ES2225891T3 - DETERGENTS THAT FIRST FREE A STRONGER ORGANIC PEROXIACIDE TYPE WHITENING TO A DISSOLUTION, FOLLOWED BY THE RELEASE OF A WEAKER PEROXIACIDE. - Google Patents

Abstract

There is provided a detergent composition containing an organic peroxyacid bleaching system capable of releasing a plurality of organic peroxyacids of different strength to a wash solution. A means is provided for delaying the release of a stronger organic peroxyacid relative to the release of a weaker organic peroxyacid. The detergent composition provides bleachable soil/stain removal capability when employed in laundry or dishwashing methods.

Description

Detergents that first release a washing solution an organic peroxyacid type bleach plus strong, followed by the release of a weaker peroxyacid.

Technical field

This invention relates to compositions detergents containing a peroxyacid bleaching system organic that can release a plurality to a wash solution of organic peroxyacids of different strength.

Background of the invention

The successful removal of bleachable dirt / stains such as blood, spinach, chocolate, coffee, tea and tomato sauce from dirty / stained substrates, it is a particular challenge for the formulator of a composition detergent for use in a washing method such as a method for dishwashing by machine or laundry.

Traditionally, the removal of such bleachable soils / stains has been possible by the use of bleaching components such as oxygenated bleaches, including hydrogen peroxide and organic peroxyacids. Organic peroxyacids are often obtained by the in situ perhydrolysis reaction between hydrogen peroxide and an organic peroxyacid bleach precursor. Alternatively, a previously formed organic peroxyacid can be used.

Usually only one compound is used precursor of bleaches or organic peroxyacid formed previously. However, it has now been established that the use of certain bleaching systems, as defined in claim 1, which can release a plurality of organic peroxyacids of Different strength to a wash solution, can provide benefits of removal of dirt / bleachable spots.

In addition, applicants have now found that when the release of the strongest of the organic peroxyacids to the washing solution is delayed in relation to the release of the weaker organic peroxyacid gives an efficacy in the Bleachable stain removal further increased.

Alternatively, applicants have found that a stain removal efficiency can be obtained bleachable equivalent from a bleaching system of mixed organic peroxyacid containing lower levels of a stronger organic peroxyacid whose release to dissolution of washing is delayed, as can be obtained for one, comparable from another mode, organic peroxyacid bleaching system that has no delayed release of the strongest peroxyacid to dissolution washing In other words, requiring a delayed release of the strongest peroxyacid, an efficacy can be obtained equivalent bleaching even if less than peroxyacid is used stronger.

Without wanting to limit himself to theory, it is believed that the The mechanism behind this development is as follows: first stage, the organic peroxyacid is released more quickly weak in the wash solution where it can act on stains easily bleachable, but may also fall prey to reactions of inefficient decomposition in the first part of the wash. Such decomposition very often results from reactions with components (such as heavy metal ions) present in the solution of washing, which are often derived from the dirty wash load. In the second stage, the strongest peroxyacid is released and can act in Bleachable spots less easily (i.e. more rebellious) in an environment where it will be less susceptible to decomposition, in the sense that any "reactive components" of the wash load will have been "spent" essentially previously when attacking the weakest acid. Thus, the strongest peroxyacid is used to achieve its greatest effect when dealing with only the most spots difficult, and "losses" due to Any parallel reactions.

Compositions have been described in the art that contain binary organic peroxyacid precursor compounds. For example, US Pat. No. 5,405,412 A describes a detergent composition containing precursor compounds of bleaches of n-acylcaprolactam and alkanoyloxybenzenesulfonate. However, the applicant does not have awareness of any description of precursor systems of mixed organic peroxyacids in which the release of a stronger organic peroxyacid deliberately retards in relation to a weaker organic peroxyacid, nor of any Teaching behavioral benefits related to this.

Therefore, it is an objective of the present invention provide compositions suitable for use in methods for washing clothes and for automatic dishwashing that have increased removal of dirt / bleachable stains.

Summary of the invention

According to one aspect of the present invention, provides a detergent composition that contains a system organic peroxyacid type bleach that can release two organic peroxyacid bleach other than a solution of washing, wherein said organic peroxyacid bleaching system it contains a source of hydrogen peroxide and a plurality of organic peroxyacid bleach precursor compounds, and where a means is provided to delay release to a washing solution of the strongest peroxyacid in relation to the release of a weaker peroxyacid, so that in the method of T50 test described herein, the time to reach a concentration which is 50% of the final concentration of said strongest peroxyacid is at least 120 seconds longer than time to reach a concentration that is 50% of the concentration end of said weaker peroxyacid, where the relative strength of peroxyacids are measured according to the "bleaching protocol of dye "described herein.

According to a preferred aspect of the present invention is provided a detergent composition containing a organic peroxyacid bleaching system that can release two organic peroxyacid bleach other than a solution of washing, where a means is provided to delay release to a stronger peroxyacid wash solution in relation to the release of the weakest peroxyacid, so that in the method of T50 test described herein, the time to reach a concentration that is 50% of the final concentration of weaker peroxyacid is less than 60 seconds, and the time to reach a concentration that is 50% of the final concentration of the strongest peroxyacid is more than 180 seconds, where the force Relative of peroxyacids is measured according to the "protocol of bleaching of the dye "described herein.

According to a preferred aspect of the present invention, the detergent composition contains only two compounds organic peroxyacid bleach precursors, ie a binary bleach precursor system.

Detailed description of the invention Organic peroxyacid bleaching system

According to one aspect of the present invention, the detergent compositions contain a bleaching system of organic peroxyacid. In a preferred execution, the system bleach contains a source of hydrogen peroxide and a plurality of peroxyacid bleach precursor compounds organic that can release at least two organic peroxyacids different to a wash solution. Peroxyacid production Organic is performed by an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of peroxide of hydrogen include perhydrate type bleaches inorganic In a preferred alternative embodiment a organic peroxyacid previously formed as a substitute for one, many or all bleach precursor compounds of organic peroxyacid. Also considered are compositions that contain mixtures of a source of hydrogen peroxide and a organic peroxyacid precursor in combination with a peroxyacid previously formed organic.

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 of 2% to 30% by weight and most preferably 5% to 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 can be include in the form of the crystalline solid without any protection additional. However, for certain perhydrate salts, the preferred embodiments of said granular compositions use a Coated form of the material, which provides better stability Storage for perhydrate salt in the granular product. Suitable coatings comprise inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic materials such as waxes, oils or soaps fatty

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, more preferably, tetrahydrate NaBO 2 H 2 O 2. 3H 2 O.

Preferred perhydrates herein are alkali metal percarbonates, particularly percarbonate of sodium. Sodium percarbonate is an addition compound that has a formula corresponding to 2Na2CO3 .3H2O2, and is commercially available As a crystalline solid.

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

Peroxyacid bleach precursor

Peroxyacid bleach precursors they are compounds that react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally, peroxyacid bleach precursors are can represent 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 is

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

--- OOHX ---

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

--- OOH

The bleaching precursor compounds of peroxyacid are preferably incorporated at a level of 0.5% to 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 peroxyacids typically contain one or more N- or groups 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, hereinafter referred to 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

2

3

4

5

       \ newpage
    

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

Preferred solubilizing groups are those -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 -CO2 - M +, in which R3 is an alkyl chain containing 1 to 4 atoms of carbon, M is a cation that provides solubility to the activator of the bleaching and X is an anion that provides solubility to the activator of bleaching. Preferably, M is an alkali metal cation, ammonium or substituted ammonium, the most preferred being sodium and potassium, and X is a halide, hydroxide, methylsulfate or anion 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, including those with the following general formulas:

6

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 1 to 10 carbon atoms and L It can be essentially any leaving group. The most preferably R1 is an alkyl group with 9 carbon atoms, R2 is an alkylene group containing 4 carbon atoms, R 5 is H, thus the organic peroxyacid released in the Perhydrolysis is an acid nonilamide peroxiadipic (NAPAA). Bleaching activating compounds Amido-substituted 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 imide 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.

Perbenzoic acid precursor compounds Suitable type N-acylated lactams have the formula:

7

in which n is from 0 to 8, preferably from 0 to 2, and R 6 is aryl, alkoxyaryl or alkaryl containing from 1 to 12 carbon atoms, or a phenyl group substituted containing 6 to 18 carbon atoms, preferably a group benzoyl

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 suitable peroxyacid precursor compound with a functional group positively charged, such as an ammonium or alkylammonium group, preferably an ethyl- or methyl-ammonium group. The cationic peroxyacid precursors are typically present in solid detergent compositions as a salt with an anion suitable, 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 alkylpercarboxylic or an alkylperoxyacid precursor amido-substituted, as described in continuation.

The cationic peroxyacid precursors are described in US Pat. No. 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- or ammonium substituted benzoyl oxybenzenesulfonates 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 trialkylammonium-methylene-benzoyl-caprolactams, and the trialkylammonium-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:

8

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

Organic peroxyacid previously formed

The organic peroxyacid bleaching system may contain in addition to, or as an alternative to, a compound precursor of organic peroxyacid bleach, a peroxyacid previously formed organic, typically at a level of 1% to 15% in 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:

9

       \ newpage
    

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. At EP-A-0170386 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. Also suitable here are mono- and di-perazelaic acids, acid mono-and di-perbrasilic acid N-phthaloylaminoperoxicaproproic.

Strength of organic peroxyacid- "Bleaching Protocol Colorant"

According to the invention, the release to a washing solution of a stronger organic peroxy acid is delays in relation to the release of one more organic peroxyacid weak.

For the purposes of the present invention, the strength of organic peroxyacid is evaluated by reference to "dye bleaching protocol" of the peroxy acid described then. In essence, this protocol compares the kinetics of the whitening action of organic peroxyacid in a coloring matter representative under controlled conditions of pH and temperature.

According to the protocol, you get a first solution containing 0.5M of a precursor compound of organic peroxyacid in distilled water (or a mixture of water spectrophotometric grade distillate / ethanol for compounds low water soluble precursors).

A second solution is obtained in three stages. In the first stage, 0.3 mg of EDTA, and 0.277g of sodium percarbonate not coated to 100ml of distilled water. The resulting peroxide solution, which is equivalent to a 0.025M active oxygen solution, buffered to pH 10.5 using a suitable buffering agent (e.g., carbonate of sodium). In the second stage 18mg of direct blue No. 1 is added to 100ml distilled water together with buffering agent to give a pH 10.5 constant. In the third stage, the peroxide solution is Mix with the dye solution.

The kinetics of the bleaching action is measured spectrometrically as follows. Initially, they are added 20 microliters of the first solution to a polystyrene cuvette 1 cm inside the spectrometer, then 4ml of the second solution by means of an automatic pipette. The time of addition of the second solution is taken as time 0, and the dye bleaching rate is measured for one second runtime of 1800 seconds. The measured wavelength is 596 nm, and the spectrometer is preferably a spectrometer of array diode HP 8452 A (registered name), although they could be used other suitable spectrometers known to those skilled in the technique. Spectrophotometric measurements are typically taken in 0.5 second intervals and readings are processed using Known single cell kinetics software.

With the given levels of organic peroxyacid and of the dye components the bleaching action of the dye It will essentially follow first-order kinetics. So, adjusting the data to a curve of an appropriate first order kinetics (it is say, exponential) you can get a speed constant for the organic peroxyacid.

The comparison of the speed constants gives a measure of the strength of organic peroxyacid, having an acid stronger a higher first order speed constant.

A whitening efficacy ratio, which compares the bleaching force of two organic peroxyacids, can be defined as the rate constant for the organic peroxyacid plus strong divided by the velocity constant for the peroxyacid weaker organic. According to a preferred aspect of the invention, the whitening efficiency ratio is preferably at least 1.1, more preferably at least 1.3, most preferably at least 1.5

Relative Release Kinetics

In an essential aspect of the invention, provides a means to delay the release of a peroxyacid stronger organic to a wash solution in relation to the release of a weaker organic peroxyacid.

Said means may comprise a means for delay the release of the strongest peroxyacid to the dissolution of washed. Alternatively, said medium may comprise a means for increase the release rate of organic peroxyacid more weak to wash solution.

Delayed release speed - media

Delayed release means may include coat the peroxyacid bleach precursor compound stronger organic with a coating or mixture of coatings Designed to provide delayed release. The coating it may comprise, for example, a water-soluble material, or it can be a coating with sufficient thickness so that the dissolution kinetics of the thick coating provide the controlled release speed.

The coating material can be applied using various methods. Any coating material is typically present in a weight ratio of the material of bleach coating from 1:99 to 1: 2, preferably 1:49 to 1: 9.

Suitable coating materials include triglycerides (eg from a vegetable oil (partially) hydrogenated, soybean oil, cottonseed oil), mono- or diglycerides, microcrystalline waxes, gelatin, cellulose, acids fatty and any of their mixtures.

Other suitable coating materials they can comprise sulfates, silicates and carbonates of metals alkaline and alkaline earth, including carbonate of calcium

The coating material is preferred as sodium silicate of SiO2: Na2O ratio of 1.6: 1 to 3.4: 1, preferably 2.8: 1, applied as an aqueous solution to give a level of 2% to 10%, (usually 3% to 5%) of solids of silicate by weight of percarbonate. It can also be included in the magnesium silicate coating.

Any coating material based on inorganic salts can be combined with binder materials organic to provide composite coatings based on a inorganic salt and an organic binder. Suitable binders include ethoxylated alcohol compounds C 10 -C 20, containing 5 to 100 moles of ethylene oxide per mole of alcohol and more preferably ethoxylated compounds of primary alcohols C 15 -C 20 containing 20 to 100 moles of ethylene oxide per mole of alcohol.

Other preferred binders include certain polymeric materials Polyvinylpyrrolidones with a weight Average molecular weight of 12,000 to 700,000 and polyethylene glycols (PEG) with an average molecular weight of 600 to 10,000 are examples of such polymeric materials Copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid, constituting maleic anhydride at least 20 mole percent of the polymer, are additional examples of polymeric materials useful as binding agents. These polymeric materials are they can use as such or in combination with solvents such as water, propylene glycol and ethoxylated compounds of alcohols C 10 -C 20 mentioned above, which They contain 5 to 100 moles of ethylene oxide per mole. Examples Additional binders include mono- and di-glycerol C 10 -C 20 ethers and also the C 10 -C 20 fatty acids.

Cellulose derivatives such as methyl cellulose, carboxymethyl cellulose, ethylhydroxyethyl cellulose and hydroxyethyl cellulose, and the homo- or copolymeric polycarboxylic acids or their salts, are other examples of binders suitable for use in this memory.

A method to apply the material of Coating involves an agglomeration. The agglomeration processes Preferred include the use of any of the materials organic binders described herein previously. Any agglomerator / mixer can be used conventional including, but not limited to, the types of tray mixers, rotary and vertical drums. The cast coating compositions can also be applied pouring or atomizing them on a moving bed of agent bleaching

Other means to provide release delayed required include mechanical means to alter the physical characteristics of the bleach in order to control its solubility and its release rate. Appropriate protocols They could include compression, mechanical injection, manual injection and solubility adjustment of the bleaching compound by selection of particle size of any component in the form of particles

Although the choice of particle size will depend so much on the composition of the component in the form of particles, as of the desire to satisfy the release kinetics delayed desired, it is desirable that the particle size be larger than 500 micrometers, preferably having an average diameter of 800 to 1,200 micrometer particle.

Additional protocols to provide the delayed release means include the right choice of any other component of the detergent composition matrix, of such that when the composition is introduced into the solution wash, the ionic strength environment provided there does it is possible that the delayed release kinetics achieved requires

Increased release speed - media

All appropriate means are considered for increase the release rate of organic peroxyacid more weak to wash solution.

Increased release means may include coat the weakest organic peroxyacid component with a coating intended to provide increased release. He coating may comprise, for example, an extremely material, or even effervescently, soluble in water.

Other means to provide release augmented required may include mechanical means to alter the physical characteristics of the weakest organic peroxyacid for increase its solubility and its release rate.

An appropriate protocol could include the selection deliberate particle size of the peroxyacid component weaker organic. The choice of particle size will depend both of the composition of the particulate component, and of the desire to satisfy the increased release kinetics desired.

Delayed Release - Kinetic Parameters

The release of the strongest organic peroxyacid in relation to the weakest organic peroxyacid component is such that, in the T50 test method described herein, the T50 value for the weakest organic peroxyacid component is at minus 120 seconds less than the T50 value for the component stronger organic peroxyacid. According to a preferred aspect, the time (T50) to reach a concentration that is 50% of the final concentration of said weaker organic peroxyacid is lower than 60 seconds, preferably less than 50 seconds, more preferably less than 40 seconds, and the time (T50) for reach a concentration that is 50% of the final concentration of said stronger organic peroxyacid is more than 120 seconds, preferably 180 to 480 seconds, more preferably 240 to 360 seconds

Delayed release - test method

The delayed release kinetics in this memory is defined with respect to a "TA test method" that measure the time to reach A% of the concentration / final level of the component when a composition containing the component is dissolves according to the standard conditions presented to continuation.

Standard conditions involve a glass of 1 liter glass precipitates filled with 1000 ml of water distilled at 20 ° C, to which 10g of composition are added. They stir contents of the beaker using a magnetic stirrer to 100 rpm The magnetic stirrer is shaped like a pea / ovule, it has a maximum dimension of 1.5cm and a minimum dimension of 0.5cm. The concentration / final level is taken as the concentration / level reached 10 minutes after adding the composition to the glass of precipitates filled with water.

Appropriate analytical methods are chosen for allow a reliable determination of final concentrations and accidental in the dissolution of the component in question, after the adding the composition to the beaker water.

Such analytical methods may include those which involve continuous monitoring of the concentration level of the component, including for example photometric methods and conductimetric

Alternatively, methods that involve taking dissolution titles at intervals of time fixed, stop the dissolution process by an appropriate means such how to quickly reduce the temperature of the title, and then determine the concentration of the component in the title by any means such as chemical titration methods.

Appropriate graphic methods can be used, including curve fitting methods, when appropriate, to allow calculation of TA value from analytical results without treating.

The particular analytical method selected for determine the concentration of the component, will depend on the nature of the component, and the nature of the composition that It contains the component.

Additional detergent components

The detergent compositions of the invention They may also contain additional detergent components. The concrete nature of these additional components, and their levels of incorporation, will depend on the physical form of the composition and of the nature of the cleaning operation for which it is going to use.

The compositions of the invention may, by example, be formulated as detergent compositions for washing hand and machine clothing, including additive compositions for laundry and compositions suitable for use in the pretreatment of stained tissues and compositions for washing machine dishes.

When formulated as suitable compositions for use in a machine wash method, eg: methods for machine washing and machine washing of dishes, the compositions of the invention preferably contain one or more additional detergent components selected from surfactants, detergency builders, enzymes, sequestrants of heavy metal ions, organic polymeric compounds, soaps suppressants, limestone soaps dispersants, agents against redeposition and dirt suspension e corrosion inhibitors The laundry compositions they may also contain, as additional detergent components, softening agents

Surfactant

The detergent compositions of the invention may contain as an optional detergent component a surfactant selected from anionic, cationic surfactants, non-ionic, ampholytic, amphoteric and hybrid ion and their mixtures

The surfactant is typically present at a level of 0.1% to 60% by weight. Levels of incorporation of Most preferred surfactants are from 1% to 35% by weight, most preferably from 1% to 20% by weight.

Preferably, the surfactant is formulated from so that it is compatible with any enzyme type components present in the composition. In liquid or gel compositions, what more preferably, the surfactant is formulated so that promote, or at least not degrade, the stability of any enzyme in these compositions.

In U.S. Patent No. 3,929,678 issued to Laughlin and Heuring on December 30, 1975 gives a typical list of anionic, nonionic, ampholytic, and hybrid ion classes, and species of these surfactants. More examples are given in "Surface Active Agents and Detergents "(Vol. I and II of Schwartz, Perry and Berch) In US Pat. No. 4,259,217, issued to Murphy on A list of surfactants is presented on March 31, 1981 suitable cationic.

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

Essentially, it can be included in the compositions any anionic surfactant useful for purposes detersives These may include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts, such as mono-, di- and tri-ethanolamine salts) of the anionic surfactants sulfates, sulphonates, carboxylates and sarcosinates

Other anionic surfactants include the 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), diesters sulfo-succinates (especially diesters C 6 -C 14 saturated and unsaturated), N-acyl-sarcosinates. They are suitable also resin acids and hydrogenated resin acids such as rosin, hydrogenated rosin and resin acids and acids hydrogenated resins present in, or derivatives of, oil of tallow.

Sulfate-type anionic surfactant

Sulfate-type anionic surfactants, suitable for use herein, include alkyl sulfates linear and branched primary, alkylethoxysulfates, oleyl glycerol fatty sulfates, alkylphenol ether and ethylene oxide sulfates, acyl (C 5 -C 17) - N- (alkyl C 1 -C 4) and N- (hydroxyalkyl C 1 - C2) - glucaminesulfates and sulfates of alkyl polysaccharides, such as sulfates of alkyl polyglycosides (described in this memory non-sulfated non-ionic compounds).

The alkylethoxysulfate type surfactants are preferably select from the group consisting of (C 10 -C 18) alkyl sulfates that have been ethoxylated with about 0.5 to about 20 moles of ethylene oxide per molecule. More preferably, the alkylethoxysulfate type surfactant is a (C 6 -C 18) alkyl sulfate, which has been ethoxylated with about 0.5 to about 20, preferably from about 0.5 to about 5 moles of ethylene oxide per molecule.

Sulfonate type anionic surfactant

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

Anionic Carboxylate Surfactant

Anionic carboxylate surfactants suitable for use herein include surfactants of alkylethoxycarboxylate type, alkylpolyethoxy polycarboxylate and soaps ("alkyl carboxyls"), especially certain secondary soaps as described herein.

The alkylethoxycarboxylates suitable for use in this report include those with the formula RO (CH 2 CH 2 O) x CH 2 COO - M +, where R is a C 6 to C 18 alkyl group, x takes values from 0 to 10, and the distribution of ethoxylate groups is such that, in a weight basis, the amount of material in which x is 0, is less that approximately 20%, and the amount of material in which x is greater than 7, is less than approximately 25%, the mean x is of approximately 2 to 4 when the average R is C 13 or less, and the x mean is about 3 to 10 when the mean R is greater than C13, and M is a cation, preferably chosen from metal alkaline, alkaline earth metal, ammonium, mono-, di-, and tri-ethanol-ammonium, the most preferably between sodium, potassium, ammonium and their mixtures with ions magnesium.

Preferred alkylethoxycarboxylates are those in which R is a C 12 to C 18 alkyl group.

Type surfactants alkylpolyethoxy polycarboxylates suitable for use in this memory 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, where at least one R1 or R2 is a succinic acid radical or acid radical hydroxysuccinic, and R 3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.

Anionic surfactant based on secondary soap

Preferred soap-based surfactants are surfactants based on secondary soaps containing a carboxyl unit connected to a secondary carbon. Carbon secondary can be in a ring structure, e.g. as in p-octylbenzoic acid, or as in alkyl substituted cyclohexylcarboxylates. The surfactants a base of secondary soaps should not preferably contain ether bonds, neither ester bonds nor hydroxyl groups. Preferably, these should not be nitrogen atoms in the head group (part amphiphilic). Surfactants based on secondary soaps usually contain 11-15 carbon atoms in total, although they can be allowed slightly more (eg, up to 16), eg p-octylbenzoic acid.

The following general structures illustrate in addition some of the surfactants based on secondary soaps preferred:

TO.

A highly preferred secondary soaps class includes secondary carboxyl materials of formula R 3 CH (R 4) COOM, wherein R 3 is CH 3 (CH 2) x and R 4 is CH 3 (CH 2) and, where y can be 0 or a integer from 1 to 4, x is an integer from 4 to 10 and the sum of (x + y) is 6-10, preferably 7-9, most preferably 8.

B.

Other preferred class of secondary soaps comprises the compounds of carboxyl in which the carboxyl substituent is in a unit ring-shaped hydrocarbyl, i.e. secondary soaps of formula R 5 -R 6 -COOM, in the that R 5 is C 7 -C 10 alkyl or alkenyl, preferably C 8 -C 9, and R 6 is a ring structure such as benzene, cyclopentane and cyclohexane. (Note: R 5 may be in the ortho, meta or para position in relation to the carboxyl in the ring.)

C.

Yet Another preferred class of secondary soaps comprises the compounds secondary carboxyl formula CH 3 (CHR) k - (CH 2) m - (CHR) n -CH (COOM) (CHR) o - (CH 2) _ {p} - (CHR) q -CH 3, wherein each R is C 1 -C 4 alkyl, in the that k, n, o, q are integers in the range of 0-8, with the proviso that the total number of carbon atoms (including carboxylate) is in the range from 10 to 18.

In each of the above formulas A, B and C, M species can be any suitable counterion, especially soluble in water.

Especially preferred surfactants based of secondary soaps to use in this memory, are members water soluble, selected from the group consisting of salts water soluble 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.

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 or alkenyl group C 15 -C 17 linear or branched, R 1 is a C 1 -C 4 alkyl group and M is an ion of a alkali metal Preferred examples are the myristyl and Oleylmethyl-sarcosinates in the form of their salts sodium.

Nonionic Surfactant

Essentially, it can be included in the compositions any nonionic surfactant useful for purposes detersives Examples of non-limiting classes of non-surfactants Useful ionics are listed below.

Nonionic surfactant of polyhydroxy acid amide type fatty

Suitable polyhydroxy fatty acid amides for use herein are those having the structural formula R 2 CONR 1 Z in which: R 1 is H, C 1 -C hydrocarbyl 4, 2-hydroxyethyl, 2-hydroxypropyl, or their mixture, preferably C 1 -C 4 alkyl, more preferably C 1 or C 2 alkyl, most preferably C 1 alkyl (is say, methyl); and R 2 is a C 5 -C 31 hydrocarbyl, preferably straight chain C 5 -C 19 alkyl or alkenyl, more preferably C 9 -C 17 alkyl or alkenyl straight chain, most preferably C 11 -C 17 alkyl or straight chain alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbon chain with at least 3 hydroxyls directly connected 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 alkyl phenol condensates

The condensates of poly (ethylene oxide), poly (propylene oxide), poly (butylene oxide) of alkylphenols They are suitable for use in this memory. In general, they are preferred condensates of poly (ethylene oxide). These compounds include condensation products of alkylphenols that have a group alkyl containing from about 6 to about 18 carbon atoms either in linear chain configuration or branched with alkylene oxide.

Non-ionic ethoxylated alcohol surfactant

Type condensation products alkyl ethoxylates of aliphatic alcohols with about 1 to about 25 moles of ethylene oxide are suitable for use in this memory. The alkyl chain of alcohol aliphatic can be linear or branched, primary or secondary, and It generally contains 6 to 22 carbon atoms. They are particularly preferred condensation products of alcohols having an alkyl group containing from 8 to 20 atoms carbon with about 2 to about 10 moles of oxide of ethylene per mole of alcohol.

Non-ionic fatty alcohol surfactant ethoxylated / propoxylated

Fatty alcohols C 6 -C 18 ethoxylates and fatty alcohols C6 {C} {C18} mixed ethoxylated / propoxylated are surfactants suitable for use herein, particularly when they are soluble in water. Preferably, fatty alcohols ethoxylates are fatty alcohols C 10 -C 18 ethoxylated with a degree of ethoxylation from 3 to 50, most preferably these are the C 12 -C 18 ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40. Preferably, the alcohols ethoxylated / propoxylated mixed fats have a length of alkyl chains of 10 to 18 carbon atoms, a degree of ethoxylation of 3 to 30 and a degree of propoxylation of 1 to 10.

Non-ionic EO / PO condensates with propylene glycol

The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of oxide of propylene with propylene glycol, are suitable for use in this memory. The hydrophobic portion of these compounds has preferably a molecular weight of about 1,500 to approximately 1,800 and exhibits insolubility in water. Examples of compounds of this type include certain of the surfactants Commercially available Pluronic ™, which are marketed by BASF.

Non ionic EO condensation products with oxide adducts of propylene and ethylenediamine

The condensation products of ethylene oxide with the product that results from the reaction of propylene oxide and ethylenediamine, are suitable for use herein. The rest hydrophobic of these products consists of the reaction product of ethylenediamine and propylene oxide in excess, and generally has a molecular weight of about 2,500 to about 3,000. Examples of this type of non-ionic surfactant include certain of commercially available Tetronic ™ compounds, marketed by BASF.

Non-ionic surfactant type alkyl polysaccharide

Alkyl polysaccharides suitable for use herein are described in the patent of USA No. 4,565,647, Filling, issued on January 21, 1986, which they have a hydrophobic group that contains about 6 to about 30 carbon atoms, preferably of about 10 to about 16 carbon atoms, and as hydrophilic group, a polysaccharide, for example, a polyglycoside, which contains from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units. You can use any saccharide reducer that contains 5 or 6 carbon atoms, for example, glucose, galactose, and galactosyl moieties may be substituted instead of glucosyl residues (Optionally the hydrophobic group is attached in positions 2, 3, 4, etc., thus giving a glucose or galactose, in opposition to a glycoside or galactoside). The links between saccharides may be, for example, between position one of the additional saccharide units and positions 2, 3, 4 and / or 6 of the preceding saccharide units.

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 they contain from 10 to 18, preferably from 12 to 14 carbon atoms; n is 2 or 3; t is from 0 to 10, preferably 0, and x is from 1.3 to 8, preferably from 1.3 to 3, most preferably from 1.3 to 2.7. He glycosyl is derived primarily from glucose.

Non-ionic fatty acid amide surfactant

Amide-type surfactants of fatty acid suitable for use herein include those that have the formula: R 6 CON (R 7) 2 in which R 6 it is an 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.

Amphoteric surfactant

Amphoteric surfactants suitable for use herein include amine oxide surfactants and alkyl-amphocarboxylic acids.

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

Amine Oxide Surfactant

Amine oxides useful herein include those compounds that have the formula R 3 (OR 4) x N 0 (R 5) 2 wherein R 3 is selected from an alkyl group, hydroxyalkyl, acylamidopropyl and alkylphenyl, or mixtures thereof, which they contain 8 to 26 carbon atoms, preferably 8 to 18 atoms carbon; R 4 is an alkylene or hydroxyalkylene group that it contains 2 to 3 carbon atoms, preferably 2 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, preferably 1 to 2 carbon atoms, or a group of poly (ethylene oxide) containing 1 to 3, preferably 1, ethylene oxide groups. R 5 groups may be linked each other, eg, by an oxygen or nitrogen atom, to form a ring-shaped structure.

These amine oxide surfactants include in particular oxides of (C 10 -C 18) alkyl dimethylamine and oxides of (C 8 -C 12) alkoxy ethyldihydroxyethylamine. Examples of such materials include oxide of dimethyloctylamine, diethyldecylamine oxide, bis- (2-hydroxyethyl) dodecylamine, oxide dimethyldodecylamine, dipropyltetradecylamine oxide, methyl ethylhexadecylamine, dodecylamidopropyl dimethylamine oxide, cetyldimethylamine oxide, stearyldimethylamine oxide, tallow dimethylamine and oxide dimethyl-2-hydroxyoctadecylamine, and dimethylcocoalkylamine oxide. Oxides of (C 10 -C 18) alkyl dimethylamines and acyl oxides (C 10 -18) ) amido-alkyldimethylamines.

Hybrid ion surfactant

Ion surfactants can also be incorporated hybrid in detergent compositions herein. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derived from amines secondary and tertiary heterocyclics, or derivatives of compounds of quaternary ammonium, quaternary phosphonium or tertiary sulfonium. Surfactants of the betaine and sultaine type are examples of Hybrid ion surfactants for use herein.

Betaine Surfactant

The betaines useful herein are those compounds that have the formula R (R ') 2 N + R 2 COO -, in which R is a group C 6 -C 18 hydrocarbyl, preferably a C 10 -C 16 alkyl group or a group (acyl C 10 -C 16) amidoalkyl, each R 1 it is typically C 1 -C 3 alkyl, preferably methyl, and R2 is a hydrocarbyl group C 1 -C 5, preferably an alkylene group C 1 -C 3, more preferably a group C 1 -C 2 alkylene. Betaine Examples suitable include cocoacylamidopropyl dimethyl betaine; hexadecyldimethyl betaine: acyl (C 12-14) amidopropyl betaine; acyl (C 8-14) amidohexyldiethyl betaine; 4 [C 14-16 acyl] methylamidodyethylammonium-1-carboxybutane; acyl (C 16-18) amidodimethyl betaine; acyl (C 12-16) amidopentanediethyl betaine; Y acyl (C 12-16) methylamidodimethyl betaine. Preferred betaines are hexanoate of C 12 -C 18 {-dimethylammonium and the acyl (C 10 -C 18) amidopropane (or -ethane) -dimethyl (or -diethyl) -betaines. Surfactants based on complex betaines are also suitable for use in this memory.

Sultaine Surfactant

The sultaines useful herein are those compounds that have the formula (R (R 1) 2 N + R 2 SO 3 - in the that R is a C 6 -C 18 hydrocarbyl group, preferably a C 10 -C 16 alkyl group, more preferably an alkyl group C 12 -C 13, each R 1 is typically C 1 -C 3 alkyl, preferably methyl, and R2 is a hydrocarbyl group C 1 -C 6, preferably an alkylene group or, preferably, hydroxyalkylene C_ {1} -C_ {3}.

Ampholytic Surfactant

Ampholytic surfactants can be incorporated into the detergent compositions herein. These surfactants can be broadly described as aliphatic derivatives of amines tertiary or secondary, or aliphatic derivatives of amines secondary and tertiary heterocyclics, in which the radical Aliphatic can be straight or branched chain.

Cationic surfactants

Cationic surfactants can also be used. in the detergent compositions herein. Suitable cationic surfactants include surfactants of quaternary ammonium, selected from type surfactants mono-N-alkyl or mono-N-alkenylammonium C 6 -C 16, preferably C_ {6} -C_ {10}, in which the remaining N positions are substituted with methyl, hydroxyethyl or hydroxypropyl.

Water soluble detergency builder compound

The detergent compositions herein invention contain as a preferred optional component a water soluble detergency builder compound, present typically 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, carbonates, bicarbonates, borates, phosphates, silicates and mixtures of any of the preceding compounds.

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.

Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis, cis-tetracarboxylates, cyclopentadiene-pentacarboxylates, 2,3,4,5-tetrahydro-furan-cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran-cis-dicarboxylates, 2,2,5,5-tetrahydrofuran-tetracarboxylates, 1,2,3,4,5,6-hexane-hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include melitic acid, pyromellitic acid, and derivatives of phthalic acid described in British Patent No. 1,425,343.

Among the above, polycarboxylates Preferred are hydroxy carboxylates which contain up to three carboxy groups per molecule, more particularly citrates.

The progenitor acids of chelating agents type monomeric or oligomeric polycarboxylates 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.

The improvers of the borate type detergency, as well as detergency builders containing borate-forming materials, which can produce borate in the storage conditions of the detergent or in the wash, but are not preferred under wash conditions less than about 50 ° C, especially at less than about 40 ° C

Examples of type detergency builders carbonate are metal carbonates alkaline earth and alkaline, including carbonate and sesqui-sodium carbonate and mixtures with ultrafine calcium carbonate, as described in the application for German Patent No. 2,321,001, published on November 15, 1973

Specific 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, sodium polymeta / phosphates, in which the degree of polymerization is in the range from about 6 to 21, and phytic acid salts.

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 2.4 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.

The silicates are present preferably in detergent compositions according to the invention at a level of 5% to 50% by weight of the composition, plus preferably from 10% to 40% by weight.

Partially soluble detergency builder compound or insoluble

The detergent compositions herein invention may contain a detergency builder compound partially soluble or insoluble, typically present 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.

Examples of detergency builders partially water soluble include laminar silicates crystalline Examples of detergency builders widely Water insoluble include sodium aluminosilicates.

Crystalline lamellar sodium silicates they have the general formula

NaMSi_ {x} O_ {2x + 1}. 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 For the purpose of the present invention, x in the previous general formula it has a value of 2, 3 or 4 and is preferably 2. The most preferred material is δ-Na_ {2} Si_ {2} 0_ {5}, available at Hoechst AG as NaSKS-6.

Laminate Sodium Silicate Material crystalline is preferably present in compositions granular detergents as a particulate material in intimate mixing with a water soluble ionizable solid material. He Water soluble ionizable solid material is selected from acids organic, salts of organic and inorganic acids and their mixtures

Suitable aluminosilicate zeolites have the unit cell formula Na_ {z} [(AlO2) z (SiO2) and] \ CdotxH2 O in which z and y are at least 6; the molar ratio of z a y is 1.0 a 0.5 and x is at least 5, preferably 7.5 to 276, plus preferably from 10 to 264. The aluminosilicate material is in hydrated form and are preferably crystalline, containing 10% to 28%, more preferably 18% to 22% water in form associated.

Ion exchange type materials aluminosilicate can be materials present in nature, but preferably they are obtained by synthesis. Materials of ion exchange of synthetic crystalline aluminosilicate type are available under the designations of Zeolita A, Zeolita B, Zeolita P, Zeolita X, Zeolita HS, Zeolita MAP and mixtures thereof. The Zeolite A has the formula

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

in which x is from 20 to 30, especially 27. Zeolite X has the formula Na_86 [(AlO2) 86 (SiO2) 106]. H2O.

Heavy metal ion sequestrant

The detergent compositions of the invention they may contain, as a preferred optional component, a heavy metal ion sequestrant. By ion sequestrant Heavy metal is understood herein as the components that they act by sequestering (chelating) heavy metal ions. These components may also have chelation capacity of calcium and magnesium, but preferably manifest a selectivity for the association of heavy metal ions, such as those of 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, that are acidic in nature, having for example functionalities of phosphonic acids or carboxylic acids, may be present well in its acid form or as a complex / salt with a counter cation suitable, such as alkali metal alkali metal, ammonium, ammonium substituted, or any of its mixtures. Preferably any of the salts or complexes are soluble in water. Molar reason of said counter cation to the heavy metal ion sequestrant It is preferably at least 1: 1.

Heavy metal ion sequestrants suitable for use herein include acid nitrilotriacetic and polyaminocarboxylic acids such as acid ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic acid, acid ethylenediamineadisuccinic acid ethylenediamineadiglutaric acid 2-hydroxy-propylenediamineadisuccinic,  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. Preferred EDDS compounds they are the free acid form and the sodium or magnesium salt or a complex this. Examples of such preferred sodium salts of EDDS include Na 2 EDDS and Na 3 EDDS. Examples of such complexes of Preferred magnesium EDDS include MgEDDS and Mg2 EDDS.

Other heavy metal ion sequestrants suitable for use herein are acid derivatives iminodiacetic such as acid 2-hydroxyethyl diacetic or acid glyceryl-iminodiacetic, described in the documents EP-A-317,542 and EP-A-399,133.

Acid sequestrants 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 this memory. Acid sequestrants are also suitable. b-alanine-N, N'-diacetic, aspartic acid-N, N'-diacetic acid, acid aspartic acid-N-monoacetic acid and acid iminodusuccinic described in 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).

Organic polymeric compound

The organic polymeric compounds are particularly preferred components of the compositions detergents according to the invention. For organic polymeric compound, essentially understands any organic polymer compound used commonly as dispersant, and agent against redeposition and soil suspension agent in detergent compositions.

The organic polymeric compound is incorporated typically 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 by no more than two carbon atoms. Polymers of the latter type are described in the document GB-A-1,596,756. Examples of such salts are the polyacrylates of Pm 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight from 20,000 to 100,000, especially 40,000 to 80,000

Other suitable organic polymeric compounds include acrylamide and acrylate polymers having a weight 3,000 to 100,000 molecular weight, and acrylate / fumarate copolymers which have a molecular weight of 2,000 to 80,000.

Polyamine compounds are useful in this memory, including those derived from aspartic acid, such such as those described in the documents EP-A-305,282, EP-A-305,283 and EP-A-351,629.

Also suitable herein are the terpolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and alcohol vinyl, particularly those that have a molecular weight average 5,000 to 10,000.

Other suitable organic polymeric compounds for incorporation into the detergent compositions of this Memory include cellulose derivatives, such as methyl cellulose, carboxymethyl cellulose, and hydroxyethyl cellulose.

More useful organic polymeric compounds are polyethylene glycols, particularly those of molecular weight 1,000-10,000, more particularly 2,000 to 8,000 and what more preferably about 4000.

Bleaching catalyst

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

Other types of bleaching catalysts include the manganese-based complexes described in the U.S. Patent No. 5,246,621 and in US Pat. 5,244,594. Preferred examples of these catalysts include

Mn IV 2 (uO) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 - (PF 6) 2, Mn III (2) (uO) 1 (u-OAc) 2 (1,4,7-trimethyl-1,4,7-triazaci-
clononano) 2 - (ClO 4) 2, Mn IV 4 (uO) 6 (1,4,7-triazacyclononane) 4 - (ClO_ {4) 2, Mn III Mn IV 4 (uO) 1 (u-OAc) 2 - (1,4,7-trimethyl-
1,4,7-triazacyclononane) 2 - (ClO 4) 3,

and their mixtures. Other types are described in the European Patent Application Publication No. 549,272. Others Suitable ligands for use herein 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 U.S. 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 (cobalt complex catalysts), in Publications of European Patent Applications No. 384,503 and 306.089 (metallo-porphyrin catalysts), the U.S. Patent No. 4,728,455 (manganese catalyst and a multidentate ligand), US Pat. No. 4,711,748 and the European patent application publication number 224.952 (catalyst with manganese absorbed on an aluminosilicate), the patent of USA No. 4,601,845 (aluminosilicate support with manganese and zinc or a magnesium salt), US Pat. No. 4,626,373 (catalyst of manganese and a ligand), US Pat. No. 4,119,557 (catalyst with a ferric complex), descriptive memory of German patent 2,054,019 (catalyst with a cobalt chelator), Canadian Patent 866,191 (salts containing metals of transition) US patent No. 4,430,243 (chelators with cations of manganese and non-catalytic metal cations) and patent USA No. 4,728,455 (manganese gluconate catalysts).

Enzyme

A preferred component of the composition Detergent is an enzyme.

Suitable enzymes include lipases, amylases, neutral and alkaline proteases, cellulases, pectinases, lactases and peroxidases commercially available, that is, enzymes that have lipolytic, amylolytic, proteolytic, cellulolytic activity, pectolytic, lactolytic and peroxidolytic respectively, conventionally incorporated in detergent compositions. In the US patents 3,519,570 and 3,533,139 enzymes are discussed adequate.

As an enzyme component they are especially Preferred protease enzymes. The available protease enzymes Commercially preferred include those sold by the Commercial designation Alcalase, Savinase, Primase, Durazym and Wait for Novo Industries A / S (Denmark), those sold under the commercial designation Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold by commercial designation Opticlean and Optimase by Solvay Enzymes. The protease enzyme can be incorporate into the compositions according to the invention a 0.0001% to 4% level of active enzyme by weight of the composition.

Preferred amylases include, for example, α-amylases obtained from a special strain of licheniformis B, described in greater detail in the document GB-1,269,839 (Novo). The amylases available Commercially preferred include, for example, those sold by the designation Rapidase by Gist-Brocades, and those sold under the Commercial designation Termamyl and BAN by Novo Industries A / S. The Amylase enzyme can be incorporated into the composition according to the invention at a level of 0.0001% to 4% active enzyme by weight of the composition.

Lipolytic enzymes (lipase) that are also prefer may be present at lipolytic enzyme levels active from 0.0001% to 4% of active enzyme by weight, preferably 0.001% to 1% by weight, most preferably from 0.001% to 0.5% by weight of the compositions.

The lipase can be of fungal or bacterial origin, obtained for example from a strain that produces lipase from Humicola sp., Thermomyces sp. o Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens . Also useful herein are lipases obtained from mutants of these chemically or genetically modified strains.

A preferred lipase is derived from Pseudomonas pseudoalcaligenes , which is described in the granted European patent EP-B-0218272.

\hbox{Marzo de 1989.}

Another preferred lipase herein is obtained by cloning the Humicola lanuginosa gene and expressing the gene in Asperpillus oryza , as a host, as described in European Patent Application EP-A-0258068, which is commercially available from Novo Industri A / S , Bagsvaerd, Denmark, under the trade designation Lipolase. This lipase is also described in US Patent No. 4,810,414, Huge-Jensen et al , issued on 7

 \ hbox {March 1989.} 

Enzyme stabilizing system

Compositions containing enzymes Preferred herein may comprise about 0.001% to about 10%, preferably about 0.005% to about 8%, most preferably of about 0.01% to about 6% by weight of a system enzyme stabilizer. The enzyme stabilizing system can be any stabilizing system that is compatible with the enzyme detersive Such stabilizing systems may comprise ion. calcium, boric acid, propylene glycol, chain carboxylic acid short, boronic acid, and mixtures thereof. These stabilizing systems they can also comprise reversible enzyme inhibitors, such as reversible protease inhibitors.

The compositions of this memory may comprise in addition to 0 to about 10%, preferably of about 0.01% to about 6% by weight of scrubbers of chlorinated bleaches, added to prevent species chlorinated bleaches present in many water supplies attack and inactivate enzymes, especially in conditions alkaline Although it may be that the chlorine levels in the water are small, typically in the range of about 0.5 ppm at approximately 1.75 ppm, the available chlorine in the total volume of water that comes into contact with the enzyme during washing It is usually large; therefore, stability during use of the enzyme can be problematic.

Suitable chlorine scrubber anions are easily affordable and, illustrated by salts that contain ammonium or sulphite cations, bisulfate, thiosulphite, thiosulfate, iodide, etc. Antioxidants such as carbamate, ascorbate, etc., organic amines such as acid ethylenediaminetetraacetic acid (EDTA) or its alkali metal salts, monoethanolamine (MEA); and their mixtures. If desired, you can also use other conventional scrubbers such as bisulfate, nitrate, chloride, sources of hydrogen peroxide such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate, as well as phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate, malate, tartrate, salicylate, etc and their mixtures.

Limestone soap dispersant compound

The compositions of the invention may contain a dispersing compound of limestone soap, which has a power limestone soap dispersant (LSDP) power), as defined below, of more than 8, preferably no more than 7, most preferably no more than 6. The compound limestone soap dispersant is preferably present at a level of 0.1% to 40% by weight, more preferably 1% to 20% in weight, most preferably from 2% to 10% by weight of the compositions

A limestone soap dispersant is a material that prevents precipitation of metal fatty acid salts alkaline, ammonium or amine, by calcium or magnesium ions. A numerical measure of the effectiveness of a limestone soap dispersant is given by the dispersing power of limestone soap (LSDP) that is determined using the limestone soap dispersion test as described in the article by H.C. Borghetty and C.A. Bergman, J. Am. Oil Chem. Soc., Volume 27, pages 88-90, (1950). This limestone soap dispersion test method is used by widely those who work in this field, and it is mentioned, by example, in the following review articles; W.N. Linfield, Surfactant Science Series, Volume 7, p3; W.N. Linfield, Tenside Surf. Det. , Volume 27, pages 159-161, (1990); Y M.K. Nagarajan, W.F. Masler, Cosmetics and Toiletries, Volume 104, pages 71-73 (1998). The LSDP is the ratio in% in Weight of dispersing agent to sodium oleate necessary for disperse limestone soap deposits formed by 0.025g of sodium oleate in 30ml of water of 333ppm hardness of CaCO3 (Ca: Mg = 3: 2) equivalent.

Surfactants that have good capacity Limestone soap dispersant will include certain amine oxides, betaines, sulfobetaines, alkylethoxysulfates and alcohols ethoxylated.

Examples of surfactants that have a non-LSDP greater than 8 for use according to the invention, include dimethyl oxide C 16 -C 18 amine, (C 12 -C 18) alkyl ethoxy sulfates with an average degree of ethoxylation of 1-5, particularly surfactant (C 12 -C 15) alkyl ethoxy sulfate with an ethoxylation degree of approximately 3 (LSDP = 4), and what C 13 -C 15 ethoxylated alcohols with a degree ethoxylation medium of 12 (LSDP = 6) or 30, sold under the Commercial designations Lutensol A012 and Lutensol A030 respectively, by BASF GmbH.

In the article by M.K. Nagarajan and W.F. Masler, found in Cosmetics and Toiletries, Volume 104, pages 71-73, (1989), soap dispersants are described polymeric limestone suitable for use herein. Examples of such polymeric limestone soap dispersants, include certain water soluble salts of acrylic acid copolymers, acid methacrylic or mixtures thereof, and a substituted acrylamide or acrylamide, where such polymers typically have a molecular weight of 5,000 to 20,000.

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 this memory can comprise essentially any known antifoam compound, including, for example, anti-foam silicone compounds and anti-foam compounds 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 herein are the compounds silicone defoamers defined herein as any antifoam compound that includes a silicone component. Such Silicone defoamer compounds also typically contain a silica component The term "silicone" as used in this memory, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl groups of various types. The Preferred silicone defoamer compounds are siloxanes, particularly polydimethylsiloxanes having units of trimethylsilyl terminal block.

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. The Suitable salts include alkali metal salts such as sodium, potassium and lithium salts, and ammonium salts 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 two or three 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, sodium, potassium and lithium), 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 silicone / silica;

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

(b)

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

(C)

 a inert fluid vehicle, most preferably comprising a C16-C18 ethoxylated alcohol with a degree of ethoxylation of 5 to 50, preferably 8 to 15, at a level of 5% at 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 herein 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

Polymeric agents for inhibition of dye transfer are preferably selected from polyamine N-oxide polymers, copolymers of N-vinyl pyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, or their combinations.

a) Polyamine N-oxide polymers

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

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

x(I)

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

x

in which P is a unit polymerizable, Y

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

,

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

O,

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

--- O ---, --- S ---, --- N ---; x es O ó 1 ;A is N

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

,

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

OR,

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

--- O ---, --- S ---, --- N ---; x is O or 1;

R are aliphatic, aliphatic ethoxylated groups, aromatic, heterocyclic or alicyclic, or any combination of the same 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:

10

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, imidazole, pyrrolidine, piperidine, quinoline, acridine and its 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, imidazole and their 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

The copolymers of N-vinylimidazole and N-vinyl pyrrolidone which have an average molecular weight in the range of 5,000 to 50,000 Preferred copolymers have a molar ratio of N-vinylimidazole to N-vinyl pyrrolidone from 1 to 0.2.

c) Polyvinylpyrrolidone

The detergent compositions herein they can also use polyvinyl pyrrolidone ("PVP") that has an average molecular weight of 2,500 to 400,000. Polyvinylpyrrolidones suitable are commercially available in ISP Corporation, New York, NY and Montreal, Canada with the names of PVP product K-15 (molecular weight 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 found commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.

d) Polyvinyloxazolidone

The detergent compositions herein they can also use polyvinyloxazolidones as agents of inhibition of transfer of polymeric dyes. These polyvinyloxazolidones have an average molecular weight of 2,500 to 400,000

e) Polyvinylimidazole

The detergent compositions herein they can also use polyvinylimidazole as an inhibiting agent 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 they also optionally contain about 0.005% to 5% in weight of certain types of hydrophilic optical brighteners.

Hydrophilic optical brighteners useful in this Memory include those with the structural formula:

eleven

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! 60! -Bis [(4-anilino-6- (N-2-bis-hydroexiethyl) -s-triazine-2-yl) amino] -2,2! 60! -Tylbenodisulfonic 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 the disodium salt of the acid 4,4'-bis [(4-anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazine-2-yl) amino] 2,2'-stilbenedisulfonic acid. This particular polishing species is 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. This particular polishing species is marketed with the Commercial designation Tinopal AMS-GX by Ciba-Geigy Corporation.

Softening agents

They can also be incorporated into the compositions laundry detergents according to the present invention agents fabric softeners. These agents can be inorganic type or organic The smectite clays described in the document GB-A-1 400 898 exemplify agents inorganic softeners. Fabric softening agents, Organic include water insoluble tertiary amines as described in document GB-A-1 514 276 and in EP-B-0 011 340.

Smectira clay levels are found normally in the range of 5% to 15%, more preferably 8% to 12% by weight, the material being added as a mixed component Dry to the rest of the formulation. Fabric softening agents, organic such as water insoluble tertiary amines or Amide type materials with two long chains are incorporated into levels of 0.5% to 5% by weight, usually 1% to 3% by weight, while high poly (ethylene oxide) materials molecular weight and water-soluble cationic materials are added at levels of 0.1% to 2%, usually from 0.15% to 1.5% in weight.

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 detergent compositions of the invention are they can formulate in any desirable way such as powders, granules, pastes, liquids and gels. Preferably, the Compositions are in the form of pills. The most preferably, the compositions are in granular form.

Liquid compositions

The detergent compositions herein invention can be formulated as detergent compositions liquid Such liquid detergent compositions comprise typically from 94% to 35% by weight, preferably from 90% to 40% in weight, most preferably from 80% to 50% by weight of a vehicle liquid, e.g. water, preferably a mixture of water and organic solvent

Gel compositions

The detergent compositions herein invention may also be in the form of gels. Such compositions are typically formulated with polyalkenyl polyether which It has a molecular weight of approximately 750,000 to approximately 4,000,000

Solid compositions

The detergent compositions of the invention they are preferably in the form of solids, such as powders and granules The granular form is preferred.

The particle size of the components of the granular compositions according to the invention should be such that no more than 5% of the particles have a diameter greater than 1.4mm and no more than 5% of the particles have a smaller diameter at 0.15mm.

The apparent density of the compositions granular detergents according to the present invention have typically an apparent density of at least 450g / l, plus usually 600 g / liter, and 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. Upper and lower limbs of the funnel respectively have 130 mm and 40 mm. It mounts such so that the lower limb is 140 mm above the upper surface of the base. The cup has a total height of 90 mm, an internal height of 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 bulk density in g / liter. The measurements are repeated as necessary.

Obtaining procedures - granular compositions

In general, detergent compositions granular according to the present invention can be obtained by a variety of methods including dry mixing, drying by spraying, agglomeration and granulation.

Washing methods

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

Machine dishwashing method

A preferred method for dishwashing a machine comprises treating dirty items selected from crockery, glassware, silverware and silverware and mixtures thereof, with an aqueous liquid that has dissolved or dispensed in the one effective amount of a machine dishwashing composition according to the invention. For an effective amount of the composition for machine dishwashing is understood typically 8g to 60g of product dissolved or dispersed in a volume washing solution of 3 to 10 liters, as are the doses Typical product and wash solution volumes commonly used in conventional methods for washing machine dishes.

Methods for washing machine clothes

The methods for washing this machine's clothes memory include treating dirty clothes with an aqueous solution of washed in a washing machine that has dissolved or dispensed in it a effective amount of a laundry detergent composition by machine according to the invention. The detergent can be added to the washing solution by means of the dispensing drawer of the washing machine or by means of a dispensing device. For a quantity Effective detergent composition is typically understood from 40g to 300g of product dissolved or dispersed in a wash solution of volume of 5 to 65 liters, as are the typical product doses and wash solution volumes commonly used in conventional methods for washing machine clothes.

In a preferred washing method herein a dispensing device containing an amount is introduced effective detergent product, in the drum of a washing machine, preferably front loading, before the start of the cycle of washed.

The dispensing device is a container for the detergent product used to release the product directly in the drum of the washing machine. Its volume capacity it should be such that it could contain enough detergent product as the one normally used in the washing method.

Once the washing machine has been loaded with the laundry, the dispensing device containing the product is placed detergent inside the drum. 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 immersion in 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, thus providing concentrations promptly located highs of components such as components water soluble detergency builders and sequestrants of heavy metal ions, in the drum of the 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 cycle washing Dispensing devices especially preferred for use according to the invention have been described in the following patents; GB-B-2,157,717, GB-B-2,157,718, EP-A-0201376, EP-A-0288345 and EP-A-0288346. 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 patent application publications European Nos 0343069 & 0343070 devices are described Especially preferred dispensers. The last request describes a device comprising a flexible bag-shaped sleeve extending from a support ring that defines a hole, adapting the hole to let in the bag enough product for a wash cycle in a wash process. A part of the washing medium flows through the hole to the bag, dissolve the product, and then the solution passes out to through the hole to the washing medium. Support ring It is provided with a masking device to prevent product access undissolved, moist, typically comprising this device walls that extend radially from a center overhang in a spoke wheel configuration, or a similar structure in which the walls have a shape helical.

Examples

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

Abbreviations used in the examples

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

 THE

: Linear (C 12) alkyl benzenesulfonate of sodium

 TAS

: Tallow alkyl sulfate sodium

 C45AS

: Rent (C_ {14} -C_ {15}) linear) sodium sulfate

 CxyEzS

: Rent (C_ {1x} -C_ {1y} branched) sodium sulfate condensed with z moles of oxide ethylene

 C45E7

: A C 14-15 primary alcohol predominantly linear condensed with an average of 7 moles of ethylene oxide

 C25E3

: A C 12-15 primary alcohol branched condensed with an average of 3 moles of oxide ethylene

 C25E5

: A C 12-15 primary alcohol branched condensed with an average of 5 moles of oxide ethylene

 CEQ

: R 1 COOH 2 CH 2 .N + (CH 3) 3 with R_ {1} = C_ {11} -C_ {13}

 QAS

: R 2 .N + (CH 3) 2 (C 2 H 4 OH) with R2 = C_12 -C14

 Soap

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

 TFAA

: (C 16 -C 18) alkyl-N-methyl glucamide of

 TPKFA

: Headed whole fraction fatty acids C_ {12} -C_ {14}

 STPP

: Anhydrous sodium tripolyphosphate

Zeolite-A

: Hydrated sodium aluminosilicate of formula

quad

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

NaSKS-6

: Silicate crystalline laminar formula δ-Na_ {2} Si_ {2} O_ {5}

 Citric acid

: Anhydrous citric acid

 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; reason 2.0)

 Sodium sulfate

: Anhydrous sodium sulfate

 Citrate

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

 MA / AA

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

 CMC

: Sodium carboximethylcelulose

 Protease

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

 Alcalase

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

 Cellulase

: Cellulite enzyme activity 1000 CEVU / g sold by NOVO Industries A / S under the trade designation Carezyme

 Amylase

: 60KNU / g activity amylolytic enzyme sold by NOVO Industries A / S under the commercial designation Termamyl 60T

 Lipase

: Activity lipolytic enzyme 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

: Nonanoyloxybenzenesulfonate in salt form Sodium

 TAED

: Tetraacetylethylenediamine - in the form of particles, designed to have a T50 value, as defined herein, less than 60 seconds

 DTPMP

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

 Photoactivated

: Sulfonated zinc zinc phthalocyanine encapsulated in bleaching dextrin soluble polymer

 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

 PVNO

: Polyvinylpyridine N-Oxide

 PVPVI

: Polyvinylpyrrolidone copolymer and vinylimidazole

 SRP 1

: Esters topped with sulfobenzoyl with chain main oxyethylene and terephthaloyl

 SRP 2

: Poly short block polymer (1,2 propylene terephthalate) diethoxylated

 Defoamer silicone

: foam control agent polydimethylsiloxane with copolymer of siloxane-oxyalkylene as dispersing agent with a reason of said foam control agent to said agent 10: 1 to 100: 1 dispersant.

 Nonionic

: C 13 -C 15 fatty alcohol mixed ethoxylated / propoxylated with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5 sold under the designation commercial Plurafac LF404 by BASF Gmbh (low training of foam)

 Metasilicate

: Sodium Metasilicate (SiO2 ratio: Na2O = 1.0)

 Phosphate

: Sodium tripolyphosphate

 480N

: Random copolymer of acrylic / methacrylic acid 3: 7, average molecular weight approximately 3,500

 Precursor Particle of NAPAA

: Coated particle containing an amido-substituted precursor particle, composed alkyl peroxyacid precursor, which can release in perhydrolysis a non-amide of peroxyandipic acid (NAPAA), where the coating comprises sodium silicate (ratio 2.0) present at a weight ratio in relation to the precursor compound of 3:97. The particle is designed to have a T50 value, as define in this memory, at least 180 seconds.

 Particle of NOBS

: Particle formed by agglomerating sodium nonanoyloxybenzenesulfonate (NOBS) with citric acid and polyethylene glycol (PEG) of Pm = 4,000 with a weight ratio of NOBS components: citric acid: PEG 75:10:15, coated with a external coating of citric acid at a weight ratio of chipboard: 95: 5 citric acid, designed to have a T50, according to defined in this memory of> 180 seconds.

 Particle of benzoylcaprolactam

: Particle of benzoylcaprolactam formed by agglomerating the precursor compound with citric acid and polyethylene glycol (PEG) of Pm = 4,000, with a ratio in weight of precursor compound components: citric acid: PEG 63:21:16, coated with an outer coating of citric acid to a reason by weight of agglomerate: citric acid coating of 95: 5, designed to have a T50, as defined herein, of> 180 seconds.

 Caprolactam cationic

: Particle containing a p- (N, N, N triethylammoniomethyl) benzoyl particle, compound caprolactam chloride precursor, formed by agglomerating the precursor compound with citric acid and polyethylene glycol (PEG) of Pm = 4,000, with a weight ratio of compound components precursor: citric acid: PEG of 63:21:16, coated with a external coating of citric acid at a weight ratio of chipboard: 95: 5 citric acid coating, designed to have a T50, as defined herein, of> 180 seconds.

 DAP particle

: Coated particle containing acid diperoxidedecanedioic, where the coating comprises silicate of sodium (ratio 2.4) at a coating level of 5%. The T50 of the particle is designed to be greater than 200 seconds.

 Nitrate bismuth

: Nitrate salt bismuth

 Paraffin

: Paraffin oil sold under the designation commercial Winog 70 by Wintershall.

 BSA

: Amylolytic enzyme sold under the designation commercial LE 17 by Novo Industries A / S (approx. 1% of activity of the enzyme)

 Sulfate

: Anhydrous sodium sulfate.

 pH

: Measured as a 1% solution in water distilled at 20 ° C.

Examples

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

Example 1

The following were prepared according to the invention laundry detergent compositions A to F:

       \ vskip1.000000 \ baselineskip
    

12

13

The following T50 values were obtained (in seconds) for each of the products A to D:

14

Example 2

The following were prepared according to the invention granular detergent compositions for laundry washing G to I (the composition I is not within the scope of the claim 1) bulk density 750 g / liter:

fifteen

16

Example 3

The following formulations were prepared detergents according to the present invention where J is a composition phosphorus-containing detergent, K is a detergent composition that It contains zeolite and L is a compact detergent composition:

17

18

Example 4

The following were prepared according to the invention compositions for machine dishwashing.

19

twenty

Example 5

The following were prepared according to the invention detergent formulations (where compositions V and W are not within the scope of claim 1):

twenty-one

22

Example 6

The following formulations were prepared detergents according to the present invention:

2. 3

24

Example 7

The following formulations were prepared high density and bleaching detergents according to the present invention:

25

26

Example 8

The following formulations were prepared high density detergents according to the present invention:

27

28

Claims (10)

1. A detergent composition containing a organic peroxyacid bleaching system that can release two organic peroxyacid bleach other than a solution of washing, wherein said organic peroxyacid bleaching system it contains a source of hydrogen peroxide and a plurality of organic peroxyacid bleach precursor compounds, and where a means is provided to delay release to a washing solution of the strongest peroxyacid in relation to the release of a weaker peroxyacid so that in the method of T50 test described herein, the time to reach a concentration which is 50% of the final concentration of said strongest peroxyacid is at least 120 seconds longer than time to reach a concentration that is 50% of the concentration end of said weaker peroxyacid, where the relative strength of the peroxyacid is measured according to the "bleaching protocol of dye "described herein. 2. A detergent composition according to the claim 1, wherein the time to reach a concentration that is 50% of the final concentration of weaker peroxyacid is less than 60 seconds, and the time to reach a concentration that is 50% of the final concentration of the strongest peroxyacid is more than 180 seconds. 3. A detergent composition according to the claim 2, wherein the time to reach a concentration that is 50% of the final concentration of Strongest organic peroxyacid is 240 to 480 seconds. 4. A detergent composition according to the claim 1, wherein said peroxyacid bleaching system Organic contains two bleaching precursor compounds of organic peroxyacid. 5. A detergent composition according to claims 1 or 4, wherein a precursor compound of Organic peroxyacid is a tetraacetylated alkylenediamine in N, N, N 1 N 1, preferably TAED. 6. A detergent composition according to the claim 5, wherein a second precursor compound of Organic peroxyacid is an alkyl peroxyacid precursor compound amido-substituted selected among those who have The following general formula: 29 in which R1 is a group alkyl with from 1 to 14 carbon atoms, R2 is a group alkylene containing from 1 to 14 carbon atoms, and R 5 is H or an alkyl group containing 1 to 10 carbon atoms, and L is a group outgoing. 7. A detergent composition according to any of claims 1 to 6, wherein said source of peroxide of Hydrogen is an inorganic perhydrate salt. 8. A detergent composition according to any claim 7, wherein said inorganic perhydrate salt is sodium tetrahydrate perborate. 9. A detergent composition according to any of claims 1 to 8, which is in granular form. 10. The use of a detergent composition according to any one of claims 1 to 9, in a method for washing of clothing, in which the detergent composition is distributed to the washing solution by means of a dispensing device introduced in the drum of a washing machine before the start of washing.