ES2221042T3 - DETERGENT COMPOSITIONS. - Google Patents

Abstract

THE PRESENT INVENTION REFERS TO DETERGENT COMPOSITIONS WITH A PH OF AT LEAST 8.0 IN A 0.5% SOLUTION BY WEIGHT, OR TO COMPONENTS OF THE SAME CONTAINING CATIONIC TENSIOACTIVE FORMULA: R 1 R 2 R 3 R 4 N + X SUP, -, WHERE R 1 IS A HYDROXIALQUIL GROUP THAT DOES NOT HAVE MORE THAN 6 CARBON ATOMS; EACH ONE OF R 2 AND R 3 IS SELECTED INDEPENDENTLY FROM C 1-4 OR RENTED RENT; R 4 IS ONE OR MIXTURES OF MORE THAN A C SUB, 5-11 OR RENTED RENT; AND X - IT IS A CONTRAION THAT DOES NOT INTERACT MBIA WITH A HYDROXIDE ION AT 20 ° C, IN A SOLUTION OF 0.5% BY WEIGHT OF THE DETERGENT COMPOSITION.

Description

Detergent compositions.

Technical field

The present invention relates to compositions laundry detergents or their components, which contain a specific cationic surfactant for use under conditions of alkaline wash, which have a counterion carefully selected. The detergent compositions of the invention are for use to provide cleaning and disposal benefits of Enhanced grease stains

Background of the invention

The use of cationic surfactants in detergent compositions is known. For example, the GB document
2040990A describes granular detergent compositions comprising cationic surfactants.

The document EP-A-121949 also describes cationic surfactants for use in detergent compositions for laundry This reference describes a broad type of cationic surfactants.

Applicants have found that a group Particular of cationic quaternary ammonium surfactants give good cleaning properties, especially in grease stains oily

It has been found that cationic compounds they are particularly beneficial in detergent compositions that additionally comprise anionic surfactants. Unintentionally limited to theory, it is believed that cationic surfactants particulars used in the detergent compositions herein invention have surprisingly good solubility. In addition, they form an association in the presence of anionic components to produce surprisingly soluble anionic / cationic complexes that they lead to unexpected benefits of their behavior: the cationic surfactant quickly and effectively comes into contact with stains and penetrates quickly and breaks the stain giving An effective grease stain removal. In addition, it is believed that after the breakdown of oily dirt, the surfactants cationics used in the present invention also form complexes with fatty acids and any other breaking product loaded negatively produced, increasing its solubility and increasing the Total cleaning capacity and dirt removal oily

However, in processing or in use in alkaline detergent conditions, it has been found that some Cationic surfactants can produce bad odors in the wash. Although not wanting to limit itself to theory, it is believed that the bad odors occur due to the exchange of the counterion of the cationic surfactant with hydroxide ions in the wash water aqueous alkaline The quaternary ammonium hydroxide product that It turns out it can then produce amine by-products with bad smell. To avoid this problem when using alkaline conditions, the particular cationic surfactants must have a counterion that have greater relative selectivity for the cationic surfactant that a hydroxide ion in aqueous solution under the conditions of use.

Summary of the invention

In accordance with the present invention, provides a laundry detergent composition that has a pH of at least 8.5 in an aqueous solution at a concentration of 0.5% by weight, or its component, comprising an improver of the detergency, an anionic surfactant and a cationic surfactant of formula I:

(I) R 1 R 2 R 3 R 4 N + X -

in which R1 is a group hydroxyalkyl having no more than 6 carbon atoms; each R 2 and R 3 are independently selected from alkyl or C 1-4 alkenyl; R 4 is an alkyl or C 5-11 alkenyl; and X - is a counterion that it is not substantially exchanged with a hydroxide ion in a 0.5% aqueous solution by weight of the detergent composition a 20 ° C

In a further aspect of the invention, the cationic surfactant comprises a mixture of surfactants Cationic formula I:

(I) R 1 R 2 R 3 R 4 N + X -

in which R1 is a group hydroxyalkyl having no more than 6 carbon atoms; each R 2 and R 3 are independently selected from alkyl or C 1-4 alkenyl; R 4 is an alkyl or C 5-11 alkenyl; and X - is a counterion that it is not substantially exchanged with a hydroxide ion in a 0.5% aqueous solution by weight of the detergent composition at 20 ° C and wherein, in the mixture of cationic surfactants of formula I, at least 10%, preferably at least 20% or even at least 50% by weight of the cationic surfactant has R 4 which is alkyl or alkenyl C_ {5-9}.

According to one more aspect of the invention, the cationic surfactant comprises a mixture of surfactants of formula I, in which there is one more alkyl chain surfactant long that has R 4 with n carbon atoms where n is 8 to 11 and a shorter alkyl chain surfactant that has (n-2) carbon atoms.

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

Suitable counterions are generally those counterions that are more electronegative than ions hydroxide.

The compositions according to the invention are preferably substantially free of bleach.

Detailed description of the invention Cationic surfactant

The cationic surfactant is present generally in the composition or its component in an amount not greater than 60% by weight, preferably not greater than 20% or even 10% by weight, most preferably in an amount not exceeding 5% or 4.5% or even 3% by weight. The maximum amount of surfactant Cationic can even be as low as 1% by weight. The benefits of the invention are found even with very small amounts of the cationic surfactant of formula I. Generally there will be at minus 0.01% by weight, preferably at least 0.05% or at least 0.1% or even 0.25% by weight of the cationic surfactant in the detergent compositions of the invention.

R1 in formula I is a group hydroxyalkyl having no more than 6 carbon atoms and preferably, the OH group is separated from the nitrogen atom of the quaternary ammonium for no more than 3 carbon atoms. The groups Preferred R 1 are -CH 2 CH 2 OH, -CH 2 CH 2 CH 2 OH, -CH 2 CH (CH 3) OH and  -CH (CH 3) CH 2 OH.

-CH 2 CH 2 OH and -CH 2 CH 2 CH 2 OH they are most preferred and -CH2CH2OH is particularly favorite. Preferably R 2 and R 3 are selected each one between ethyl and methyl groups and most preferably both, R2 and R3 are methyl groups. Preferred R 4 groups they have at least 6 or even at least 7 carbon atoms. R 4 it can have no more than 9 carbon atoms, or even no more than 8 or 7 carbon atoms R 4 can be C 5-9 or C_ {11}. Preferred R 4 groups are alkyl groups linear Linear R 4 groups having 8 to 8 are preferred. 11 carbon atoms, or 7 to 9 carbon atoms. The groups More preferred R 4 are C 6-11 alkyl or a C 6-9 alkyl or C 11 alkenyl.

The counterion, X in formula I, can be any counterion that is not substantially exchanged with an ion hydroxide in a 0.5% aqueous solution by weight of the composition detergent at 20 ° C, so that the formation of foul-smelling compounds

An appropriate method to determine if the counterion is not substantially exchanged with a hydroxide ion it described in J. Phys. Chem. 1986, 90, 3366-3368 "Use of Reactive Counterion Type Micelles for the Determination of Selectivity Coefficients "by Maria da Graca Nascimento, Sebastiao A. F. Miranda and Faruk Nome. Preferred counterions for use in the present invention have a selectivity coefficient for the ion exchange in the presence of hexadecialtrimethylammonium ion at 25 ° C, of at least 2.5, preferably at least 3 or even at least 3.5 (see table I in the reference indicated above).

Suitable counterions usually have greater electronegativity than hydroxide ions. Examples Preferred are chloride, bromide and nitrate ions. It preferred particularly chloride

While in the scope of this invention are pure or substantially pure cationic compounds, it has found that mixtures of cationic surfactants of formula I can be particularly effective, for example, mixtures surfactants in which R 4 may be a combination of groups linear C 8 and C 10 alkyl, or C 9 alkyl groups and C_ {11}. According to one aspect of the invention in the composition there are present a mixture of cationic surfactants of formula I, the mixture comprising a chain I surfactant shorter alkyl and a longer alkyl chain surfactant of formula I. The cationic alkyl chain surfactant plus long is preferably selected from the surfactants of formula I in which R 4 is an alkyl group having n atoms carbon, where n is 8 to 11; chain surfactant shorter alkyl is preferably selected from those of formula I where R 4 is an alkyl group having (n-2) carbon atoms. In the systems of mixed cationic surfactants, generally there will be 5 to 95% in weight of longer alkyl chain surfactants, preferably 30 to 95%, more preferably at least 50% in weight referred to the total cationic surfactant. Generally there will be 5 to 95% by weight of shorter alkyl chain surfactant, preferably 5 to 70% by weight, more preferably 35 to 65% in weight. Preferably there will be at least 40% by weight of surfactant of shorter alkyl chain referred to total cationic surfactant in the detergent composition or its component.

Additional detergent components

Detergent compositions or their components according to the present invention may also contain additional detergent components. The concrete nature of these additional components, and their levels of incorporation, depend on the physical form of the composition or its component and on the specific nature of the washing operation for which They will use.

The compositions or their components of the invention preferably contain one or more components additional detergents selected from surfactants additional, detergency builders, sequestrants, bleaches, bleach precursors, catalysts bleaching, organic polymeric compounds, additional enzymes, soaps suppressants, limestone soaps dispersants, dirt and anti-redeposition agents additional, dirt release agents, perfumes and corrosion inhibitors

Additional surfactant

Detergent compositions or their components according to the invention preferably contain a additional surfactant selected from anionic surfactants, nonionic, cationic, ampholytic, amphoteric and hybrid ion and their mixtures

A typical list of anionic, non-ionic classes, amphibitic and ionic hybrids, and species of these surfactants, is presented in US Pat. 3,929,678, issued to Laughlin and Heuring on December 30, 1975. More are given examples in "Surface Active Agents and Detergents" (Vol. I and II from Schwartz, Perry and Berch). In US Pat. 4,259,217, Issued to Murphy on March 31, 1981, a list of suitable cationic surfactants.

When present, surfactants ampholytic, amphoteric and hybrid ion are generally used in combination with one or more anionic and / or non-surfactants ionic

Anionic surfactant

In a particularly preferred embodiment of the invention, detergent compositions comprise additionally an anionic surfactant. Any surfactant Anionic useful for detersive purposes is suitable. These can include salts (including, for example, sodium, potassium salts, ammonium and substituted ammonium, such as mono-, di- and salts tri-ethanolamine) of anionic surfactants sulfates, sulphonates, carboxylates and sarcosinates. The ones are preferred anionic sulfate surfactants.

Other suitable anionic surfactants include isethionates, such as acyl isethionates, N-acyl-taurates, acid amides fatty acids of tauride, alkylsuccinates and sulfo-succinates, monoesters of sulfo-succinates (especially monoesters C 12 -C 18 saturated and unsaturated), sulfo-succinate diesters (especially C 6 -C 14 saturated diesters e unsaturated), N-acyl-sarcosinates. Resin acids and resin acids are also suitable hydrogenates such as rosin, hydrogenated rosin and acids resins and hydrogenated resin acids present in, or derivatives of tallow oil.

Sulfate-type anionic surfactant

Sulfate-type anionic surfactants, suitable for use in the compositions of the invention, include linear and branched, primary and secondary alkyl sulfates, alkylethoxysulfates, fatty sulfates of oleyl glycerol, ether sulfates of alkylphenol and ethylene oxide, acyl C 5 -C 17 -N- (alkyl C_ {1} -C_ {4}) and -N- (hydroxyalkylC 1 -C 2) - glucaminesulfates and alkyl polysaccharide sulfates, such as alkyl polyglucoside sulfates (Describing in this invention non-sulphated compounds not ionic).

Type surfactants alkylethoxy sulfate are preferably selected of the group consisting of (C 9 -C 22) alkyl sulfates which have been ethoxylated with 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the type surfactant alkylethoxy sulfate is a (C 11 -C 18) alkyl sulfate, most preferably C 11 -C 15, which has been ethoxylated with 0.5 to 7, preferably with 1 to 5 moles of oxide of ethylene per molecule.

A particularly preferred aspect of the The invention employs mixtures of the alkyl sulfate surfactants and preferred alkylethoxysulfates. Such mixtures have been described. in PCT patent application No. WO 93/18124.

Sulfonate type anionic surfactant

Anionic sulphonate surfactants, suitable for use in the present invention, include salts of the linear (C 5 -C 20) alkyl benzenesulfonates, alkyl estersulfonates, (C 6 -C 22) alkane primary sulfonates or secondary, olefin sulphonates C 6 -C 24, polycarboxylic acids sulphonates, alkyl glycerolsulfonates, acyl glycerolsulfonates fatty, fatty oleyl glycerolsulfonates, and any of their mixtures

Particularly preferred compositions of the present invention further comprise a surfactant anionic, selected from alkyl sulfate surfactants and / or alkylbenzenesulfonate of formulas II and III, respectively:

(II) R 5 OSO 3 {} - M +

(III) R 6 SO 3 {} - M +

in which R 5 is a remainder linear or branched alkyl or alkenyl having 9 to 22 atoms carbon, preferably C 12 to C 18 alkyl most preferably C 16 to C 18 alkyl, or as found in secondary alkyl sulfates; R 6 is (C 10 -C 20) alkyl benzene, preferably (C 10 -C 16) alkyl benzene lo plus preferably (C 11 -C 13) alkyl benzene; M + and M '+ can vary independently and are selected between alkali metals, alkaline earth metals, alkanolammonium and ammonium.

The compositions of the invention particularly Preferred comprise both an alkyl sulfate surfactant and a alkylbenzene surfactant, preferably in ratios of II to III from 15: 1 to 1: 2, most preferably from 12: 1 to 2: 1.

Quantities of one or mixtures of more than one anionic surfactant in the preferred composition may be from 1% to 50%, however, preferably, the anionic surfactant is is present in amounts of 5% to 40% by weight of the composition. Preferred amounts of the surfactant of alkyl sulfate of formula II is from 3% to 40%, or more preferably 6% to 30% by weight of the detergent composition. The amounts Preferred alkylbenzenesulfonate surfactant of formula III in the detergent composition are at least 1%, preferably at least 2%, or even at least 4% or at least 10% by weight. The Preferred amounts of the alkylbenzenesulfonate surfactant are up to 23%, more preferably not more than 20%, most preferably up to 15% or even 10%.

The performance benefits that are obtained when an anionic surfactant is also used in the compositions of the invention, they are particularly useful for surfactants longer carbon chain length anionics such as which have a carbon chain length of C 12 or higher, particularly C_ {14/15} or even up to lengths C 16-18 carbon chain.

In preferred embodiments of the compositions detergents of the invention comprising an anionic surfactant there will be enough excess anionic surfactants, preferably a weight ratio of anionic to cationic surfactant of 50: 1 to 2: 1, most preferably 30: 1 to 8: 1. However, the benefits of the invention are also achieved when the ratio of cationic surfactant to anionic surfactant is substantially stoichiometric, for example from 3: 2 to 4: 3.

In a preferred embodiment of the invention, the Essential cationic surfactant of formula I blends well with part or all of one or more anionic surfactants before the addition of the other components of the detergent composition for provide an easily soluble anionic / cationic complex. I know you may prefer to mix substantially amounts well stoichiometric anionic and cationic surfactant before Addition to the other detergent components, including any additional anionic surfactant.

Anionic Carboxylate Surfactant

Anionic carboxylate surfactants suitable include type surfactants alkylethoxy carboxylate, alkylpolyethoxy polycarboxylate and soaps ("alkyl carboxyls"), especially certain secondary soaps as described in the present invention.

Alkylethoxy carboxylates suitable include those with the formula RO (CH 2 CH 2 O) x CH 2 COO - M +, wherein R is a C 6 to C 18 alkyl group, x takes values from 0 to 10, and the distribution of ethoxylated groups is such that, in terms of weight, the amount of material in which x is 0 It is less than 20% and M is a cation. The surfactants of Suitable alkyl polyethoxy polycarboxylate include those who have the formula RO- (CHR_ {1} -CHR 2 -O) -R_ {3} wherein R is a C 6 to C 18 alkyl group, x is 1 to 25, R_ {1} and R2_ are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, radical hydroxysuccinic acid, and mixtures thereof, and R 3 is selected from group consisting of hydrogen, substituted or unsubstituted hydrocarbon replace that has between 1 and 8 carbon atoms and their mixtures

Suitable surfactants based on soaps include surfactants based on secondary soaps that they contain a carboxyl unit connected to a secondary carbon. Preferred surfactants based on secondary soaps for use  in the present invention, they are water soluble members, selected from the group consisting of water soluble salts of acid 2-methyl-1-undecanoic, acid 2-ethyl-1-decanoic, acid 2-propyl-1-nonanoic, 2-butyl octanoic acid and acid 2-pentyl-1-heptanoic. Certain soaps can also be included as suppressors of suds.

Alkali metal sarcosinate type surfactant

Other suitable anionic surfactants are those alkali metal sarcosinates of formula R-CON (R 1) CH 2 COOM, in which R is an alkyl group or linear or branched C 15 -C 17 alkenyl, R 1 is a C 1 -C 4 alkyl group and M is an ion of an alkali metal. Preferred examples are the miristil- u oleoyl methyl sarcosinates in form of your sodium salts.

Alkoxylated nonionic surfactant

In this invention they are essentially suitable any alkoxylated nonionic surfactants. The ones are preferred ethoxylated and propoxylated nonionic surfactants. They are suitable linear or branched alkoxylated groups.

Preferred alkoxylated surfactants are can select from the non-ionic condensate classes of alkylphenols, ethoxylated nonionic alcohols, non-fatty alcohols ethoxylated / propoxylated ionic, non-ionic condensates ethoxylate / propoxylate with propylene glycol, and the products of nonionic ethoxylate condensation with oxide adducts of propylene / ethylenediamine.

Non-ionic alkoxylated alcohol surfactant

The condensation products of alcohols aliphatic with 1 to 25 moles of alkylene oxide, particularly ethylene oxide and / or propylene oxide, are suitable for use in The present invention. The aliphatic alcohol alkyl chain It can be linear or branched, primary or secondary, and contains generally from 6 to 22 carbon atoms. Are particularly preferred condensation products of alcohols having a alkyl group containing from 8 to 20 carbon atoms with 2 to 10 moles of ethylene oxide per mole of alcohol.

Nonionic surfactant of polyhydroxy acid amide type fatty

Polyhydroxy fatty acid amides suitable for use in the present invention are those that have the structural formula R 2 CONR 1 Z in which: R 1 is H, C 1 -C 4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, ethoxy, propoxy, or mixture thereof, preferably alkyl C 1 -C 4, more preferably C 1 alkyl or C 2, most preferably C 1 alkyl (ie, methyl); and R2 is a hydrocarbyl C 5 -C 31, preferably alkyl or C 5 -C 19 linear chain alkenyl, plus preferably alkyl or alkenyl C_ {9} -C_ {17} linear chain, the most preferably alkyl or alkenyl C 11 -C 17 straight chain, or their mixture; and Z it is a polyhydroxyhydrocarbyl having a hydrocarbon chain linear with at least 3 hydroxyls connected directly to the chain, or its alkoxylated derivative (preferably ethoxylated or propoxylated). Z will preferably be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a Glicityl

Non-ionic fatty acid amide surfactant

Amide-type surfactants of fatty acid Suitable include those with the formula: R 6 CON (R 7) 2 in which R 6 is a alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms, and each R 7 is selected from the group that consists of hydrogen, C1-C4 alkyl, C 1 -C 4 hydroxyalkyl, and - (C 2 H 4 O) x H; where x is in the range from 1 to 3.

Non-ionic surfactant type alkyl polysaccharide

In U.S. Patent No. 4,565,647 of Filling, issued on January 21, 1986 described alkyl polysaccharides suitable for use in the present invention, which have a hydrophobic group containing 6 at 30 carbon atoms and a hydrophilic polysaccharide group, by example a polyglycoside, containing from 1.3 to 10 units of saccharide.

Alkyl polyglycosides preferred have the formula

R 2 O (C n H 2 O) t (glycosyl) x

in which R2 is selected from group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, in which the alkyl groups it contains from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is 1.3 to 8. Glycosyl is derived primarily from glucose.

Preferably the detergent compositions for washing clothes they comprise from 0.5% to 20%, by weight of a nonionic surfactant.

Amphoteric surfactant

Amphoteric surfactants suitable for use in the present invention include surfactants based on oxides of amines and alkyl-amphocarboxylic acids.

Suitable amine oxides include those compounds that have the formula R 3 (OR 4) x N 0 (R 5) 2 wherein R 3 is selected from alkyl group, hydroxyalkyl, acylamidopropyl and alkylphenyl, or mixtures thereof, which they contain from 8 to 26 carbon atoms; R 4 is a group alkylene or hydroxyalkylene containing from 2 to 3 atoms of carbon, or mixtures thereof; x is 0 to 5, preferably 0 to 3; Y each R 5 is an alkyl or hydroxyalkyl group containing 1 to 3, or a group of poly (ethylene oxide) containing from 1 to 3 ethylene oxide groups. Oxides of (C 10 -C 18) alkyl dimethylamines and the oxides of acyl (C 10 -18) amido-alkyldimethylamines.

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

Hybrid ion surfactant

They can also be incorporated into the compositions detergents or their components according to the invention hybrid ion surfactants. These surfactants can be describe broadly as derivatives of secondary amines and tertiary, derivatives of secondary heterocyclic amines and tertiary, or derivatives of quaternary ammonium compounds, quaternary phosphonium or tertiary sulfonium. The surfactants of Type betaines and sultains are examples of ionic surfactants hybrids for use in the present invention.

Suitable betaines are those compounds having the formula R (R ') 2 N + R 2 COO- in which R is a C 6 -C 18 hydrocarbyl group, each R 1 is typically C 1 -C 3 alkyl, and R 2 is a C 1 -C 5 hydrocarbyl group. Preferred betaines are hexanoate of C 12 -C 18 {-dimethylammonium and the acyl (C 10 -C 18) amidopropane (or  -ethane) -dimethyl (or diethyl) betaines. The Complex betaine-based surfactants are also suitable for use in the present invention.

Additional cationic surfactants

The compositions of the invention are found preferably substantially free of ammonium compounds quaternary of formula I but in which R 1, R 2, R 3 or R 4 is an alkyl group greater than C 11. Preferably, the composition must contain less than 1%, preferably less than 0.1% by weight or even less than 0.05% and most preferably less 0.01% by weight of compounds of formula I having a group linear (or even branched) alkyl having 12 or more atoms of carbon.

Another suitable group of cationic surfactants which can be used in the detergent compositions of the invention they are cationic ester type surfactants. The surfactant of cationic ester type is a compound that has properties surfactants comprising at least one ester bond (i.e. -COO-) and at least one cationically charged group. The Preferred cationic ester surfactants are water dispersible

Surfactants of the cationic ester type suitable, including choline ester surfactants, They have been described for example in US Pat. nºs 4,228,042, 4,239,660 and 4,260,529.

In cationic ester type surfactants preferred, the ester bond and the cationically charged group are separated from each other in the surfactant molecule by a group spacer consisting of a chain comprising at least three atoms (i.e. chain length of three atoms), preferably three to eight atoms, more preferably three at five atoms, most preferably three atoms. The atoms that they form the chain of the spacer group are selected from the group that consists of carbon, nitrogen and oxygen atoms and any of their mixtures, with the proviso that any nitrogen atom or oxygen in said chain connects only with carbon atoms in the chain. Thus, the spacer groups that have, for example, -O-O- (ie peroxide) bonds, -N-N-, and -N-O- are excluded, while the spacer groups that have, for example links -CH_ {2} -O-CH_ {2} - and -CH 2 -NH-CH 2 - are included In a preferred aspect, the spacer group chain it comprises only carbon atoms, most preferably, the chain It is a hydrocarbyl chain.

Alkalinity

In the detergent compositions herein invention an alkalinity system is present for provide a detergent composition that has a pH of at least 8.5 at a concentration of 0.5% by weight of the detergent composition  in aqueous solution. The detergent composition may be alkaline. stronger and can have a pH of at least 9.0 or even at least 9.5 or 10.0 in a 0.5% by weight aqueous solution. System alkalinity comprises components that can provide species alkaline in solution. Examples of alkaline species include: carbonate, bicarbonate, hydroxide, the various silicate anions, percarbonate, perborates, perfosphates, persulfate and persilicate. Such alkaline species can be formed, for example, when dissolve in alkaline salts selected from salts carbonate, bicarbonate, hydroxide or silicate, including silicate crystalline, alkali metal or alkaline earth metal sheet and salts percarbonate, perborates, perfosphates, persulfate and persilicate, and Any of your mixtures.

Examples of carbonates are carbonates of alkaline earth and alkali metals, including carbonate and sodium sesquicarbonate and any of its mixtures with carbonate of ultrafine calcium, as described in the patent application German No. 2,321,001, published on November 15, 1973.

Suitable silicates include silicates of water-soluble sodium with a SiO2: Na2O ratio of 1.0 to 2.8, with ratios of 1.6 to 2.0 being preferred, and 2.0 being the most preferred. The silicates may be in the form of the anhydrous salt or of a hydrated salt. The most preferred silicate is the silicate of sodium with a SiO2: Na2O ratio of 2.0.

Preferred crystalline laminar silicates for use in the present invention have the general formula

NaMSi_ {x} O_ {2x + 1} \ cdot and H2O

where M is sodium or hydrogen, x is a number from 1.9 to 4 and is a number from 0 to 20. In the document EP-A-0164514 silicates are described crystalline sodium laminators of this type, and in the documents DE-A-3417649 and DE-A-3742043 methods are described for its preparation In this invention, in the above formula general x preferably has a value of 2, 3 or 4 and is preferably 2. The most preferred material is δ-Na_ {2} Si_ {2} O_ {5}, available in Hoechst AG as NaSKS-6.

Water soluble detergency builder compound

Detergent compositions according to the present invention preferably contain a compound improving the water soluble detergency, typically present in compositions detergents at a level of 1% to 80% by weight, preferably 10% to 70% by weight, most preferably, from 20% to 60% by weight of the composition.

The detergency builder compounds Suitable water soluble, include polycarboxylates water-soluble monomers, or their acid forms, acids homo- or co-polymeric polycarboxylic acids or their salts, in which the polycarboxylic acid comprises at least two radicals carboxylic acids separated from each other by no more than two atoms of carbon, borates, phosphates, and mixtures of any of the compound precedents.

The carboxylate detergency builder or polycarboxylate can be monomeric or oligomeric, although monomeric polycarboxylates are generally preferred by Cost reasons and benefits.

Suitable carboxylates containing a group carboxy include water soluble salts of lactic acid, acid glycolic and its ether derivatives. The polycarboxylates that contain two carboxy groups include water soluble salts of acid succinic, malonic acid, acid (ethylenedioxy) -diacetic, maleic acid, acid diglycolic, tartaric acid, tartronic acid and fumaric acid, as well such as ether carboxylates and sulfinyl carboxylates. The polycarboxylates that they contain three carboxy groups include, in particular, citrates, water soluble aconitrates and citraconates, as well as derivatives succinates such as the carboxymethyloxysuccinates described in the British Patent No. 1,379,241, the lactoxysuccinates described in British Patent No. 1,389,732, and the aminosuccinates described in Dutch patent application 7205873, and the materials of oxypolycarboxylates such as 2-oxa-1,1,3-propane-tricarboxylates which are described in British Patent No. 1,387,447.

Polycarboxylates containing four groups carboxy include the oxydisuccinates described in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane-tetracarboxylates and 1,1,2,3-propane-tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulphosuccinate derivatives described in British patents no. 1,398,421 and 1,398,422 and in US Pat. No. 3,936,448, and the sulfonated pyrolyzed citrates described in the patent British No. 1,439,000. Preferred polycarboxylates are those hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.

The progenitor acids of chelating agents monomeric or oligomeric polycarboxylate type or mixtures thereof with its salts, eg citric acid or mixtures of a citrate and acid citrus, are also considered as useful improver components of detergency.

Borate type detergency builders, as well as detergency builders that contain materials Borate trainers, which can produce a borate in the Detergent storage conditions or washing conditions are water soluble detergency builders useful herein invention.

Suitable examples of improvers of water soluble phosphate type detergency, are the alkali metal tripolyphosphates, sodium pyrophosphates, potassium and ammonium, sodium and potassium pyrophosphates and ammonium, sodium and potassium orthophosphates, polymeta / phosphates sodium, in which the degree of polymerization is in the range from 6 to 21, and phytic acid salts.

Partially soluble detergency builder compound or insoluble

The detergent compositions or their components, of the present invention may contain a compound improving partially soluble or insoluble detergency, present typically in detergent compositions at a level of 1% to 80% in weight, preferably from 10% to 70% by weight, most preferably, from 20% to 60% by weight of the composition.

Examples of detergency builders widely insoluble in water include aluminosilicates of sodium.

Suitable aluminosilicate zeolites have the unit cell formula Na_ {z} [(AlO2) z (SiO2) and] \ cdot xH2O in which z e y are at least 6; the molar ratio of z to y is 1.0 to 0.5 and x is at least 5, preferably 7.5 to 276, plus preferably from 10 to 264. The aluminosilicate materials are in hydrated form and are preferably crystalline, containing 10% to 28%, more preferably 18% to 22% water in form associated.

The aluminosilicate zeolites can be materials present in nature, but preferably They get by synthesis. Type ion exchange materials synthetic crystalline aluminosilicates are available under the designations of Zeolite A, Zeolita B, Zeolita P, Zeolita X, Zeolite HS, and mixtures thereof. Zeolite A has the formula

Na 12 [(AlO 2) 12 (SiO 2) 12] \ cdot xH_ {2} O

in which x is from 20 to 30, especially 27. The zeolite X has the formula

Na_86 [(AlO2) 86 (SiO2) 106] \ cdot 276 H2O.

Another preferred aluminosilicate zeolite is the zeolite MAP detergency builder.

The zeolite MAP may be present at a level of 1% to 80%, more preferably 15% to 40% by weight of the compositions

The zeolite MAP is described in EP document 384070A (Unilever). It is defined as a metal aluminosilicate alkaline of the zeolite P type that has a silicon ratio to aluminum not exceeding 1.33, preferably within the range of  0.9 to 1.33 and more preferably within the range of 0.9 to 1.2.

Of particular interest is the zeolite MAP that has a ratio of silicon to aluminum not exceeding 1.15 and more particularly not greater than 1.07.

In a preferred aspect, the improver of the zeolite MAP detergency has a particle size, expressed as a d 50 value of 1.0 to 10.0 micrometers, more preferably of 2.0 to 7.0 micrometers, most preferably 2.5 to 5.0 micrometers

The value d 50 indicates that 50% by weight of the particles have a smaller diameter than the one shown. In Particularly, the particle size can be determined by conventional analytical techniques such as determination microscopic using an electronic scanning microscope or by a laser granulometer. In EP 384070A, describe other methods to set the d_ {50} values.

Heavy metal ion sequestrant

The detergent compositions or their components, according to the present invention, preferably contain as a Optional component a heavy metal ion sequestrant. By "heavy metal ion sequestrant" is understood in the present invention the components that act by sequestering (chelating) heavy metal ions. These components can also have the ability to chelate calcium and magnesium, but preferably they manifest a selectivity for association of heavy metal ions, such as iron, manganese and copper.

Heavy metal ion sequestrants they are generally present at a level of 0.005% to 20%, preferably from 0.1% to 10%, more preferably from 0.25% to 7.5% and most preferably from 0.5% to 5% by weight of the compositions

Heavy metal ion sequestrants suitable for use in the present invention include phosphonates organic, such as amino-alkylene-poly (alkylene phosphonates), ethane-1-hydroxy diphosphonates of alkali metals and nitrile-trimethylene phosphonates.

Among the previous chemical species are prefer diethylenetriamino-penta- (methylene phosphonate), ethylenediamine-tri- (methylene phosphonate), hexamethylene diamine tetra (methylene phosphonate) e hydroxy-ethylene-1,1-diphosphonate.

Another heavy metal ion sequestrant suitable for use in the present invention includes acid nitrile-triacetic acid polyaminocarboxylic acid such as acid ethylenediaminetetraacetic acid ethylenetriamine-pentaacetic acid ethylenediamine disuccinic acid ethylenediamine diglutaric acid 2-hydroxy-propylenediamino-disuccinic, or any of its salts. Acid is especially preferred ethylenediamine-N, N-disuccinic (EDDS) or its salts of alkali metals, alkaline earth metals, ammonium or substituted ammonium, or mixtures thereof.

Other heavy metal ion sequestrants suitable for use in the present invention are those derived from imino-diacetic acid such as acid 2-hydroxyethyl diacetic or acid glyceryl-imino-diacetic, described in documents EP-A-317,542 and EP-A-399,133. Kidnappers acid iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid-N-carboxymethyl acid N-2-hydroxypropyl-3-sulfonic  described in the document EP-A-516.102 are also suitable in the present invention. Kidnappers are also suitable acid β-alanine-N, N'-diacetic, aspartic acid-N, N'-diacetic acid, acid aspartic acid-N-monoacetic acid and acid iminodusuccinic described in the document EP-A-509,382.

The document EP-A-476,257 describes kidnappers suitable based on amino groups. The document EP-A-510,331 describes kidnappers suitable derivatives of collagen, keratin or casein. The document EP-A-528,859 describes a suitable acid sequestrant alkyl iminodiacetic. Also suitable are the dipicolinic acid and acid 2-phosphonobutane-1,2,4-tricarboxylic. Acid is also suitable Glycineamide-N, N'-disuccinic (GADS), acid ethylenediamine-N-N'-diglutaric (EDDG) and acid 2-hydroxypropylene diamine-N-N'-disuccinic (HPDDS).

Organic peroxyacid bleaching system

A preferred element of the detergent compositions or their components according to the invention is an organic peroxyacid bleaching system. In a preferred embodiment, the bleaching system contains a source of hydrogen peroxide and an organic peroxyacid type bleach precursor compound. The production of the organic peroxyacid is carried out by an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaching agents. In an alternative preferred embodiment, a previously formed organic peroxyacid is incorporated directly into the composition. Compositions containing mixtures of a source of hydrogen peroxide and an organic peroxyacid precursor in combination with a previously formed organic peroxyacid are also considered.

Bleaches of inorganic perhydrate type

Inorganic perhydrate salts are a source Preferred hydrogen peroxide. These salts are incorporated normally in the form of the alkali metal salt, preferably sodium salt at a level of 1% to 40% by weight, more preferably from 2% to 30% by weight and most preferably from 5% at 25% by weight of the compositions.

Examples of inorganic perhydrate salts include salts perborate, percarbonate, perfosphate, persulfate and persilicate Inorganic perhydrate salts are normally the alkali metal salts. The inorganic perhydrate salt is can include in the form of a crystalline solid without any additional protection For certain salts perhydrate, however, preferred embodiments of such granular compositions they use a coated form of the material that best provides storage stability for the perhydrate salt in the product granular and / or a delayed release of the perhydrate salt upon entering contact the granular product with water. Coatings Suitable comprise inorganic salts such as a silicate of alkali metal, carbonate or borate salts or mixtures thereof, or materials organic such as waxes, oils or fatty soaps.

Sodium perborate is a perhydrate salt preferred and may be in the form of the monohydrate of nominal formula NaBO 2 H 2 O 2 or tetrahydrate NaBO_2H2 {O2} \ cdot3H2 {O}.

Preferred perhydrates herein are alkali metal percarbonates, particularly percarbonate of sodium. Sodium percarbonate is an addition compound that has a formula corresponding to 2Na_ {2} CO_ {3} \ cdot3H_ {2} O2, and is available commercially as a crystalline solid.

Potassium peroximonopersulfate is another salt inorganic perhydrate presenting utility in the compositions detergents of the present invention.

Precursor of peroxyacid bleaches

The type bleach precursors peroxy acid are the compounds that react with peroxide of hydrogen in a perhydrolysis reaction to produce a peroxyacid Generally, type bleach precursors peroxy acid can be represented as

\uelm{C}{\uelm{\dpara}{O}}

---LX ---

 \ uelm {C} {\ uelm {\ dpara} {O}} 

--- L

in which L is a leaving group and X is essentially any functionality, such that, when performing a perhydrolysis, the structure of the peroxyacid produced it is

\uelm{C}{\uelm{\dpara}{O}}

---OOHX ---

 \ uelm {C} {\ uelm {\ dpara} {O}} 

--- OOH

The bleaching precursor compounds of peroxyacid type are preferably incorporated at a level of 0.5% at 20% by weight, more preferably from 1% to 15% by weight, most preferably from 1.5% to 10% by weight of the compositions detergents

The bleaching precursor compounds of Suitable peroxyacid type typically contain one or more N- groups or O-acyl, whose precursors can be selected Among a wide range of classes. The right classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. In the document GB-A-1586789 examples are described of useful materials included in these classes. In the documents GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386 SE describe suitable esters.

Outgoing groups

The leaving group, hereafter cited as group L, must be reactive enough for the reaction of perhydrolysis occurs within the optimal time frame (eg a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize to use in the bleaching composition.

Preferred L groups are selected from the group consisting of:

one

two

and mixtures thereof, in which R1 is a alkyl, aryl or alkylaryl group containing from 1 to 14 atoms of carbon, R 3 is an alkyl chain containing from 1 to 8 atoms  carbon, R 4 is H or R 3, R 5 is a chain of alkenyl containing 1 to 8 carbon atoms, and Y is H or a solubilizing group. Any of the groups R1, R3 and R 4 may be substituted essentially with any group functional including, for example, alkyl, hydroxy, alkoxy groups, halogen, amino, nitrosyl, amido and ammonium or alkylammonium

Preferred solubilizing groups are -SO 3 <+> - M +, -CO 2 - M +, -SO4 {+} - M +, -N + (R 3) 4 X - and O <- -N (R 3) 3, and most preferably -SO 3 M - and -CO 2 M -, in which R 3 is an alkyl chain containing 1 to 4 carbon atoms, M is a cation that provides solubility to the bleach activator and X It is an anion that provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or ammonium cation. substituted, with sodium and potassium being most preferred, and X is an anion of halide, hydroxide, methylsulfate or acetate.

Acid bleach precursors alkyl percarboxylic

Acid bleach precursors alkyl percarboxylic form percarboxylic acids when performing a perhydrolysis. Precursors of this type Preferred provide peracetic acid when performing a perhydrolysis

Type precursor compounds Preferred alkyl-percarboxylic type imide include tetraacetylated alkylenediamines in N, N, N 1, N 1 in which the alkylene group contains 1 to 6 carbon atoms, particularly those compounds in which the alkylene group It contains 1, 2 and 6 carbon atoms. Particularly preferred is the tetraacetylethylenediamine (TAED).

Other acid precursors Preferred alkyl percarboxylic include 3,5,5-trimethylhexanoyloxybenzene sulfonate (iso-NOBS) sodium, sodium nonanoyloxybenzene sulphonate (NOBS), sodium acetoxybenzene sulphonate (ABS) and pentaacetyl glucose.

Alkyl peroxyacid precursors amido-substituted

The precursor compounds of alkyl peroxyacids amido-substituted are suitable herein invention, including those with the following formulas general:

\delm{C}{\delm{\dpara}{O}}

---

\delm{N}{\delm{\para}{R ^{5} }}

---R^{2}---

\delm{C}{\delm{\dpara}{O}}

---L

\hskip1cm

o

\hskip1cm

R^{1}---

\delm{N}{\delm{\para}{R ^{5} }}

---

\delm{C}{\delm{\dpara}{O}}

---R^{2}---

\delm{C}{\delm{\dpara}{O}}

---LR1 ---

 \ delm {C} {\ delm {\ dpara} {O}} 

---

 \ delm {N} {\ delm {\ para} {R5}} 

--- R2 ---

 \ delm {C} {\ delm {\ dpara} {O}} 

--- L

 \ hskip1cm 

or

 \ hskip1cm 

R1 ---

 \ delm {N} {\ delm {\ para} {R5}} 

---

 \ delm {C} {\ delm {\ dpara} {O}} 

--- R2 ---

 \ delm {C} {\ delm {\ dpara} {O}} 

--- L

in which R1 is a group alkyl containing from 1 to 14 carbon atoms, R2 is a alkylene group containing from 1 to 14 carbon atoms, and R 5 is H or an alkyl group containing from 1 to 10 carbon atoms and L can be essentially any leaving group. Compounds amido-substituted bleach activators of this type are described in the document EP-A-0170386.

Perbenzoic acid precursor

Perbenzoic acid precursor compounds they provide perbenzoic acid when performing perhydrolysis. The suitable O-acylated perbenzoic acid precursor compounds include the benzoyl oxybenzene sulfonates substituted and unsubstituted, and benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, and those of imida type including N-benzoyl succinimide, tetrabenzoyl ethylenediamine and ureas N-benzoyl substituted. Acid precursors Suitable imidazole type perbenzoic include N-benzoyl-imidazole and N-benzoyl-benzimidazole. Others useful precursors of perbenzoic acid containing groups N-acyl include N-benzoyl-pyrrolidone, dibenzoyl-taurine and acid benzoyl pyroglutamic.

Precursors of cationic peroxyacids

Peroxyacid precursor compounds cationics produce cationic peroxyacids when performing a perhydrolysis

Typically, peroxyacid precursors cationics are formed by replacing the peroxyacid part of a peroxy acid precursor compound suitable for a functional group positively charged, such as an ammonium or alkylammonium group, preferably an ethyl- or methyl-ammonium group. The cationic peroxyacid precursor compounds are typically present in solid detergent compositions as a salt with a suitable anion, such as a halide ion.

The peroxyacid precursor compound to be being cationically substituted in this way can be a compound perbenzoic acid precursor, or a substituted derivative thereof, as described above. Alternatively, the compound peroxyacid precursor may be an acid precursor compound alkyl percarboxylic or a precursor of amido-substituted alkyl peroxyacid, as described below.

The cationic peroxyacid precursors are described in US Patents 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; the English Patent 1,382,594; European patents 475,512, 458,396 and 284,292; and in Japanese patent 87-318,332.

In English patent application no. 9407944.9 and U.S. patent applications Nos. 08/298903, 08/298650, 08/298904 and 08/298906 describe examples of precursors of preferred cationic peroxyacids.

Suitable cationic peroxyacid precursors include any of the alkyl compounds or benzoyl oxybenzene sulfonates substituted ammonium or alkylammonium, acylated caprolactams in N and monobenzoyl-tetraacetyl-glucose-benzoyl-peroxides. Preferred cationic peroxyacid precursors of the class of Preferred N-acylated caprolactams include the trialkyl-ammonium-methylene-benzoyl-caprolactams, and the trialkyl-ammonium-methylene-alkyl-caprolactams.

Organic peroxyacid precursors of the benzoxazine type

Precursor compounds are also suitable. of the benzoxazine type as described, for example in EP-A 332,294 and EP-A-482,807, particularly those that have the formula:

3

in which R1 is H, alkyl, alkylaryl, aryl, or arylalkyl.

Organic peroxyacid previously formed

The bleaching system with a peroxyacid Organic may contain in addition to, or as an alternative to, a precursor compound of organic peroxyacid bleaches, a previously formed organic peroxyacid, typically at a level from 1% to 15% by weight, more preferably from 1% to 10% by weight of the composition.

A preferred class of peroxyacid compounds Organic are the amido-substituted compounds, of The following general formulas:

\delm{C}{\delm{\dpara}{O}}

---

\delm{N}{\delm{\para}{R ^{5} }}

---R^{2}---

\delm{C}{\delm{\dpara}{O}}

---OOH

\hskip1cm

o

\hskip1cm

R^{1}---

\delm{N}{\delm{\para}{R ^{5} }}

---

\delm{C}{\delm{\dpara}{O}}

---R^{2}---

\delm{C}{\delm{\dpara}{O}}

---OOHR1 ---

 \ delm {C} {\ delm {\ dpara} {O}} 

---

 \ delm {N} {\ delm {\ para} {R5}} 

--- R2 ---

 \ delm {C} {\ delm {\ dpara} {O}} 

--- OOH

 \ hskip1cm 

or

 \ hskip1cm 

R1 ---

 \ delm {N} {\ delm {\ para} {R5}} 

---

 \ delm {C} {\ delm {\ dpara} {O}} 

--- R2 ---

 \ delm {C} {\ delm {\ dpara} {O}} 

--- OOH

in which R1 is a group alkyl, aryl or alkylaryl having 1 to 14 carbon atoms, R2 is an alkylene, arylene and alkylarylene group containing from 1 to 14 carbon atoms, and R 5 is H or an alkyl group, aryl or alkylaryl containing from 1 to 10 carbon atoms. In the EP-A-0 170386 are described amido-substituted organic peroxyacid compounds of this kind.

Other organic peroxyacids include diacyl and tetraacyl peroxides, especially acid diperoxidedecanedioic acid, diperoxytetradecanedioic acid and acid diperoxyhexadecanedioic. They are also suitable here. invention mono- and di-perazelaic acids, acid mono-and di-perbrasilic acid N-phthaloylaminoperoxicaproproic.

Bleaching catalyst

The compositions of the invention contain optionally a bleach catalyst containing a metal of transition. A suitable type of bleaching catalyst is a catalyst system comprising a heavy metal cation with a catalytic activity of defined bleaching, such as cations of copper, iron or manganese, an auxiliary metal cation that has little or no catalytic activity of bleaching, such as zinc or aluminum cations, and a sequestrant that has constants of stability defined for catalytic metal cations and auxiliary, particularly ethylenediaminetetraacetic acid, the ethylenediaminetetramethylene phosphonic acid and its soluble salts in Water. Such catalysts are described in US Pat. 4,430,243.

Other types of bleaching catalysts include the manganese-based complexes described in the U.S. Patent 5,246,621 and in US Pat. 5,244,594. Preferred examples of these catalysts include Mn IV 2 (u-O) 3 (1,4,7-trimethyl-1,4,7-triaza-cyclononane) 2 -PF 6) 2, Mn III 2 (uO) 1 (u-OAc) 2 (1,4,7-trimethyl-1,4,7-triaza-cyclononane) 2 - ( ClO 4) 2, Mn IV 4 (u-O) 6 (1,4,7-triaza-cyclononane) 4 - (ClO 4) 2, Mn II IMn IV 4 (uO) 1 (u-OAc) 2 - (1,4,7-trimethyl-1,4,7-triaza-cyclononane) 2 - (ClO 4) 3, and their mixtures. Other types are described in the publication of European patent application no. 549,272. Other suitable ligands for use in the present invention include 1,5,9-trimethyl-1,5,9-triaza-cyclododecane, 2-methyl-1,4,7-triaza-cyclononane, 2-methyl-1,4,7-triaza-cyclononane, 1,2,4,7-tetramethyl-1,4,7-triaza-cyclononane, and their mixtures.

See US patents 4,246,612 and 5,227,084 for examples of suitable bleach catalysts. See also U.S. Patent No. 5,194,416 which teaches complexes. manganese (IV) mononuclear such as Mn (1,4,7-trimethyl-1,4,7-triazacyclononane) (OCH 3) 3 - (PF 6). Still, another type of bleaching catalyst, as described in the U.S. Patent No. 5,114,606, is a water soluble complex of manganese (III) and / or (IV), with a ligand that is a compound non-carboxylate polyhydroxy, which has at least three consecutive C-OH groups. Other examples include Mn binuclear complexes complexed with ligands tetra-N-dentate and bi-N-toothed, including N 4 Mn III (u-O) 2 Mn IV N 4) + Y [Bipy 2 Mn III (u-O) 2 MnIVbipy 2] - (CIO 4) 3.

More suitable bleaching catalysts are described, for example, in European patent application no. 408.131 (complex cobalt catalysts), in publications European Patent No. 384,503 and 306,089 (catalysts of metallo-porphyrins), US Pat. nº 4,728,455 (manganese catalyst and a multidentate ligand), the U.S. Patent No. 4,711,748 and European Patent Application No. of publication 224,952 (catalyst with absorbed manganese on a aluminosilicate), US Pat. No. 4,601,845 (support of aluminosilicate with manganese and zinc or a magnesium salt), U.S. Patent No. 4,626,373 (manganese catalyst and a ligand), US Pat. No. 4,119,557 (catalyst with a ferric complex), German patent specification 2,054,019 (catalyst with a cobalt chelating agent), Canadian patent 866.191 (salts containing transition metals) patent USA No. 4,430,243 (chelators with manganese cations and cations of non-catalytic metals) and US Pat. No. 4,728,455 (manganese gluconate catalysts).

Additional Enzymes

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

Preferred additional enzyme materials include commercially available enzymes. These enzymes include enzymes selected from lipases, cellulases, hemicellulases, peroxidases, proteases, glucoamylases, amylases, xylanases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pululanases, tannasas, pentosanasas, malanasas, β-glucanases, arabinosidases, hyaluronidase, Chondroitinase, laccasa or mixtures thereof.

A preferred combination of additional enzymes in a detergent composition of the invention includes a mixture of Conventionally applicable enzymes such as lipase, protease, amylase, cutinase and / or cellulase together with one or more enzymes that They degrade the cell wall of plants. In US patents No. 3,519,570 and 3,533,139 suitable enzymes are exemplified.

Suitable proteases are the subtilisins that are obtained from particular strains of B. subtilis and B. licheniformis (subtilisin BPN and BPN '). A suitable protease is obtained from a strain of Bacillus , which has a maximum activity over the pH range of 8-12, developed and sold as ESPERASE® by Novo Industries A / S of Denmark, hereinafter referred to as "Novo." The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 to Novo. Other suitable proteases include ALCALASE®, DURAZYM® and SAVINASE® de Novo and MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® (Protein-treated Maxacal) from Gist-Brocades. Proteolytic enzymes also cover modified bacterial serine proteases, such as those described in European patent application with serial number 87 303761.8, filed on April 28, 1987 (particularly on pages 17, 24 and 98), and what is referred to in the present invention as "Protease B", and in European Patent Application 199,404, of Venegas, published on October 29, 1986, which refers to a modified bacterial serine proteolytic enzyme, which is referred to as in the present invention "Protease A". It is appropriate what is called "Protease C" in the present invention, which is a variant of an alkaline serine protease produced by Bacillus , in which lysine has replaced arginine at position 27, tyrosine has replaced valine at position 104, the serine has replaced asparagine at position 123, and the alanine has replaced threonine at position 274. Protease C is described in EP 90915958: 4 corresponding to WO 91/06637, published on May 16, 1991. Also included in the present invention are genetically modified variants, particularly of Protease C.

A preferred protease, referred to as "Protease D", is a carbonyl hydrolase variant that has an amino acid sequence that is not found in nature, which is derived from a carbonyl hydrolase precursor, substituting a different amino acid by a plurality of amino acid residues at a position of said carbonyl hydrolase that is equivalent to the +76 position, preferably also in combination with one or more amino acid residue positions that are equivalent to those selected from the group that consists of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and / or +274, according to the numbering of subtilisin produced by Bacillus amyloliquefaciens , as described in WO 95/10591 and in the patent application of C. Ghosh et al ., "Bleaching Compositions Comprising Protease Enzymes", with the Ser number US ie 08 / 322.677, filed on October 13, 1994 USA.

They are also suitable for the present invention. the proteases described in patent applications EP 251,446 and WO 91/06637, the BLAP® protease described in WO 91/02792 and its variants described in WO 95/23221.

See also a protease with a high pH value produced by Bacillus sp . NCIMB 40338, described in WO 93/18140 A, de Novo. Enzymatic detergents comprising a protease, one or more other types of enzymes, and a reversible protease inhibitor are described in patent application WO 92/03529 A, de Novo. When desired, a protease having decreased adsorption and increased hydrolysis is available as described in WO 95/07791, of Procter & Gamble. A recombinant trypsin protease type for detergents, suitable in the present invention, is described in WO 94/25583, de Novo. Other suitable proteases are described in EP 516.200, from Unilever.

In the detergent compositions herein invention one or a mixture of enzymes can be incorporated proteolytic, generally at a level of 0.0001% to 2%, preferably from 0.001% to 0.2%, more preferably from 0.005% to 0.1% pure enzyme by weight of the composition.

If present in the compositions detergents of the present invention, the enzyme component Lipolytic is generally present at 0.00005% levels at 2% active enzyme by weight of the detergent composition, preferably 0.001% to 1% by weight, most preferably of 0.0002% to 0.05% by weight of active enzyme in the composition Detergent.

Lipolytic enzymes suitable for use in the present invention include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19,154, as described in English Patent 1,372,034. Suitable lipases include those that show a positive immunological cross-reaction with the lipase antibody, produced by the Pseudomonas Hisorescent IAM 1057 microorganism. This lipase is available from Amano Pharmaceutical Co., Nagoya, Japan, under the trade designation Lipase P "Amano ", hereinafter referred to as" Amano-P ". Other suitable commercial lipases include Amano-CES, lipases produced by Chromobacter viscosum , eg Chromobacter viscosum var. NRRLB 3673 lipolyticum commercially available from Toyo Jozo Co., Tagata, Japan; lipases produced by Chromobacter viscosum , from US Biochemical Corp. USA. and from Disoynth Co., the Netherlands; and lipases produced by Pseudomonas gladioli . Especially suitable lipases are lipases such as M1 Lipase® and Lipomax® (from Gist-Brocades) and Lipolase® and Lipolase Ultra® (Novo), which have been found to be very effective when used in combination with the compositions of the present invention Also suitable are the lipolytic enzymes described in EP 258.068, WO 92/05249 and WO95 / 22615, by Novo Nordisk, and in WO 94/03578, WO 95/35381 and WO 96/00292, by Unilever.

Also suitable are cutinases [EC 3.1.1.50], which can be considered as a special class of lipase, specifically lipases that do not require any interfacial activation. The addition of cutinases to detergent compositions has been described in eg, WO-A-88/09367 (Genencor); WO 90/09446 (Plant Genetic System) and WO 94/14963 and WO 94/14964 (Unilever). The LIPOLASE enzyme derived from Humicola lanuginosa and commercially available from Novo (see also EP 341,947), is a preferred lipase for use in the present invention.

Another preferred lipase for use in the present invention is the D96L lipolytic enzyme variant of the native lipase derived from Humicola lanuginosa . Most preferably, the strain of Humicola lanuginosa DSM 4106 is used.

By "L96sa lipolytic enzyme variant" is meant the lipase variant as described in patent application WO 92/05249 in which the native Humicola lanuginosa lipase has the aspartic acid residue (D) in position 96 changed to leucine (L). According to this nomenclature said substitution of aspartic acid to leucine in position 96 is shown as: D96L. To determine the activity of the D96L enzyme, the standard LU test (Analytical method, internal Novo Nordisk AF 95/6-GB 1991.02.07) can be used. A substrate for D96L was prepared by emulsifying glycerin tributyrate (Merck) using gum arabic as an emulsifier. The lipase activity was tested at pH 7 using the statistical method of pH.

The detergent compositions of the invention they can also contain one or a mixture of more than one enzyme amylase (α and / or β). WO 94/02597, de Novo Nordisk A / S, published on February 3, 1994, describes cleaning compositions that incorporate mutant amylases. See also WO 95/10603, by Novo Nordisk A / S, published on April 20, 1995. Other amylases known for use in cleaning compositions include both α- and β-amylases. The α-amylases are known in the art and include those described in US Pat. ; 5,003,257; EP 252,666; WO / 91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341; and the specification of the English patent No. 1,296,839 (Novo). Other suitable amylases are amylases with increased stability, which are described in WO94 / 18314, published on August 18, 1994, and in WO 96/05295, of Genencor, published on February 22, 1996, and variants of Amylases that have an additional modification in the parent immediate, available in Novo Nordisk A / S, described in the WO 95/10603, published in April 1995. They are also Suitable amylases described in EP 277 216, WO 95/26397 and WO 96/23873 (all of them from Novo Nordisk).

Examples of products from Commercial α-amylases are Purafect Ox Am® from Genencor, and Termamyl®, Ban®, Fungamyl® and Duramyl®, all of them available at Novo Nordisk A / S Denmark. The document WO95 / 26397 describes other suitable amylases: α-amylases characterized by having a specific activity that is at least 25% greater than the activity specific to Termamyl® in a temperature range of 25ºC at 55 ° C, and at a pH value in the range of 25 to 10, measured by the Phadebas® analysis system of the activity of α-amylases. Variants of the above enzymes, described in WO 96/23873 (of Novo Nordisk). Other preferred amylolytic enzymes with improved properties with respect to the level of activity and the combination of thermostability and a higher level of activity, it described in WO95 / 35382.

If present, amylolytic enzymes will they generally incorporate into the detergent compositions of the present invention at a level of 0.0001% to 2%, preferably of 0.00018% to 0.06%, more preferably 0.00024% to 0.048% enzyme pure by weight of the composition.

The detergent compositions of the invention may additionally incorporate one or more cellulase enzymes. Suitable cellulases include both bacterial and fungal cellulases. Preferably, these will have an optimum pH value between 5 and 12 and an activity above 50 CEVU (Cellulose Viscosity Unit = cellulose viscosity units). Suitable cellulases are described in US Pat. 4,435,307, from Barbesgoard et al ., J61078384 and WO96 / 02653, which describe fungal cellulases produced respectively from Humicola Insolens, Trichoderma, Thielavia and Sporotrichum . EP 739,982 describes cellulases isolated from new Bacillus species. Suitable cellulases are also described in GB-A-2,075,028; GB-A-2,095,275 and DE-OS-2,247,832 and WO95 / 26398.

Examples of such cellulases are cellulases produced by a strain of Humicola Insolens ( Humicola grisea var. Thermoidea), particularly Humicola strain DSM 1800. Other suitable cellulases are cellulases that originate from Humicola insolens , which have a molecular weight of approximately 50 KDa, an isoelectric point of 5.5 and contain 415 amino acids; and a 43 kD endoglucanase, derived from Humicola insolens , DSM 1800, which exhibits cellulase activity; A preferred endoglucanase component has the amino acid sequence described in PCT Patent Application No. WO 91/17243. Suitable cellulases are also EGIII cellulases from Trichoderma longibrachiatum , which are described in WO 94/21801, of Genencor, published on September 29, 1994. Especially suitable cellulases are cellulases that have color care benefits. Examples of such cellulases are the cellulases described in European Patent Application No. 91202879.2, filed on November 6, 1991 (Novo). Carezyme and Celluzyme (from Novo Nordisk A / S) are especially useful. See also WO 91/17244 and WO 91/21801. Other cellulases suitable for obtaining tissue care and / or cleaning properties are described in WO 96/34092, WO 96/17994 and WO 95/24471.

They can also be incorporated into the compositions detergents of the invention peroxidases enzymes. Enzymes peroxidases are used in combination with oxygen sources, eg a percarbonate, perborate, persulfate, hydrogen peroxide, etc. These are used for "bleaching in solution", that is, for prevent the transfer of dyes or pigments that have been removed from the substrates during washing operations towards other substrates in the wash solution. Peroxidases enzymes are known in the art and include, for example, peroxidase of horseradish, ligninase and haloperoxidase such as chloro- and bromine peroxidase. Detergent compositions that they contain peroxidases are described, for example, in applications of PCT international patents WO 89/099813, WO 89/09813 and in the European Patent Application No. 91202882.6, filed on 6 November 1991, and European Patent Application No. 96870013.8, filed on February 20, 1996. The enzyme is also suitable laccasa

Preferred intensifiers are the Phenothiazines and substituted phenoxazines, acid 10-phenothiazine-propionic (PPT), acid 10-ethyl-phenothiazine-4-carboxylic  (EPC), acid 10-phenoxazine-propionic (POP) and 10-methyl-phenoxazine (described in WO 94/12621) and substituted syringates (alkylatingards) substituted C 3 -C 5) and phenols. The Percarbonate or sodium perborate are preferred sources of peroxide of hydrogen.

Said cellulases and / or peroxidases, if are present, are normally incorporated into the composition detergent at levels of 0.0001% to 2% of active enzyme by weight of the detergent composition

Such additional enzymes, if found present, they are normally incorporated into the detergent composition a 0.0001% to 2% levels of active enzyme by weight of the composition Detergent. Additional enzymes can be added as separate individual ingredients (pearls, granules, liquids stabilized, etc., which contain an enzyme) or as mixtures of two or more enzymes (eg co-granulates).

Enzyme oxidation inactivators

Other suitable detergent ingredients, which they can be added are enzyme oxidation inactivators, which They are described in the European patent application pending with 92870018.6, filed on January 31, 1992. Examples of said enzyme oxidation inactivators are ethoxylated tetraethylene polyamines.

Enzymatic materials

A range of enzymatic materials and means for incorporation into synthetic detergent compositions are also described in WO 9307263 A and WO 9307260 A, filed by Genencor International, WO 8908694 A, filed by Novo, and US Pat. 3,553,139, January 5, 1971 to McCarty et al . Enzymes are further described in US Pat. 4,101,457, of Place et al ., July 18, 1978, and 4,507,219 of Hughes, March 26, 1985. Enzymatic materials useful for liquid detergent formulations, and their incorporation into said formulations, are described in the patent of USA 4,261,868, April 14, 1981 to Hora et al . Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are described and exemplified in US Pat. 3,600,319, August 17, 1971 to Gedge et al , and patents EP 199,405 and EP 200,586 October 29, 1986, of Venegas. Enzyme stabilization systems are also described, for example, in US Pat. 3,519,570. A useful strain of Bacillus , sp. AC13, which provides proteases, xylanases and cellulases, is described in WO 9401532 A, de Novo.

Organic polymeric compound

The organic polymeric compounds are additional preferred components of the detergent compositions or its components of the present invention, and are found preferably present as components of any components of the particulate detergent composition where they can act by joining the component in the form of particles. By "organic polymeric compound" is meant any organic polymer compound commonly used as dispersant, agents against redeposition or for dirt suspension in detergent compositions, including any of the compounds high molecular weight organic polymers described as clay flocculating agents in the present invention.

Such organic polymeric compound is incorporated generally in the detergent compositions of the invention at a level of 0.1 to 30%, preferably 0.5% to 15%, the most preferably from 1% to 10% by weight of the compositions.

Examples of organic polymeric compounds include homo- or copolymeric polycarboxylic organic acids soluble in water or its salts, in which the polycarboxylic acid it comprises at least two carboxyl radicals separated from each other for no more than two carbon atoms. The latter polymers type are described in the document GB-A-1,596,756. Examples of such salts are polyacrylic acid or polyacrylates of MW 1,000-5,000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of 2,000 to 100,000, especially 40,000 to 80,000. The polyimaleates or polymers of Polyimaleic acid and its salts are also suitable examples.

The polyamine compounds useful in the present invention, including those derived from acid aspartic, including polyaspartic acid and what is described in EP-A-305,282, EP-A-305,283 and EP-A-351,629.

They are also suitable for incorporation into the compositions of the present invention, the terpolymers that contain monomer units selected from maleic acid, Acrylic acid, aspartic acid and alcohol or vinyl acetate, particularly those that have an average molecular weight of 1,000 to 30,000, preferably 3,000 to 10,000.

Other suitable organic polymeric compounds for incorporation into the detergent compositions of the Present invention include cellulose derivatives, such as methyl cellulose, carboxymethyl cellulose, hydroxypropyl methylcellulose, ethylhydroxyethyl cellulose and hydroxyethyl cellulose.

More useful organic polymeric compounds are polyethylene glycols, particularly those of molecular weight 1,000 to 10,000, more particularly 2,000 to 8,000 and most preferably about 4,000.

Cationic dirt removal compounds / against redeposition

The detergent composition or its components of the invention may comprise ethoxylated amine compounds water-soluble cationics with removal properties of dirt-clay / particulate dirt and / or against redeposition. These cationic compounds are described. in more detail in the documents EP-B-111965, US 4659802 and US 4664848. Of these cationic compounds are particularly preferred cationic monoamines, diamines or triamines ethoxylated. Especially preferred are monoamines, diamines and ethoxylated cationic thiamines, of the formula:

4

in which X is a non-ionic group selected from the group consisting of H, alkyl C 1 -C 4 or ether or ester group of hydroxyalkyl, and mixtures thereof, a is 0 to 20, preferably 0 a 4 (eg ethylene, propylene, hexamethylene) b is 2, 1 or 0; for cationic monoamines (b = 0), n is preferably at least 16, with a typical range of 20 to 35; for diamines or triamines cationic, n is preferably at least about 12 with a typical range from about 12 to about 42

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

Soap suppressor system

The detergent compositions of the invention, when formulated for use in machine wash compositions, preferably comprise a suds suppressor system, present at a level of 0.01% to 15%, preferably 0.05% to 10%, most preferably from 0.1% to 5% by weight of the composition.

Suppressive systems of suitable soaps for use in the present invention can essentially comprise any known antifoam compound, including, for example, anti-foam silicone compounds and anti-foam compounds of 2-alkyl alkanol.

In the present invention it is understood by antifoam compound any compound or compound mixtures that act by decreasing the formation of foam or soaps produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.

Antifoam compounds particularly Preferred for use in the present invention are the compounds silicone defoamers defined in this invention as Any compound that includes a silicone component. Such Silicone defoamer compounds also typically contain a silica component The term "silicone" as used in The present invention, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers that They contain siloxane units and hydrocarbyl groups of various types. Preferred silicone defoamer compounds are those siloxanes, particularly polydimethylsiloxanes that have trimethylsilyl terminal block units.

Other suitable antifoaming compounds include monocarboxylic fatty acids and their soluble salts. These materials are described in US Patent No. 2,954,347; issued on September 27, 1960 to Wayne St. John. Acids monocarboxylic fatty acids and their salts, used as suppressors of soaps typically have hydrocarbon chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms.

Suitable salts include metal salts alkalines such as sodium, potassium and lithium salts, and salts of ammonium and alkanolammonium.

Other suitable antifoaming compounds include, for example, fatty esters (for example, triglycerides of fatty acids) of high molecular weight, fatty acid esters of monovalent alcohols, aliphatic ketones C 18 {C 40 {for example, stearone), N-alkylated aminotriazines such as tri- a hexa-alkylmelamines or di- a tetra-alkyldiamine chlortriazines formed as cyanuric chloride products with 2 or 3 moles of an amine primary or secondary containing 1 to 24 carbon atoms, oxide of propylene, bisestearic acid amide and alkali metal monostearyl diphosphates (for example, potassium, sodium and lithium) phosphates, and phosphate esters.

A preferred suds suppressor system understands

(a) antifoam compound, preferably silicone antifoaming compound, most preferably a silicone defoamer compound comprising in combination

(i)

polydimethylsiloxane, at a level of 50% at 99%, preferably 75% to 95% by weight of the antifoam compound of sylicon; Y

(ii)

silica, at a level of 1% to 50%, preferably 5% to 25% by weight of the antifoam compound of silica / silicone;

in which said compound Silica / silicone defoamer is incorporated at a 5% level at 50%, preferably 10% to 40% in weight;

(b) a dispersant compound, the most preferably comprising a comb copolymer of silicone glycol with a content of poly (oxide of alkylene) of 72-78% and an oxide ratio of ethylene to propylene oxide of 1: 0.9 to 1: 1.1, at a level of 0.5% at 10%, preferably 1% to 10% by weight; a comb copolymer of particularly preferred silicone glycol of this type is DC0544, commercially available in DOW Corning with the trade name DC0544;

(c) an inert fluid vehicle, comprising, more preferably an ethoxylated alcohol C 16 -C 18 with an ethoxylation degree of 5 to 50, preferably 8 to 15, at a level of 5% to 80%, preferably 10% to 70%, by weight;

The document EP-A-0210731 describes a system highly soapy particle suds suppressor preferred and comprises a silicone antifoam compound and a organic vehicle that has a melting point in the range of 50 ° C to 85 ° C, wherein the organic vehicle comprises a monoester of glycerol and a fatty acid that has a carbon chain that It contains 12 to 20 carbon atoms. The document EP-A-0210721 describes other systems suds suppressors in the form of preferred particles, in the that the organic vehicle is an alcohol or fatty acid that has a carbon chain containing 12 to 20 carbon atoms, or a mixture thereof, with a melting point of 45 ° C to 80 ° C.

Polymeric agents for transfer inhibition of dyes

The detergent compositions of this invention they can also comprise from 0.01% to 10%, preferably from 0.05% to 0.5% by weight of polymeric agents for inhibition of dye transfer

Transfer inhibition agents polymeric dyes are preferably selected from polyamine N-oxide polymers, copolymers of N-vinyl pyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or their combinations, whereby these polymers can be polymers crosslinked

a) Polyamine N-oxide polymers

Suitable polyamine N-oxide polymers for use in the present invention contain units that have the following structural formula:

\melm{\delm{\para}{R}}{Ax}{\uelm{\para}{P}}

(I)

 \ melm {\ delm {\ para} {R}} {Ax} {\ uelm {\ para} {P}} 

in which P is a unit polymerizable, Y

\uelm{C}{\uelm{\dpara}{O}}

---

\uelm{N}{\uelm{\para}{R ^{1} }}

---,

\hskip0,5cm

\uelm{N}{\uelm{\para}{R ^{1} }}

---

\uelm{C}{\uelm{\dpara}{O}}

---,

\hskip0,5cm

\uelm{C}{\uelm{\dpara}{O}}

O,

\hskip0,5cm

\uelm{C}{\uelm{\dpara}{O}}

,

\hskip0,5cm

-O-,

\hskip0,5cm

-S-,

\hskip0,5cm

---

\uelm{N}{\uelm{\para}{R ^{1} }}

---, x es 0 ó 1;A is ---

 \ uelm {C} {\ uelm {\ dpara} {O}} 

---

 \ uelm {N} {\ uelm {\ para} {R1}} 

---,

 \ hskip0,5cm 

 \ uelm {N} {\ uelm {\ para} {R1}} 

---

 \ uelm {C} {\ uelm {\ dpara} {O}} 

---,

 \ hskip0,5cm 

 \ uelm {C} {\ uelm {\ dpara} {O}} 

OR,

 \ hskip0,5cm 

 \ uelm {C} {\ uelm {\ dpara} {O}} 

,

 \ hskip0,5cm 

-OR-,

 \ hskip0,5cm 

-S-,

 \ hskip0,5cm 

---

 \ uelm {N} {\ uelm {\ para} {R1}} 

---, x is 0 or 1;

R1 is H or an alkyl C 1-6 linear or branched; or it can form a heterocyclic group with R;

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

The N-O group can be represented by the following general structures:

\melm{\delm{\para}{(R _{3} ) _{z} }}{N}{\uelm{ \uparrow }{O}}

---(R_{2})y

\hskip1cm

o

\hskip1cm

\biequal

\uelm{N}{\uelm{ \uparrow }{O}}

---(R_{1})x(R_ {1}) x ---

 \ melm {\ delm {\ para} {(R 3) _ {z}}} {N} {\ uelm {\ uparrow} {O}} 

--- (R2) and

 \ hskip1cm 

or

 \ hskip1cm 

 \ biequal 

 \ uelm {N} {\ uelm {\ uparrow} {O}} 

--- (R_ {1}) x

in which R_ {1}, R2_, and R 3 are aliphatic groups, aromatic, heterocyclic groups or alicyclics or combinations thereof, x o / y y o / y z is 0 or 1 and at which the nitrogen of the N-O group can be attached, or in the which in nitrogen of the N-O group is part of these groups The N-O group can be part of the unit polymerizable (P) or may be attached to the polymer chain main or a combination of both of them.

Suitable polyamine N-oxides in which the N-O group is part of the polymerizable unit, they comprise polyamine N-oxides in which R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. A class of said polyamine N-oxides comprises the group of N-oxides of polyamine in which the group nitrogen N-O is part of the R-group. Preferred polyamine N-oxides are those in which R is a heterocyclic group such as pyridine, pyrrole N-substituted, imidazole, pyrrolidine N-substituted, piperidine, quinoline, acridine and their derivatives.

Other suitable polyamine N-oxides are those polyamine oxides to which the N-O group is attached to the polymerizable unit. A preferred class of these Polyamine N-oxides comprise the polyamine N-oxides that have the general formula (I) in which R is an aromatic group, heterocyclic or alicyclic in which the group nitrogen functional N-O is part of said group R. Examples of these classes are polyamine oxides in which R is a heterocyclic compound such as pyridine, pyrrole N-substituted, imidazole and its derivatives.

Polyamine N-oxides can be obtained in almost any degree of polymerization. The degree of polymerization It is not critical of the condition that the material has the Water solubility and the desired dye suspension power. Typically, the average molecular weight is within the range of 500 to 1000000;

b) Copolymers of N-vinyl pyrrolidone and N-vinylimidazole

Copolymers are suitable in this invention. of N-vinylimidazole and N-vinylpyrrolidone that have a weight range Preferred average molecular weight of 5,000 to 100,000, or 5,000 to 50,000. The preferred copolymers have a molar ratio of N-vinylimidazole to N-vinyl pyrrolidone from 1 to 0.2.

c) Polyvinylpyrrolidone

The detergent compositions herein invention can also use polyvinyl pyrrolidone ("PVP") which has an average molecular weight of 2,500 to 400,000. Suitable polyvinylpyrrolidones are available commercially at ISP Corporation, New York, NY and Montreal, Canada with the product names PVP K-15 (weight molecular from the viscosity of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000). PVP K-15 is also available in ISP Corporation Other suitable polyvinylpyrrolidones that are found commercially available at BASF Corporation include Sokalan HP 165 and Sokalan HP 12.

d) Polyvinyloxazolidone

The detergent compositions herein invention can also use polyvinyloxazolidones as polymeric dye transfer inhibiting agents. Said polyvinyloxazolidones have an average molecular weight of 2,500 to 400,000.

e) Polyvinylimidazole

The detergent compositions herein invention can also use polyvinylimidazole as an agent of inhibition of transfer of polymeric dyes. Sayings polyvinylimidazoles preferably have an average molecular weight from 2,500 to 400,000.

Optical brightener

The detergent compositions herein invention also optionally contain about 0.005% at 5% by weight of certain types of optical brighteners hydrophilic

Hydrophilic optical brighteners useful in present invention include those having the formula structural:

5

in which R_ {1} is selected between anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is select between N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morpholino, chlorine and amino; and M is a cation that forms salts such as sodium or potassium.

When in the previous formula, R_ {1} is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is acid 4,4'-bis [(4-anilino-6- (N- 2-bis-hydroexiethyl) -s-triazine-2-yl) amino] -2,2'-stilbenedisulfonic acid and the disodium salt. This particular polishing species is commercialize with the commercial designation Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the brightener preferred hydrophilic optic useful in detergent compositions of this memory

When in the previous formula, R_ {1} is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is salt acid disodium 4,4'-bis [(4-anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazine-2-yl) amino] -2,2'-stilbenedisulfonic acid. These particular polishing species are marketed with the commercial designation Tinopal-5BM-GX by Ciba-Geigy Corporation.

When in the above formula R_ {1} is anilino, R2 is morpholino and M is a cation such as sodium, the brightener is the acidic sodium salt 4,4'-bis [(4-anilino-6-morpholino-s-triazine-2-yl) amino] 2,2'-stilbenedisulfonic acid.  These particular polishing species are marketed with the trade name Tinopal AMS-GX by Ciba-Geigy Corporation.

Polymeric dirt removal agent

In the present detergent compositions they can optionally use polymeric removal agents of Known dirt, hereafter "SRA". Whether use, SRAs will generally comprise from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight, of the compositions.

Preferred SRAs typically have segments hydrophilic to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments for deposit on hydrophobic fibers and remain adhered to same until the wash and rinse cycles are completed, serving in this way as an anchor for segments hydrophilic This can cause spots to appear later. of the treatment with SRA are cleaned more easily in procedures subsequent wash.

Preferred SRAs include esters of oligomeric terephthalate, typically prepared by procedures which involve at least one transesterification / oligomerization, to often with a metal catalyst such as a titanium alkoxide (IV). Such esters can be obtained using additional monomers capable of being incorporated into the structure of the ester through one, two, three, four or more positions, without, of course, forming a densely crosslinked global structure.

Suitable SRAs include a sulphonated product of a substantially linear ester oligomer formed by a terephthaloyl and oxyalkylenoxy repeated unit oligomeric or polymeric backbone chain and sulfonated terminal moieties covalently bonded to the backbone, for example as described in the U.S. Patent No. 4,968,451, of November 6, 1990, by JJ Scheibel and EP Gosselink. Such ester oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate ("DMT") and 1,2-propylene glycol ("PG") in a two-stage transesterification / oligomerization process; and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRAs include the end-capped 1,2-propylene / polyoxyethylene terephthalate polyesters of US Pat. No. 4,711,730 of December 8, 1987, by Gosselink et al ., for example, those produced by transesterification / oligomerization of poly (ethylene glycol) methyl ether, DMT, PG and poly (ethylene glycol) ("PEG"). Other examples of SRAs include: partially partial and fully anionic terminally terminated oligomeric esters of US Pat. No. 4,721,580 of January 26, 1988, to Gosselink, such as ethylene glycol ("EG") oligomers, PG, DMT and Na-3,6-dioxa-8-hydroxyoctanesulfonate; oligomeric non-ionic block polyester compounds capped in US Pat. No. 4,702,857 of October 27, Gosselink, for example produced from DMT, PEG and EG and / or PG topped with methyl (Me), or a combination of DMT, EG and / or PG, PEG topped with Me and Na-dimethyl-5-sulfoisophthalate; and terminally anionic capped terephthalate esters, especially sulfoaroyl, of US Pat. No. 4,877,896, of October 31, 1989, from Maldonado, Gosselink et al ., the latter being typical of SRAs useful in laundry and fabric conditioning products, an example being an ester composition prepared from the monosodium salt of m-sulfobenzoic acid, PG and DMT, optionally but preferably further comprises PEG added, eg, PEG 3400.

SRAs also include: simple copolymer blocks of ethylene terephthalate or propylene terephthalate with poly (ethylene oxide) or poly (propylene oxide), see US Patents 3,959,230 to Hays, May 25, 1976 and 3,893,929 to Basadur, July 8, 1975; cellulosic derivatives such as the hydroxy ether cellulosic polymers available in Dow METHOCEL; alkyl (C 1 -C 4) celluloses and hydroxyalkyl (C 4) celluloses, see US Patent 4,000,093, December 28, 1976 to Nicol, et al .; and methylcellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit of about 1.6 to about 2.3 and a viscosity of the solution of about 80 to about 120 centipoise measured at 20 ° C as an aqueous solution at 2 %. Such materials are available as METOLOSE SM100 and METOLOSE SM200 which are the commercial designations of methylcellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.

Additional classes of SRA include: (I) non-ionic terephthalates that use diisocyanate coupling agents to bind polymeric ester structures, see US Patents 4,201,824, Violland et al ., And 4,240,918, Lagasse et al .; and (II) SRA with carboxylate terminal groups obtained by the addition of trimellitic anhydride to known SRAs to convert terminal hydroxyl groups to trimellitate esters. With proper catalyst selection, the trimellitic anhydride bonds with the polymer terminals through a carboxylic acid ester isolated from trimellitic anhydride rather than through the opening of the anhydride bond. As starting materials, non-ionic or anionic SRAs can be used provided they have terminal hydroxyl groups that can be esterified. See US Pat. 4,525,524 Tung et al . Other classes include (III) anionic SRAs based on terephthalate of the urethane binding variety, see US Patent 4,201,824, to Violland et al .;

Other optional ingredients

Other optional ingredients suitable for your Inclusion in the compositions of the invention include perfumes, loading colors and salts, with sodium sulfate being a salt of preferred load

Composition Form

The compositions according to the invention can take a variety of physical forms, including granular forms, in tablets, flakes, pills and sticks and liquids. Liquids They may be aqueous or non-aqueous and may be in the form of a gel. The compositions may be pretreatment compositions or conventional washing detergents. The compositions are particularly the so-called granular detergent compositions concentrates adapted to be added to a washing machine using a dispensing device placed in the machine drum with the load of dirty clothes.

Such granular detergent compositions or their components according to the present invention can be obtained by a variety of methods including drying by spraying, dry mixing, extrusion, agglomeration and granulation. The quaternized cationic surfactant can be added to the other detergent components by mixing, agglomeration (preferably combined with a vehicle), granulation or as a spray dried component.

The compositions according to the present invention can also be used in or in combination with compositions with bleaching additives, for example those They comprise chlorinated bleaches.

In one aspect of the invention the size of mean particle of the components of the granular compositions according to the invention should preferably be such that no more 15% of the particles have a diameter greater than 1.8 mm and not more than 15% of the particles have a diameter of less than 0.25 mm. Preferably the average particle size is such that from 10% to 50% of the particles have a particle size of 0.2 mm to 0.7 mm in diameter

The term average particle size as defined in the present invention is calculated by passing through a sieve a sample of the composition into a series of fractions (typically 5 fractions) on a series of sieves, preferably Tyler sieves. The fractions by weight obtained from this mode is plotted against the size of the filter opening. The average particle size is taken as the opening size through which 50% by weight of the sample.

In a further aspect of the invention, at least 80%, preferably at least 90% by weight of the composition comprises average particle size particles of at least 0.8 mm, more preferably at least 1.0 mm and most preferably 1.0, or 1.5 to 2.5 mm Most preferably at least 95% of the particles They will have such average particle size. Such particles are prepared preferably by an extrusion process.

The volumetric density of the compositions granular detergents according to the present invention have typically a volumetric density of at least 400, preferably 600 g / liter, more preferably 650 g / liter at 1200 g / liter Bulk density is measured by a funnel. simple and a cup device consisting of a conical funnel rigidly molded on a base and provided with a valve hinge on its lower limb to allow emptying funnel contents in an axially aligned cylindrical cup arranged under the funnel. The funnel is 130 mm high and has internal diameters of 130 mm and 40 mm at their respective extremities upper and lower. It is mounted in such a way that the limb lower be 140 mm above the upper surface of the base. The cup has a total height of 90 mm, an internal height 87 mm and an internal diameter of 84 mm. Its nominal value is 500 ml.

To carry out a measurement, the funnel with powder by throwing it by hand, the valve opens hinge and let the powder fill the cup. He retires from the team the full cup and excess dust is removed from the cup by passing a straight edge instrument, for example a knife, through its top edge Then, the full cup and the weight value are weighed of the powder obtained, bends to provide a value of volumetric density in g / liter. The measurements are repeated as necessary.

Compacted solids can be manufactured using any suitable compaction procedure, such as pressing, agglomeration or extrusion, preferably pressing. Preferably, the tablets for use in washing procedures of plates, are manufactured using a standard rotary press using compression forces of 5 to 13 kN / cm2, more preferably of 5 to 11 kN / cm2 so that the compacted solid has a minimum hardness of 176N to 275N, preferably 195N to 245N, measured by a hardness test C100 supplied by I. Holland instruments. This procedure can be used to prepare tablets homogeneous or layered of any size or shape. Preferably The tablets are symmetrical to ensure uniform dissolution of The tablet in the wash solution.

Laundry method

The machine wash methods of the present invention typically comprise treating dirty clothes with an aqueous wash solution in a washing machine that has dissolved or dispensed an effective amount of a detergent composition for Machine wash clothes according to the invention. By a effective amount of the detergent composition is understood from 10 g to 300 g of product dissolved or dispersed in a wash solution of volume of 5 to 65 liters, as are the typical product doses and the wash solution volumes commonly used in conventional methods of washing clothes by machine. The Dosage depends on the particular conditions such as water hardness and dirtiness of dirty clothes.

The detergent composition can be dispensed, by example, from the dispenser drawer of a washing machine or you can spread on dirty clothes in the machine.

In a preferred aspect of use, a dispensing device in the washing method. The device Dispenser is loaded with detergent product and used to Introduce the product directly into the machine drum washing machine before the start of the wash cycle. His ability in volume should be such that it could contain enough product detergent like the one normally used in the method of washed.

The dispensing device containing the detergent product is introduced into the drum before starting the wash, before, simultaneously or after the washer has been loaded with dirty clothes. When the wash cycle begins the washing machine, water is introduced into the drum and the drum rotates  periodically The design of the dispensing device should be such that it allows to contain the dry detergent product but that then allow the release of this product during the cycle of washing in response to its agitation as the drum rotates and also as a result of its contact with the wash water.

To allow product release detergent during washing, the device may have a number of holes through which the product can pass. Alternatively, the device may be made of a material. that is permeable to the liquid product but impervious to the product solid, which will allow the release of the dissolved product. Preferably, the detergent product will be rapidly released to the beginning of the wash cycle providing high concentrations of product promptly located on the machine drum washing machine at this stage of the wash cycle.

Preferred dispensing devices are reusable and designed in such a way that the integrity of the container is kept both in its dry state and during the wash cycle In the following patents; GB-B-2,157,717, GB-B-2,157,718, EP-A-0201376, EP-A-0288345 and EP-A-0288346 have been described especially preferred dispensing devices for use with the composition of the invention An article published by J.Bland in Manufacturing Chemist, November 1989, pages 41-46 also describes dispensing devices especially preferred for use with granular products for laundry that are of the type commonly known as "granuleta". In PCT patent application No. WO94 / 11562, describes another preferred dispensing device for use with the Compositions of this invention.

In patent application publications European Nos 0343069 & 0343070 devices are described Especially preferred dispensers. The last request describes a device comprising a flexible sheath in the form of bag that extends from a support ring that defines a hole, adapting the hole to let the bag into enough product for a wash cycle in a process of washed. A part of the washing medium flows through the hole towards the bag, dissolve the product, and then the solution passes outside through the hole to the washing medium. The ring of support is provided with a masking device for avoid access of undissolved, moist product, understanding typically this device radially extending walls from a central projection in a spoke wheel configuration, or a similar structure in which the walls have a shape helical.

Alternatively, the dispensing device It can be a flexible container, such as a bag or sack. The bag can be of fibrous construction coated with a material waterproof protector, so that it retains the contents, as described in the European patent application published with No. 0018678. Alternatively, you can make a water-insoluble synthetic polymeric material provided with a sealed or closed edge designed to break in aqueous medium, as described in published European patent applications with Nos. 0011500, 0011501, 0011502 and 0011968. A convenient way Water-sealable closure comprises a water soluble adhesive arranged along and sealing an edge of the sack made of a water-impermeable polymeric film, such as polyethylene or Polypropylene.

Machine dishwashing method

Any suitable methods are provided for machine dishwashing or cleaning dirty tableware, particularly dirty silver.

A preferred method of dishwashing a machine comprises treating dirty items selected from crockery, glassware, crockery, silver and cutlery and their mixtures, with a aqueous liquid that has dissolved or dispensed in the amount Effective of a machine dishwashing composition according to the invention. For an effective amount of the composition for machine dishwashing it is understood from 8 g to 60 g of product dissolved or dispersed in a volume wash solution 3 to 10 liters, such as typical product doses and volumes of wash solution commonly used in conventional machine dishwashing methods.

Packaging of the compositions

The forms of bleaching compositions commercially available can be packaged in any suitable container including paper ones, cardboard, plastic materials and any sheet materials adequate. In European Patent Application No. 94921505.7, describes a preferred form of packaging.

Abbreviations used in the examples

In detergent compositions, the Abbreviations that identify the components have the following meanings:

THE:

linear (C12) alkyl benzenesulfonate of sodium

TAS:

Sodium tallow alkyl sulfate

CxyAS:

(C 1x-C 1y) alkyl sulfate of sodium

C46SAS:

Alkyl (C 14 -C 16) secondary (2,3) sodium sulfate

CxyEzS:

(C 1x-C 1y) alkyl sulfate of sodium condensed with z moles of ethylene oxide

CxyEz:

C_ {1x} -C_ {1y} alcohol predominantly linear primary condensed with a mean of z moles of ethylene oxide

QAS 1:

Chloride R 2 .N + (CH 3) 2 (C 2 H 4 OH) with R2 = linear alkyl C_ {9} -C_ {11}

QAS 2:

Chloride R 2 .N + (CH 3) 2 (C 2 H 4 OH) with about 50% R2 = C8 linear alkyl; approximately 50% R2 = C10

QAS 3:

Chloride R 2 .N + (CH 3) 2 (C 2 H 4 OH) with about 40% R 2 = linear C 11 alkyl; approximately 60% R2 = linear alkyl C9

QAS 4:

Bromide R 2 .N + (CH 3) 2 (C 2 H 4 OH) with R2 = linear alkyl C6

QAS 5:

Chloride R 2 .N + (CH 3) 2 (C 2 H 4 OH) with R2 = linear alkyl C10

Soap:

Linear sodium alkylcarboxylate derived from a 80/20 mixture of tallow and coconut oils.

CFAA:

(coconut) alkyl (C 12 -C 14) N-methylglucamide

TFAA:

Rent (C 16 -C 18) N-methylglucamide

TPKFA:

Heated whole fraction fatty acids C_ {12} -C_ {14}

STPP:

Anhydrous Sodium Tripolyphosphate

TSPP:

Tetrasodium pyrophosphate

Zeolite A:

Hydrated sodium aluminosilicate of formula Na 12 (AlO 2 SiO 2) 12 .27H 2 O which has a primary particle size in the range of 0.1 to 10 micrometers

Zeolite MAP:

MAP hydrated sodium aluminosilicate zeolite which has a silicon to aluminum ratio of 1.07

NaSKS-6:

Crystalline laminar silicate of formula δ-Na_ {2} Si_ {2} O_ {5}

Citric acid:

Citric acid anhydrous

Borate:

Sodium borate

Carbonate:

Anhydrous sodium carbonate with a size of particle between 200 µm and 900 µm

Baking soda:

Anhydrous sodium bicarbonate with a distribution particle size between 400 µm and 1200 µm

Silicate:

Amorphous Sodium Silicate (SiO2: Na2O = 2.0: 1)

Sodium sulfate:

Anhydrous sodium sulfate

Citrate:

Trisodium citrate dihydrate with activity 86.4% with a particle size distribution between 425 µm and 850 \ mum

MA / AA:

1: 4 maleic / acrylic acid copolymer, weight average molecular approximately 70,000

AA:

Molecular Weight Sodium Polyacrylate Polymer medium 4,500

CMC:

Sodium carboximethylcelulose

Cellulose Ether:

Methylcellulose ether with a degree of 650 polymerization available at Shin Etsu Chemicals

Protease:

4KNPU / g activity proteolytic enzyme sold by NOVO Industries A / S under the trade designation Savinase

Alcalase:

Proteolytic enzyme of 3AU / g activity sold by NOVO Industries A / S

Cellulase:

Activity cellulite enzyme 1000 CEVU / g sold by NOVO Industries A / S under the trade designation Carezyme

Amylase:

Amylolytic enzyme activity 120KNU / g sold by NOVO Industries A / S under the commercial designation Termamyl 120T

Lipase:

Lipolytic enzyme activity 100 kLU / g sold by NOVO Industries A / S under the trade designation Lipolase

Endolasa:

Activity endoglunase enzyme 3000 CEVU / g sold by NOVO Industries A / S

PB4:

Sodium perborate tetrahydrate of formula nominal NaBO_2 .3H2 {2} O.H2 {O2}

PB1:

Anhydrous sodium perborate bleach Nominal formula NaBO_2 .H2 {2}

Percarbonate:

Sodium percarbonate of nominal formula 2Na2CO3 .3H2O2

NOBS:

Nonanoyloxybenzene sulfonate in sodium salt form

TAED:

Tetraacetylethylenediamine

Mn Catalyst:

Mn IV 2 (m-O) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (PF 6) 2, as described in U.S. Patents 5,246,621 and 5,244,594.

DTPA:

Pentaacetic Diethylenetriamine Acid

DTPMP:

Diethylenetriamine penta (methylene phosphonate), marketed by Monsanto with the commercial designation Dequest 2060

Photoactivated bleach:

{} \ Zsk Phthalocyanine sulfonated encapsulated in dextrin soluble polymer bleaching

Brightener 1:

4,4'-bis (2-sulfoestiryl) biphenyl disodium

Brightener 2:

4,4'-bis (4-anilino-6-morpholino-1.3.5-triazin-2-yl) amino) stilbene-2: 2'-disulfonate disodium

HEDP:

1,1-hydroxyethane acid diphosphonic

EDDS:

Acid ethylenediamine-N, N-disuccinic

QEA:

bis ((C 2 H 5 O) (C 2 H 4 O n) (CH 3) - N + - C 6 H 12 -N <+> - (CH3) bis ((C2H5O) - (C 2 H 4 O) n), in which n = from 20 to 30

PEGX:

Polyethylene glycol, with a molecular weight of x

PEO:

Poly (ethylene oxide) with a molecular weight of 50,000

TEPAE:

Tetraethylenepentaamine ethoxylate

PVP:

Polyvinylpyrrolidone Polymer

PVNO:

Polyvinylpyridine N-Oxide

PVPVI:

Copolymer of polyvinylpyrrolidone and vinylimidazole

SRP 1:

Sulfobenzoyl-terminated esters with chain main oxyethylene and terephthaloyl

SRP 2:

Poly (1.2 propylene terephthalate) polymer Short block diethoxylated

Defoamer silicone:

{} \ hskip0,3cm Polydimethylsiloxane foam control with copolymer siloxane-oxyalkylene {} \ hskip0.3cm as an agent dispersant with a ratio of said foam control agent a said agent {} \ dispersion from 10: 1 to 100: 1.

Wax:

Paraffin wax

In the following examples all levels are give in% by weight of the composition:

Example 1

The following detergent compositions granules for washing high density clothes A to F in particular utility in washing conditions of a European machine are Examples of the present invention:

6

7

Example 2

The following detergent compositions granules for washing clothes G to I of particular utility in Washing conditions of a European machine are examples of the present invention:

8

9

Example 3

The following detergent formulations of Particular utility in washing conditions of a European machine they are examples of the present invention.

10

eleven

Example 4

The following detergent formulations Granular are examples of the present invention. Formulation N It is particularly suitable for use in washing conditions of A Japanese machine The O to S formulations are particularly suitable for use in washing conditions of a machine USA

12

13

14

Example 5

The following detergent formulations Granular are examples of the present invention. Formulations W and X are particularly useful in conditions of washing a US machine And it is particularly useful in conditions of Japanese machine wash.

fifteen

16

Example 6

The following detergent compositions granules of particular utility in washing conditions of a European machine are examples of the present invention.

17

18

Example 7

The following detergent compositions are Examples of the present invention:

19

twenty

Example 8

The following detergent formulations are Examples of the present invention:

twenty-one

Example 9

The following detergent stick compositions for washing clothes are examples of the present invention.

22

Claims (18)

1. A laundry detergent composition having a pH of at least 8.5 in an aqueous solution at a concentration of 0.5% by weight, or its component, which comprises a detergency builder, an anionic surfactant and a cationic surfactant of formula I (I) R 1 R 2 R 3 R 4 N + X - in which R1 is a group hydroxyalkyl having no more than 6 carbon atoms; each R 2 and R 3 are independently selected from alkyl or C 1-4 alkenyl; R 4 is an alkyl or C 5-11 alkenyl; and X - is a counterion that it is not substantially exchanged with a hydroxide ion in a 0.5% aqueous solution by weight of the detergent composition a 20 ° C 2. A laundry detergent composition according to claim 1, wherein the composition comprises a mixture of cationic surfactants of formula I: (I) R 1 R 2 R 3 R 4 N + X - in which R1 is a group hydroxyalkyl having no more than 6 carbon atoms; each R 2 and R 3 are independently selected from alkyl or C 1-4 alkenyl; R 4 is an alkyl or C 5-11 alkenyl; and X - is a counterion that it is not substantially exchanged with a hydroxide ion in a 0.5% aqueous solution by weight of the detergent composition at 20 ° C and wherein, in the mixture of cationic surfactants of formula I, at least 10% by weight has R 4 which is alkyl or alkenyl C_ {5-9}. 3. A laundry detergent composition according to claim 1 or claim 2, wherein the counterion X - is selected from the group consisting of ions chloride, bromide and nitrate. 4. A laundry detergent composition according to claim 3, wherein the X - counterion is ion chloride. 5. A laundry detergent composition according to any preceding claim, wherein the surfactant cationic is present in an amount of 0.01% to 20% in composition weight. 6. A laundry detergent composition according to claim 5, wherein the cationic surfactant is is present in an amount of 0.05% to 5% by weight of the composition. 7. A laundry detergent composition according to any preceding claim, wherein in the compound cationic of formula I, R1 is --- CH2CH2OH or --- CH 2 CH 2 CH 2 OH; R 2 and R 3 are each methyl; R 4 is C 6-11 alkyl. 8. A laundry detergent composition according to any preceding claim, wherein in the compound cationic of formula I, R 4 is a group C 6-9 or C 11, preferably being a C 6-9 alkyl or alkenyl group. 9. A laundry detergent composition according to any preceding claim, comprising a mixture of cationic surfactants that are compounds of formula I which they comprise a compound of formula I in which R 4 is a group higher alkyl having n carbon atoms where n is 8 to 11 and a compound of formula I in which R 4 is an alkyl group lower which has (n-2) carbon atoms. 10. A detergent composition for washing clothing according to claim 9, wherein the cationic surfactant it comprises 5 to 95% by weight of a compound of formula I having a higher alkyl group and 5 to 95% of a compound of formula I which has a lower alkyl group. 11. A detergent composition for washing clothing according to any preceding claim, comprising additionally an anionic surfactant selected from anionic surfactants having the formula II or III: (II) R 5 OSO 3 {} - M + (III) R 6 SO 3 {} - {M} + in which R 5 is a remainder linear or branched alkyl having 9 to 22 carbon atoms; R 6 is (C 10-20) alkyl benzene; M +, M '+ are each selected from alkali metals, alkaline earth metals, alkanolammonium and ammonium. 12. A detergent composition for washing clothing according to claim 11, wherein the anionic surfactant it comprises both an anionic surfactant of formula II and a anionic surfactant of formula III in a weight ratio of II: III from 15: 1 to 1: 2. 13. A detergent composition for washing clothing according to claim 11 or claim 12, wherein the anionic surfactant II is a (C 16-18) primary or secondary alkyl, linear or branched) sulfate and in which the anionic surfactant III is a (C 11-13) alkyl benzenesulfonate. 14. A detergent composition for washing clothing according to any preceding claim, comprising additionally a nonionic surfactant selected from the group that consists of alcohol ethoxylates, alkylphenol ethoxylates, polyhydroxy fatty acid amides, alkyl polyglycosides and mixtures thereof. 15. A detergent composition for washing clothing according to any of claims 11 to 14 which understands: (a) from 0.25% to 3% by weight of a surfactant cationic of formula I; (I) R 1 R 2 R 3 R 4 N + X - in which R1 is a group hydroxyalkyl having no more than 6 carbon atoms; each R 2 and R 3 are independently selected from alkyl or C 1-4 alkenyl; R 4 is an alkyl or C 6-11 alkenyl; and X - is a counterion (b) from 3% to 40%, by weight of an alkyl sulfate primary or secondary linear or branched chain as surfactant (II); (c) from 6% to 23%, by weight of alkylbenzenesulfonate as surfactant III; Y (d) from 0.5% to 20%, by weight, of a non-surfactant ionic. 16. A detergent composition for washing clothing according to any preceding claim, found substantially free of bleach. 17. A detergent composition for washing clothing according to claim 1, wherein the composition is formed combining a cationic surfactant of formula I: (I) R 1 R 2 R 3 R 4 N + X - in which R1 is a group hydroxyalkyl having no more than 6 carbon atoms; each R 2 and R 3 are independently selected from alkyl or C 1-4 alkenyl; R 4 is an alkyl or C 6-11 alkenyl; and X - is a counterion that it is not substantially exchanged with a hydroxide ion in a 0.5% by weight aqueous solution of the detergent composition at 20 ° C, and an alkalinity system with one or more detergent components optional 18. A method of washing clothes in a washing machine domestic, in which a dispensing device is inserted that contains an effective amount of a solid detergent composition according to any preceding claim, in the washing machine before start the washing, in which said dispensing device allows the progressive release of said detergent composition in the wash solution during washing.