and most preferably 0.1-5% by weight of the composition.

Suitable suppression systems may include any known antifoam compound, including, for example, silicone 2-alkyl and alkanol antifoam compounds.

By anti-foam compound is meant any compound or mixture of compounds which acts to suppress foaming or suds formation caused by a detergent solution solution, especially when mixing the solution.

A preferred suds suppression system consists of:

(a) antifoam compounds, more preferably silicone antifoam compounds, and most preferably silicone antifoam compounds consisting of a combination of (i) polydimethylsiloxane in an amount of 50-99%, more preferably 75-95% by weight of a silicone antifoam compound; and (ii) silica (silica) in an amount of 1-50%, more preferably 5-25% by weight of the silicone / silica antifoam compound, wherein said silica / silicone antifoam combination is provided in an amount of 5-50%, more preferably 10-40% by weight;

(b) dispersing compounds, most preferably consisting of a rake silicone-glycol copolymer having a polyoxyalkalene content of 72-78% by weight, and an ethylene oxide to propylene oxide ratio of 1: 0.9 to 1: 1.1, in an amount of 0.5-10% by weight %, more preferably 1-10 wt. a particularly preferred silicone-glycol rake copolymer of this type is DC0544, commercially available from DOW Corning under the trade designation DC0544;

(c) an inert carrier fluid consisting of ethoxylated ethoxylation of 5-50, more preferably 10-70% by weight.

A preferred system for suppressing the formation of a compound, preferably an alcohol C ₁₆ _ ₁₈ with a degree of 8-15 in an amount of from 5 to 80% suds for use herein comprises a mixture of an alkylated siloxane of the aforementioned type, and solid silica.

The solid silica may be fumed, precipitated, or prepared by a gel forming technique. Its particles have an average size of 0.1-50 microns, preferably 1-20 microns, and a surface area of at least 50m ² / g. These particles can be made hydrophobic by the action of dialkylsilyl and / or trialkylsilyl groups, either by coupling directly or with the aid of a silicone resin. Particles hydrophobised with dimethyl and / or trimethylsilyl groups are preferred. The antifoam compound suitable for the detergent compositions of the invention preferably comprises an amount of silica such that the weight ratio of silica: silicone is in the range of 1: 100 to 3:10, more preferably 1:50 to 1: 7.

Another suitable soap suppression system is hydrophobically silane (most preferably trimethylsilane) silica having a particle size of 10-20 nanometers and a specific surface area above 50 m ² / g, intimately mixed with a fluid dimethyl silicone of molecular weight 500-200.000 at a silicon: silane oxide weight ratio 1: 1 to 1: 2.

A very preferred soap suppression system is described in EP-A-0210731 and consists of a silicone antifoam compound and an organic carrier having a melting point of 50-85 ° C, wherein the organic carrier consists of a monoester of glycerin and a 12-20 carbon chain fatty acid carbon. Another such preferred system is described in EP-A-0210721, wherein the organic carrier is a fatty acid or alcohol having a chain of 12-20 carbon atoms, or mixtures thereof, with a melting point of 45-80 ° C.

Another highly preferred suds suppression system is disclosed in related European Application 91870007.1 to Procter and Gamble Co .; these systems comprise a silicone antifoam compound, a carrier material, an organic coating material, and glycerin with a glycerin: silicone weight ratio of 1: 2 to 3: 1. Related European Application 91201342.0 also discloses as a highly preferred suds suppression system consisting of a silicone antifoam compound, a carrier material, an organic coating and a crystalline or amorphous aluminosilicate at an aluminosilicate: silicone weight ratio of 1: 3 to 3: 1. Starch is the preferred carrier in both of the highly preferred granular soap control agents described.

An exemplary soap suppression system is an agglomerated component formed by an agglomeration process consisting of:

(i) 5-30%, preferably 8-15% by weight, of a component with a silicone antifoam compound, preferably consisting of a combination of polydimethylsiloxane and silica.

(ii) 50-90%, preferably 60-80% by weight, of a component comprising a carrier material, preferably starch;

(iii) 5-30%, preferably 10-20% by weight of a component comprising an agglomerating binder, wherein such a binder may be any compound or mixture typically used as an agglomerating binder; the most preferred such agglomerating binder compound is an ethoxylated C 18 ^-is alcohol ^{with a} 50-100 ^{degree of} ethoxylation; and (iv) 2-15%, preferably 3-10% by weight of fatty cid Hydrated C ₁₂ _ _18th

Polymeric dye transfer inhibitors

The detergent compositions of the invention may also contain 0.01-10%, preferably 0.05-0.5% by weight of a polymeric dye transfer inhibitor.

Polymeric N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, and combinations thereof are preferably selected as polymeric dye transfer inhibiting agents.

a) Polymers of polyamine N-oxide

The polyamine-N-oxide aqueous polymers for use in the present invention comprise cells having the following structural formula:

Ax i

Wherein P is a polymerizable cell to which an R-N-O group may be attached, or the R-N-O group is part of a polymerizable cell, or a combination of both;

0 0

II II II

AjcNC, CO, C, -O-, -S-, -N-; x Is 0 sky 1;

R is aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic groups, or combinations thereof, to which nitrogen of the N-O group can be attached or in which the nitrogen of the N-O group is part of these groups.

The N-0 group is represented by the following structural formula:

and 0 ^{(R 1) x} f 2 ^{R) y} '= N (R ₁₎ x (R3) _z or wherein Rl, R2, and R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or / and y or / az is zero or 1, and wherein the nitrogen of the N-O group may be attached to or part of these groups. Group

N-O may be part of a polymerizable link (P) or may be 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 cell are polyamine N-oxides in which aliphatic, aromatic, alicyclic or heterocyclic groups are selected as R. Preferred polyamine N-oxides are those in which R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidone, piperidine, quinoline, acridine, and derivatives thereof.

Another class of these polyamine-N-oxides is the group of polyamine-N-oxides in which the N-O group is attached to the R group. Other suitable polyamine-N-oxides are those in which the N-0 group is attached to the polymerizable cell .

A preferred class of polyamine N-oxides are those having the general formula (1) and R is an aromatic, heterocyclic or alicyclic group in which the nitrogen of the N-O function is part of the R group. Examples of this class are polyamine-N-oxides wherein R is a heterocyclic compound such as pyridine, pyrrole, imidazole, and derivatives thereof.

Another preferred class of polyamine N-oxides are those having the general formula (1) and R is an aromatic, heterocyclic or alicyclic group in which the nitrogen of the N-O function is attached to said R group. Examples of this class are polyamine oxides, wherein the R groups are aromatics such as phenyl.

Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has color transfer inhibiting properties. Examples of suitable backbones are polyvinyl, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof.

The amine-N-oxide polymers of this invention have a typical amine to amine-N-oxide ratio of 10: 1 to 1: 1000000. However, the number of amine oxide groups in the polyamine oxide polymer can be varied by appropriate copolymerization or by a suitable degree of

N-oxidation. A ratio of amine to amine N-oxide of 2: 3 to 3 is preferred

1: 1000000, more preferably 1: 4 to 1: 1000000, and most preferably is

1: 7 to 1: 1000000. The polymers of this invention include non-oriented or block copolymers in which one monomer type is an amine N-oxide and the other is either an amine N-oxide or nothing. The polyamine N-oxide amine oxide cell has a PKa < 10, more preferably PKa < 7, most preferably PKa < 6.

The polyamine oxides can be obtained at any degree of polymerization. The degree of polymerization is not critical provided the material has the necessary water solubility and color retention capability. A typical mean molecular weight is 500-1,000,000, preferably 1,000-50,000, more preferably 2,000-30,000, and most preferably 3,000-20,000.

b) Copolymers of N-vinylpyrrolidone and N-vinilimidazole

Preferred polymers of the invention are copolymers

N-vinylimidazole and N-vinylpyrrolidone having an average molecular weight of 5,000-50,000, more preferably 8,000-30,000, and most preferably 10,000-20,000. Conveniently

N-vinylimidazole-N-vinylpyrrolidone copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone of 1: 0.2, more preferably

0.8: 0.3, and most preferably 0.6: 0.4.

c) Polyvinylpyrrolidone

Polyvinylpyrrolidone (PVP) having a mean molecular weight of 2,500-400,000, preferably 5,000-200,000, more preferably 5,000-50,000, and most preferably 5,000-15,000 is also used in the detergent compositions of the invention. A suitable polyvinylpyrrolidone is commercially available from ISP Corporation

New York and Montreal, Canada, under the trade names PVP K-15 i (average molecular weight 10,000), PVP K-30 (average molecular weight 40,000), PVP K-60 (average molecular weight 160,000) and PVP K- 90 (average molecular weight 360.000). Other suitable polyvinylpyrrolidones commercially available from BASF

Cooperation are Sokalan HP 165 and Sokalan HP 12.

Polyvinylpyrrolidone is used in the detergent compositions of the invention in an amount of 0.01-5%, preferably 0.05-3%, and more preferably 0.1-2% by weight of the detergent. The amount of polyvinylpyrrolidone delivered to the wash solution is 0.5-250ppm, more preferably 2.5-150ppm, and most preferably 5-100ppm.

d) Polyvinyloxazolidone

Polvinyloxazolidone is also used as a polymeric dye transfer inhibiting agent in the detergent compositions of the present invention. These are polyvinyloxazolidones with an average molecular weight of 2,500-400,000, preferably 5,000-200,000, more preferably 5,000-50,000, and most preferably 5,000-15,000.

Polyvinyloxazolidone is used in the detergent compositions of the invention in an amount of 0.01-5%, more preferably 0.05-3% and most preferably 0.1-2% by weight of the detergent. The amount of polyvinyloxazolidone fed to the wash solution is 0.5-250ppm, more preferably 2.5-150ppm, and most preferably 5-100ppm.

(e) Polyvinylimidazole

Polvinylimidazole is also used as a polymeric dye transfer inhibiting agent in the detergent compositions of the present invention. These polyvinylimidazoles have an average molecular weight of 2,500-400,000, more preferably 5,000-50,000, and most preferably 5,000-15,000.

Polyvinylimidazole is used in the detergent composition in an amount of 0.01-5%, more preferably 0.05-3%, and most preferably 0.1-2% by weight of the detergent. The amount of polyvinylimidazole introduced into the wash solution is 0.5-250ppm, more preferably 2.5-150ppm, and most preferably 5-100ppm.

Optical brightening

Also, 0.005-5% by weight of a certain type of hydrophilic optical brightener, which also has a color transfer inhibiting effect, is used in the detergent compositions.

If used, the composition of the invention will preferably contain 0.01-1% by weight of the optical brightener

The hydrophilic optical brighteners used according to the present invention have the structural formula:

wherein R 11 is selected from anilino, N-2-bis-hydroxymethyl 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 the above formula R 1 is anilino, R ₂ is N-2-bis-hydroxyethyl and M is cation eg sodium, then the brightener is 4,4-bis [(4-anilino-6- (N-2-bis- hydroxyethyl) -s-triazinyl) amino] -2,2-stilbenedisulfonic acid and the disodium salt. This special type of brightener is sold under the trade name Tinopal-UNPA-GX by Ciba-Geigy.

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

When R 6 in the above formula is anilino, and when R _{2 is} N-2-hydroxyethyl-N-2-methylamino and H is a cation, e.g. sodium, the brightener is 4,4-bis-14-anilino -6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2,2-stilbenedisulfonic acid-disodium salt. This type of brightener is sold under the trade name Tinopal 5BM-GX by Ciba Geigy.

If R 1 in the above formula is anilino, R _{2 is} morpholino, and M is cationic sodium, then the brightener is 4,4-bis- [4-anilino-6-morphilino-s-triazin-2-yl) stilbenedisulfonic acid-sodium salt .

amino] 2,2 This type of brightener is sold under the trade name Tinopal AMS-GX by Ciba Geigy.

The specific type of optical brightener chosen for use in the present invention provides the advantage of a particularly effective color transfer inhibitor when used in combination with the polymeric color transfer inhibiting agents described above. The combination of these selected polymeric materials (eg, PVNO and / or PVPVI) with these selected optical brighteners (eg, Tinopal UNPA-GX, Tinopal 5BM-GX and / or Tinopal AMS-GX) provides significantly better inhibition of color transfer in aqueous wash solutions, than each of the two detergent components when used alone. Without wishing to be bound by theory, it is believed that these brighteners work in this manner because they have a high affinity for the textile material in the wash solution and therefore deposit thereon relatively quickly. The extent to which the brighteners are deposited on the fabric in the wash solution can be defined by a parameter called the exhaustion coefficient. This coefficient is generally the ratio of a) the fabric-brightener material to b) the initial brightener concentration in the wash solution. In the context of the present invention, brighteners with a relatively high exhaustion coefficient are most suitable for inhibiting color transfer.

It will be appreciated, however, that other conventional optical brighteners may be selected and used in detergent compositions to achieve conventional brightening of the textile material rather than actual inhibition of color transfer. Such use is conventional and well known to detergent formulators.

Softening agents

According to the present invention, laundry softening agents are also incorporated into the laundry detergent composition. These agents may be of the inorganic or organic type. An example of inorganic plasticizers is the smectite clay described in GB-A-1 400 898. Organic textile softeners contain the water-insoluble tertiary amines disclosed in GB-A-1 514 276 and in EP-B-0 011 340.

The amount of smectite clay added is in the range of normally 5-15%, more preferably 8-12% by weight, wherein the material is added as a mixed component to the rest of the formulation. Organic fabric softeners such as water-insoluble tertiary amines or long double-chain amides are used in an amount of 0.5-5% by weight, normally 1-3% by weight, while high molecular weight polyethylene oxides and water-soluble cationic materials are used in the amount 0.1-2%, normally 0.15-1.5% by weight.

Other optional ingredients

Other optional ingredients suitable for incorporation into the detergent compositions of the invention include fragrances, colorants and filler salts, with sodium sulfate being a suitable filler.

Form of detergent compositions

The detergent compositions of the invention may be formulated in any desired form, such as powders, granules, pastes, liquids and gels (jellies). It is not preferred that the compositions be in the form of tablets, most preferably in the form of granules

Liquid detergent compositions

The detergent compositions of the present invention can be formulated as liquid detergent compositions. Such liquid detergent compositions typically comprise 94-35%, more preferably 90-40%, and most preferably 80-50% by weight of a liquid carrier such as water, more preferably a mixture of water and an organic solvent.

Gel preparations

The detergent compositions of the invention may also be in the form of a gel. Such typical compositions are formulated with a polyalkenyl polyether having a molecular weight of 750,000-4,000,000.

of the invention preferably as a powder or composition of 450g / liter,

Solid means

The detergent compositions herein are formulated in the form of solids, granules.

It is preferred that the particle size of the granular composition be such that at most 5% of the particles are larger than 1.4mm in diameter, and at most 5% of the particles are smaller than 0.15mm in diameter.

The bulk density of the granular detergent according to the invention is typically at least more usually at least 600g / liter, and most preferably

650-1200 g / liter.

The bulk density is measured by a simple funnel-cup device consisting of a conical funnel fixedly mounted on a base and provided with a flap at the lower end to allow the contents of the funnel to be emptied into an axially positioned cylindrical vessel under the funnel. The funnel has 130mm at the top and 40mm at the bottom. It is mounted so that the lower end is 140 mm above the top surface of the substrate. The container has a total height of 90mm, an internal height of 87mm and an internal diameter of 84mm. Its nominal volume is 500ml.

The measurement is carried out by manually filling the funnel with the powder, opening the flap, and filling the powder with the powder. The filled container is removed from the frame and the excess powder is withdrawn with a straight tool such as a knife. The full container is then weighed and the powder value obtained is doubled to obtain a bulk density in g / liter. The measurement is repeated as necessary.

Manufacturing processes— granular means

The general granular detergent compositions of the present invention can be made by a variety of methods including dry mixing, spray drying, agglomeration and granulation.

Washing methods

The compositions of the invention can be used in virtually any washing or cleaning method, including machine washing and dishwashing methods.

Machine dishwashing

A preferred method of machine dishwashing is to wash the soiled items of glass, pots, cutlery and cutlery and clumps thereof with an aqueous solution with dissolved or dispersed effective amounts of the machine dishwashing composition of the present invention. By an effective amount of the composition is meant typically 8-60g of product dissolved or dispersed in a 3-10 liter wash solution, which are typical product doses and solution volumes commonly used in conventional machine dishwashing methods.

Rack washing methods

Machine washing methods consist of washing dirty laundry with an aqueous washing solution in a washing machine in which an effective amount of the machine washing detergent composition of the present invention is dissolved or dispersed. The detergent can be added to the washing solution either through the dispersion drawer of the washing machine or by means of a distributor device. A typical effective amount of detergent composition is 40-300g of product dissolved or dispersed in a wash solution of 5-65 liters, which are typical product and solution volumes commonly used in conventional machine washing methods.

In a preferred washing method, a dispensing device containing an effective amount of detergent composition is inserted into the drum of the washing machine, preferably with front loading, before the start of the washing cycle.

The dispensing device is a detergent container used to deliver the product. Its volume must be such that the detergent composition is in quantity, directly into the washing machine. contained enough that is normally used in washing.

After the washing machine has been filled with laundry, the dispenser containing the detergent composition is placed in the drum. At the beginning of the washing cycle of the machine, water is introduced into the drum, which begins to rotate periodically. The design of the dispensing device must be such as to allow it to be filled with dry detergent composition, but thereafter to allow release of the composition during the wash cycle as a result of agitation as the drum rotates and also as a result of immersion of the composition in the wash water.

For this release of the detergent product during washing, the dispensing device must have a number of openings through which the composition can pass. Alternatively, the device may be made of a material which is liquid pervious and impermeable to the solid product, allowing release of the dissolved composition. It is preferred that the detergent composition be rapidly released at the beginning of the wash cycle to provide a transient locally high concentration of components such as a water-soluble binder (base) component and a heavy metal ion masking component at this stage of the wash cycle. .

Preferred dispensing devices are reusable and are designed so that their integrity is maintained both in the dry state and during the wash cycle. Particularly preferred dispensing devices useful in accordance with the present invention have been described in the following patents: GB-B-2,157,717, GB-B-2,157,718, EP-A-0201376, EP-A-0288345 and EP-A-0288346.

Article by J. Bland, Manufacturing Chemist, sheet. 1989, pp. 41-46 also discloses a highly preferred dispersion device for granular detergents of the type commonly known as granulate.

Highly preferred dispensing devices are disclosed in published European Patent Applic. Publ. 0343069 and 0343070. This last application describes a device consisting of a flexible bag attached to a support ring forming an opening, the opening being adapted to allow a quantity of detergent sufficient for one wash cycle of the washing process, a portion of the washing medium flowing through the opening into the bag, dissolving the detergent, and the solution then flows out through the opening into the detergent medium. The carrier ring is provided with a mask preventing the wetted undissolved agent from flowing out; the mask arrangement consists of radial walls extending from the central protrusion in the form of a spoke wheel or the like in which the walls are helical.

The identification abbreviations of the detergent composition components have the following meanings;

XYAS: Sodium C1-C6-alkylsulfate

24EY: predominantly linear primary alcohol condensed i2-14 ^C with an average of Y moles of ethylene oxide

XYEZ; Predominantly linear primary C1-C4-y-alcohol condensed on average with Z moles of ethylene oxide

XYEZS: Sodium C1-C4-y-alkylsulfate condensed on average from mole of ethylene oxide per mole

TFAA; C ₁₆ -C ₁₈ -alkyl N-methylglucamide

Silicate: Amorphous sodium silicate (SiO ₂ : Na ₂ O = 2.0 ratio)

NaSKS-6: Crystalline layered silicate with the formula delta-Na ₂ Si ₂ O ₅

Carbonate; Anhydrous sodium carbonate

Polycaroboxylate: 1: 4 maleic acid / acrylic acid copolymer, average molecular weight 80,000

Zeolite A: Hydrated sodium aluminosilicate of formula Na ₁₂ (AlO ₂ SiO ₂ ) ₁₂ .27H ₂ O with primary particle size 1-10 microns

Citrate: Trisodium citrate dihydrate

Percarbonate: Whitening anhydrous sodium porkarbonate with emporic (fast-releasing particles)

Percarbonate: (slow-release particles)

TAED:

TAED:

(slowly released particle)

Benzoyl-:

caprolactam (slowly released particle)

TAED:

(slowly released particle)

EDDS:

(slowly release particles) Protease:

Amylase:

with the formula 2Na ₂ CO ₃ .3H ₂ O ₂ coated with a mixed salt of the formula Na ₂ SO ₄ .n.Na ₂ CO ₃ , where n is 0.29 and the weight ratio of percarbonate to mixed salt is 39: 1

Bleaching anhydrous sodium percarbonate coated with sodium silicate (SiO ₂ : Na ₂ O = 2: 1 ratio) at a percarbonate to silicate weight ratio of 39: 1

Tetraacetyl-ethylenediamine

A particle formed by agglomeration of TAED with citric acid and polyethylene glycol (PEG) of mol. weight = 4.000, at a weight ratio of TAED: citric acid: PEG 75:10:15, coated with an outer coating of citric acid at an agglomerate: citric acid weight ratio of 95: 5

Particle formed by agglomeration of benzoyl-caprolactam (BzCl) with citric acid and polyethylene glycol (PEG) by mol. weight = 4,000, with the weight ratio of BzCl: acid components. citric acid: PEG 63:21:16, coated with an outer coating of citric acid at wt. agglomerate: acid ratio lemon 95: 5

Particle formed by agglomeration of TAED with partially neutralized polycarboxylate at a weight ratio of TAED: polycarboxylate of 93: 7, coated with polycarboxylate at wt. agglomerate: coating ratio 94: 6

Particle formed by spray drying EDDS with MgSO ₄ at a weight ratio of 26:74

Proteolytic enzyme sold under the trade name Savinase by Novo Industries A / S having an activity of 13 KNPU / g.

Amylolithic enzyme sold under the commercial

Cellulose

Lipase

CMC:

HEDP

EDDS:

PVNO:

Granulám! soap foam suspensor (inhibitor)

Metasilicate: Phosphate: 480N:

PB1:

Cationic: lactam

DETPMP:

Bismuth nitrate

Paraffin

BSA termed Termamyl 60T by Novo Industries A / S with an activity of 300 KNU / g

Cellulosolytic enzyme sold by Novo Industries A / S with activity 1000 CEVU / g Lipolytic enzyme sold under the trade name Lipolase by Novo Industries A / S with activity 165 KLU / g

Carboxymethylcellulose sodium salt

1,1-hydroxyethane-diphosphonic acid

Ethylenediamine-Ν, Ν-disuccinic acid (S, S) -isomer, in the form of the sodium salt

Poly (4-vinylpyridine) -N-oxide, a copolymer of vinylimidazole and vinylpyrrolidone with an average molecular weight of 10,000

12% silicone / SiO ₂ , 18% stearyl alcohol, 70% starch in granular form

Mixed ethoxylo- / propoxylated fatty alcohol ^c 13-15 ^with P ^r ethoxylation degree 3,8 and avg. degree of propoxylation 4.5, sold under commer. named Plurafac LF404 by BASF GmbH (weak foaming)

Sodium metasilicate (SiO ₂ : Na ₂ O ratio = 1,0) Sodium tripolyphosphate

3: 7 non-oriented acrylic / methacrylic acid copolymer, medium mol. 3.500 Sodium perborate monohydrate, anhydrous - in the form of compact particles delaying the release of hydrogen peroxide

Cationic peroxyacid bleach precursor-trialkylammonium methylene-C8-alkyl-caprolactam salt with tosylate

Diethylene-triamine-penta (methylenephosphonic acid), sold under the name Dequest 2060 by Monsanto bismuth nitrate salt

Paraffin oil sold under the name Winog 70 by Wintershall

Amylolytic enzyme sold under the name LE17 by Novo Industries A / S (approximately 1% enzyme activity)

Sulfate: Anhydrous sodium sulfate pH: Measure a 1% solution in distilled water at

Deň: 18 ° C

Example 1

The following laundry detergent compositions were prepared - the numbers indicate the weight percent of the component. Composition A is comparative, compositions B to E are according to the invention.

AND (B) C D E 45AS / 25AS 9.1 9.1 9.1 9.1 7.0 35AE3S 2.3 2.3 2.3 2.3 4.0 24E5 4,5 4,5 4,5 4,5 3.0 TFAA 2,0 2,0 2,0 2,0 2,0 Zeolite A 13.2 13.2 13.2 13.2 15.0 On SKS-6 / acid. lemon (79:21) 15.6 15.6 15.6 15.6 13.0 Krabonát 7.6 7.6 7.6 7.6 8.0 TAED (quick release) 6.3 - · - · TAED (slow release) 5.0 2.3 5.0 Benzoyl-caprolactam (slow release) ·· » 5.0 2.7 Percarbonate (fast release) 22.5 «A» 22.5 Percarbonate (slow release) - - 22.5 22.5 - - PB1 - - - - 16.0 DETPMP 0.5 0.8 - - - EDDS (fast release particle) 0.3 0.75 0.5 Protease 0.55 1,27 0.55 1,27 1.3 Lipase 0.15 0.15 0.15 0.15 0.2 Cellulose 0.28 0.28 0.28 0.28 0.3 Amylase 0.27 0.27 0.27 0.27 0.3 Polycarboxylate 5.1 5.1 5.1 5.1 5.1 CMC 0.4 0.4 0.4 0.4 0.4 PVNO 0.03 0.03 0.03 0.03 0.03 Granular soap foam inhibitor (inhibitor) Tracks / miscellaneous up to 100% 1.5 1.5 1.5 1.5 1.5

For formulation A to D, the following T50 values were obtained (in seconds):

T50 AND (B) C D Protease <60 <60 <60 <60 Peroxyacid 130 190 205 240 AVO 95 225 230 115

Comparative tests

Test method - stain removal ·

Preparation of rag samples ·

Three white cotton sheets were prewashed in a non-biological strong detergent without bleach. A set of six 6 x 6 cm test cloths was cut from each sheet. Spots were evenly painted on each set of cloths.

In addition, EMPA pre-treated cloths were also used.

In total, the following cloth sets were used:

Enzymatic stains: Grease stain:

Grass White coffee

Bleachable spots: Lipstick

EMPA: Blood;

EMPA: Blood Milk Ink (BMI)

All sets of textile samples were subjected to one washing cycle in an automatic washing machine. Then the panel of experts evaluated stain removal using a four-point Scheffe scale. The combination of the averages of the paired results from each set of comparisons is shown below, where composition A is used as a reference. *

More details: The Miele 698WM washer was used and a short cycle of 40 ° C was selected. Hardness of water used: 12 ° German (Ca: Mg = 3: 1). 75 g of detergent was used in a dispenser in the middle of the laundry. One cloth of each type was washed together with 2.7 kg of ballast linen - slightly soiled sheets (1 week of home use).

Comparative testing - stain removal

The above test method was performed by comparing the effectiveness of composition B with reference composition A in removing stains of various types. The results were as follows:

Type of stains Result (PSU) EMPA: blood + 2,8 * EMPA BMI + 1,6 * Grass + 1,0 * White coffee + 1,1 * Lipstick +0.8

♦ Validity with a probability of 95%

Example 2

According to the invention, the following machine dishwashing compositions containing a bleaching component have been prepared (in parts by weight)

AND (B) C D E F G Citrate 15.0 15.0 15.0 15.0 15.0 15.0 480N 6.0 6.0 6.0 6.0 6.0 6.0 - Carbonate 17.5 17.5 17.5 17.5 17.5 17.5 - Phosphate - - - - - - 38.0 Silicate (as Si ° ₂ ) O what 8.0 8.0 03 / O 8.0 8.0 14.0 Metasilicate (as SiO ₂ ) 1,2 1/2 1,2 1/2 1,2 1,2 2.5 PNI 1,2 1/2 1.5 1.5 1/5 2.2 1,2 TAED (slow release) 2.2 2.2 2.2 3.5 • n 2.2 2.2 Cationic lactam - - - - 3.3 - - Paraffin 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Bismuth nitrate 0.2 0.2 0.2 0.3 0.4 0.2 Protease 2,0 2,0 2,0 2,0 2,0 2,0 2,0 Anyláza 1.5 1/5 1/5 1/5 1.5 1.5 - BSA - - - - - - 1.5

DETPMP 0.13 0.13 0.13 0.13 0.13 0.13 - HEDP 1.0 1.0 1.0 1.0 1/0 1/0 - Nonionic 2,0 2,0 2,0 2,0 2,0 2,0 1/5 Sulphate 23.0 22.8 22.4 22.7 22.2 21.5 0.3 various incl. humidity up to 100% pH (in 1% solution) 10.7 10.7 10.7 10.7 10.7 10.7 11.0

+ \) c

Claims (8)

Patent claims A detergent composition comprising (a) an enzyme; and (b) an organic peroxyacid bleach system, wherein the composition provides for delaying the release of the organic peroxyacid into the wash solution as compared to the enzyme release, such that in the T50 assay described herein, the time to reach a concentration equal to 50% of the maximum enzyme concentration is less than 120 seconds, and the time to reach a concentration equal to 50% of the maximum concentration of organic peroxyacid is greater than 180 seconds. The detergent composition of claim 1, wherein the time to reach a concentration equal to 50% of the maximum concentration of organic peroxyacid is 180-480 seconds. A detergent composition comprising (a) an enzyme; and (b) an organic peroxyacid bleach system, wherein the composition provides for delaying the release of the organic peroxyacid into the wash solution as compared to the enzyme release, such that in the T50 assay described herein, the time to reach a concentration equal to 50% of the maximum enzyme concentration is at least 100 seconds less than the time required to reach 50% of the maximum concentration of organic peroxyacid. The detergent composition of any one of claims 1-3, wherein the organic peroxyacid bleaching system comprises a combination of (i) a hydrogen peroxide source; and (ii) an organic peroxyacid bleach precursor compound (precursor) The detergent composition of claim 4, wherein the peroxyacid bleach starting compound (precursor) after perhydrolysis provides a peroxyacid which is (i) or (ii) perbenzoic acid or a non-cationic substituted derivative thereof; cationic peroxyacid The detergent composition of claim 5, wherein the peroxyacid bleach precursor compound (precursor) is a group consisting of: (a) amide-substituted bleach precursor, having the general formula: 0 0 II II R'4> N-R 2 -C-L, RS 0 0 II II R1-N-C-R2-C-L AND R 5 where R ¹ is an aryl or alkaryl group having 1-14 carbon atoms, R ² is arylene or alkarylene having 1-14 carbon atoms, R ⁵ is hydrogen or alkyl, aryl or alkaryl having 1-10 carbon atoms, L is a leaving group se group; or (b) bleach precursor N-acylated lactam of the formula: ⁰ í OC — CH2 — CH2 _and II. II ^R_C i wherein n is 0-8, preferably 0-2, R ⁶ is aryl-alkoxyaryl or alkaryl of 1-12 carbon atoms, or substituted phenyl of 6-18 carbon atoms; and mixtures a) and b) The detergent composition of claim 4, wherein the peroxyacid bleach precursor is Where is H, alkyl, 8. 9. ^K 2 ' ^m 3' is selected and R 5 is according to claim 4, wherein said is an inorganic perhydrate alkaryl, aryl, arylalkyl, and wherein the same or different substituents from the following: H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxy, amino, alkylamino, -COOR 9, wherein R 8 is H or alkyl and carbonyl functions. The detergent composition of claim 4, wherein said peroxyacid bleaching starting compound is tetraacetyl ethylenediamine. Detergent composition hydrogen peroxide salt source. The detergent composition of claim 9, wherein said inorganic perhydrate salt is an alkali metal percarbonate. A detergent composition according to any one of the claims 1-10, further comprising a bleach catalyst. The detergent composition of claim 11, wherein said bleach catalyst is a Mn ^IV 2 (µO) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononan) ₂ - (PFg) ₂ , Mn ^IIi: 2 (µ- O) (µ-OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononan) ₂ (C _{10 4} ) ₂ ; Mn ^IV 4 (µ-O) ₆ (1,4,7-triazacyclononan) _4- ( _C 10 ₄ ) ₂ ; Mn ^{I: CI} Mn ^IV 4 (u-0)! (u-OAc) _2- (1,4,7-trimethyl-1,4,7-triazacyclononan) _2- (C1O ₄ ) _3- i (1,4,7-trimethyl-1,4,7-triazacyclononan) (OCH ₃ ) ₃ (PFg) Co (2,2-bispyridylamine) Cl ₂ ; Di- (isothiocyanato) bispyridylamine cobalt (II); Tris-dipyridylamine-cobalt (II) perchlorate; Co (2,2-bispyridylamine) _2- O ₂ C10 ₄ ; Bis- (2,2 bispyridylamine) copper (II) perchlorate; Tris (di-2-pyridylamine) iron (II) perchlorate; Mn-gluconate; Mn (CF ₃ SO ₃ ) ₂ ; Co (NH ₃ ) ₅ Cl; binuclear Mn complexed with tetra-N-dentate and bi-Ndentate as ligand, including N ₄ Mn ^III (µO) 2Mh ^IV N4) and [Bipy ₂ Mn ^III (µ-0) 2Mn ^Iv bipy2] - (C10 ₄ ) ₃ and mixtures thereof. A detergent composition according to any one of the claims 1-12, which is free of chlorine as a bleach component. A detergent composition according to any one of the claims 1-13, which is not in the form of tablets. Use of a detergent composition according to any one of claims 1-14 in a method of washing laundry, wherein the detergent composition is incorporated into the wash solution by means of a dispensing device inserted into the drum of the washing machine before starting the wash.