ES2229227T3 - DETERGENT COMPOSITIONS. - Google Patents

Abstract

There is provided a detergent composition containing: (a) a source of peroxide compounds (b) a peroxyacid bleach precursor composition comprising i) an organic peroxyacid bleach precursor compound, ii) an H2O2 scavenging material, wherein said organic peroxyacid bleach precursor compound and said H2O2 scavenging material are in close physical proximity within said composition. The composition is useful in the bleaching of stains from stained coloured fabrics. The H2O2 scavenging material acts to inhibit 'patchy' fabric discolouration to said fabrics during the stain bleaching process.

Description

Detergent compositions.

Technical field

This invention relates to compositions detergents containing a source of hydrogen peroxide and a peroxyacid-based bleach precursor composition. Plus in particular, it refers to a material of H2O2 containing a bleach precursor composition based on peroxy acid, within a detergent composition.

Background of the invention

The satisfactory removal of soils or bleachable stains such as tea soils, fruit juices, and soils of colored vegetables, present in stained tissues, constitutes a special challenge for the formulator of a bleaching composition to be used in a washing method of clothes. Traditionally, the removal of these bleachable spots has been facilitated by the use of bleaching components such as oxygen bleach, which include hydrogen peroxide and organic peroxyacids. Organic peroxyacids are frequently obtained by the " in situ " perhydrolysis reaction, between hydrogen peroxide and the organic peroxyacid-based bleach precursor.

The increase in the use of precursors of organic peroxyacid-based bleach has been reflected in the decrease in laundry washing temperatures, which has been seen accompanied by an increase in the proportion of tissues of color. As a result of these trends, a problem that has been most significant fact is irregular localized discoloration or "by zones" in the colors of the fabrics and in the materials, caused by the generation of high species concentrations bleachers in localized places. They can originate high transient concentrations for various reasons. The species bleaches can themselves have a solubility intrinsically low, or its solubility can be diminished by the presence of other materials such as phases of viscous surfactant, or the agitation regime in the environment Immediate bleaching species may not be enough energetic enough to disperse the dissolved bleaching substance. When a component of the composition is a precursor of peroxyacid-based bleach, the potential problem is exacerbated. In addition to the possibility of high concentrations occurring point perhydroxyl ion as a result of dissolution of inorganic perhydrate normally contained in laundry detergent compositions, perhydrolysis of peroxyacid-based bleach precursor may result in significant point bleach concentrations based on peroxyacid In particular, this happens when the composition detergent contains high levels (for example more than 3% by weight) of peroxyacid bleach precursor and / or when used As a source of hydrogen peroxide, sodium percarbonate.

The authors of this application have found that the problem of irregular localized discoloration or "by zones" can be particularly angry with compounds peroxyacid bleach precursors that at perhydrolyze provide a peroxyacid that is an acid perbenzoic, or a non-cationic substituted derivative thereof, or a cationic peroxyacid. It has also been found that they are the compounds of the precursor of the type of benzoxazine, in particular, those that give Place to the problem.

The development of so-called products concentrates and their application through dispensing devices which are introduced into the machine drum along with the load of tissues, has only exacerbated these problems.

Consequently, there is a need for provide detergent compositions in which the precursor of organic peroxyacid-based bleach is incorporated into a way that minimizes and preferably prevents fading irregularly located or "by zones" of the colors of the tissues during dissolution and perhydrolysis in the liquid of wash, and continue to provide an acceptable disposal of dirt and bleachable stains present in soiled tissues and stained

The prior art contains numerous examples. of organic peroxyacid bleach precursors coated or agglomerated to increase its stability during storage in detergent compositions and / or to influence its dissolution behavior.

The document EP-A-0070474 describes precursors of organic peroxyacid bleach, granules, prepared by spray drying an aqueous dispersion pumpable containing an N-acyl compound or O-acyl together with at least one cellulose ether soluble in water, starch or starch derivative, in a ratio in Activator weight vs. coating from 98: 2 to 90:10

The document GB-A-1507312 describes coating organic peroxyacid bleach precursors with a mixture of alkali metal salts of fatty acids C 8 -C 22, mixed with fatty acids corresponding. The document GB-A-1381121 uses a coating melted based on fatty acid mixtures C_ {14} -C_ {18}, among other substances, for protect solid peroxyacid bleach precursors organic GB-A-1441416 describes a similar procedure that uses a mixture of acids C 12 -C 14 fatty acids, and aliphatic alcohols C_ {10} -C_ {20}. The document EP-A-0375241 describes extrudates of bleach precursor based on organic peroxyacids, stabilized, in which acid-based precursors are mixed (rent C 5 -C 18) - peroxycarboxylic, with a binder selected from anionic surfactants and not ionic, film-forming polymers, fatty acids, or mixtures of these binders.

The document EP-A-0356700 describes compositions comprising a peroxide based bleach precursor organic, a film-forming polymer, water soluble, and 2-15% of a carboxylic or hydroxycarboxylic acid versatile C 3 -C 6, to improve the stability and ease of dispersion or solubility. It mixes dry carboxylic acid, of which citric acid constitutes a preferred example, with the bleach precursor based on organic peroxyacid, and then granulated with the forming polymer of movie. It is claimed that citric acid provides a increased dissolution rate for precursor granules of bleach based on organic peroxyacid.

The document EP-A-0382464 refers to a procedure for coating or encapsulating solid particles, including bleaching compounds and bleach precursors to organic peroxyacid base, in which a dough is formed molten lining material in which the particles they form a dispersed phase, the mixture is destabilized, and then causes it to disintegrate to provide a material in the form of particles in which the dispersed phase particles are embedded in the continuous (coating) phase. They describe various coating materials, and it is taught that some materials, such as poly (acrylic acid) and the cellulose acetate phthalate, are useful when the Release of the coated material depends on the pH.

GB 1315937 describes compositions comprising a peroxide resistant enzyme strain of hydrogen, a compound that in aqueous solution releases peroxide from hydrogen, and a hydrogen peroxide collector. EP document 240057 describes a granular bleach activator composition which does not contain phosphorus, which comprises a bleach activator finely divided, an inorganic or organic salt, soluble in water, a water-soluble film-forming polymer, and a smectite or aluminosilicate clay material.

Thus, in the prior art the main emphasis on the protection of the bleach precursor to organic peroxyacid base against a hostile environment during storage, and relatively little attention has been paid to dissolution characteristics of the coated or agglomerated material When you are being employed. In cases where it has been proposed the coating and / or agglomeration with sparsely materials soluble such as fatty acids, this has resulted in a perhydrolysis rate of bleach precursor based on organic peroxyacid that is lower than what would be produced if not would have been protected in this way, thus reducing efficiency of the resulting peroxycarboxylic acid based bleach. Any use of more rapidly soluble materials, such as Citric acid has been made in the context of a component of chipboard in which the objective has been a faster dissolution of the bleach precursor based on organic peroxyacid. At JP 57296 provides another approach to resolve the problem of tissue deterioration, mixing together a water insoluble mineral substance, a bleach precursor of peroxyacid, and a bleach compound, in a ratio of said mineral substance to said precursor and bleaching compound from 1:99 to 90:10, preferably 20:80 to 65:35. The substance Water insoluble mineral is selected from acid clay, activated clay, kaolin, bentonite, diatomaceous earth and perlite, and it is claimed that it inhibits discoloration without inhibiting action bleach EP 028432 refers to "deterioration punctual "caused in the tissues, which produces areas in the tissue small and localized deterioration (usually with a diameter not greater than 2 - 5 mm) due to the slow dissolution of the system bleach. Said document describes a detergent composition that It contains granules, comprising 5% to 80% of a precursor of peroxyacid-based bleach, 15% to 60% of a silicate insoluble in water, and from 5% to 40% of a non-ionic binder inside of a solid detergent composition. This silicate compound insoluble in water, of which smectite clay is a preferred representative, is mixed with the bleach precursor based on peroxyacid, and is additionally bound with the nonionic surfactant. It is claimed that this combination provides rapid generation of peroxycarboxyl anions when added to a source of hydrogen peroxide. Anyway, since the Perhydrolysis begins as soon as the detergent product begins to dissolve and forms an environment of hydrogen peroxide alkaline, the problem of localized concentrations of peroxyacid-based bleach continues unresolved.

A solution to this problem would be to delay the beginning of perhydrolysis, in order to avoid the problems of deterioration of the color of the tissues that are associated with the dissolution behavior of other product components detergents An illustrative description is found in the WO 92/13798, in which they can be used as materials coating for bleach precursors based on peroxy acid, acidic materials that have characteristics specified, in order to delay the onset of perhydrolysis during the initial phases of dissolution / dispersion of product in the pre-liquid aqueous wash.

However, the compositions containing These acidic coating materials are expensive and require complex processes In addition, it has been found that the prevention of tissue color deterioration is limited in the presence of high levels of bleach precursors based on peroxyacid

The authors of the present application have found, surprisingly, that the problem of localized discoloration irregular or "by areas" of the tissues can be reduced from significantly by the close physical proximity of a H 2 O 2 capture material and the precursor composition of bleach containing bleach precursor based on organic peroxyacid. It has been found that the inclusion of the material H2O2 sensor does not significantly impede the release of the peroxyacid into the washing liquid, nor the ability of the composition to remove stains bleachable

In addition, it has been found that arranging a material H 2 O 2 sensor in close physical proximity with a bleach precursor based on organic peroxyacid in the breast of a bleach precursor composition, increases the stability of said precursor material during the storage.

It is understood by "close physical proximity" an agglomerate or extruded in which said pickup material of H 2 O 2 and said bleach precursor based on Organic peroxyacids are found in an intimate mixture. May mean also a bleach precursor particle coated with at least one layer, in which at least one layer It contains the H 2 O 2 sensor. It must be understood by "close proximity" that the pickup material and the peroxyacid-based bleach precursor are not two discrete particles separated in the detergent composition.

For the purposes of the present invention, the H 2 O 2 capture material contained in a composition of peroxyacid bleach precursor within a detergent composition, is defined as follows:

A pickup material of H2O2 is a compound that reduces the level of H 2 O 2 produced by a source of active oxygen in a pre-washing liquid aqueous, reacting with said H2O2 through any of the following processes: decomposition, neutralization and absorption, and any combination thereof, and that does not form finally an organic peroxyacid compound.

Summary of the invention

In accordance with the present invention, provides a detergent composition containing:

(to)

a source of peroxide compounds

(b)

a peroxyacid-based bleach precursor composition which     understands

i)

a peroxyacid-based bleach precursor compound organic,

ii)

a pickup material of H2O2,

in which said compound bleach precursor based on organic peroxyacid and said H 2 O 2 capture material are in close proximity physics within said composition, so that the material H2O2 sensor and bleach precursor compound based on organic peroxyacid are not two discrete particles separated in the detergent composition, Y

in which said collector of H 2 O 2 is a heavy metal ion selected from elements contained in the fourth and fifth rows of columns third to twelfth of the table periodic.

Preferably, said precursor compound of bleach based on organic peroxyacid and said pickup material of H2O2 are in close contact, most preferably in intimate mixing within said precursor composition of bleach.

The pickup material of H2O2 is selected from compounds that react with H 2 O 2 a through a decomposition process.

It is also provided in the present invention. a process for producing a detergent composition that It contains: (a) a source of peroxide compounds, (b) a peroxyacid-based bleach precursor composition which comprises i) a bleach precursor compound based on organic peroxyacid, ii) a H2O2 capture material, wherein said bleach precursor compound based on organic peroxyacid and said H2O2 capture material they are in close physical proximity within said composition, so that the H 2 O 2 capture material and the organic peroxy acid based bleach precursor compound they are not two discrete particles separated in the composition detergent, which includes the operations of:

to)

prepare a precursor agglomerate of peroxyacid-based bleach by mixing a precursor compound of organic peroxyacid bleach with a material H 2 O 2 sensor, to which is added and then mixed a binder material,

b)

treat said agglomerates with a lining material,

C)

dry off said coated agglomerates, and

d)

incorporate said agglomerates coated dried to a detergent composition containing a source of peroxide compounds,

in which the pickup material of H 2 O 2 is selected from a heavy metal ion, a catalase enzyme, and an enzyme of peroxidase

Detailed description of the invention

An essential feature of the invention is a source of peroxide compounds combined with a composition of peroxyacid-based bleach precursor within a detergent composition Hydrogen peroxide is a compound of preferred peroxide. Preferred sources of hydrogen peroxide include percarbonate and perborate. The sources of compound of peroxide also include perhydrate based bleaches inorganic, and bleaches based on perfosphate, persulfate and persilicate

Bleaches based on inorganic perhydrate

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

Examples of inorganic perhydrate salts include perborate and percarbonate. Perhydrate salts Inorganic are normally alkali metal salts. Salt inorganic perhydrate can be included as a crystalline solid Without additional protection. However, for some salts of perhydrate the preferred embodiments of these compositions granular employ a coated form of the material, which provides better storage stability for salt of perhydrate in the granular product.

Sodium perborate can be found in form of the monohydrate, of the nominal formula NaBO 2 H 2 O 2, or NaBO 2 H 2 O 2 tetrahydrate · 3H 2 O.

Sodium percarbonate, which is a perhydrate preferred to be included in compositions according to the invention, is an addition compound having a formula corresponding to 2Na_ {2} CO_ {3} \ cdot3H_ {2}, and is commercially available as a crystalline solid. Very preferably, the percarbonate is incorporated into these compositions in a coated form that provides stability to the product.

An appropriate coating material that provides product stability comprises mixed sulfate salts and Water soluble alkali metal carbonates. These coatings, and coating procedures, have been described above in GB 1,466,799, granted to Interox on March 9, 1977. The weight ratio of Coating material based on mixed salt versus percarbonate is in the range of 1: 200 to 1: 4, more preferably from 1: 99 to 1: 9, and most preferably from 1: 49 to 1: 19. Preferably, the mixed salt is composed of sodium sulfate and sodium carbonate, and has the general formula Na_ {2} SO_ {4} .n.Na_ {2} CO 3 {where n is worth 0.1 to 3, preferably n is worth 0.3 to 1.0, and most preferably n is worth from 0.2 to 0.5.

They can also be used advantageously inside of the present invention other non-limiting examples of silicate-containing coatings (alone or with borate salts or boric acids or other inorganic compounds), waxes, oils, fatty soaps

Bleach precursor composition based on peroxy acid

The bleach based precursor composition of peroxyacid comprises, as essential components, a precursor of bleach based on organic peroxyacid, and a material H 2 O 2 sensor.

Bleach precursor based on organic peroxyacid

The compositions according to the invention also include peroxyacid bleach precursors (bleach activators). Normally the peroxyacid bleach precursors at a level of 30% at 95% by weight of the bleach precursor composition, preferably at least 55% by weight and most preferably at least 60% by weight thereof. In absolute terms, the precursor of peroxyacid-based bleach accounts for approximately 1% to 20% by weight of the detergent compositions, more preferably 1% a 10%, and most preferably 1% to 7%.

The bleach precursors based on peroxyacid that can be included in the composition according with the invention typically contain one or more groups N-acyl or O-acyl, may be Selected these precursors from a wide range of classes. The Suitable classes include anhydrides, esters, imides, nitriles and acylated derivatives of imidazoles and oximes, and in the document GB-A-1586789 examples are described of useful materials within these classes.

In the documents GB-A-836988, 864798, 1147871, 2143231, and EP-A-0170386 are described suitable esters. Acylation products are also suitable of sorbitol, glucose and all saccharides with benzoylating agents and acetylants.

Precursor compounds O-acylated specific include 3,5,5-trimethylhexanoyloxybenzenesulfonates, benzoyloxybenzenesulfonates, cationic derivatives of benzoyloxybenzenesulfonates, nonanoyl-6-aminocaproyloxybenzene sulphonates, monobenzoyltetraacetyl glucose, and pentaacetyl glucose. Phthalic anhydride is a precursor of suitable anhydride type. In the documents GB-A-855735, 907356 and GB-A-1246338 compounds are described N-acylates useful.

Preferred precursor compounds of type imide include N-benzoylsuccinimide, tetrabenzoylethylenediamine, N-substituted ureas with benzoyl and alkylene diamines N, N-N ', N'-tetraacetylated in the which alkylene group contains 1 to 6 carbon atoms, in particular those compounds in which the alkylene group It contains 1, 2 and 6 carbon atoms. A very precursor compound preferred is the N, N-N ', N'-tetraacetylethylenediamine (TAED)

In the document GB-A-955735 are described in general N-acylated precursor compounds of the class lactam Although the broader aspect of the invention contemplates the use of any lactam useful as a precursor of peroxyacid, the Preferred materials include caprolactams and Valerolactams.

The bleach precursors based on Caprolactam, suitable, have the formula:

one

in which R1 is H or a group alkyl, aryl, alkoxyaryl or alkylaryl containing from 1 to 12 carbon atoms, preferably 6 to 12 atoms of carbon.

Appropriate valerolactams have the formula:

2

in which R1 is H or a group alkyl, aryl, alkoxyaryl or alkylaryl containing from 1 to 12 carbon atoms, preferably 6 to 12 carbon atoms. In highly preferred embodiments, R1 is selected from phenyl, heptyl, octyl, nonyl, 2,4,4-trimethylpentyl, decenyl, and mixtures of the same.

The most preferred materials are those that are normally solids at <30 ° C, in particular derivatives phenyl, i.e. benzoylvalerolactam, benzoylcaprolactam, and its substituted benzoylated analogs such as derivatives with chlorine, amino, nitro, alkyl, aryl and alkoxy.

Precursor materials based on caprolactam and valerolactam in which the remainder R1 contains at least 6 carbon atoms, preferably from 6 to about 12 carbon atoms, provide after perhydrolysis peroxyacids with hydrophobic character that provide capacity Nucleophilic cleaner and body dirt. The compounds of precursor in which R 1 comprises 1 to 6 carbon atoms they provide hydrophilic bleaching species that are particularly effective for bleaching beverage stains. In the present invention mixtures of caprolactams and "hydrophobic" and "hydrophilic" valerolactams, typically with weight ratios of 1: 5 to 5: 1, preferably 1: 1, for get advantages of removing mixed spots.

Another preferred class of precursor materials of bleach include cationic bleach activators, derivatives of valerolactam and acylcaprolactam compounds, of formula:

3

in which x is worth 0 or 1, the R, R 'and R' 'substituents are each alkyl groups C1-C10 or C2-C4 hydroxyalkyl, or either [(C_ {H} {2y}) O] n -R '' ' where y = 2-4, n = 1-20, and R '' ' is a C1-C4 alkyl or hydrogen group, and X is a anion.

Suitable imidazoles include N-benzoylimidazole and N-benzoylbenzimidazole, and other precursors of peroxyacid containing useful N-acyl groups, include N-benzoylpyrrolidone, dibenzoyltaurine, and benzoyl pyroglutamic acid.

Another preferred class of activator compounds of peroxyacid-based bleach are the amide compounds replaced that have the following general formulas:

\hskip1cm

ó

\hskip1cm

R^{1}C(O)N(R^{5})R^{2}C(O)LR 1 N (R 5) C (O) R 2 C (O) L

 \ hskip1cm 

or

 \ hskip1cm 

R 1 C (O) N (R 5) R 2 C (O) L

in which R1 is a group aryl or alkylaryl with about 1 to about 14 carbon atoms, R2 is an alkylene, amylene and alkylarylene containing from about 1 to about 14 carbon atoms, R 5 is H or an alkyl, aryl group, or alkylaryl containing 1 to 10 carbon atoms, and L can be essentially any removable group. R1 contains preferably from about 6 to about 12 atoms of carbon. R2 preferably contains from about 4 to approximately 8 carbon atoms. R1 may be alkyl of linear or branched chain, substituted aryl or alkylaryl which it contains branching, substitution, or both, and it can be obtained from both synthetic and natural sources, which They include for example tallow fat. Variations are permissible structural structures for R2. The substitution may include alkyl, aryl, halogen, nitrogen, sulfur and other groups typical substituents or organic compounds. R 5 is, preferably, H or methyl. R1 and R5 must not contain, preferably, more than 18 carbon atoms in total. At EP-A-0170386 are described bleach activator compounds substituted with amide, of East kind.

Benzoxazine-based organic peroxyacid precursors

Also suitable are precursor compounds of the type of benzoxacin, as described for example in the EP-A-332,294 and EP-A-482,807, in particular those They have the formula:

4

including benzoxacin replaced from kind

5

       \ newpage
    

in which R1 is H, alkyl, alkylaryl, aryl, arylalkyl, secondary or tertiary amines, and in which R 2, R 3, R 4 and R 5 can be same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxy, amino, alkyl-amino, COOR 6 (where R 6 is H or a alkyl group) and functions carbonyl

A precursor of the benzoxazine type Especially preferred is:

6

H 2 O 2 collector material

Bleach Precursor Compositions useful for the purpose of the invention contain a material H 2 O 2 sensor. In an essential aspect, the material H2O2 sensor and bleach precursor compound a organic peroxyacid base found in close proximity physical, more preferably in close contact, and very preferably in intimate mixing within said composition, for form a particulate material of precursor of bleach.

The pickup material of H2O2 is selected from compounds that react with H 2 O 2 a Through a decomposition.

Compounds suitable for the purpose of the invention, which react with H2O2 through a process Decomposition are selected from heavy metal ions, catalase enzymes, peroxidase enzymes, or any mixtures thereof.

Heavy metal ions (abbreviated IMP)

IMPs may be present within the precursor composition as salts itself, in the form of an oxide metallic, or vehicular by a mineral compound.

When in the bleach composition they use IMP as salts themselves it is preferred to include separately in the detergent composition a heavy metal ion sequestrant that will hijack the IMP, especially after the first dissolution / dispersion phases of the base bleach precursor of peroxide. Preferably, this metal ion sequestrant heavy, as will be described later, will be present within the molar excess detergent composition of the IMP.

A preferred H2O2 capture material it is a heavy metal ion (IMP) present within the precursor composition at levels below 5% by weight, preferably less than 1% by weight, and most preferably less than 0.1% by weight of the precursor composition of bleach.

These IMPs are selected from items. contained in the fourth and fifth rows of columns third to twelfth of the periodic table. Preferred IMP are Fe, Cu and Mn. He iron, copper and manganese level in the bleach composition it must be less than 5000 ppm, preferably 1000 ppm. In In particular, the copper level must be less than 50 ppm.

IMPs can also be carried by mineral compounds They are suitable vehicles materials for IMP mineral materials containing at least 200 ppm of IMP, and preferably at least 500 ppm.

A possible vehicle material is a material non-three-dimensional phyllosilicate ore.

Preferably, the mineral material of non-three-dimensional phyllosilicate is present in such an amount that the weight ratio of phyllosilicate mineral material does not three-dimensional relative to bleach precursor compound a organic peroxyacid base, or with respect to said peroxyacid Organic preformed in the bleach composition, be placed in a value of 1: 1 to 1:99, preferably 1: 2 to 1:49, more preferably from 1: 3.5 to 1:19.

In this invention it is understood as material of non-three-dimensional phyllosilicate a silicate mineral material in the which essentially flat sheets have been formed (two-dimensional) being shared with the neighboring tetrahedra three of the four Oxygens of each silicate tetrahedron. This definition excludes those silicates that have a bond structure three-dimensional more complex, which are sometimes called "structure minerals". The ore materials of non-three-dimensional phyllosilicate preferred in the present invention include clay ore materials and silicates crystalline laminates. For clarity, it will be noted that the non-three-dimensional phyllosilicate mineral material, as used in the present invention, excludes loading compounds zeolite-based active ingredients of sodium aluminosilicate which, without However, they may be included in the detergent compositions of the invention as active load components optional

Preferably, the mineral material of non-three-dimensional phyllosilicate is present as a component of a particleboard containing the precursor compound of organic peroxyacid-based bleach, and optionally others detergent compounds, which include organic binders polymers

Suitable vehicles include silicates crystalline laminates that have the general formula:

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

in which M is sodium or hydrogen, x is a number from 1.9 to 4, and y is a number from 0 to 20. In the EP-A-0 164 514 SE describe crystalline stratified sodium silicates of this type, and in documents DE-A-3 417 649 and DE-A-3 742 043 are described Methods to prepare them. In the present invention, and within the General formula above, x preferably has a value of 2, 3 or 4, and preferably worth 2. The most preferred material is δ-Na_ {2} Si_ {2} O_ {5}, available from Hoechst AG with the name of NaSKS-6.

In granular detergent compositions, the crystalline layered silicate material is present preferably as a particulate material in mixture intimate with a solid, water soluble ionizable material. This solid, water soluble ionizable material is selected from organic acids, salts of organic and inorganic acids, and mixtures thereof.

Enzymes as capture materials of H2O2

Other material of H2O2 preferred, with a decomposition process of H2O2, is an enzyme of the catalase type. This enzyme, also called heme enzyme, catalyzes the decomposition of hydrogen peroxide in water and oxygen, so that 1 mg of enzyme breaks down at least 0.1 mmol of H 2 O 2 per minute, at pH 7 and 25 ° C, and found in animals, plant cells, bacteria and fungi. Bliss Catalase contains four equal sized subunits, arranged tetrahedrally, totaling an approximate molecular weight of 240,000. Each subunit consists of a single associated polypeptide chain. with a single prosthetic group of protoporphyrin IX iron. The catalases are usually incorporated into the precursor composition of bleach at levels below 5% by weight of the composition of precursor, preferably less than 1% by weight of the precursor composition.

Preferred catalase are Terminox®, marketed by NOVO Industries A / S, and Fermocolase®, marketed by Finnsugar.

They are also suitable as collectors of H 2 O 2 peroxidase enzymes. These enzymes of peroxidase include, for example, horseradish peroxidase, ligninase, and haloperoxidases such as chloro-peroxidase and bromo-peroxidase.  When used, this enzyme is usually incorporated into the bleach precursor composition at levels below 5% in weight of the precursor composition, preferably less than 1% by weight of the precursor composition.

The incorporation of other ingredients besides organic peroxy acid based bleach precursor compound and from the material of H 2 O 2, it may result advantageous, in particular for the preparation of the material of precursor of particulate bleach and also for increase the stability of detergent compositions in which particulate materials have been included. In In particular, some types of agglomerates may require the addition of one or more binding agents to help agglutinate the organic peroxy acid based bleach precursor compound and the capture material of H 2 O 2, in order to produce particulate materials with physical characteristics acceptable. The binding agents may be present at a level from 0% to 40% by weight of the particulate material. Preferably, the binding agents will be in intimate mixing with the peroxyacid-based bleach precursor compound organic and with the capture material of H2O2. The agents Preferred binders have a melting point between 30 ° C and 70 ° C, or a substantial aqueous solubility. Preferably, the binding agents are present in amounts of 1-30% by weight of the particulate material, and most preferably in amounts of 5-20% in weight of the material in the form of particles.

Preferred binding agents include the C 10 -C 20 alcohol ethoxylates which contain 5-100 moles of ethylene oxide per mole of alcohol, and more preferably the primary alcohol ethoxylates C_ {15} -C_ {20} containing 20-100 moles of ethylene oxide per mole of alcohol. Preferred are ethoxylate-based binders alcohol of ethoxylated tallow with 15 moles of ethylene oxide per mole of alcohol (abbreviated TAE 25), and ethoxylated tallow alcohol with 50 moles of ethylene oxide per mole of alcohol (abbreviated TAE fifty).

Other preferred binding agents include Some polymeric materials. They are examples of these materials polyvinylpyrrolidone polymers with an average molecular weight of 12,000 to 700,000 and polyethylene glycols with an average weight of 600 to 10,000 They are additional examples of useful polymer materials such as binding agents the copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid, in which the maleic anhydride constitutes at least 20 mol% of the polymer. He Preferred binder to be employed in the present invention is a copolymer of maleic acid and acrylic acid with a weight 70,000 molecular. An acid homopolymer is also suitable acrylic. These polymeric materials can be used as such or in combination with solvents such as water, propylene glycol and alcohol ethoxylates C_ {10} -C_ {20} containing 5-100 moles of ethylene oxide per mole, before mentioned. Additional examples of binding agents include ethers of monoglycerol and diglycerol, and also acids C 10 -C 20 fatty. Can also be used for this purpose solutions of some inorganic salts, with inclusion of sodium silicate.

They are other examples of binding agents suitable cellulose derivatives, including derivatives of nonionic alkylcellulose such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose e hydroxyethylcellulose, and homopolymer polycarboxylic acids or copolymers, or their salts.

The particulate material may include also other components that are conventional in the detergent compositions, provided these are not themselves incompatible Examples of such components include dispersants based on lime soap and active fillers. I also know can provide the material in the form of precursor particles of bleach, with a coating material. Said material of coating may be selected from poly (acrylic acid), cellulose acetate, copolymer polycarboxylic acids and acids aliphatic carboxylic monomers such as citric acid. In the EP 382464 and WO 92/13798 descriptions are offered illustrative These components and their components will be described below. levels of incorporation, but the total level of the components is normally ranges from 5% to 50% by weight of the bleach precursor composition. The precursor or the peroxyacid-based precursors should preferably form the main component of the precursor composition, that is, 50% to 95% by weight of the particulate material, preferably at least 55% by weight and most preferably at least 60% by weight thereof.

When the particulate material of bleach precursor is provided with a material of coating, a preferred optional component is an agent sprinkler, used at a level of 1% to 5% by weight, in particular for those compositions in which said composition of bleach precursor is in the form of agglomerate. This dusting component improves the creep of the composition of precursor, and preferably takes the form of a compound inorganic insoluble in water, with a particle size <50 micrometers, preferably 1-10 micrometers. The Examples of these compounds include synthetic zeolites and hydrophobic silicas The application of the dusting agent can take place simultaneously or after application of the coating material.

The bleach precursor compositions a peroxyacid base can be prepared in various ways, using equipment known in the art, and the process can take place from discontinuously, that is, in batches, or continuously. In a batch process, to prepare material realizations preferred agglomerate of the invention a chipboard is used Eirich or Lodige FM, while the continuous process can employ a Shugi Mixer mixer or a Lodige CB or KM mixer. Be prefers a combination of the Lodige CB and KM mixers.

A preferred procedure to produce a detergent composition of the invention comprises the operations from:

to)

prepare a precursor agglomerate of peroxyacid-based bleach by mixing a precursor compound of organic peroxyacid bleach with a material H 2 O 2 sensor, with which a mixture is then mixed binder material,

b)

treat said agglomerates with a lining material,

C)

dry off said coated agglomerates, and

d)

incorporate said agglomerates coated, dried, in a detergent composition containing a source of peroxide compounds.

Additional detergent components

The detergent compositions of the invention They may also contain additional detergent components. The exact nature of these additional components and levels of incorporation of them will depend on the physical form of the composition and the exact nature of the washing operation for which will be used.

For example, the compositions can be formulated of the invention as detergent compositions for hand washing and machine, including additive compositions for washing clothing, and compositions suitable for use in pretreatment of stained tissues.

The compositions of the invention contain preferably one or more additional detergent components selected from surfactants, active fillers, compounds organic polymers, additional enzymes, foam suppressors, dispersants of calcium soaps, suspending agents of the dirt and anti-redeposition, and inhibitors of corrosion and optical clarifiers.

Surfactant

The detergent compositions of the invention preferably contain as an additional detergent component a surfactant selected from anionic, cationic surfactants, nonionic amphoteric, amphoteric and hybrid ion, and mixtures of same.

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

In US Patent 3,929,678, granted to Laughlin and Heuring on December 30, 1975 offers a typical listing of anionic, non-ionic, ampholytic and hybrid ion classes, and species of these surfactants. Additional examples are offered in "Surface Active Agents and Detergents" (volumes I and II by Schwartz, Perry and Berch). In US Patent 4,259,217, granted to Murphy on March 31, 1981 offers a list of surfactants suitable cationic.

When present, surfactants amphoteric, amphoteric and hybrid ion are usually employed in combination with one or more anionic surfactants and / or not ionic

Anionic surfactant

In the composition you can essentially include any anionic surfactant useful for detersive purposes. These anionic surfactants may include salts (which include, by example, sodium, potassium, ammonium salts, and ammonium salts substituted such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulphonate, carboxylate and sarcosinate

Other anionic surfactants include the isethionates such as acyl isethionates, N-acyl restaurants, tauride fatty acid amides of methyl, alkylsuccinates and alkylsulfosuccinates, monoesters of sulphosuccinate (especially monoesters C 12 -C 18 saturated and unsaturated), sulphosuccinate diesters (especially diesters C 6 -C 14 saturated and unsaturated), N-acylsarcosinates. Acids are also suitable resins and hydrogenated resin acids, such as rosin, hydrogenated rosin, and resin acids and resin acids hydrogenates present in tallow oil or derivatives of same.

Anionic Sulfate Surfactant

Suitable anionic sulfate surfactants to be used in the present invention include alkyl sulfates linear and branched primaries, alkyl ethoxy sulfates, (oleoyl fatty) -glycerol sulfates, alkylphenol ethylene oxide ether sulfates, (acyl C 5 -C 17) - N- (alkyl C 1 -C 4) - glucamine sulfates and (acyl C 5 -C 17) - N- (hydroxyalkyl C 1 -C 2) - glucamine sulfates, and alkylpolysaccharide sulfates such as sulfates of alkyl polyglucoside (non-sulfated and non-ionic compounds are described herein).

The surfactants of alkyl ethoxy sulfate are selected preferably from the group consisting of alkyl sulfates C_ {6} -C_ {18} that have been ethoxylated with about 0.5 to about 20 moles of oxide ethylene per molecule. More preferably, the surfactant of alkyl ethoxy sulfate is a C 6 -C 18 alkyl sulfate which has been ethoxylated with approximately 0.5 to approximately 20 moles of ethylene oxide per molecule, preferably about 0.5 to about 5 moles of ethylene oxide per molecule

Anionic Sulfonate Surfactant

Suitable anionic sulphonate surfactants to be used in the present invention include the salts of C 5 -C 20 linear alkylbenzenesulfonates, alkyl ester sulphonates, primary alkanesulfonates or secondary C 6 -C 22, olefin sulphonates C 6 -C 24, polycarboxylic acids sulphonates, alkyl glycerolsulfonates, acyl fatty glycerolsulfonates, oil fatty glycerolsulfonates, and any mixture of same.

Anionic carboxylate surfactant

Anionic carboxylate surfactants suitable for use in the present invention include the alkyl ethoxycarboxylates, the surfactants of alkyl polyethoxy polycarboxylate, and soaps ("alkyl-carboxyls"), especially some secondary soaps as described herein memory.

Alkyl ethoxycarboxylates Preferred to be employed in the present invention include the that have the formula RO (CH 2 CH 2 O) x CH 2 COO - M + in where R is a C 6 to C 18 alkyl group, x ranges from 0 to 10, and the distribution of ethoxylate is such that, on a weight basis, the amount of material in which x is 0 is less than approximately 20%, and the amount of material in which x is greater that 7 is less than about 25%, the average value of x is it ranges from approximately 2 to 4 when the average R is C_ {13} or lower, and the average value of x is approximately 3 to 10 when the average R is greater than C 13, and M is a cation, preferably selected from alkali metal, metal alkaline earth, ammonium, mono-, di- and tri-ethanolammonium, most preferably a cation of sodium, potassium, ammonium, and mixtures thereof with ions of magnesium. The alkyl ethoxycarboxylates are those in which R is a C 12 to C 18 alkyl group.

The surfactants of alkyl polyethoxy polycarboxylate suitable for use in the present invention include the that have the formula RO- (CHR_ {1} -CHR 2 -O) -R_ {3} where R is a C 6 to C 18 alkyl group, x is worth 1 to 25, R1 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 an R 1 or R 2 is a succinic acid radical or a radical hydroxysuccinic acid, and R 3 is selected from the group composed of hydrogen, substituted or unsubstituted hydrocarbon that It has between 1 and 8 carbon atoms, and mixtures thereof.

Anionic secondary soap surfactant

Preferred soap surfactants are secondary soap surfactants containing a carboxyl unit connected to a secondary carbon. The secondary carbon can be located in an annular structure, for example as in the p-octylbenzoic acid, or as it happens in alkyl substituted cyclohexylcarboxylates. Surfactants of secondary soap should not preferably contain joints ether, ester bonds or hydroxyl groups. Preferably, you should not there are nitrogen atoms in the head group (amphiphilic portion). Secondary soap surfactants usually contain a total number of 11-15 carbon atoms, although it can tolerate a slightly larger number (for example up to 16), for example p-octylbenzoic acid.

The following general structures illustrate Some of the preferred secondary soap surfactants:

TO.

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

B.

Other class of preferred secondary soaps comprises those carboxylic compounds in which the carboxyl substituent is found on a ring hydrocarbyl unit, that is, secondary formula soaps R 5 -R 6 -COOM, where 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: R5 can be found in ortho, goal or for relation to the carboxyl of the ring).

C.

Yet Another preferred class of secondary soaps comprises compounds with secondary carboxyl of 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 where k, n, o, q are integers in the range of 0-8, provided that the total number of atoms of Carbon (including carboxylate) is in the range of 10 to 18.

In each of the preceding formulas A, B and C, species M can be any suitable counterion, especially a counterion that confers water solubility.

They are secondary soap surfactants especially preferred for use in the present invention water soluble members selected from the group consisting of water soluble salts of acid 2-methyl-1-undecanoic, acid 2-ethyl-1-decanoic, acid 2-propyl-1-nonanoic, acid 2-butyl-1-octanoic and acid 2-pentyl-1-heptanoic.

Alkali metal sarcosinate surfactant

Other suitable anionic surfactants are those alkali metal sarcosinates of formula R-CON (R 1) CH 2 COOM, where R it is a C 5 -C 17 alkyl or alkenyl group linear or branched, R1 is an alkyl group C 1 -C 4 and M is an alkali metal ion. Preferred examples are myristyl-methylsarcosinate and oleyl-methylsarcosinate in the form of its salts Sodium

Nonionic Surfactant

In the compositions you can include essentially any nonionic surfactant useful for the detersive purpose. Listed below are classes illustrative, not limiting, of useful nonionic surfactants.

Non-ionic fatty acid amide surfactant polyhydroxy

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

Non-ionic alkylphenol condensates

The condensates of poly (ethylene oxide), poly (propylene oxide) and poly (butylene oxide) with alkylphenols are suitable for use herein invention. In general, condensates with poly (oxide of ethylene). These compounds include condensation products. of alkylphenols having an alkyl group containing from about 6 to about 18 carbon atoms, either in a linear chain configuration with alkylene oxide that is in a branched chain configuration with the oxide of alkylene

Nonionic ethoxylated alcohol surfactant

The condensation products of alkyl ethoxylate with aliphatic alcohols that possess about 1 to about 25 moles of ethylene oxide are suitable for use in the present invention. Chain Alkyl alcohol aliphatic can be linear or branched, primary or secondary, and generally contains 6 to 22 atoms of carbon. Particularly preferred products are condensation of alcohols having an alkyl group containing from 8 to 20 carbon atoms, with approximately 2 to approximately 10 moles of ethylene oxide per mole of alcohol.

Nonionic 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 invention, in particular when they are soluble in water. Preferably, the ethoxylated fatty alcohols are the alcohols C 10 -C 18 fatty, ethoxylated with a degree of ethoxylation of 3 to 50, most preferably are the alcohols C 12 -C 18 ethoxylated fatty acids with a degree of ethoxylation from 3 to 40. Preferably, fatty alcohols mixed ethoxylated / propoxylated have a chain length alkyl 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 the present invention The hydrophobic portion of these compounds has preferably a molecular weight of about 1500 to approximately 1800, and presents insolubility in water. The examples of compounds of this type include some of the surfactants commercially available Pluronic ™, marketed by BASF

Nonionic ethylene oxide condensation products with propylene oxide / ethylenediamine adducts

The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine are suitable for use herein invention. The hydrophobic portion of these products is constituted for the reaction product of ethylenediamine and propylene oxide in excess, and generally has a molecular weight of approximately 2500 to about 3000. Examples of this type of nonionic surfactant include some of the compounds commercially available Tetronic ™, marketed by BASF

Non-ionic alkylpolysaccharide surfactant

In US Pat. number 4,565,647 of Filling, granted on January 21, 1986, are described alkylpolysaccharides suitable for use herein invention, which have a hydrophobic group containing about 6 to about 30 carbon atoms, with preference of about 10 to about 16 atoms of carbon, and a polysaccharide group, for example a polyglycoside, hydrophilic, containing from about 1.3 to about 10 saccharide units, preferably about 1.3 to approximately 3 saccharide units, and most preferably of about 1.3 to about 2.7 saccharide units. Be you can use any saccharide reducer containing 5 or 6 atoms carbon, for example glucose and galactose, and galactosyl portions can replace glucosyl portions (optionally the hydrophobic group is attached at positions 2, 3, 4, etc., giving thus place a glucose or galactose, instead of a glycoside or galactoside). For example, intersaccharide bonds may be present between a position of saccharide units additional and positions 2, 3, 4 and / or 6 of the units of saccharide precedents.

Preferred alkyl polyglycosides have the formula

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

in which R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in the which alkyl groups contain 10 to 18 carbon atoms, preferably from 12 to 14 carbon atoms; n is worth 2 or 3; t ok from 0 to 10, preferably 0; and x is worth 1.3 to 8, preferably from 1.3 to 3, most preferably from 1.3 to 2.7. Preferably, the glycosyl is derived from the glucose.

Non-ionic fatty acid amide surfactant

The fatty acid amide surfactants suitable for use in the present invention are those that they have the formula R 6 CON (R 7) 2 in the which R 6 is an alkyl group containing from 7 to 21 atoms of carbon, preferably 9 to 17 carbon atoms, and each of R 7 is selected from the group consisting of hydrogen, C 1 -C 4 alkyl, hydroxyalkyl C 1 -C 4, and (C 2 H 4 O) x H, where x is in the range of 1 to 3.

Amphoteric surfactant

The amphoteric surfactants suitable to be employed in the present invention include surfactants of amine oxide and acids alkyl anfocarboxylic.

A suitable example of an acid alkyl-anfocarboxylic that can be used in the The present invention is the Miranol (TM) C2M Conc., manufactured by Miranol, Inc., Dayton, NJ.

Amine Oxide Surfactant

The amine oxides useful herein invention include compounds having the formula R 3 (OR 4) x N 0 (R 5) 2, in which R 3 is selected from alkyl group, hydroxyalkyl, acylamido-propoyl and alkylphenyl, or mixtures thereof, containing from 8 to 26 carbon atoms, preferably 8 to 18 carbon atoms; R 4 is a group alkylene or hydroxyalkylene containing from 2 to 3 atoms of carbon, preferably 2 carbon atoms, or mixtures of the same, x is worth 0 to 5, preferably 0 to 3; and each R5 is an alkyl or hydroxyalkyl group containing 1 to 3 atoms of carbon, preferably 1 to 2 carbon atoms, or a poly (ethylene oxide) group containing 1 to 3 groups of ethylene oxide, preferably 1 group of ethylene oxide. The R 5 groups may be linked together, for example through of an oxygen or nitrogen atom, to form a structure cancel.

In particular, these oxide surfactants of amine include (alkyl) oxide C 10 -C 18) - dimethylamine and oxide of (alkoxy C 8 -C 18) - ethyldihydroxyethylamine. Examples of these materials include oxide of dimethyloctylamine, diethyldecylamine oxide, bis (2-hydroxyethyl) dodecylamine, oxide of dimethyldodecylamine, dipropyltetradecylamine oxide, methyl ethylhexadecylamine, dodecylamidopropyl dimethylamine oxide, cetyldimethylamine oxide, stearyldimethylamine oxide, sebacyldimethylamine, and oxide dimethyl-2-hydroxyoctadecylamine. Be prefer (alkyl) oxide C 10 -C 18) - dimethylamine and (acylamide oxide) C 10 -C 18) - alkyldimethylamine.

Hybrid ion surfactant

Ion surfactants can also be incorporated hybrid in the detergent compositions of the present invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of amines secondary and tertiary heterocyclics, or derivatives of compounds of quaternary ammonium, quaternary phosphonium or tertiary sulfonium. They are illustrative hybrid ion surfactants to be used in the present invention the surfactants of betaine and of sultaine

Betaine surfactant

The betaines useful in the present invention are the compounds that have the formula R (R 1) 2 N + R 2 COO - in which R it is a C 6 -C 18 hydrocarbyl group, preferably a C 10 -C 16 alkyl group or a group (acylamido C 10 -C 16) -alkyl, each R 1 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. The betaine examples suitable include (acylamide of coconut) -propyldimethyl betaine; hexadecyldimethyl betaine; (acylamide C 12 -C 14) -propyl betaine; (acylamide C 8 -C 14) -hexyl dimethyl betaine;  4 [(acil C 14 -C 16) -methylamidodyethylammonium] -1-carboxybutane; (acylamide C 16 -C 18) -dimethylbetaine; (acylamide C 12 -C 16) -pentanediethylbetaine;  (acyl C 12 -C 16) -methylamidodimethyl betaine. They are preferred betaines (C 12 -C 18) - dimethylhexanoate of ammonium and the (acylamido C 10 -C 18) - propane (or ethane) dimethyl (or diethyl) betaines. They are also suitable to be betaine surfactants employed in the present invention complex.

Sultaine Surfactant

The sultaines useful in the present invention are the compounds that have the formula R (R 1) 2 N + R 2 SO 3 - in the which 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 C1-C3 alkyl, preferably methyl, and R 2 is a C 1 -C 6 hydrocarbyl group, preferably a C 1 -C 3 alkylene group or well, preferably, a hydroxyalkylene group.

Amphiphite Surfactant

In the detergent compositions herein invention amphiphilic surfactants can be incorporated. Can be broadly describe these surfactants as derivatives aliphatic secondary or tertiary amines, or derivatives aliphatic of secondary and tertiary heterocyclic amines, in which aliphatic radical can be straight chain or branched.

Cationic surfactants

In the detergent compositions herein The invention can also be used cationic surfactants. The suitable cationic surfactants include surfactants of quaternary ammonium selected from surfactants of mono-N- (alkyl or alkenyl C 6 -C 16, preferably C 6 -C 10) - ammonium in the which the remaining positions in N are substituted with groups methyl, hydroxyethyl or hydroxypropyl.

Water soluble active filler compound

The detergent compositions herein invention preferably contain an active filler compound water soluble, typically present at a level of 1% to 80% in weight, preferably 10% to 70% by weight, and most preferably 20% to 60% by weight of the composition.

Water soluble active fillers, suitable, include water soluble monomeric polycarboxylates, or its acidic forms, homopolymer polycarboxylic acids or copolymers, or their salts, in which polycarboxylic acid comprises at least two carboxylic radicals separated from each other for no more than two carbon atoms, carbonates, bicarbonates, borates, phosphates, silicates, and mixtures of any of the previous.

The active carboxylate or polycarboxylate can be monomer type or oligomer type, although monomeric polycarboxylates are generally preferred by Cost and result reasons.

Carboxylates containing a carboxy group, suitable, include water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. The polycarboxylates containing two carboxy groups include salts Water soluble succinic acid, malonic acid, acid (ethylenedioxy) diacetic, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as ether carboxylates and sulfinyl carboxylates. The polycarboxylates that they contain three carboxyl groups include, in particular, citrates soluble in water, aconitrates and citraconatos, as well as derivatives of succinate such as the carboxymethyloxysuccinates described in the British patent number 1,379,241, lactoxysuccinates described in British patent number 1,389,732 and aminosuccinates described in the application of the Netherlands 7205873, and the materials of oxypolycarboxylate such as 2-oxa-1,1,3-propanotricarboxylates described in British patent number 1,387,447.

Polycarboxylates containing four groups carboxy include oxydisuccinates described in the British patent No. 1,261,829, 1,1,2,2-ethanotetracarboxylates, 1,1,3,3-propanotetracarboxylates and 1,1,2,3-propane-tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulphosuccinate derivatives described in British patents Nos. 1,398,421 and 1,398,422, and in US Pat. number 3,936,448, and the sulfonated pyrolyzed citrates described in the British patent number 1,439,000.

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

Of the above, polycarboxylates Preferred are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.

They are also considered as useful components of active charges the precursor acids of the chelating agents of monomeric or oligomeric polycarboxylate, or mixtures thereof with its salts, for example citric acid or citrate / acid mixtures citric.

Active base loads can also be used borate, as well as active fillers containing materials borate formers, which can produce borate under the conditions of detergent storage or under washing conditions, but they are not preferred under washing conditions below about 50 ° C, especially below about 40 ° C

They are examples of active loads based on carbonate alkaline earth metal carbonates and metal alkaline, which include sodium carbonate and sesqui-sodium carbonate, and mixtures thereof with ultrafine calcium carbonate, as described in the application of German patent number 2,321,001, published on November 15 of 1973.

They are specific examples of active loads water-soluble phosphate-based metal tripolyphosphates alkaline, sodium pyrophosphate, potassium and ammonium, pyrophosphate sodium and potassium and ammonium, sodium and potassium orthophosphate, sodium polymethaphosphate in which the degree of polymerization It varies from 6 to 21, and salts of phytic acid.

Suitable silicates include silicates of water soluble sodium, with a SiO2 ratio: Na2O of 1.0 to 2.8, proportions of 1.6 to 2.4 being preferred, and being The proportion 2.0 is very preferred. Silicates can be found in anhydrous salt form or in the form of hydrated salt. Silicate more preferred is sodium silicate with a proportion SiO2: Na2O of 2.0.

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

Active soluble compound partially soluble or insoluble

The detergent compositions herein invention may contain a partially active loading compound soluble or insoluble, typically present at a level of 1% to 80% in composition weight, preferably from 10% to 70%, very preferably from 20% to 60% by weight of the composition.

Examples of partially active loads Water soluble include crystalline layered silicates. Examples of remarkably insoluble active loads in water include sodium aluminosilicates.

The crystalline layered silicates have the general formula

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

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

The crystalline layered sodium silicate is preferably present in granular detergent compositions as a particulate material, in intimate mixing with a solid ionizable material, soluble in water. Ionizable material Water soluble solid is selected from organic acids, salts of organic and inorganic acids, and mixtures thereof.

Suitable aluminosilicate zeolites have the unit cell formula Na_ {z} [(AlO2) z (SiO2) y] xH2 O in which z and y are at least 6; the molar ratio of z to y is it ranges from 1.0 to 0.5, and x is at least 5, preferably 7.5 to 276, more preferably from 10 to 264. The aluminosilicate material is found in hydrated form and is preferably crystalline, containing 10% to 28% water in bound form, plus preferably from 18% to 22% of water in bound form.

The aluminosilicate zeolites can be materials present in nature, but preferably are of synthetic origin Materials are available ion exchangers based on crystalline aluminosilicates synthetics with the names Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS, and mixtures thereof. Zeolite A has the formula

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

in which x is worth 20 to 30, in special 27. Zeolite X has the formula Na 86 [(AlO 2) 86 (SiO 2) 86] 276H 2 O.

Heavy metal ion sequestrant

The detergent compositions herein invention may preferably contain an ion sequestrant Heavy metal. By heavy metal ion sequestrants components that act are understood herein sequestering (chelating) heavy metal ions, especially after the first phases of dissolution / dispersion of peroxyacid bleach precursor. To do this, the heavy metal ion sequestrant will be present in the detergent composition as a separate component of the composition of peroxyacid bleach precursor. These heavy metal ion sequestrants may also have chelation capacity of calcium and magnesium, but show preferential way a selectivity to fix metal ions heavy such as iron, manganese and copper.

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

Heavy metal ion sequestrants, that are acidic in nature, and that have for example phosphonic acid or carboxylic acid functionalities, can be present in its acid form or as a complex or salt with a suitable counter-cation such as an alkali or ion alkali metal, ammonium or substituted ammonium ion, or any mixture thereof. Preferably, any salt or complex is soluble in water. The molar ratio of said counter-cation regarding the ion sequestrant of Heavy metals are preferably located at least 1: 1.

Heavy metal ion sequestrants, suitable for use in the present invention include organic phosphonates such as aminoalkylene poly (alkylene phosphonates), metal ethane-1-hydroxy diphosphonates  alkaline, and nitrilotrimethylene phosphonates.

Among the cited species are preferred diethylenetriaminopenta (methylene phosphonate), ethylenediaminotri (methylene phosphonate), hexamethylenediaminetetra (methylene phosphonate) e hydroxyethylene-1,1-diphosphonate.

Other heavy metal ion sequestrants Suitable for use in the present invention include the nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic acid, ethylenediamine disuccinic acid, ethylenediamine dihydric acid, 2-hydroxypropylene diamine disodium acid, or any salt thereof.

Acid is especially preferred ethylenediamino-N, N'-disuccinic (EDDS), or alkali metal, alkaline earth metal salts, of ammonium or substituted ammonium thereof, or mixtures thereof. Preferred EDDS compounds are the free acid form and the salts or complexes of sodium or magnesium thereof. The examples of these preferred sodium salts of EDDS include Na2 EDDS and Na 3 EDDS. Examples of these EDDS magnesium complexes Preferred include MgEDDS and Mg2 EDDS.

Other heavy metal ion sequestrants suitable for use in the present invention are derivatives of iminodiacetic acid such as acid 2-hydroxyethylacetic acid or acid glyceryl-iminodiacetic, described in the EP-A-317,542 and EP-A-399,133.

They are also suitable in the present invention. acid-based sequestrants iminiodiacetic-N-2-hydroxypropylsulfonic and acid aspartic-N-carboxymethyl-N-2-hydroxypropyl-3-sulfonic, described in the document EP-A-516.102. Are also suitable acid sequestrants β-alanine-N, N'-diacetic, of aspartic acid-N, N'-diacetic, of aspartic acid-N-monoacetic acid, and of iminodisuccinic acid described in the document EP-A-509,382.

The document EP-A-476,257 describes kidnappers amino-based, suitable. The document EP-A-510,331 describes kidnappers suitable derivatives of collagen, keratin or casein. The document EP-A-528,859 describes a alkyl iminodiacetic acid sequestrant suitable. Dipicolinic acid and acid are also suitable. 2-phosphonobutane-1,2,4-tricarboxylic. Acid is also suitable Glycineamide-N, N'-Disuccinic (GADS).

Bleach catalyst

The compositions optionally contain a bleach catalyst containing a transition metal.

A suitable type of bleach catalyst is a catalyst system comprising a heavy metal cation with defined bleach catalysis activity, such as copper, iron or manganese cations, a metal cation assistant who has little or no catalysis activity bleach, such as zinc or aluminum cations, and a sequestrant that has stability constants defined for the catalytic and auxiliary metal cations, in particular acid ethylenediaminetetraacetic acid ethylenediaminetetra (methylene phosphonic), and soluble salts in water from them. These catalysts are described in the U.S. Patent 4,430,243.

Other types of bleach catalysts include the manganese-based complexes described in the patent from the USA 5,246,621 and in US Pat. 5,244,594. The Preferred examples of these catalysts include Mn IV 2 (u-O) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 - (PF 6) 2, Mn III 2 (uO) 1 (uO) Ac 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 - (ClO 4) )_{2}, Mn IV 4 (u-O) 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 mixtures thereof. Others are described in the publication of European patent application number 549,272. Other ligands suitable for use in the present invention include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triaza-cyclononane, and mixtures thereof.

The bleach catalysts useful in compositions of the present invention can be selected also in the manner that is appropriate for the present invention. To find examples of suitable bleach catalysts see US Pat. No. 4,246,612 and U.S. Pat. number 5,227,084. See also US Pat. number 5,194,416, which describes mononuclear complexes of manganese (IV) such as Mn (1,4,7-trimethyl-1,4,7-triazacyclononane) (OCH 3) 3 - (PF 6).

Another type of bleach catalyst, such as described in US Pat. number 5,114,606, is a water soluble complex of manganese (III) and / or (IV) with a ligand which is a carboxylate-free polyhydroxy compound that It has at least three consecutive C-OH groups. The Preferred ligands include sorbitol, iditol, dulcitol, mannitol, xylitol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose, and mixtures of same.

U.S. Pat. number 5,114,611 describes a bleach catalyst comprising a metal complex of transition, which include Mn, Co, Fe, or Cu, with a non-ligand macrocyclic These ligands have the formula:

\uelm{C}{\uelm{\para}{R _{2} }}

-B-

\uelm{C}{\uelm{\para}{R _{3} }}

=N-R^{4}R1 -N =

 \ uelm {C} {\ uelm {\ para} {R 2}} 

-B-

 \ uelm {C} {\ uelm {\ para} {R3}} 

= NR 4

in which each of R1, R 2, R 3 and R 4 may be selected from H, groups alkyl and aryl substituted such that each R 1 -N = C-R 2 and each R 3 -C = N-R 4 form a ring of five or six members. Said ring may be substituted. further. B is a bridging group selected from O, S, CR 5 R 6, NR 7 and C = O, in which R 5, R 6, and R 7 can each be H, alkyl groups or aryl groups, with inclusion of substituted or unsubstituted groups. Ligands Preferred include pyridine, pyridazine, pyrimidine rings, pyrazine, imidazole, pyrazole, and triazole. Optionally, said rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide, and nitro. It preferred particularly the 2,2'-bispyridylamine ligand. The Preferred bleach catalysts include complexes of bispyridylmethane and bispyridyl amine with Co, Cu, Mn, Fe. highly preferred catalysts include Co (2,2'-bispyridylamine) Cl2, di (isothiocyanate) bispyridylamine-cobalt (II), trispyridylamine-cobalt (II) perchlorate, Co (2,2'-bispyridylamine) 2 O 2 ClO 4,  perchlorate of bis- (2,2'-pyridylamine)-copper (II), perchlorate of tris (di-2-pyridylamine)-iron (II), and mixtures of same.

Other examples include complexed binuclear Mn with tetra-N-dentate ligands and bi-N-dentate, including N 4 Mn III (u-O) 2 Mn IV N 4) + Y [Bipy 2 Mn III (u-O) 2 Mn IV bipy 2) - (ClO 4) 3.

Other bleach catalysts are described, for example, in the European patent application publication No. 408,131 (catalysts based on cobalt complexes), European patent applications numbers 384.503 and 306.089 (catalysts based on metalloporphyrins), US 4,728,455 (manganese catalysts and multidentate ligand) US document 4,711,748 and European Patent Application Publication Number 224.952 (catalyst based on manganese absorbed on aluminosilicate), US 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), US 4,626,373 (catalyst based on manganese and ligand), US 4,119,557 (ferric complex catalyst), patent specification German 2,054,019 (cobalt chelator based catalyst), Canadian document 866,191 (salts containing metals of transition), US 4,430,243 (chelators with cations of manganese and non-catalytic metal cations), and US document 4,728,455 (catalysts based on manganese gluconate).

In the compositions and methods of the present invention, the bleach catalyst is typically employed in a catalytically effective amount. "Catalytically effective amount" means an amount that is sufficient, regardless of the conditions of the comparative test), to increase the bleaching and the removal of the stain or stains of interest outside the target substrate. The test conditions may vary depending on the type of washing device used and the user's habits. Some users choose to use very hot water; others use warm or even cold water in washing operations. Naturally, the catalytic behavior of the bleach catalyst will be affected by these circumstances, and the levels of bleach catalyst employed in the fully formulated detergent and bleach compositions can be adjusted appropriately. In practice, and without being in any case a limitation, the compositions and methods of the present invention can be adjusted to provide on the order of at least one part per ten million active species of bleach catalyst in the aqueous wash liquid , and preferably will provide from about 1 ppm to about 200 ppm of the catalyst species in the washing liquid. To further illustrate this point, at 40 ° C and pH 10, under European conditions, using perborate and a bleach precursor, a concentration of manganese catalyst of the order of 3 micromolar is effective. In the US conditions a 3-5 fold increase in concentration may be necessary to achieve the same
results.

Enzyme

Another preferred ingredient, useful in detergent compositions are one or more additional enzymes.

Preferred additional enzyme materials include lipases, amylases, neutral and alkaline proteases, esterases, cellulases, pectinases, lactases and peroxidases commercially available, conventionally incorporated into detergent compositions Suitable enzymes are discussed in the US patents Nos. 3,519,570 and 3,533,139.

Protease enzymes commercially available, preferred, include those marketed with trade names Alcalase, Savinase, Primase, Durazym and Esperase by Novo Industries A / S (Denmark), those marketed with trade names Maxatase, Maxacal and Maxapem by Gist-Brocades, those marketed by Genencor International, and those marketed under the trade name Opticlean and Optimase by Solvay Enzymes. You can incorporate the protease enzyme in the compositions according to the invention at a level from 0.0001% to 4% by weight of active enzyme with respect to the composition.

Preferred amylases include, for example, α-amylases obtained from a special strain of B. licheniformis, described in more detail in the document GB-1,269,839 (Novo). Amylases commercially available, preferred, include, for example, those marketed with the trade name Rapidase by Gist-Brocades, and those marketed under the trade name Termamyl and BAN by Novo Industries A / S. Amylase enzyme can be incorporated into the composition according to the invention at a level from 0.0001% to 2% by weight of active enzyme with respect to the composition.

Lipolytic enzyme (lipase) may be present at active lipolytic enzyme levels from 0.0001% to 2% by weight, preferably from 0.001% to 1% by weight, and most preferably from 0.001% to 0.5% by weight with respect to the composition.

The lipase may be of fungal or bacterial origin, and may have been obtained, for example, from a lipase-producing strain of Humicola sp., Thermomyces sp., Or Pseudomonas sp., Including Pseudomonas pseudoalcaligenes or Pseudomonas fluorescens . Also useful in the present invention are lipases from mutants of these strains, chemically or genetically modified.

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

Another preferred lipase in the present invention is obtained by cloning the Humicola lanuginosa gene and expressing the gene in Aspergillus oryza , as a host, as described in European patent application EP-A-0258 068, which is commercially available from Novo Industri A / S, Bagsvaerd, Denmark, with the trade name of Lipolase. This lipase is also described in US Pat. No. 4,810,414, of Huge-Jensen et al., issued March 7, 1989.

Organic polymer compound

Organic polymer compounds are additional preferred components of the detergent compositions according to the invention. Here, the expression "organic polymer compound" means essentially any  organic polymer compound commonly used as dispersant, anti-redeposition agent and suspending agent of dirt, in detergent compositions, but excluding any of the high weight organic polymer compounds Molecular described herein as flocculating agents of clays.

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

Examples of organic polymer compounds include homo- or polycarboxylic acids water-soluble co-polymers, or their salts, in the which polycarboxylic acid comprises at least two radicals carboxyl separated from each other by no more than two carbon atoms. In GB-A-1,596,756 is describe polymers of the latter type. They are examples of such salts molecular weight polyacrylates 2,000-10,000 and its copolymers with anhydride maleic, said copolymers having a molecular weight of 20,000 to 1000, especially from 40,000 to 80,000.

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

Polyamine compounds are useful in the present invention, and include aspartic acid derivatives such as those described in the documents EP-A-305282, EP-A-305283 and EP-A-351629.

They are also suitable in the present invention. terpolymers containing selected monomer units of acid maleic, acrylic acid, poly (aspartic acid) and vinyl alcohol, in particular those with an average molecular weight of 5,000 to 10,000

Other suitable organic polymeric compounds to be incorporated into the detergent compositions of the Present invention include cellulose derivatives such as methyl cellulose, carboxymethyl cellulose, and hydroxyethyl cellulose.

They are useful organic polymer compounds additional polyethylene glycols, particularly those that have molecular weight from 1,000 to 10,000, more particularly from 2,000 to 8,000, and most preferably about 4,000.

Foam suppressor system

When formulated to be used in machine wash compositions, detergent compositions of the invention preferably comprise a suppressor system of foam present at a level of 0.01% to 15% by weight of the composition, preferably from 0.05% to 10% by weight, and most preferably from 0.1% to 5% by weight of the composition.

The foam suppressor systems suitable for be employed in the present invention may comprise essentially any known antifoam compound, with inclusion, for example, of antifoaming compounds based on silicone and antifoaming compounds based on 2-alkyl alkanol.

Herein, "compound" is understood as antifoam any compound or mixture of compounds that act to reduce the formation of foam produced by a solution of a detergent composition, in particular in the presence of agitation of said solution.

They are particularly antifoaming compounds preferred to be used in the present invention compounds silicone based defoamers, which are defined herein memory like any antifoam compound that includes a silicone component These anti-foaming compounds based on Silicone typically also contain a silica component. Such as used herein, and in general in the industry, The term "silicone" comprises a variety of polymers of relatively high molecular weight, containing units of siloxane and hydrocarbyl groups of different types. The compounds Preferred silicone based defoamers are siloxanes, in particular polydimethylsiloxanes having units terminal blockers based on trimethylsilyl.

Other suitable antifoaming compounds include monocarboxylic fatty acids and soluble salts of same. These materials are described in US Pat. No. 2,954,347, issued on September 27, 1960 to Wayne St. John Monocarboxylic fatty acids, and their salts, to be used as foam suppressors, typically have chains of hydrocarbyl of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms Suitable salts include metal salts alkaline such as sodium, potassium and lithium salts, and ammonium and alkanolammonium salts.

Other suitable antifoaming compounds include, for example, high weight fatty acid esters molecular (for example fatty acid triglycerides), esters of fatty acids with 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-chlorotriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 atoms of carbon, propylene oxide, acid amide bis-stearic, and monostearyl phosphates and alkali metal di-metal phosphate ester (for example sodium, potassium, lithium).

The copolymers of ethylene oxide and oxide propylene, in particular mixed fatty alcohols ethoxylated / propoxylated with an alkyl chain length of 10 at 16 carbon atoms, a degree of ethoxylation of 3 to 30, and a degree of propoxylation from 1 to 10, are also compounds defoamers suitable for use herein invention.

Antifoam compounds based on 2-alkyl alkanols suitable for use in the The present invention has been described in DE 40 21 265. The 2-alkylalkane suitable for use in the present invention they are composed of a C 6 alkyl chain to C 16 carrying a terminal hydroxy group, and said chain alkyl is substituted in position a by an alkyl chain C_ {1} to C_ {10}. In the compositions according to the present invention mixtures of 2-alkyl alkanoles.

A preferred foam suppressor system understands

(to)

antifoam compound, preferably silicone-based anti-foaming compound, very preferably a silicone-based antifoaming compound that includes, in combination,

(i)

polydimethylsiloxane, at a level of 50% at 99% by weight of the silicone-based antifoaming compound, preferably 75% to 95% by weight; Y

(ii)

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

wherein said silica / silicone based antifoaming compound is incorporated at a level of 5% to 50% in
weight, preferably 10% to 40% by weight;

(b)

a dispersing compound, which most preferably contains a glycol and silicone comb copolymer with a content of 72-78% polyoxyalkylene and an oxide ratio from ethylene to propylene oxide from 1: 0.9 to 1: 1.1, at a level of 0.5% at 10% by weight, preferably 1% to 10% by weight; a copolymer of glycol and silicone comb type of this type, particularly preferred, is the DCO544, commercially available from Dow Corning under the trade name DCO544;

(C)

a inert carrier fluid compound, which most preferably comprises a C 16 -C 18 ethoxylated alcohol, with a degree of ethoxylation from 5 to 50, preferably from 8 to 15, at a level of 5% to 80% by weight, preferably 10% to 70% by weight;

A system in the form of particles suppressor of foam, useful in the present invention and preferred, comprises a mixture of an alkylated siloxane of the type described in what antecedent, and solid silica.

The solid silica can be a smoked silica, a precipitated silica, or silica prepared by the technique of gel formation Suitable silica particles have a average particle size of 0.1 to 50 micrometers, preferably 1 to 20 micrometers, and a specific surface area of at least 50 m2 / g. You can make these silica particles be hydrophobic by treating them with dialkylsilyl and / or groups trialkylsilyl, either directly bonded on silica or by means of a silicone resin. It is preferred to use a silica whose particles have been made hydrophobic with groups dimethylsilyl or trimethylsilyl. A defoaming compound in form of particles, preferred to be included within the detergent compositions according to the invention, contains conveniently an amount of silica such that the ratio in Silica to silicone weight is in the range of 1: 100 to 3:10, preferably from 1:50 to 1: 7.

Another system in the form of particles suppressor of suitable foam is represented by a silanized silica of hydrophobic way (most preferably trimethyl-silanized) which has a size of particle within the range of 10 nanometers to 20 nanometers, and a specific surface area exceeding 50 m 2 / g, mixed intimately with liquid dimethylsilicone that has a molecular weight medium within the range from about 500 to approximately 200,000, in a silicone weight ratio regarding silanized silica from about 1: 1 to approximately 1: 2.

In the document EP-A-0210731 describes a system in the form of highly preferred foam suppressor particles, which It comprises a silicone-based antifoaming compound and a organic vehicle material that has a melting point in the range of 50 ° C to 85 ° C, in which the organic carrier material they comprise a glycerol monoester and a fatty acid having a carbon chain containing 10 to 20 carbon atoms. He EP-A-0210721 describes other systems in the form of foam suppressor particles preferred, in which the organic carrier material is an acid or fatty alcohol that have a carbon chain containing 12 to 20 carbon atoms, or a mixture thereof, with a point of melting from 45 ° C to 80 ° C.

In EP 495345, in the name of Procter and Gamble Company, other systems are described in the form of highly preferred foam suppressor particles, comprising silicone-based antifoaming compound, a carrier material, an organic coating material, and glycerol, in a proportion  by weight of glycerol with respect to antifoam compound based on 1: 2 to 3: 1 silicone. EP 517298 also describes highly foam suppressor particle systems preferred, comprising antifoam compound based on silicone, a carrier material, a coating material organic, and crystalline or amorphous aluminosilicate, in a proportion by weight of aluminosilicate with respect to antifoam compound a 1: 3 to 3: 1 silicone base. In the two systems described above foam control, in granular form, highly preferred, the Preferred carrier material is starch.

A system in the form of particles suppressor of foam, illustrative to be used in the present invention is a particle agglomerate component, prepared by an agglomeration process, comprising, in combination,

(i)

from 5% to 30% by weight of the component, preferably 8% to 15% in weight, of silicone-based antifoaming compound, comprising preferably, in combination, polydimethylsiloxane and silica;

(ii)

from 50% to 90% by weight of the component, preferably 60% to 80% in weight, of carrier material, preferably starch;

(iii)

from 5% to 30% by weight of the component, preferably 10% to 20% in weight, of agglomerate binder compound, where, herein invention, such a compound can be any compound typically used as a binder for agglomerate, or mixtures of several of these compounds, said compound most preferably comprising chipboard binder an ethoxylated alcohol C 16 {C 18}, with a degree of ethoxylation from 50 to 100; Y

(iv)

from 2% to 15% by weight, preferably 3% to 10% by weight, of acid C 12 -C 22 hydrogenated fatty.

Clay flocculating agent

The compositions of the invention may contain a clay flocculating agent, preferably present in a level from 0.005% to 10% by weight of the composition, plus preferably from 0.05% to 5% by weight, and most preferably from 0.1% at 2% by weight.

The weight ratio of mineral compound of clay with respect to clay flocculating agent is situated preferably in 300: 1 to 1: 1, more preferably 80: 1 up to 10: 1, and most preferably from 60: 1 to 20: 1.

The clay flocculating agent acts together the clay compound particles within the solution of washing and helping, therefore, the deposition of the same on the surface of the tissues that are being washed. By Therefore, this functional requirement is different from that of the compounds clay dispersants that are commonly added to compositions washing detergents, in order to help eliminate clay stains of the tissues, and allow their dispersion in the within the wash solution.

In the present invention they are preferred as clay flocculating agents organic polymer materials that they have a molecular weight of 100,000 to 10,000,000, preferably from 150,000 to 5,000,000, more preferably from 200,000 to 2,000,000

Suitable organic polymeric materials comprise homopolymers or copolymers containing units selected monomers of alkylene oxide, in particular oxide ethylene, acrylamide, acrylic acid, vinyl alcohol, vinyl pyrrolidone, and ethyleneimine. Homopolymers of ethylene oxide, acrylamide and acrylic acid.

       \ newpage
    

European patents numbers EP-A-299,575 and EP-A-313,146, on behalf of Procter and Gamble Company, describe organic polymeric agents clay flocculants, preferred for use herein invention.

They are also suitable in the present invention. inorganic clay flocculating agents, whose typical examples They include lime and alum.

Dye transfer polymeric agents

The detergent compositions herein invention may also comprise from 0.01% to 10% by weight, preferably from 0.05% to 0.5% by weight of polymeric agents dye transfer inhibitors.

The polymeric agents that inhibit dye transfer are preferably selected from polymers of poly (N-oxides of amine), copolymers of N-vinyl pyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, or combinations thereof.

a) Polymers of poly (N-amine oxides)

Polymers of poly (amine N-oxides) suitable for use in the present invention contain units that have the following structural formula:

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

(I)

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

where P is a unit polymerizable, to which the group can be attached R-N-O, or where the group R-N-O is part of the unit polymerizable, or a combination of both of them.

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

,

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

O,

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

, -O-, -S-, -N-; x es 0 ó 1A is N

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

,

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

OR,

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

, -O-, -S-, -N-; x is 0 or 1

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

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

7

wherein R_ {1}, R2_, and R 3 are aliphatic, aromatic, heterocyclic or alicyclics, or combinations thereof, x o / e y o / y z are 0 or 1, and where the nitrogen of the N-O group can be bound or where the nitrogen of the N-O group forms Part of these groups. The N-O group can be part of the polymerizable unit (P) or it may be attached to the polymer skeleton, or a combination of both situations.

Suitable poly (N-oxides of amine), in which the N-O group is part of the unit polymerizable, they comprise poly (N-amine oxides) in the which R is selected from aliphatic, aromatic groups, alicyclic or heterocyclic. A class of sayings poly (amine N-oxides) comprises the group of poly (amine N-oxides) in which the group nitrogen N-O is part of the R. Son group preferred poly (N-amine oxides) those in which R it is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine, and derivatives of same.

Another class of said poly (N-oxides of amine) comprises the group of poly (N-oxides of amine) in the which nitrogen of the N-O group is attached to group R.

       \ newpage
    

Other suitable poly (amine oxides) are the poly (amine oxides) in which the group N-O is attached to the polymerizable unit.

The preferred classes of these poly (N-amine oxides) are the poly (N-oxides of amine) which have the general formula (I) in which R is a group aromatic, heterocyclic or alicyclic in which the nitrogen of the N-O functional group is part of said group R. They are examples of these classes are poly (amine oxides) in which R it is a heterocyclic compound such as pyridine, pyrrole, imidazole, and derivatives thereof.

Another preferred class of poly (N-oxides of amine) are the poly (amine oxides) that have the general formula (I) in which R are aromatic, heterocyclic or alicyclics in which the nitrogen of the functional group N-O is linked to these R groups. They are examples of these classes the poly (amine oxides) in which the R groups They can be aromatic such as phenyl.

You can use any other skeleton polymer, as long as the amine oxide polymer formed is soluble in water and possesses properties of inhibition of dye transfer They are examples of polymer skeletons Suitable polyvinyl, polyalkylene, polyesters, polyethers, polyamides, polyimides, polyacrylates, and mixtures thereof.

The amine N-oxide polymers of the present invention typically have an amine ratio to Amine N-oxide from 10: 1 to 1: 1,000,000. However, you can vary the amount of amine oxide groups present in the poly (amine oxide) polymer by copolymerization adequate or through an adequate degree of N-oxidation Preferably, the proportion of amine  with respect to amine N-oxide, it ranges from 2: 3 to 1: 1,000,000. More preferably it is situated from 1: 4 to 1: 1,000,000, and most preferably it ranges from 1: 7 to 1: 1,000,000. The polymers of the present invention actually comprise random or block copolymers in which one type of monomer it is an amine N-oxide and the other type of monomer, or it is a Amine N-oxide, or it is not. The amine oxide unit of the poly (amine N-oxides) has a pKa <10, preferably pKa <7, more preferably pKa <6.

The poly (N-oxides of amine) with almost any degree of polymerization. The degree of polymerization is not critical as long as the material has the Water solubility and the suspending power of dyes, desired. Typically, the average molecular weight is within the range 500 to 1,000,000, preferably 1,000 to 50,000, more preferably from 2,000 to 30,000, and most preferably from 3,000 to 20,000

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

Preferred polymers to be used in the The present invention may comprise a polymer selected from copolymers of N-vinylimidazole and N-vinyl pyrrolidone in which said polymer have an average molecular weight in the range of 5,000 to 50,000, more preferably from 8,000 to 30,000, most preferably from 10,000 to 20,000. The copolymers of N-vinylimidazole and Preferred N-vinyl pyrrolidone have a ratio molar of N-vinylimidazole with respect to N-vinyl pyrrolidone from 1 to 0.2, more preferably from 0.8 to 0.3, most preferably from 0.6 to 0.4.

c) Polyvinylpyrrolidone

The detergent compositions herein memory can also use polyvinylpyrrolidone ("PVP") with an average molecular weight of 2,500 to 400,000, preferably of 5,000 to 200,000, more preferably 5,000 to 50,000, and very preferably 5,000 to 15,000. There are polyvinylpyrrolidones suitable, commercially available from ISP Corporation, New York, NY and Montreal, Canada, under the trade names PVP K-15 (molecular weight per viscosity 10,000), PVP K-30 (average molecular weight 40,000), PVP K-60 (average molecular weight 160,000), and PVP K-90 (average molecular weight 360,000). I also know PVP is available from ISP Corporation K-15 Other suitable polyvinylpyrrolidones, which are found commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.

Polyvinylpyrrolidone can be incorporated into the detergent compositions of the present invention at a level of 0.01% to 5% by weight of the detergent, preferably 0.05% to 3% in weight, and more preferably from 0.1% to 2% by weight. The amount of Polyvinylpyrrolidone contributed to the washing solution is placed preferably 0.5 ppm to 250 ppm, preferably 2.5 ppm to 150 ppm, more preferably 5 ppm to 100 ppm.

d) Polyvinyloxazolidone

The detergent compositions herein invention can also employ polyvinyloxazolidones in quality of dye transfer polymeric agents. These polyvinyloxazolidones have an average molecular weight of 2,500 to 400,000, preferably 5,000 to 200,000, more preferably 5,000 to 50,000, and most preferably 5,000 to 15,000.

The amount of polyvinyloxazolidone incorporated in detergent compositions it can amount to 0.01% up to 5% in weight, preferably 0.05% to 3% by weight, and more preferably 0.1% to 2%. The amount of polyvinyloxazolidone contributed to the solution of washing is typically 0.5 ppm to 250 ppm, preferably 2.5 ppm at 150 ppm, more preferably 5 ppm to 100 ppm.

e) Polyvinylimidazole

The detergent compositions herein invention may also employ polyvinylimidazoles as dye transfer polymeric agents. Sayings polyvinylimidazoles preferably have an average molecular weight from 2,500 to 400,000, more preferably 5,000 to 50,000, and very preferably 5,000 to 15,000.

The amount of polyvinylimidazole incorporated into the detergent compositions may amount to 0.01% up to 5% in weight, preferably 0.05% to 3% by weight, and more preferably 0.1% to 2%. The amount of polyvinylimidazole contributed to the solution of washing is typically 0.5 ppm to 250 ppm, preferably 2.5 ppm at 150 ppm, more preferably 5 ppm to 100 ppm.

Optical bleach

The detergent compositions herein invention may also optionally contain about 0.005% by weight to 5% by weight of certain types of bleach hydrophilic optics that also provide an inhibitory action of dye transfer. If you get to use these optical brighteners, the compositions of the present invention preferably comprise about 0.01% by weight to 1% in Weight of these optical brighteners.

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

8

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

When in the above formula R_ {1} is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the optical bleach is acidic 4,4'-bis [(4-anilino-6- (N-2-bis-hydroxyethyl) -s-triazin-2-yl) amino] -2,2'-stilbendisulfonic acid,  and its disodium salt. This particular kind of optical bleach It is marketed under the trade name of Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the bleach preferred hydrophilic optic useful in detergent compositions of This memory.

When in the above formula R_ {1} is anilino,  R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the optical bleach is salt acid disodium 4,4'-bis [(4-anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2,2'-stilbendisulfonic acid. particular kind of optical bleach is marketed under The trade name of Tinopal 5BM-GX by Ciba-Geigy Corporation.

When in the above formula R 1 is anilino, R 2 is morpholino and M is a cation such as sodium, the optical bleach is the sodium salt of 4,4'-bis [(4-anilino-6- acid] morpholino- s -triazin-2-yl) amino] -2,2'-stilbendisulfonic acid. This particular species of optical bleach is marketed under the trade name of Tinopal AMS-GX by Ciba-Geigy Corporation.

The specific species of optical bleach selected to be employed in the present invention provides especially effective advantages of inhibition behavior dye transfer when used in combination with dye transfer polymeric agents, selected, described above. Combining these selected polymeric materials (for example PVNO and / or PVPVI) with the selected optical brighteners (for example Tinopal UNPA-GX, Tinopal 5BM-GX and / or Tinopal AMS-GX) provides inhibition of dye transfer in aqueous wash solutions significantly better than that provided by any of these two components of detergent compositions if used alone Without being bound by theory, it is believed that these optical whiteners act because they have a high affinity towards the tissues within the wash solution, and therefore they deposit relatively quickly on these tissues. He degree to which optical brighteners are deposited on the tissues within the wash solution can be defined by a parameter called "exhaustion coefficient". In In general, the exhaustion coefficient is the ratio of a) the optical bleaching material deposited on the tissue with respect to b) the initial concentration of bleach in the washing liquid. Bleaching agents with relatively depletion coefficients elevated are best suited to inhibit the transfer of dyes in the context of the present invention.

Naturally, it will be appreciated that optionally Other types of conventional optical bleaching compounds, in order to provide advantages of conventional "optical whitening" of the tissues, instead of a true inhibitory effect of the dye transfer This job is conventional and well known in detergent formulations.

Cationic fabric softening agents

They can also be incorporated into the compositions according to the present invention cationic softening agents of tissues. These agents may be present as components separated, or as components of clay materials hydrophobically activated, which have already been described herein memory. Suitable cationic fabric softening agents, include water insoluble tertiary amines or materials of di (long chain) amide, as described in the GB-A-1,514,276 and EP-B-0.011.340.

Typically cationic agents are incorporated fabric softeners at total levels of 0.5% by weight to 15% in weight, usually from 1% by weight to 5% by weight.

Other optional ingredients

Other optional ingredients suitable to be included in the compositions of the invention include perfumes, dyes and filler salts, being a preferred filler salt sodium sulfate.

Composition Form

The detergent compositions herein invention can be formulated in any desirable way, by example powders, granules, pastes, and tablets.

Preferably, the particle size of the components of granular compositions according to the invention should be such that no more than 5% of the particles have a diameter greater than 1.4 mm, and not more than 5% of the particles have a diameter less than 0.15 mm.

The granular detergent compositions of according to the present invention typically have a density bulk bulk of at least 450 g / liter, more usually at least 600 g / liter and more preferably 650 g / liter at 1200 g / liter

Processing procedures - granular compositions

In general, detergent compositions granular according to the present invention can be made by various methods, including mixing in dry, spray drying, agglomeration and granulation.

Methods of washing clothes

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

The machine wash methods of the present invention typically comprise treating in a washing machine the clothes soiled with an aqueous wash solution containing dissolved or dispersed therein an effective amount of a detergent composition for machine washing according to the invention. The detergent can be added to the wash solution, or either through the dispenser drawer of the washing machine, or by means of a dispensing device. It is understood by "a effective amount of the detergent composition "from 40 to 300 g of product dissolved or dispersed in a wash solution with a volume of 5 to 65 liters, since these are the product doses and wash solution volumes commonly used in methods of conventional machine wash.

In a preferred washing method of the present invention, is introduced into the drum of a washing machine front loading, before starting the wash cycle, a device dispenser containing an effective amount of product Detergent.

The dispensing device is a container for the detergent product, which is used to supply the product directly inside the drum of the washing machine. His capacity volumetric should be such that it can contain a sufficient quantity of detergent product, which would normally be used in the method of  washed.

Once the machine has been loaded with clothes washed, the dispensing device is placed inside the drum Contains the detergent product. At the beginning of the wash cycle of the washing machine introduces water into the drum and rotates Periodically the drum. The design of the dispensing device must be such that it achieves containment of the dry detergent product, but then allow the release of this product during the cycle of washing in response to 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 various openings through which the product can pass. By way of alternatively, the device may be made of a material that is permeable to a liquid but impervious to the solid product, which will allow the release of the dissolved product. Preferably, the detergent product will be released quickly. at the beginning of the wash cycle, thus providing, transiently, high localized concentrations of product inside the drum of the washing machine, in this phase of the cycle of washed.

Preferred dispensing devices are reusable, and are designed in a way that maintains the integrity of the container both in the dry state and during wash cycle Dispensing devices have been described especially preferred for use in accordance with the invention, in the following patent documents: GB-B-2,157,717, GB-B-2,157,718, EP-A-0201376, EP-A-0288345 and EP-A-0288346. An article by J. Bland published in Manufacturing Chemist, November 1989, pages 41-46, also describes devices especially preferred dispensers to be used with granular wash products, which are commonly the type known as "granulette".

In patent application publications European numbers 0343069 and 0343070 devices are described Especially preferred dispensers. The request cited in last place describes a device comprising a sheath flexible in the form of a bag that extends from a ring support defining a hole, the hole being adapted for admit enough product into the bag for a cycle of washing in a washing process. A portion of the washing medium flows through the hole into the bag, dissolves the product, and the solution comes out later, through the hole, Towards the washing medium. The support ring is equipped with a masking set that prevents the exit of wet product but not dissolved, and this set typically comprises partitions that are extend radially from a central button, with a configuration spoke wheel, or a similar structure in which the Partitions have a helical shape.

Alternatively, the dispensing device It can be a flexible container, such as a bag or pocket. The bag may have a fibrous construction coated with a water-impermeable protective material so that it retains its content, as described in the European patent application published number 0018678. Alternatively, it may be formed by a water-insoluble synthetic polymer material provided with an edge closure or general closure designed to break into aqueous medium, as described in the applications European Patent Publication Numbers 0011500, 0011501, 0011502, and 0011968. A convenient form of closure capable of opening in water comprises a water soluble adhesive arranged as a closure at along an edge of a bag formed by a polymer film waterproof, such as polyethylene or polypropylene.

Packaging of the compositions

The commercialized executions of bleaching compositions can be packaged in any suitable container, including those built with paper, cardboard, plastic materials and any stratified material.

Abbreviations used in the examples

In detergent compositions, the abbreviated component identifications have the following meanings:

THE

: (linear C12 alkyl) benzenesulfonate sodium

TAS

: (tallow alcohol) sodium sulfate

XYAS

: (rent C 1X-C 1Y) sodium sulfate

25EY

: a primary alcohol C 12 -C 15 predominantly linear condensed with an average of Y moles of oxide of ethylene

XYEZ

: a primary alcohol C_ {1X} -C_ {1Y} predominantly linear condensed with an average of Z moles of oxide of ethylene

XYEZS

: (rent C 1X-C 1Y) condensed sodium sulfate with an average of Z moles of ethylene oxide per mole

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

: (rent C 16 -C 18) - N-methylglucamide

Silicate

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

NaSKS-6

: crystalline layered silicate of formula δ-Na2 {Si} {2} O5 {

Baking soda

: anhydrous sodium bicarbonate with a distribution of particle size between 400 µm and 1200 µm

Carbonate

: anhydrous sodium carbonate

MA / AA

: 1: 4 copolymer of maleic acid and acrylic acid, average molecular weight approximately 70,000.

STPP

: anhydrous sodium tripolyphosphate

Zeolite A

: hydrated sodium aluminosilicate of formula Na 12 (AlO 2 SiO 2) 12 .27H 2 O, which has a primary particle size in the range of 1 to 10 micrometers

Citric acid

: anhydrous citric acid

Citrate

: trisodium citrate dihydrate

Percarbonate

: anhydrous sodium percarbonate bleach coated with a sodium silicate coating (ratio SiO 2: Na 2 O = 2: 1), with a weight ratio of 39: 1 sodium silicate percarbonate

PB1

: anhydrous sodium perborate bleach of formula Nominal NaBO_2 .H2 {2}

PB4

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

TAED

: tetraacetylethylenediamine particle formed agglomerating TAED with a 1: 4 copolymer of maleic acid and acid acrylic having an average molecular weight of approximately 70,000, with a TAED weight ratio: copolymer of 85:10, and then coating said agglomerate with a coating of said copolymer in an agglomerated weight ratio: coating of 95: 5

NOBS

: nonanoyloxybenzenesulfonate in salt form sodium

Protease

: proteolytic enzyme marketed by Novo Industries A / S with the trade name Savinase, and with a 13 KNPU / g activity

Protease #

: proteolytic enzyme marketed by Novo Industries A / S with the trade name Savinase, and with a 4 KNPU / g activity

Protease \ alm {2}

: proteolytic enzyme marketed by Genencor under the trade name FN3

Alcalase

: proteolytic enzyme marketed by Novo Industries A / S, with an activity of 3 AU / g

Amylase

: amylolytic enzyme marketed by Novo Industries A / S with the trade name Termamyl 60T, and with a 300 KNU / g activity

Amylase #

: amylolytic enzyme marketed by Novo Industries A / S with the trade name Termamyl 120T, and with a 600 KNU / g activity

Cellulase

: cellulosic enzyme marketed by Novo Industries A / S with an activity of 1000 CEVU / g

Lipase

: lipolytic enzyme marketed by Novo Industries A / S with the trade name Lipolase, and with a 165 KLU / g activity

Endolasa

: endoglucanase A marketed by Novo Industries ACE

CMC

:sodium carboxymethylcellulose

DETPMP

:acid diethylenetriaminopenta (methylene phosphonic), marketed by Monsanto with the trade name Dequest 2060

HEDP

:acid hydroxyethane-1,1-diphosphonic

EDDS

:acid ethylenediamino-N, N'-disuccinic, isomer [S, S] in the form of sodium salt

PVNO

: copolymer of poly (4-vinylpyridine) -N-oxide, vinylimidazole and vinylpyrrolidone, which has an average molecular weight of 10,000

PVPVI

: polyvinylpyrrolidone copolymer and vinylimidazole

Clay

: calcium montmorillonite marketed by Colin Stewart Minchem Ltd, and containing 50 ppm Cu, 8000 ppm Fe and 80 ppm of Mn

Acid clay

: calcium montmorillonite treated with an acid organic, marketed by Sud CHemie AG

Granular suppressor of foam

: 12% silicone / silica, 18% off stearyl alcohol, 70% starch, in granular form

SRA (agents for detach the dirt)

: esters topped with sulfobenzoyl, with oxyenyloxy skeleton and terephthaloyl

Metolose

: carboxy-methoxy ether

Sulfate

: anhydrous sodium sulfate

Optical bleach one

: 4,4'-bis (2-sulfoestyryl) biphenyl disodium

Optical bleach 2

: 4,4'-bis (4-anilino-6-morpholino-1,3,5-triazin-2-yl) amino) -tylben-2,2'-disulfonate disodium

Bleach photoactivated

: zinc phthalocyanine sulfonated encapsulated in soluble dextrin polymer

Defoamer silicone

: foam controller a polydimethylsiloxane base with copolymer of siloxane-oxyalkylene as dispersing agent, with a ratio of said foam controller to said agent 10: 1 to 100: 1 dispersant

Example 1

In an Eirich Mixer RV02 mixer (trade name) a chipboard was prepared with the following formulation:

% in weight TAED 85 Clay**  \; 5 MA / AA * with p.mol. 70,000 10 \ overline {100}  \ hskip1cm * supplied as Sokolan 45 (trade name) of BASF  \ hskip1cm ** of the type Bentonite, from Colin Stewart Minchem Ltd,  \ hskip1,5cm and containing 8,000 ppm of Fe, 50 pppm of Cu, and 80 ppm of  \ hskip1,5cm Mn

TAED and clay were added to the mixer Eirich, and they were pre-mixed. Powder temperature It was 25 ° C. It was added to the powder mixture, with the shovels and the bowl of the Eirich turning, in the course of 30 seconds, a solution aqueous of the MA / AA binder, which was at a temperature of 60 ° C. The resulting mass was continued mixing for 30 seconds. After the mixing was stopped, the product was extracted agglomerated out of the Eirich mixer, and dried further in a fluidized bed dryer to a moisture content of 2%. The product was then screened, and the materials removed with a size greater than 1180 micrometers and less than 250 micrometers

Example 2

The same procedure was repeated as in the previous example, with the exception that the clay was replaced, in the same quantities, by an acid clay of the Tonsil P type, from Sud Chemie AG.

Example 3

In an Eirich Mixer RV02 mixer (trade name) a chipboard was prepared with the following formulation:

% in weight TAED 80 Clay**  \; 5 MA / AA * with p.mol. 70,000 10 \ overline {95}  \ hskip1cm * supplied as Sokolan 45 (trade name) of BASF  \ hskip1cm ** of the type Bentonite, from Colin Stewart Minchem Ltd,  \ hskip1,5cm and containing 8,000 ppm of Fe, 50 pppm of Cu, and 80 ppm of  \ hskip1,5cm Mn.

TAED and clay were added to the mixer Eirich, and they were pre-mixed. The temperature of powder was 25 ° C. It was added to the powder mixture, with the shovels and the Eirich mixer bowl rotating, over the course of 30 seconds, the molten binder, which was at a temperature of 60 ° C. The resulting mass was continued mixing for 30 seconds After the mixing was stopped, the agglomerated product out of the Eirich mixer, and dried additionally in a fluidized bed dryer. Later sifted the product, and materials with a size were removed greater than 1180 micrometers and less than 250 micrometers. TO the resulting agglomerate was then coated with a copolymer MA / AA at a coating level: chipboard of 5:95.

Example 4

In a continuous dual Lodige process, in which intervened a mixer with high shear CB Lodige, followed by a KM Lodige low shear mixer, it prepared a chipboard with the following formulation:

% in weight TAED 75 Clay** 10 MA / AA * with p.mol. 70,000 10 \ overline {95}  \ hskip1cm * supplied as Sokolan 45 (trade name) of BASF  \ hskip1cm ** of the type Bentonite, from Colin Stewart Minchem Ltd,  \ hskip1,5cm and containing 8,000 ppm of Fe, 50 pppm of Cu, and 80 ppm of  \ hskip1,5cm Mn.

The TAED and the clay at the entrance opening of the CB Lodige, with 25 ° C being the powder temperature. It was also added continuously to the CB Lodige the molten binder, which was a temperature of 60 ° C. The resulting mass was transferred to the Lodige KM to make the final size larger. He then dried the wet agglomerated product in a fluidized bed dryer for reduce humidity to the desired value of 2%. Then it was screened the product, and materials with a size larger than 1700 micrometers and less than 425 micrometers. Then you the resulting agglomerate, with a MA / AA copolymer, at a coating level: chipboard 5:95

Example 5

The following compositions were prepared washing detergents A, B, C, D and E. A and B are compositions comparatives, and C to E are in accordance with the invention.

9

* (1) as in the Example one  \ hskip0.2cm (2) as in the Example 2  \ hskip0.2cm (3) as in Example 3

Example 5 Comparative efficacy trials

Test protocol one

Proof of localized irregular discoloration or "by zones" in tissues

The formulations A to E were subjected to an assay Full scale machine wash using 12 washing machines Miele automatic (model WM W698) adjusted to the wash cycle short at 40 ° C for each formulation. Water of 12º hardness was used German (= 1.8 moles of Ca2 + / liter). They were numbered from 1 to 24  scraps of fabrics that were to be placed in washing machines, and that had been prepared from clothing stores prestige, as detailed below:

10

Each machine was loaded with a filler load of  approximately 1.9 kg of clean sheets, and on top of them the following materials: a tissue patch, 100 g of the formulation, dispensed from a "granulette" dispensing device, from type described in the document EP-A-343.070 and supplied commonly for use with Ariel Ultra detergent (name commercial) marketed by The Procter and Gamble Company, and a second scrap of cloth on top of it. The scraps of 30 were folded cm x 30 cm so that they catch the granulette during first phases of dissolution / dispersion of the composition detergent containing the bleach precursor composition. At the end of the cycle the scraps were removed and air dried free.

Next, the discoloration of the tissue of the retales, using a system of qualification..

Three color scraps were used as patterns that presented different degrees of irregular localized deterioration or "by zones" of the color of the fabric, to establish a scale of 6 points in which 0 represents "no discoloration" and 5 It represents "extreme discoloration." The three patterns serve to define the intermediate points between the different discoloration descriptions, namely

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0 without discoloration one very light discoloration 2 light discoloration 3 discoloration clearly appreciable 4 very discolored 5 discoloration extreme

Two expert panelists were summoned, and they They averaged their results.

Comparative test one

Localized irregular discoloration or "by zones" in woven

Using the previous test protocol 1 to compare irregular localized discoloration or "by areas" of tissues, as a consequence of the use of formulations A to E, The following results were obtained

eleven

it can be seen that C to E formulations according to the invention produces considerably less irregular localized discoloration or "by zones "in the tissues, which formulations A and B that are not of agreement with the invention.

Test protocol 2

Stain removal

Three white cotton sheets were pre-washed in an energetic detergent, without bleaching, and non-biological. Later tea stains were applied to a sheet, wine stains to the second sheet, and coffee stains to the third. From each sheet they were cut groups of six retales for tests, with a size of 6 cm x 6 cm.

The tissue scrap groups were subjected to a washing cycle in an automatic washing machine. Then the removal of tea, wine and coffee stains was evaluated, using a well established method of clarity measurement.

Referring to it in more detail, a Miele 756 WM washing machine, and the cycle program was selected short at 40 ° C. Water with 12º of German hardness was used (= 1.8 moles of Ca2 + / liter). 100 g of detergent were used, dispensed from a "granulette" dispensing device. A scrap was washed of each type of fabric along with a filler load of approximately 1.9 kg of slightly dirty sheets.

Dirt removal was evaluated by LAB (clarity) measurements using the eye spectrophotometer of X-rite color (trademark). It was used as reference an unstained cotton sheet. The index was calculated stain removal, ΔR, as follows:

ΔR = (L_ {washed} - L_ {without \ washing}) / (L_ {without \ washing} - L_ {reference}) x 100

where the differences \ DeltaR less than 4% are not significant.

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Comparative test 2

Stain removal

The previous test protocol 2 was followed to compare the effectiveness of compositions B and C to eliminate different types of bleach sensitive spots. The results obtained were the following:

       \ vskip1.000000 \ baselineskip
    

ΔR (%) B C Tea 78 76 Came 82 83 Coffee 75 74

       \ vskip1.000000 \ baselineskip
    

It is observed that the removal of stains obtained for each of Compositions B and C it is comparable. So, the presence of HMI as a H 2 O 2 sensor, and Carried in a clay, in Composition C, does not compromise significantly the ability to remove stains from this composition versus that of Composition B. It is also appreciated that the perhydrolysis behavior of the bleach precursor does not It is significantly compromised.

Example 6

The following compositions were prepared laundry detergents F to J according to the invention:

       \ vskip1.000000 \ baselineskip
    

12

13

* (1) as in the Example one  \ hskip0.2cm (2) as in the Example 2  \ hskip0.2cm (3) as in Example 3  \ hskip0.2cm (4) as in Example 4

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Example 7

The following formulations were prepared detergents according to the invention, in which the Formulation K is a phosphorus-containing detergent composition, formulation L is a detergent composition containing zeolite, and formulation M is a compact detergent composition:

14

 \ hskip0,5cm * (4) as in the Example 4

Example 8

The following formulations were prepared N and O detergents, in accordance with the present invention:

16

 \ hskip2cm * (4) as in Example 4, replacing TAED with NOBS

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Example 9

The following formulations P and Q were prepared of high-density detergents containing bleach, of according to the present invention:

17

 \ hskip2cm * (4) as in the Example 4

Example 10

The following R and S formulations were prepared of high density detergents, in accordance with this invention:

19

 \ hskip2cm * (4) as in the Example 4

Claims (17)

1. A detergent composition containing:

(to)

a source of peroxide compounds

(b)

a peroxyacid-based bleach precursor composition, which understands

(i)

a peroxyacid-based bleach precursor compound organic,

(ii)

a pickup material of H 2 O 2

in which said compound bleach precursor based on organic peroxyacid and said H 2 O 2 capture material are in close proximity physics within said composition, so that the material H2O2 sensor and bleach precursor compound based on organic peroxyacid are not two discrete particles separated in the detergent composition, Y in which said collector of H 2 O 2 is a heavy metal ion selected from elements contained in the fourth and fifth rows of columns third to twelfth of the table periodic. 2. A detergent composition according to the claim 1, wherein said heavy metal ion is selected from Fe, Cu and Mn, and mixtures thereof. 3. A detergent composition according to a any of claims 1-2, in which said heavy metal ion is in an amount less than 5%  by weight of the bleach precursor composition, preferably in an amount less than 1%, and more preferably in an amount less than 0.1%. 4. A detergent composition according to a any of claims 1-3, wherein said bleach precursor is present at a level higher than 3% by weight of the detergent composition. 5. A detergent composition according to a any of claims 1-4, in which said bleach precursor is selected from those they contain one or more N- or O-acyl groups. 6. A detergent composition according to the claim 5, wherein said bleach precursor is N, N-N ', N'-tetraacetylethylenediamine. 7. A detergent composition according to a any of claims 1-6, in which said bleach precursor composition is a chipboard additionally bound with a binder. 8. A detergent composition according to the claim 7, wherein said precursor agglomerate of bleach is also provided with a coating material. 9. A detergent composition according to the claim 8, wherein said coating material is selected from poly (acrylic acid), cellulose acetate, acids polycarboxylic copolymers and aliphatic carboxylic acids monomers, and mixtures thereof. 10. A detergent composition according to a any of claims 1-9, in which said active oxygen source is a peroxide source of hydrogen, preferably a perhydrate based bleach inorganic. 11. A detergent composition according to claim 10, wherein said bleach based on Perhydrate is sodium perborate or sodium percarbonate. 12. A detergent composition according to a any of claims 1-11, which it comprises a surfactant material, and which also incorporates a heavy metal ion sequestrant, this being selected Ultimate of organic phosphonates, nitrilotriacetic acid, and acids polyaminocarboxylic. 13. A detergent composition according to the claim 12, wherein said ion sequestrant of Heavy metals is ethylenediamine diisuccinate (EDDS). 14. A detergent composition according to one of the claims 12 or 13, wherein said ion sequestrant of heavy metals is present as a separate component of said peroxyacid-based bleach precursor composition. 15. A procedure to produce a detergent composition containing (a) a source of compounds of peroxide, (b) a bleach precursor composition based on peroxyacid comprising i) a bleach precursor compound a  organic peroxyacid base, ii) a capture material of H 2 O 2, wherein said bleach precursor compound a organic peroxyacid base and said pickup material of H 2 O 2 are in close physical proximity within said bleach composition, so that the material H2O2 sensor and bleach precursor compound based on organic peroxyacid are not two discrete particles separated in the detergent composition, which comprises operations of:

to)

prepare a precursor agglomerate of peroxyacid-based bleach by mixing a precursor compound of organic peroxyacid bleach with a material H 2 O 2 sensor, to which is added and then mixed a binder material,

b)

treat said agglomerates with a lining material,

C)

dry off said coated agglomerates, and

d)

incorporate said agglomerates coated dried to a detergent composition containing a source of peroxide compounds,

where the pickup material of H 2 O 2 is selected from a heavy metal ion, a catalase enzyme, and an enzyme of peroxidase 16. A method according to claim 15, in which the pickup material of H 2 O 2 is an ion of heavy metal selected from elements contained in the fourth and fifth rows of the third through twelfth columns of the table periodically, and said heavy metal ion is carried in a mineral material containing at least 200 ppm of said ion of heavy metal. 17. A method according to claim 16, in which said mineral material is a clay.