ES2216011T3 - DETERGENTS CONTAINING A HEAVY METAL SEQUENCER AND A PEROXIACID DELAYED BLEACHING SYSTEM. - Google Patents

Abstract

A DETERGENT COMPOSITION IS PROVIDED THAT CONTAINS: (A) A HEAVY METAL ION INHIBITOR; AND (B) A WHITENING SYSTEM OF AN ORGANIC PEROXIACIDE WHERE A MEDIA IS PROVIDED TO DELAY THE RELEASE TO A WASHING SOLUTION OF SUCH PEROXIACIDED WHITENING RELEASE WITH RESPECT TO THE RELEASE OF HEAVY METAL INHIBITOR IONS. PREFERIBLY SUCH COMPOSITION ADDITIONALLY CONTAINS (C) A WATER SOLUBLE ADDITIVE WHERE A MEDIUM IS PROVIDED TO DELAY THE RELEASE TO A SOLUTION OF BUTTER SUCH PEROXIACID WITH RESPECT TO THE RELEASE OF SUCH ADDITIVE SOLUBLE. A WASHING PRE-TREATMENT METHOD IS ALSO PROVIDED.

Description

Detergents containing a sequestrant from heavy metals and a peroxyacid bleach system of delayed release.

This invention relates to compositions detergents containing a metal ion sequestrant heavy and an organic peroxyacid bleaching system, where provides a means to delay the release of the bleach organic peroxyacid in the wash solution, in relation to the release of the heavy metal ion sequestrant.

Successful removal of dirt / stains bleachable on dirty substrates / stained with tea, fruit juice and vegetables that leave a trace of color is a particular challenge for the formulator of a detergent composition for use in a method of washing such as an automatic method of washing clothes or crockery.

Traditionally, the removal of such dirt / bleachable stains has been possible thanks to the use of bleaching components such as oxygenated bleaches, including hydrogen peroxide and organic peroxyacids. Organic peroxyacids are usually obtained by the in situ perhydrolysis reaction between hydrogen peroxide and a precursor to the organic peroxyacid bleach.

A problem encountered with the use of certain organic peroxyacid bleaching in laundry methods is a tendency for these organic peroxyacid bleaching agents affect the color stability of the tissues in the wash. The Types of tissue damage may include discoloration of tissue colors or color bleaching in localized areas leaving "patches."

Thus, the detergent formulator faces the double challenge of formulating a product that eliminates the maximum dirt / bleachable spots, but with a minimum incidence of unwanted effects of bleach on color stability of the tissues.

The applicant has found that the incidence of unwanted effects on tissue color stability and generated by the use of organic peroxyacid bleaching agents in a washing method may be related to the speed of release of peroxyacid bleach in the wash solution and also with the absolute level of peroxyacid present in the solution washing

A fast release speed of peroxy acid bleach in the wash solution tends to increase the likelihood of unwanted effects on the stability of the color of the tissues, as is the case with an absolute high level of the bleach in the wash solution.

While a decrease in either the speed of release of peroxyacid bleach, or of the absolute level of Bleach used in washing tends to improve this problem, such decrease may be accompanied by a negative effect on the dirt / bleachable stain removal power.

However, now the applicant has found that when a composition is used that contains both a heavy metal ion sequestrant as a source of peroxyacid bleach, and when a means is provided for delay the release of peroxyacid bleach in a solution washing with respect to the release of the ion sequestrant from heavy metals, an improved removal of dirt / bleachable spots. Additionally, when using the composition in a laundry method, you also get a decrease in the tendency for negative effects to be observed on the stability of the colors of the fabrics.

The applicant has also found that they can get stain / bleachable dirt removal benefits when a dirty substrate is pretreated with a solution that contains a heavy metal ion sequestrant, and optionally a water soluble detergency builder, before washing it in a method using a bleach that contains a product Detergent.

Therefore, an object of the present invention is to provide compositions suitable for use in methods of automatic washing of dishes and clothes, which produce better disposal of bleachable spots.

It is also an object of the present invention provide compositions for use in a laundry method where said compositions have less tendency to cause negative effects on the stability of the colors of the tissues.

A related object of the present invention is provide a stain / dirt pretreatment method that involves pretreating the dirty substrate with a solution that contains a heavy metal ion sequestrant and optionally a water soluble detergency builder, before washing it with a detergent product containing bleach.

Compendium of the invention

According to one aspect of the present invention, provides a detergent composition containing:

(a) a heavy metal ion sequestrant; Y

(b) a peroxyacid bleaching system organic

where a means is provided to delay the release of said organic peroxyacid with respect to the release of said heavy metal ion sequestrant in a solution wash such that, in the T50 test method described herein, the time to obtain a concentration that is 50% of the final concentration of the heavy metal ion sequestrant be less than 120 seconds and the time to get a concentration that is 50% of the final concentration of the organic peroxyacid is greater than 180 seconds.

According to another aspect of the present invention, provides a detergent composition containing:

(a) a heavy metal ion sequestrant; Y

(b) a peroxyacid bleaching system organic

where a means is provided to delay the release of said organic peroxyacid with respect to the release of said heavy metal ion sequestrant in a solution wash such that, in the T50 test method described herein, the time to obtain a concentration that is 50% of the final concentration of the heavy metal ion sequestrant be at least 100 seconds, preferably at least 120 seconds, more preferably at least 150 seconds less than the time in obtain a concentration that is 50% of the final concentration of said organic peroxyacid.

Said organic peroxyacid bleaching system preferably comprises a combination of

(i) a source of hydrogen peroxide; Y

(ii) a bleaching precursor compound organic peroxyacid

According to a preferred aspect of the present invention, said composition additionally contains

(c) a water soluble booster

where a means is provided to delay the release of said organic peroxyacid with respect to the release of said water soluble detergency builder in a washing solution such that, in test method T50 here described, the time to obtain a concentration that is 50% of said final concentration of said detergency builder Water soluble is less than 120 seconds and the time to get a concentration that is 50% of the final concentration of said Organic peroxyacid is greater than 180 seconds.

In accordance with another aspect of this invention, a washing method is provided comprising the stages of:

(one)

apply a solution, free of bleach, of a composition containing a heavy metal ion sequestrant to a dirty substrate;

(two)

let bliss solution remains in contact with said dirty substrate for a effective time interval;

(3)

wash said dirty substrate using a washing method that involves the use of a detergent composition containing bleach.

Heavy metal ion sequestrant

The detergent compositions of the invention contain a heavy metal ion sequestrant. For him concept "heavy metal ion sequestrant" is understand in the present invention the components that act sequestering (chelating) heavy metal ions. These components may also have chelation capacity of calcium and magnesium, but preferably manifest a selectivity for the association of heavy metal ions, such like iron, manganese and copper.

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

Heavy metal ion sequestrants, that are acidic in nature, having for example functionalities of phosphonic acids or carboxylic acids, may be present either in its acid form or as a complex / salt with a counterion appropriate cation, such as an alkali metal ion or alkaline earth, ammonium, substituted ammonium, or Any of your mixtures. Preferably, any of the salts / complexes are soluble in water. The molar relationship of said cation counterion to the heavy metal ion sequestrant is preferably at least 1: 1.

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

Among the previous chemical species are prefer diethylene triamine penta- (methylene phosphonate), ethylene diamino-tri- (methylene phosphonate), hexamethylene diamino tetra- (methylene phosphonate) and hydroxy-ethylene-1,1-diphosphonate.

Another heavy metal ion sequestrant suitable for use in the present invention includes acid nitrilotriacetic and polyaminocarboxylic acids such as acid ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic acid, acid ethylenediamine disuccinic acid ethylenediaminodiglutaric acid 2-hydroxypropylene diamine disuccinic, or any of Your salts

Acid is especially preferred ethylenediamine-N, N-disuccinic (EDDS) or its alkali metal salts, metals alkaline earth, ammonium or substituted ammonium, or their mixtures Preferred EDDS compounds are the free acid form. and the sodium or magnesium salt or a complex thereof. Examples of such preferred sodium salts of EDDS include Na2 EDDS and Na 3 EDDS. Examples of such preferred magnesium complexes of EDDS include MgEDDS and Mg2 EDDS.

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

Acid sequestrants iminodiacetic-N-2-hydroxypropyl sulfonic acid and aspartic acid-acid N-carboxymethyl-N-2-hydroxypropyl-3-sulfonic described in the document EP-A-516.102 are also suitable in the present invention. Kidnappers are also suitable alanine-N, N'-diacetic acid, acid aspartic acid-N, N'-diacetic acid, acid aspartic acid-N-monoacetic acid and acid iminodusuccinic described in the document EP-A-509,382.

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

Organic peroxyacid bleaching system

An essential feature of the invention is an organic peroxyacid bleaching system. In a preferred embodiment, the bleaching system contains a source of hydrogen peroxide and an organic peroxyacid bleach precursor compound. The production of the organic peroxyacid is carried out by an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include perhydrated inorganic bleaches. In an alternative preferred embodiment, a previously formed organic peroxyacid is incorporated directly into the composition. Compositions containing mixtures of a source of hydrogen peroxide and an organic peroxyacid precursor in combination with a previously formed organic peroxyacid are also considered.

Perhydrated inorganic bleaching agents

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

Examples of inorganic perhydrated salts Suitable include perborate salts, percarbonate, perfosphate, persulfate and persilicate and any of their mixtures. Salts inorganic perhydrates are normally metal salts alkaline Inorganic perhydrated salt can be included as of a crystalline solid without any additional protection. Without However, for certain perhydrated salts, the embodiments preferred of said granular compositions use a form Coated material, which provides better stability of storage for perhydrated salt in the granular product.

Sodium perborate may be in the form monohydrate with the nominal formula NaBO 2 H 2 O 2 or Tetrahydrate NaBO 2 H 2 O 2 .3H 2 O.

The alkali metal percarbonates, particularly sodium percarbonate, they are perhydrates preferred for inclusion in the compositions according to the invention. It has been found that the compositions containing percarbonate show less tendency to form undesirable gels in presence of surfactants and water than similar compositions containing perborate It is believed that this is typically because the percarbonate has less specific surface area and less porosity than perborate monohydrate. This low specific surface as well as the low porosity act preventing joint gelation with fine particles of surfactant agglomerates and therefore It is not harmful to the dosage.

Sodium percarbonate is a compound of addition that has a formula corresponding to 2Na2CO3 .3H2O2, and is commercially available in the form of a crystalline solid. Percarbonate is incorporated as more preferably in said compositions in a coated form which provides stability within the product.

An appropriate coating material, which provides stability to the product comprises a mixed salt of a water soluble alkali metal carbonate and sulfate. Sayings coatings, together with coating procedures, have been described previously in the patent GB-1,466,799, granted to Interox on March 9, 1977. The weight ratio of the mixed salt that acts as a material percarbonate coating falls 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 consists of sodium and sodium carbonate and has the general formula Na_ {SO} {4} .n.Na_ {CO2} where n is 0.1 to 3, preferably n is 0.3 to 1.0 and most preferably n is 0.2 to 0.5.

Within the present invention, they can be use other coatings that contain silicate (alone or with borate salts or boric acids or other inorganic components), Waxes, oils and fatty soaps.

Potassium peroximonopersulfate is another salt inorganic perhydrate used in detergent compositions of the present invention.

Peroxyacid bleach precursor

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

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

---LX ---

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

--- L

where L is a leaving group and X is essentially any functionality, such that, when experiencing perhydrolysis, the peroxyacid structure produced it is

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

---OOHX ---

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

--- OOH

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

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

The applicant has found that the damage in form of "patches" may be associated in particular with peroxyacid bleaching precursor compounds, which when perhydrolyze provide a peroxyacid that is

(i) a perbenzoic acid or a substituted derivative non-cationic thereof; or

(ii) a cationic peroxyacid.

It has also been found that precursors Benzoxazines are especially sensitive to the problem.

Outgoing groups

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

Preferred L groups are selected from the group consisting of:

one

two

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

---CH = CH_{2},

\hskip1cm

---O---CH =

\uelm{C}{\uelm{\para}{Y}}

---CH = CH_{2},--- O --- CH =

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

--- CH = CH2,

 \ hskip1cm 

--- O --- CH =

 \ uelm {C} {\ uelm {\ para} {Y}} 

--- CH = CH2,

3

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

= CHR^{4},

\hskip1cm

y

\hskip1cm

---

\delm{N}{\delm{\para}{R ^{3} }}

---

\melm{\delm{\dpara}{O}}{S}{\uelm{\dpara}{O}}

---

\uelm{C}{\uelm{\para}{Y}}

H---R^{4}---OR---

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

= CHR 4,

 \ hskip1cm 

Y

 \ hskip1cm 

---

 \ delm {N} {\ delm {\ para} {R3}} 

---

 \ melm {\ delm {\ dpara} {O}} {S} {\ uelm {\ dpara} {O}} 

---

 \ uelm {C} {\ uelm {\ para} {Y}} 

H --- R 4

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

Preferred solubilizing groups are those -SO 3 <+> - M +, -CO 2 - M +, -SO 4 M -, -N + (R 3) 4 X - and O? N (R3) 3, and most preferably -SO 3 -M + and -CO 2 -M +, in which R 3 is a chain of alkyl containing 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is a anion that provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or ammonium cation. substituted, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.

Perbenzoic acid precursors and derivatives thereof

Perbenzoic acid precursor compounds They provide perbenzoic acid when experiencing perhydrolysis.

Perbenzoic acid precursor compounds appropriate O-acylates include the benzoyl oxybenzene sulphonates substituted and unsubstituted, including, for example, a benzoyl-oxybenzene sulfonate:

4

The products of benzoylation of sorbitol, glucose, and all saccharides with agents of benzoylation, including, for example:

5

Ac = COCH 3; Bz = benzoyl.

\hbox{piroglutámico.}

Perbenzoic acid precursor compounds of the imide type include N-benzoyl succinimide, tetrabenzoyl ethylenediamine, and N-benzoyl substituted ureas. Suitable perbenzoic acid precursor compounds of the imidazole type include N-benzoyl-imidazole and N-benzoyl-benzimidazole, and other perbenzoic acid precursor compounds with useful N-acyl groups include N-benzoyl-pyrrolidone, dibenzoyl-taurine and benzoyl acid-

 \ hbox {pyroglutamic.} 

Other perbenzoic acid percussors include the benzoyl diacyl peroxides, the benzoyl tetraacyl peroxides, and the compound that has the formula:

6

Phthalic anhydride is another precursor compound of appropriate perbenzoic acid in the present invention:

7

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

8

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

Precursor compounds of perbenzoic acid derivatives

The acid derivative precursor compounds perbenzoic provide substituted perbenzoic acids to experience perhydrolysis

Acid derivatives precursor compounds Appropriate substituted perbenzoic include any of the perbenzoic acid precursor compounds described in this invention, in which the benzoyl group is substituted essentially with any functional group not loaded positively (i.e. non-cationic) that includes, for example, alkyl, hydroxy, alkoxy, halogen, amino, nitrosyl and amido

A preferred class of precursor compounds of substituted perbenzoic acids are the compounds amido-substituted, of the following formulas general:

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

---

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

---R^{2}---

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

---L

\hskip1cm

o

\hskip1cm

R^{1}---

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

---

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

---R^{2}---

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

---LR1 ---

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

---

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

--- R2 ---

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

--- L

 \ hskip1cm 

or

 \ hskip1cm 

R1 ---

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

---

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

--- R2 ---

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

--- L

in which R1 is an aryl group or alkylaryl having 1 to 14 carbon atoms, R2 is a arylene or alkylarylene group containing from 1 to 14 atoms of carbon, and R 5 is H or an alkyl, aryl or alkylaryl group which It contains 1 to 10 carbon atoms and L can be essentially Any outgoing group. R1 preferably contains from 6 to 12 carbon atoms R2 preferably contains from 4 to 8 carbon atoms R1 can be aryl, substituted aryl or alkylaryl containing a branching, a substitution, or both things, and can originate in any synthetic sources or natural sources including, for example, tallow fat. Similar structural variations are permissible for R2. The substitution may include alkyl, aryl, halogen groups, nitrogen, sulfur and other typical or compound substituent groups organic R 5 is preferably H or methyl. R1 and R5 they must not contain more than 18 carbon atoms in total. Compounds amido-substituted bleach activators of this type are described in the document EP-A-0170386.

Precursor compounds of cationic peroxyacids

Peroxyacid precursor compounds cationics produce cationic peroxyacids when experimenting perhydrolysis

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

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

The cationic peroxyacid precursor compounds are described in US Pat. 4,904,406;
4,751,015; 4,988,451; 4,397,757; 5,269,962: 5,127,852: 5,093,022; 5,106,528; in British Patent 1,382,594; in EP Patents 475,512; 458,396 and 284,292; and in JP 87-318.332.

In British Patent Application No. 9407944.9 and U.S. Patent Applications no. 08/298903, 08/298650, 08/298904 and 08/298906 describe examples of precursors of preferred cationic peroxyacids.

Precursor compounds of cationic peroxyacids Suitable include any of the alkyl compounds or benzoyl oxybenzene sulphonates substituted ammonium or alkylammonium, acylated caprolactams in N and monobenzoyl-tetraacetyl-glucose-benzoyl-peroxides.

A benzoyl-oxybenzene sulfonate preferred cationically substituted is the derivative 4- (trimethyl-ammonium) -methyl benzoyl-oxybenzene sulfonate:

9

An alkyloxybenzene sulfonate Cationically preferred substituted has the formula:

10

Precursor compounds of cationic peroxyacids from the class of preferred N-acylated caprolactams include the trialkyl-ammonium-methylene-benzoyl-caprolactams, particularly the trimethyl-ammonium-methylene-benzoyl-caprolactam:

eleven

Other peroxyacid precursor compounds cationics of the class of preferred N-acylated caprolactams, include the trialkyl-ammonium-methylene-alkyl-caprolactams:

12

where n is 0 to 12.

Other cationic peroxyacid precursor compound preferred is chloride 2- (N, N, N-trimethyl-ammonium) -ethyl-4-sulfophenylcarbonate of sodium.

Acid bleach precursor compounds alkyl percarboxylic

The bleaching precursor compounds of type alkyl-percarboxylic acid form acids percarboxylic when experiencing perhydrolysis. The compounds preferred precursors of this type provide peracetic acid when experiencing perhydrolysis.

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

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

Alkyl peroxyacid precursor compounds amido-substituted

The alkylperoxyacid precursor compounds amido-substituted are also appropriate, including those with the following general formulas

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

---

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

---R^{2}---

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

---L

\hskip1cm

o

\hskip1cm

R^{1}---

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

---

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

---R^{2}---

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

---LR1 ---

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

---

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

--- R2 ---

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

--- L

 \ hskip1cm 

or

 \ hskip1cm 

R1 ---

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

---

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

--- R2 ---

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

--- L

where R 1 is an alkyl group that Contains from 1 to 14 carbon atoms, R2 is an alkylene group containing from 1 to 14 carbon atoms, and R 5 is H or a group alkyl containing 1 to 10 carbon atoms and L can be essentially any leaving group. R1 contains preferably from 6 to 12 carbon atoms. R2 contains preferably from 4 to 8 carbon atoms. R1 can be straight or branched chain alkyl containing a branching, a substitution, or both, and may originate in any synthetic sources or natural sources including, by example, sebum fat. Similar structural variations are allowable for R2. The substitution may include groups alkyl, aryl, halogen, nitrogen, sulfur and other groups typical substituents or organic compounds. R 5 is preferably H or methyl. R1 and R5 should not contain more than 18 carbon atoms in total. Activating compounds of Amido-substituted bleaching of this type is described in the document EP-A-0170386.

Organic peroxyacid precursors of the benzoxazine type

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

13

including substituted benzoxazines from kind

14

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

An especially preferred precursor compound The type of benzoxazine is:

fifteen

Organic peroxyacid previously formed

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

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

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

---

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

---R^{2}---

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

---OOH

\hskip1cm

o

\hskip1cm

R^{1}---

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

---

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

---R^{2}---

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

---OOHR1 ---

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

---

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

--- R2 ---

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

--- OOH

 \ hskip1cm 

or

 \ hskip1cm 

R1 ---

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

---

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

--- R2 ---

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

--- OOH

in which R 1 is an alkyl, aryl or arylalkyl having 1 to 14 carbon atoms, R2 is a alkylene, arylene and arylalkylene group containing from 1 to 14 carbon atoms, and R 5 is H or an alkyl, aryl or alkylaryl containing from 1 to 10 carbon atoms. R1 preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon atoms. R1 can be a straight or branched chain alkyl group, aryl group or alkylaryl substituted with a branching, a substitution or both things, and may originate from synthetic sources or sources natural including, for example, tallow fat. Variations Similar structural structures are permissible for R2. The replacement may include alkyl, aryl, halogen, nitrogen, sulfur and other typical substituent groups or organic compounds. R 5 It is preferably H or methyl. R1 and R5 should not contain more than 18 carbon atoms in total. In the document EP-A-0170386 compounds are described amido-substituted organic peroxyacids of this kind.

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

Chlorine bleach

The compositions of the present invention are preferably free of chlorine bleach.

Bleaching catalyst

The invention also includes within its scope compositions containing a catalytically effective amount of a bleach catalyst such as a manganese salt soluble in water.

The bleach catalyst is used in a catalytically effective amount in the aqueous compositions of the present invention By "catalytically effective amount" is understand an amount that is sufficient, whatever the comparative test conditions, to intensify bleaching and the removal of the stain or stains of interest in the substrate chosen as objective. Thus, in a washing operation of tissues, the substrate chosen as the target will typically be a stained fabric, for example, with various food stains. For automatic dishwashing, the substrate chosen as objective can be, for example, a cup or a porcelain plate with tea stains, or a plate of polyethylene stained soup tomato. The test conditions will vary, depending on the type of Used washing machine and user habits. So, the automatic front loading washing machines of those used in Europe generally use less water and higher concentrations of Detergent than top-loading machines in American style. Some machines have considerably more wash cycles Long than others. Some users prefer to use water very hot; others use warm or cold water in washing operations of tissues. Naturally, the catalytic behavior of bleach catalyst will be affected by such considerations, and the bleach catalyst levels used in fully formulated detergents and bleaching compositions can be adjusted properly. As a practical matter, and not to limitation title, bleaching compositions and procedures in this memory can be adjusted to provide the order of at minus one part for ten million of the catalyst species of active bleaching in the aqueous washing medium, and will provide preferably from about 1 ppm to about 200 ppm, of the catalyst species in the wash solution. For better illustrate this point, a concentration of the order of 3 micromolar manganese catalyst is effective at 40 ° C and pH 10, in European conditions using perborate and a precursor of bleach (eg, benzoyl-caprolactam). In American conditions, it may be necessary to increase the concentration 3-5 times to get them results. Conversely, the use of a bleach precursor and the perborate manganese catalyst can allow the formulator obtain a bleaching equivalent to a lower level of use of the perborate than in products that do not contain the manganese catalyst.

The material of the bleach catalyst in the The present invention may comprise the free acid or be in form. of any suitable salt.

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

Other types of bleaching catalysts include the manganese-based complexes described in the U.S. Patent 5,246,621 and in US Pat. 5,244,594. Preferred examples of these catalysts include

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

Mn III 2 (uO) 1 (u-OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 - (ClO 2) 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 their mixtures. Other types are described in the European Patent Application Publication No. 549,272. Others Suitable ligands for use in the present invention include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane, and their mixtures.

See US patents 4,246,612 and 5,227,084 for examples of suitable bleach catalysts. See also US Pat. No. 5,194,416 teaching complexes manganese (IV) mononuclear such as Mn (1,4,7-trimethyl-1,4,7-triazacyclononane) (OCH 3) 3 - (PF 6). Still, another type of bleach catalyst, as described in U.S. Patent No. 5,114,606, is a water soluble complex of manganese (II), (III) and / or (IV), with a ligand that is a compound non-carboxylate polyhydroxy, which has at least three consecutive C-OH groups. Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylitol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose and mixtures thereof.

U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a metal complex of transition, including Mn, Ce, Fe or Cu, with a non-ligand (macro) cyclic. 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} {R2}} 

--- B ---

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

= N --- R 4

where R 1, R 2, R 3, and R 4 are they can select in each case between H, alkyl and aryl groups substituted such that each R1 -N = C-R2 and R 3 -C = N-R 4 form a ring of five or six members. Said ring may additionally be replaced. B is a bridge group selected from O, S, CR 5 R 6, NR 7 and C = O, in which each of the R 5, R 6 and R 7 may be H, alkyl or aryl groups, including substituted or unsubstituted groups. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole rings, pyrazole and triazole. Optionally, said rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide and nitro. The ligand is particularly preferred. 2,2'-bis-pyridylamine. The Preferred bleach catalysts include Co complexes, Cu, Mn, Fe, -bis-pyridylmethane and -bis-pyridylamine. Highly preferred catalysts include Co (2,2'-bis-pyridylamine) Cl2, di (isothiocyanate) bis-pyridylamine-cobalt (II), tris-dipyridylamine-cobalt (II) -perchlorate, Co (2,2-bis-pyridylamine) 2 O 2 ClO 4, bis- (2,2'-bis-pyridylamine)-copper (II) -perchlorate, tris (di-2-pyridyl-amine)-iron (II) -perchlorate and its mixtures

Other examples include Mn gluconate, Mn (CF 3 SO 3) 2, Co (NH 3) 5 Cl, and the binuclear Mn complexed with tetra-N-dentate ligands and bi-N-serrated, included 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.

The bleach catalysts are also they can prepare by combining in aqueous medium a soluble ligand in water with a water-soluble manganese salt and concentrating the resulting mixture by evaporation. In the present invention, You can use any convenient water-soluble manganese salt. Manganese (II), (III), (IV) and / or (V) is available in the Market on a commercial scale. In some cases, it may already be present enough manganese in the wash solution, but it is generally preferred to add Mn cations in the compositions to ensure its presence in catalytically effective amounts. Thus, the sodium salt of the ligand and a selected member of the group consisting of MnSO4, Mn (ClO4) 2 or MnCl2 (less preferred) dissolve in water at ratios ligand molars: manganese salt in the range of approximately 1: 4 to 4: 1 at neutral or slightly alkaline pH. The water can be deoxygenated first by boiling and cooled with a nitrogen purge The resulting solution is evaporated (if desired under N2) and the resulting solid is used in the bleaching and detergent compositions of the present invention Without further purification.

In an alternative mode, a water-soluble manganese source, such as MnSO4, is added to the bleaching / cleaning composition or to the aqueous bleaching / cleaning bath comprising the ligand. Apparently some kind of complex is formed in situ and an improved bleaching power is guaranteed. In such an in situ process, it is convenient to use a considerable molar excess of the ligand over manganese, and the mole ratios of ligand: M typically range from 3: 1 to 15: 1. The additional ligand also serves to sweep ions of stray metals such as iron and copper, thus protecting the bleach from decomposition. A possible system of this class is described in European Patent Application Publication No. 549,271.

Although the structures of some manganese complexes that catalyze the bleach described here, you can speculate that they understand chelates or other hydrated coordination complexes, which result of the interaction of the carboxyl and nitrogen atoms of the ligand with the manganese cation. Similarly, the oxidation state of manganese cation during the catalytic process is not known with certainty, and may be the state of Valencia (+ II), (+ III), (+ IV) or (+ V). Due to the six points of binding to the manganese cation which are possible for ligands, you can speculate reasonably with which species may exist multi-nuclear and / or "cage" structures in aqueous bleaching media. Whatever the shape of the active species of ligand with Mn that really exists, acts from a seemingly catalytic way to provide bleaching power on persistent stains, such as tea, ketchup, coffee, blood and the like

Other bleach catalysts are described, for example, in the European Patent application with the number of publication 408,131 (complex cobalt catalysts), in European Patent applications with publication numbers 384,503 and 306,089 (catalysts of metallo-porphyrins), US Pat. 4,728,455 (manganese catalyst and a multidentate ligand), the Patent of USA 4,711,748 and the European Patent application with the number of publication 224,952 (catalyst with manganese absorbed on a aluminosilicate), US Pat. 4,601,845 (support of aluminosilicate with manganese and zinc or a magnesium salt), U.S. Patent 4,626,373 (manganese catalyst and a ligand), US Pat. 4,119,557 (catalyst with a complex ferric), German Patent specification 2,054,019 (catalyst with a cobalt chelating agent), Canadian Patent 866.191 (salts containing transition metals), Patent USA 4,430,243 (chelators with manganese cations and cations of non-catalytic metals) and US Pat. 4,728,455 (catalyst of gluconate-manganese).

Relative kinetics of releases

In an essential aspect of the invention, provides a means to delay the release of the bleach organic peroxyacid in a wash solution with respect to the release of the heavy metal ion sequestrant.

Said means may comprise a means for delay the release of the organic peroxyacid bleach in the wash solution

Alternatively said means may comprise a means to advance the release of the ion sequestrant from heavy metals to the solution.

Delayed Release-Medium Speed

The medium provides delayed release of an organic peroxyacid bleach source itself in the wash solution, or when the peroxyacid source is a precursor compound of the organic peroxyacid, the delayed release medium may comprise a means to inhibit or prevent the perhydrolysis reaction in situ that releases the organic peroxyacid in the solution. For example, said medium could include delaying the release of the source of hydrogen peroxide in the washing solution, for example, delaying the release of any inorganic perhydrated salt, which acts as a source of hydrogen peroxide, in the washing solution.

The delayed release medium includes coating any suitable component with a coating or a mixture of coatings intended to provide delayed release. By therefore, the coating may comprise, for example, a water-soluble material, or it can be a coating with sufficient thickness so that the kinetic dissolution conditions of the thick coating provide the controlled speed of release.

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

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

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

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

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

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

Cellulose derivatives such as methyl cellulose, carboxymethyl cellulose, ethylhydroxyethyl cellulose and hydroxyethyl cellulose, and homo- or copolymeric polycarboxylic acids or their salts, are other examples of suitable binding agents for use in The present invention.

A method to apply the material of Coating implies an agglomeration. The processes of Preferred agglomeration includes the use of any one of the organic binder materials that have been described in this invention above. Any device can be used Conventional agglomerator / mixer including, but not limited to a, the types of tray mixers, rotary drums and vertical Molten coating compositions can be also apply by pouring or atomizing by projection on a moving bed of bleaching agent.

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

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

Additional protocols to provide the controlled release means include the appropriate choice of any other component of the detergent composition matrix, so that when the composition is introduced into the wash solution, the ionic strength environment there provided makes it possible to achieve kinetic conditions Delayed release required.

Increased release-medium speed

All appropriate means are considered for increase the release rate of the ion sequestrant from heavy metals to the solution.

The early release means may include coat any suitable component with a coating intended to provide early release. Therefore the coating may comprise, for example, a highly material Water soluble, or even effervescent.

Other means to provide release delayed required include mechanical means to alter the Physical characteristics of the metal ion sequestrant heavy in order to increase its solubility and speed release.

An appropriate protocol could include the selection deliberate particle size of any component that contain a heavy metal ion sequestrant. The chose the particle size will depend so much on the composition of the particulate component as of the wish that the desired forward release kinetics. It is desirable that the size particle size is less than 1,200 micrometers, and preferably that have a particle diameter of 1,100 to 500 micrometers.

Additional protocols for providing the delayed release medium include the appropriate choice of any matrix components of the detergent composition, or any particulate component containing the heavy metal ion sequestrant, so that when the composition is introduced into the wash solution, the ionic strength environment provided there allows to obtain the increased release kinetics
required

Relative release-parameter speed kinetic

The bleaching component release organic peroxyacid of the peroxyacid bleaching system with respect to that of the heavy metal ion sequestrant component is such that in the T50 test method described here the difference between the time to produce a concentration that is 50% of the final concentration of said metal ion sequestrant heavy is less than 120 seconds, preferably less than 90 seconds, more preferably less than 60 seconds, and the time in produce a concentration that is 50% of the final concentration of said organic peroxyacid bleach is greater than 180 seconds, preferably 180 to 480 seconds, more preferably 240 to 360 seconds

In an extremely preferred aspect of the invention, the release of bleach is such that in the method of T50 test described here the time to obtain an oxygen level Total available (AvO) that is 50% of the final level is greater than 180 seconds, preferably 180 to 480 seconds, more preferably from 240 to 360 seconds. A method to determine AvO levels described in European Patent Application No. 93870004.4.

In another preferred aspect of the invention, when the source of per-oxyacid bleach is a peroxyacid bleach precursor, used in combination with a source of hydrogen peroxide, the release kinetics of hydrogen peroxide in the wash solution in relation to the of the heavy metal ion sequestrant component is such that in the T50 test method described here, the time to obtain a concentration that is 50% of the final concentration of said heavy metal ion sequestrant is less than 120 seconds, preferably less than 90 seconds, more preferably less than 60 seconds, and the time to obtain a concentration that is 50% of the final concentration of said hydrogen peroxide is greater than 180 seconds, preferably 180 to 480 seconds, more preferably from 240 to 360 seconds.

The last wash concentration of heavy metal ion sequestrant is typically 0.0001% at 0.05% by weight, but preferably greater than 0.001%, more preferably greater than 0.002%.

The last wash concentration of any inorganic perhydrate bleach is typically 0.005% to 0.25% by weight, but preferably is greater than 0.05%, more preferably greater than 0.075%.

The last wash concentration of any peroxyacid precursor is typically 0.001% to 0.08% by weight, but preferably it is from 0.005% to 0.05%, most preferably from 0.015% to 0.05%.

Delayed Release-Test Method

The delayed release kinetics is defined here with respect to a TA test method that measures the time in get A% of the concentration / final level of that component when a composition containing the agreement component is dissolved with the classic conditions that are exposed now.

Classic conditions involve a glass of 1 liter glass filled with 1,000 ml of distilled water at 20 ° C, at 10 g of the composition are added. The contents of the glass are stir using a magnetic stirrer set at 100 rpm. The magnetic stirrer has round or oval shape with one dimension 1.5 cm maximum and a minimum dimension of 0.5 cm. The concentration / final level is taken to be the concentration / level obtained 10 minutes after the addition of the composition to the glass full of water.

Appropriate analytical methods are chosen for allow a reliable determination of concentrations incidental and final solution of the component of interest after the addition of the composition to the water of the glass.

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

Alternatively, methods that they involve separating titles from the solution at time intervals determined, stop the dissolution process by a means appropriate such as rapidly decreasing the temperature of the title, and then determining the concentration of the component in the title by any means such as a value method chemical.

When appropriate, methods can be used suitable graphics, including curve fitting methods, to allow calculation of the TA value from the results gross analytics

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

Water soluble detergency builder compound

The detergent compositions herein invention may contain as a highly preferred component a water soluble detergency builder compound, present typically in detergent compositions at a level of 1% to 80% in weight, preferably from 10% to 70% by weight, most preferably, from 20% to 60% by weight of the composition.

In a very preferred aspect of the invention a means to delay the release of the bleach in a wash solution with respect to the release of preferred water soluble detergency builder component. Said means may comprise equivalents of any of the delayed release means described herein to obtain the delayed release of bleaching components, described here before.

Preferably, said delayed release medium is chosen so that in the test method described herein the time to obtain a concentration that is 50% of the final concentration of said water-soluble reinforcer is less than 120 seconds, preferably less than 90 seconds , more preferably less than 60 seconds
two.

The last wash concentration of any Water soluble improver is typically 0.005% to 0.4% by weight, preferably from 0.05% to 0.35%, more preferably from 0.1% to 0.3%

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

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

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

Polycarboxylates containing four groups carboxy include the oxydisuccinates described in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane-tetracarboxylates and 1,1,2,3-propane-tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulphosuccinate derivatives described in British Patents no. 1,398,421 and 1,398,422 and in US Pat. No. 3,936,448, and the sulphonated pyrolyzed citrates described in the Patent  British No. 1,439,000.

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

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

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

The improvers of the borate type detergency, as well as the enhancers of the detergency containing borate-forming materials, which they can produce a borate in the storage conditions of the detergent or washing, but not preferred in conditions wash at less than about 50 ° C, especially at less than approximately 40 ° C.

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

Specific examples of improvers of water soluble phosphate type detergency, are tripolyphosphates of alkali metals, sodium, potassium and ammonium pyrophosphates, sodium and potassium and ammonium pyrophosphates, orthophosphates of sodium and potassium, polymeta / sodium phosphates, in which the degree of polymerization is worth between about 6 and 21, and acid salts phytic

Suitable silicates include silicates of water-soluble sodium with a SiO2: Na2O ratio of 1.0 to 2.8, with 1.6 to 2.4 ratios being preferred, and with the highest preference a ratio of 2.0. The silicates can be in form of anhydrous salt or a hydrated salt. Sodium silicate  with a SiO 2 ratio: Na 2 O of 2.0 is the silicate plus favorite.

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

Additional detergent components

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

For example, the compositions of the invention can be formulated as laundry detergent compositions by hand or by machine, including additive compositions for casting and compositions suitable for use in pretreatment of stained fabrics and compositions for automatic washing of the crockery.

When formulated as suitable compositions for use in an automatic washing method, e.g. washing methods automatic crockery and clothing, preferably compositions of the invention contain one or more components additional detergents selected from surfactants, improvers of water-insoluble detergent, polymeric compounds organic, additional enzymes, foam suppressants, dispersants of alkaline soaps, suspending agents and anti-redeposition of dirt and inhibitors of corrosion. The laundry compositions can also contain, as additional detergent components, agents softeners

Surfactant

The detergent compositions of the invention may contain as a further detergent component a surfactant selected from anionic, cationic, nonionic surfactants, ampholytic, amphoteric and hybrid ion and mixtures thereof.

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

Preferably, the surfactant is formulated to that is compatible with any enzyme component present in the composition. In compositions in liquid or gel state, the surfactant is most preferably formulated so that favor, or at least not degrade, the stability of any Enzyme in these compositions.

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

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

Anionic surfactant

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

Other anionic surfactants include the isethionates, such as acyl isethionates, N-acyl-taurates, acid amides methyl tauride fatty acids, alkyl succinates and sulphosuccinates, monoesters of sulfosuccinates (especially monoesters C 12 -C 18 saturated and unsaturated), sulphosuccinate diesters (especially diesters C 6 -C 14 saturated and unsaturated), N-acyl-sarcosinates. They are suitable also resin acids and hydrogenated resin acids such as rosin, hydrogenated rosin and resin acids and acids hydrogenated resins present in, or derivatives of, oil of tallow.

Anionic sulfate surfactant (s)

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

Type surfactants alkylethoxy sulfate are preferably selected of the group consisting of (C 6 -C 18) alkyl sulfates  that have been ethoxylated with approximately 0.5 to approximately 20 moles of ethylene oxide per molecule. More preferably, the alkylethoxy sulfate surfactant is a (C 6 -C 18) alkyl sulfate, which has been ethoxylated with about 0.5 to about 20, preferably about 0.5 to about 5 moles of ethylene oxide per molecule.

Sulfonate type anionic surfactant

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

Anionic Carboxylate Surfactant

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

Preferred alkylethoxycarboxylates for use here include the formula ones RO (CH 2 CH 2 O) x CH 2 COO - M + 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 where x is 0 is less than about 20%, and the amount of material where x is greater than 7 is less than approximately 25%, the average value of x is approximately 2 to 4 when R is of average C_ {13} or less, and the average value of x is about 2 to 4 when R is on average greater than C 13, and M is a cation, preferably chosen from a metal alkaline, alkaline earth metal, ammonium, mono-, di- and tri-ethanolammonium, most preferably from of sodium, potassium, ammonium and mixtures with magnesium ions. The Preferred alkylethoxycarboxylates are those in which R is a group C 12 to C 18 alkyl.

Surfactants alkyl polyethoxy polycarboxylate suitable for use here include those with the formula RO- (CHR1 -CHR2 -O) -R3 where R is a C 6 to C 18 alkyl group, and x is 1 to 25. R 1 and R 2 are selected from the group consisting of hydrogen, acid methyl radical, succinic acid radical, acid radical hydroxysuccinic, and mixtures thereof, where at least one R1 or R2 is a succinic acid radical or acid radical hydroxysuccinic and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon that has between 1 and 8 carbon atoms, and mixtures of them.

Surfactant based on anionic secondary soaps

Preferred surfactants based on soaps are surfactants based on secondary soaps containing a carboxyl unit connected to a secondary carbon. Carbon Secondary may be located in a ring structure, e.g. as in p-octylbenzoic acid, or as in alkyl substituted cyclohexyl carboxylates. The surfactants based on secondary soaps preferably not they will contain no ether link, no ester link and neither hydroxyl group. Preferably there will be no nitrogen atom in the head group (ambiflic portion). Base surfactants  of secondary soaps usually contain a total of 11-15 carbon atoms, although they can be tolerated some more (eg up to 16), eg acid p-octylbenzoic.

The following general structures illustrate additionally some of the preferred surfactants based on secondary soaps

TO.

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

B.

Other class Preferred secondary soaps comprises the compounds carboxylics in which the carboxylic substituent is in a hydrocarbon ring unit, i.e. secondary soaps of formula 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: R 5 may be in ortho, goal or for respect of the carboxyl in the ring).

C.

Still another class Preferred secondary soaps comprise carboxylic compounds side effects of formula CH 3 (CHR) k - (CH 2) m - (CHR) N-CH (COOM) (CHR) O- (CH 2) p - (CHR ) q -CH3, where each R is C 1 -C 4 alkyl, where k, n, or, which are integers in the range 0-8, provided that the total number of carbon atoms (including the carboxylate) is in the range of 10 to 28.

In each of the formulas A, B and C above, species M can be any suitable counter ion, especially if it confers water solubility.

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

Surfactant of the metal sarcosinate type (s) alkaline (s)

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

Nonionic Surfactant

Essentially, it can be included in the compositions any anionic surfactant useful for purposes detersive Listed below are illustrative classes but not Limitations of useful non-ionic surfactants.

Nonionic surfactant based on fatty acid amides nonionic polyhydroxy

Polyhydroxy fatty acid amides suitable for use here are the ones with the structural formula R 2 CONR 1 Z where: R 1 is H, hydrocarbyl C 1 -C 4, 2-hydroxyethyl, 2-hydroxypropyl, or one of its mixtures, preferably C 1 -C 4 alkyl, more preferably C 1 or C 2 alkyl, most preferably C 1 alkyl (ie, methyl); R2 is a hydrocarbyl C 5 -C 31, preferably alkyl or C 5 -C 19 linear chain alkenyl, plus preferably alkyl or alkenyl C_ {9} -C_ {17} linear chain, the most preferably alkyl or alkenyl C_ {11} -C_ {17} linear chain, or one of its mixtures; and Z is polyhydroxyhydrocarbyl having a chain of linear hydrocarbyl with at least 3 hydroxyls directly attached to the chain, or one of its alkoxylated derivatives (preferably ethoxylated or propoxylated). Z will preferably be obtained from a reducing sugar in a reductive amination reaction; plus preferably Z is a glyclyl.

Non-ionic alkylphenol condensates

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

Surfactant based on non-ionic ethoxylated alcohol

Compound type condensation products alkyl ethoxylates of aliphatic alcohols with about 1 to about 25 moles of ethylene oxide they 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 about 2 to about 10 moles of ethylene oxide per mole of alcohol.

Non-ionic fatty alcohol surfactant ethoxylated / propoxylated

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

Non-ionic EO / PO condensates with propylene glycol

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

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

The condensation products of ethylene oxide with the product that results from the reaction of propylene oxide and ethylenediamine, are suitable for use in the present invention. The hydrophobic residue of these products consists of the product of reaction of ethylenediamine and propylene oxide in excess, and has generally a molecular weight of about 2,500 to Approximately 3,000 Examples of this type of surfactant do not Ionic include certain of the Tetronic® surfactants commercially available, which are sold by BASF.

Non-ionic surfactant type alkyl polysaccharide

Alkyl polysaccharides Suitable for use herein are described in US Pat. 4,565,647, of Llenado, issued on January 21, 1986, which has a hydrophobic group containing about 6 to about 30 carbon atoms, preferably of about 10 to about 16 carbon atoms and a polysaccharide, eg, a polyglycoside, containing the group hydrophobic from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units. You can also use any saccharide reducer containing 5 or 6 carbon atoms; for example, it you can use glucose, galactose and galactosyl moieties instead of glucosyl residues (Optionally the hydrophobic group is attached to the positions 2, 3, 4, etc., thus giving glucose or galactose instead of a glycoside or galactoside). Intersaccharide bonds can be, for example, between the position one of the units additional saccharides and positions 2, 3, 4 and / or 6 of the preceding saccharide units.

Alkyl polyglycosides preferred have the formula

R2 O (CNH2 nO) t (glycosyl) x

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

Non-ionic fatty acid amide surfactant

Acid Amide Surfactants Suitable fatty to use here are those that have the formula: R 6 CON (R 7) 2 where R 6 is a group alkyl containing 7 to 21, preferably 9 to 17 atoms of carbon, and each 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

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

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

Surfactant based on amine oxides

Useful amine oxides here include the compounds of formula R 3 (OR 4) x NO) (R 5) 2 where R 3 is selected from an alkyl, hydroxyalkyl group, acyl amidopropyl and alkylphenyl, or mixtures thereof, containing from 8 to 26 carbon atoms, preferably 8 to 18 carbon atoms; R 4 is an alkylene or hydroxyalkylene group containing 2 to 3 carbon atoms, preferably 2 atoms carbon, or mixtures thereof; x is 0 to 5, preferably 0 to 3; and each R 5 is an alkyl or hydroxyalkyl group that it contains 1 to 3, preferably 1 to 2 carbon atoms, or a poly (ethylene oxide) group containing 1 to 3 oxide groups of ethylene, preferably 1. The R 5 groups can be linked between yes, eg through an oxygen or nitrogen atom, to form A ring structure

These surfactants based on amine oxides they include in particular alkyl oxide C 10 -C 18 -dimethylamines and alkoxy oxides C 8 -C 18 -ethyl dihydroxyethyl amine. Examples of these materials include dimethyloctylamine oxide, diethyldecylamine oxide bis- (2-hydroxyethyl) dodecylamine, oxide dimethyldodecylamine, dipropyltetradecylamine oxide, methyl ethylhexadecylamine oxide dodecylamidopropyl dimethyl amine oxide cetyldimethylamine, stearyl dimethyl amine oxide, sebodimethyl amine and oxide dimethyl-2-hydroxyoctadecylamine. I know prefer alkyldimethylamine oxides C 10 -C 18 and the oxides of acylamido-alkyldimethylamines C_ {10-18}.

Hybrid ion surfactant

Surfactants can also be incorporated ionic hybrids in detergent compositions in this invention. These surfactants can be described in the sense broad as derivatives of secondary and tertiary amines, derivatives of secondary and tertiary heterocyclic amines, or derivatives of quaternary ammonium, quaternary phosphonium or sulfonium compounds tertiary. Betaine and sultaine surfactants are examples of hybrid ionic surfactants for use herein invention.

Betaine surfactant

The betaines used here are the compounds that have the formula R (R 1) 2 N + R 2 COO -, where R is a C 6 -C 18 hydrocarbyl group, preferably a C 10 -C 16 alkyl group or a group (acyl C 10 -C 16) amidoalkyl, each R 1 it is typically C 1 -C 3 alkyl, preferably methyl, and R2 is a hydrocarbyl group C 1 -C 5, preferably an alkylene group C 1 -C 3, more preferably a group C 1 -C 2 alkylene. Betaine Examples Suitable include cocoacylamidopropyldimethyl betaine; hexadecyldimethyl betaine; (acyl C 12-14) -amidopropyl betaine; (acyl C 8-14) -amidohexyldiethylbetaine; 4 - [(acilC 14-16) methylamidodyethylammonium] -1-carboxybutane; (acylC 16-18) amidodimethyl betaine; (acyl C 12-16) amidopentanediethylbetaine; (acyl C 12-16) methylamidodimethyl betaine. The Preferred betaines are hexanoate of C 12-18 -dimethylammonium and acyl C_ {10-18} -amidopropane (or -ethane) -dimethyl (or -diethyl) -betaines. Surfactants based on Complex betaines are also suitable for use herein. invention.

Sultaine Surfactant

The useful sultains here are the compounds that they have the formula (R (R 1) 2 N + R 2 SO 3 - - where R it is a C 6 -C 18 hydrocarbyl group, preferably a C 10 -C 16 alkyl group, more preferably an alkyl group C 12 -C 13, each R 1 is typically C 1 -C 3 alkyl, preferably methyl, and R 2 is a C 1 -C 6 hydrocarbyl group, preferably a C 1 -C 3 alkylene group or, preferably, hydroxyalkylene.

Ampholytic Surfactant

Surfactants can also be incorporated ampholytic in detergent compositions in this invention. These surfactants can be generically described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of secondary and tertiary amines heterocyclics in which the aliphatic radical can be chain linear or branched.

Cationic surfactants

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

Partially soluble detergency builder compound or insoluble

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

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

Crystalline lamellar sodium silicates they have the general formula

NaMSi_ {x} O_ {2x + 1}. And H2O

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

Preferably, the sodium silicate material crystalline laminar is present in detergent compositions granular as a particulate material intimately mixed with a solid, ionizable, water soluble material. Solid material, ionizable, water soluble, is selected from acids organic, salts of organic and inorganic acids and mixtures of they.

Suitable aluminosilicate-based zeolites they have unit cells of formula Na_ {z} [(AlO2) z (SiO2) y]. XH 2 O where z e y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably 7.5 to 276, plus preferably from 10 to 264. The aluminosilicate materials are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in form associated.

Ion exchange materials based on aluminosilicates can be materials present in nature, but preferably they are obtained by synthesis. Under the denominations Zeolita A, Zeolita B, Zeolita P, Zeolita X, Zeolita MAP, Zeolita HS and their mixtures, are available materials ion exchange, based on aluminosilicate, crystalline and synthetic Zeolite A has the formula

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

where x is from 20 to 30, especially 27. The zeolite X has the formula Na_86 [(AlO2) 86 (SiO2) 106]. 276 H2O.

Enzyme

Another optional ingredient useful in Detergent compositions is one or more additional enzymes.

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

Commercially available protease enzymes include those sold by the trade name Alcalase, Savinase, Primase, Durazym and Esperase by Novo Industries A / S (Denmark), those sold under the trade name Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor Intemational, and those sold by the trade name Opticlean and Optimase by Solvay Enzymes. Enzyme Protease can be incorporated into the compositions according to the invention at a level of 0.0001% to 4% of active enzyme by weight of the composition.

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

Lipolytic enzymes (lipases) may be present in levels of active lipolytic enzyme from 0.0001% to 2% in weight, preferably from 0.001% to 1% by weight, most preferably from 0.001% to 0.5% by weight of the compositions.

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

A preferred lipase is derived from Pseudomonas pseudoalcaligenes , which is described in the European Patent granted 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 thanks to Novo Industri A / S, Bagsvaerd, Denmark, by the trade name Lipolase. This lipase is also described in US Pat. 4,810,414, Huge-Jensen et al. , issued on March 7, 1989.

Enzyme stabilizing system

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

The compositions of the present invention may comprise in addition to 0 to about 10%, preferably of about 0.01% to about 6% by weight of agents chlorinated bleach sweepers, which are added to prevent the chlorine bleaching species present in the water of many aquifers attack and inactivate enzymes, especially in alkaline conditions Although chlorine levels in the water they can be small, typically in the range of about 0.5 ppm to approximately 1.75 ppm, the available chlorine in the total volume of water that comes into contact with the enzyme during dishwashing it is usually large; consequently the Stability of enzymes in use can be problematic.

Suitable chlorine sweeper anions are widely available and illustrated by salts that contain ammonium or sulphite cations, bisulfate, thiosulphite, thiosulfate, iodine, etc. Antioxidants such as carbamate can also be used, ascorbate, etc., organic amines such as acid ethylenediaminetetracetic (EDTA) or its alkali metal salts, monoethanolamine (MEA), and mixtures thereof. If desired, you can also use other conventional sweepers such as bisulfate, nitrate, chloride, sources of hydrogen peroxide such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate, as well as phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate, malate, tartrate, salicylate, etc., and mixtures thereof.

Organic polymeric compound

The organic polymeric compounds are preferred components of the detergent compositions, according with the invention By organic polymeric compound is meant essentially any polymeric organic compound used currently as dispersants and as suspending agents and anti-redeposition of dirt in detergent compositions.

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

Examples of organic polymeric compounds include homo- or copolymeric polycarboxylic organic acids soluble in water or its salts, in which the polycarboxylic acid it comprises at least two carboxyl radicals separated from each other for no more than two carbon atoms. The latter polymers type are described in the document GB-A-1,596,756. Examples of such salts are the polyacrylates of PM 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of 20,000 to 100,000, especially 40,000 to 80,000

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

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

Terpolymers containing monomer units selected from maleic acid, acrylic acid, poly (acid aspartic) and vinyl alcohol, particularly those with a average molecular weight 5,000 to 10,000 are also suitable here.

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

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

Dispersing compound of calcareous soap

The compositions of the present invention may contain a dispersing compound based on calcareous soaps, which It has a dispersing powder based on calcareous soap (LSDP), as defined here below not greater than 8, preferably not greater than 7, most preferably not greater than 6. The compound dispersant based on calcareous soaps is present preferably at a level of 0.1% to 40% by weight, more preferably from 1% to 20% by weight, most preferably from 2% to 10% by weight of the compositions.

A limestone soap dispersant is a material which prevents the precipitation of metal fatty acid salts alkaline, ammonium or amine, by calcium or magnesium ions. A numerical measure of the effectiveness of a dispersant based on limestone soap is given by the dispersing power of limestone soap  (LSDP) that is determined using the soap dispersion test limestone described in an article by H. C. Borghetty and C.A. Bergman, J. Am. Oil. Chem. Soc., Volume 27, pages 88-90, (1950). This dispersion test method of calcareous soaps is widely used by experts in the sector and is described, for example, in the following Articles: W.N. Linfteld, Surfactant Science Series, volume. 7, p. 3; W.N. Linfield, Tenside Surf. Det., Volume 27, p. 159-161, (1990); and M.K. Nagarajan, W.F. Masler, Cosmetics and Toiletries, volume 104, p. 71-73, (1989). LSDP is the percentage weight ratio of agent sodium oleate dispersant required to disperse deposits of calcareous soap formed by 0.025 g of sodium oleate in 30 ml of water whose equivalent hardness corresponds to 333 ppm of CaCO 3 (Ca: Mg = 3: 2).

Among surfactants with good capacity certain limestone soaps dispersant will include certain oxides of amines, betaines, sulfobetains, alkyl ethoxy sulfates and ethoxylated alcohols.

Examples of surfactants with a LSDP not higher 8 for use according to the invention include oxides of C 16 -C 18 dimethylamines, C 12 -C 18 alkylethoxysulfates with a grade 1-5 ethoxylation medium, particularly a C 12 -C 15 alkylethoxysulfate surfactant with an ethoxylation degree of approximately 3 (LSDP = 4), and C 13 -C 15 ethoxylated alcohols with a degree ethoxylation medium of either 12 (LSDP = 6) or 30, sold by trade names Lutensol A012 and Lutensol A030 respectively, by BASF GmbH.

Polymeric dispersants of calcareous soaps Suitable for use here are described in the article by M.K. Nagarajan and W.F. Masler, in Cosmetics and Toiletries, volume 104, pp. 71-73, (1989). Examples of such dispersants Polymers of calcareous soaps include certain soluble salts in water of copolymers of acrylic acid, methacrylic acid or its mixtures, and a substituted acrylamide or acrylamide, where such polymers typically have a molecular weight of 5,000 to 20,000

Soap suppressor system

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

Foam suppressor systems suitable for use in this invention they can comprise essentially any known antifoam compound, including, for example, anti-foam silicone compounds, anti-foam compounds type 2-alkyl and alkanol.

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

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

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

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

Copolymers of ethylene oxide and propylene oxide, particularly ethoxylated / propoxy fatty alcohols
sides with an alkyl chain length of 10 to 16 carbon atoms, a degree of ethoxylation of 3 to 30 and a degree of propoxylation of 1 to 10, are also suitable antifoaming compounds for use herein.

In DE 40 21265, they are described suitable antifoaming compounds of the class 2-alkyl alkanols. The 2-alkyl alkanols suitable for use here consist of a C 6 to C 16 alkyl chain that it carries a terminal hydroxy group, and said alkyl chain is substituted at the position with a C 1 alkyl chain a C_ {10}. In the compositions according to the present invention mixtures of 2-alkyl alkanols.

A preferred suds suppressor system understands

(to)

compound defoamer, preferably silicone defoamer compound, most preferably a silicone antifoaming compound that comprises in combination

(i)

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

(ii)

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

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

(b)

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

(c)

a compound inert vehicle fluid, most preferably comprising a C16-C18 ethoxylated alcohol with a degree of 5 to 50 toxylation, preferably 8 to 15, at a level of 5% at 80%, preferably 10% to 70%, by weight;

A preferred system as a foam suppressor that it is useful here in the form of particles comprising a mixture of a alkylsiloxane of the type described hereinbefore and silica solid.

The solid silica can be a silica of pyrolysis, a precipitated silica or a silica prepared by the gel formation technique. The right silica particles they have an average particle size of 0.1 to 50 micrometers, preferably 1 to 20 micrometers and a specific surface of at least 50 m2 / g. These silica particles can be made hydrophobic by treating them with dialkylsilyl groups and / or groups trialkylsilyl either directly bonded on silica or by Medium of a silicone resin. It is preferred to use a silica whose particles have become hydrophobic with dimethyl and / or groups trimethylsilyl. A particulate antifoam compound, preferred for inclusion in detergent compositions of according to the invention suitably contains a quantity of silica such that the weight ratio of silica to silicone falls within in the range of 1: 100 to 3:10, preferably 1:50 to 1: 7.

Other foam suppressor system, suitable and in particle form, is represented by a silica silanada (the most preferably trimethyl silanate) hydrophobic with a particle size in the range of 10 nanometers to 20 nanometers and a specific surface area exceeding 50 m2 / g, intimately mixed with dimethylsilicone fluid with a weight molecular in the range of about 500 to about 200,000 at a weight ratio of silicone to silica silanada of about 1: 1 to about 1: 2.

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

Other foam suppressor systems, in the form of Particles and highly preferred are described in the Application for European Patent 91870007.1, in process with this, to name of Procter and Gamble Company, whose systems comprise silicone antifoam compound, a carrier material, a organic coating material and glycerol at a weight ratio of glycerol to silicone antifoam compound from 1: 2 to 3: 1. The European Patent Application 91201342.0, in process with the present, also describes foam suppressor systems, in form of particles and highly preferred, comprising a compound silicone defoamer, a vehicle material, a material of organic coating and crystalline or amorphous aluminosilicate at a aluminosilicate weight ratio: antifoam compound 1: 3 to 3: 1 silicone. The preferred vehicle material in both foam control agents, granular and highly preferred, described above, it is starch.

A foam suppressor system, in the form of particles, illustrative to use here is an agglomerated component in particles, prepared by an agglomeration procedure, which comprises, in combination

(i)

from 5% to 30%, preferably from 8% to 15% by weight of the compound component silicone defoamer which preferably comprises polydimethylsiloxane and silica combination;

(ii)

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

(iii)

from 5% to 30%, preferably from 10% to 20% by weight of the component, of compound chipboard binder, where said compound can be here any compound, or mixtures thereof, typically employed as binders for agglomerates, most preferably said agglomerate binder compound comprises an alcohol ethoxylated C 16 -C 18 with a degree of ethoxylation from 50 to 100; Y

(iv)

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

Polymeric agents transfer inhibitors dyes

The detergent compositions in this invention may also comprise from 0.01% to 10%, preferably from 0.05% to 0.5% by weight of polymeric agents inhibiting the dye transfer

Polymeric agents inhibiting the dye transfer are preferably selected from poly (N-oxide amine) polymers, copolymers of N-vinyl pyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, or their combinations.

a) Polyamine N-oxide polymers

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

25

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

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

,

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

O, C, -O-, -S-, -N-; x es 0 o 1;A is N

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

,

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

O, C, -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:

16

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

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

Another class of said polyamine N-oxides comprises the group of polyamine N-oxides in which nitrogen of the N-O group is linked to R-group.

Other suitable polyamine N-oxides are those polyamine oxides to which the N-O group is attached to the polymerizable unit.

A preferred class of these N-oxides of polyamine comprises the polyamine N-oxides having the formula general (I) where R is an aromatic, heterocyclic or alicyclic in which the nitrogen of the functional group N-O is part of that group R. Examples of these classes are polyamine oxides in which R is a compound heterocyclic such as pyridine, pyrrole, imidazole and their derivatives.

Another preferred class of these N-oxides of polyamine comprises the polyamine N-oxides having the formula general (I) where R is an aromatic, heterocyclic or alicyclic in which the nitrogen of the functional group N-O is linked to these groups R. Examples of these classes are the poly (amine oxides) where the R groups can be aromatic, such as phenyl.

Any polymer chain can be used with such that the amine oxide polymer formed is water soluble and has dye transfer inhibitory properties. Examples of suitable polymer chains are polyvinyl, polyalkylene, polyesters, polyethers, polyamide, polyimides, polyacrylates and their mixtures

The amine N-oxide polymers of the present invention typically have an amine to N-oxide ratio of amine from 10: 1 to 1: 1000000. However, the amount of oxide groups of amine present in the poly (amine oxide) polymer can be modify by appropriate copolymerization or by an appropriate degree of N-oxidation. Preferably, the ratio of amine to amine N-oxide is from 2: 3 to 1: 1000000. More preferably from 1: 4 to 1: 1000000. most preferably from 1: 7 to 1: 1000000. The polymers of the present invention actually encompass random or block copolymers, where one type of monomer is a Amine N-oxide and the other type of monomer is or is not an N-oxide of amine. The amine oxide unit of the poly (N-oxides of amines) has a pKa <10, preferably pKa <7, plus preferably pKa <6.

The poly (amine oxides) can be obtained almost in any degree of polymerization. The degree of polymerization does not it is critical of the condition that the material has the Water solubility and the desired dye suspension power. Typically, the average molecular weight is within the range of 500 to 1,000,000; preferably 1,000 to 50,000, more preferably 2,000 to 30,000, and most preferably 3,000 to 20,000.

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

Preferred polymers for use herein may comprise a polymer selected from copolymers of N-vinylimidazole N-vinylpyrrolidone, wherein said polymer has an average molecular weight in the range from 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 N-vinyl pyrrolidone preferred have a molar ratio of N-vinylimidazole 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 invention can also employ a polyvinylpyrrolidone ("PVP") with an average molecular weight of 2,500 to 400,000, preferably from 5,000 to 200,000, and most preferably from 5,000 to 15,000. Other suitable polyvinylpyrrolidones are found commercially available from ISP Corporation, New York, NY and Montreal, Canada, under the product names PVP K-15 (molecular weight based on viscosity equal to 10,000), PVP K-30 (average molecular weight equal to 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000). PVP K-15 is also available at ISP Corporation. Other suitable polyvinylpyrrolidones that are found commercially available at BASF Corporation include Sokalan HP 165 and Sokalan HP 12.

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

d) Polyvinyloxazolidone

The detergent compositions herein invention can also use polyvinyloxazolidones as polymeric dye transfer inhibiting agents. Said polyvinyloxazolidones have an average molecular weight of 2,500 to 400,000, 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 be from 0.01% to 5% by weight, preferably from 0.05% to 3% by weight, and more preferably from 0.1% to 2% by weight. The amount of polyvinyloxazolidone discharged in the wash solution it is typically 0.5 ppm to 250 ppm, preferably from 2.5 ppm to 150 ppm, more preferably from 5 ppm to 100 ppm

e) Polyvinylimidazole

The detergent compositions herein invention can also use polyvinylimidazole as an agent of inhibition of transfer of polymeric dyes. Preferably said polyvinylimidazoles have a molecular weight average in the range of 2,500 to 400,000, more preferably of 5,000 to 50,000, and most preferably 5,000 to 15,000.

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

Optical brightener

The detergent compositions of this invention they can also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners that they also provide a transfer inhibitory action of dyes When used, the compositions herein preferably they will comprise from about 0.01% to 1% by weight of such optical brighteners.

Hydrophilic optical brighteners useful in the present invention are those with the formula structural:

17

where R_ {1} is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is select from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morpholino, chlorine and amino; and M is a cation that forms such a salt like sodium or potassium.

When in the previous formula, R_ {1} is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is acid 4,4 ', - bis [(4-anilino-6- (N-2-bis-hydroxyethyl) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid and its disodium salt. This particular kind of brightener is commercially available by trade name Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the brightener preferred hydrophilic optic useful in detergent compositions of The present invention.

When in the previous formula, R_ {1} is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is the disodium salt of acid 4,4 ', - bis [(4-anilino-6- (N-2-bis-hydroxyethyl) -N-methylamino] -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid. This particular kind of brightener is available in the market by the trade name Tinopal SBM-GX by Ciba-Geigy Corporation.

When in the above formula R_ {1} is anilino, R2 is morpholino and M is a cation such as sodium, the brightener is acid 4,4'-bis [(4-anilino-6-morpholino-s-triazin-2-yl) amino] 2,2'-stilbenedisulfonic acid, sodium salt This particular kind of brightener is available in the market by trade name Tinopal-AMS-GX by Ciba-Geigy Corporation.

The kind of specific optical brightener selected for use in the present invention provides especially good benefits of inhibitory efficacy of dye transfer when used in combination with polymeric agents transfer inhibitors dyes, described hereinabove, selected. The combination of such selected polymeric materials (e.g. PVNO and / or PVPVI) with such selected optical brighteners (eg, Tinopal UNPA-GX, Tinopal 5BM-GX and / or Tinopal AMS-GX) provides significantly improved inhibition of dye transfer in aqueous wash solutions in comparison with these two components of the detergent composition When used alone. Without linking to any theory, it is believed that these brighteners act in this way because they have high affinity towards the tissues in the wash solution and, therefore, are deposited relatively quickly on these tissues. The degree to which these brighteners are deposited on the tissues in the wash solution can be defined by a parameter called "consumption coefficient". The coefficient consumption, in general, is the ratio of a) the material brightener deposited on the tissue a b) the concentration initial rinse aid in wash waters. The brighteners with relatively high consumption coefficients are most suitable for inhibiting the transfer of dye in the context of the present invention.

Of course, it will be appreciated that optionally can use other types of optical brighteners conventional in the present compositions to provide the conventional benefits of "shine" of the tissues, instead of a true dye transfer inhibitory effect. Such use is conventional and well known in formulations. detergents

Softening agents

In laundry detergent compositions of according to the present invention can also be incorporated fabric softening agents. These agents can be of type Organic or inorganic Examples of inorganic softening agents are the smectite clays described in the document GB-A-1,400,898. Between agents organic fabric softeners, amines are included water insoluble tertiary, such as those described in the documents GB-A-1,514,276 and EP-B-0.011.340.

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

Other optional ingredients

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

Composition Form

The detergent compositions of the invention are they can formulate in any desirable form, such as powders, granules, pastes, liquids and gels.

Liquid compositions

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

Gel-shaped compositions

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

Solid compositions

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

The particle size of the components of granular compositions according to the invention preferably it will 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 volumetric density of the compositions granular detergents according to the present invention typically it is at least 450 g / liter, more usually at least 600 g / liter and more preferably 650 g / liter at 1,200 g / liter.

Bulk density is measured by a funnel. simple and a cup device consisting of a conical funnel rigidly molded on a base and provided with a valve hinge on its lower limb to allow emptying funnel contents in an axially aligned cylindrical cup arranged under the funnel. The funnel measures 130 mm and 40 mm in its respective upper and lower ends. It is mounted in such a way that the lower limb is 140 mm above the surface upper base. The cup has a total height of 90 mm, one internal height of 87 mm and an internal diameter of 84 mm. Its value Nominal is 500 ml.

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

Manufacturing procedures-compositions granulated

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

Washing methods

The compositions of the invention can be use essentially in any washing or cleaning method, including automatic methods of washing clothes and dishes.

Automatic dishwashing method

A preferred automatic method of washing tableware comprises treating dirty items selected from pans, glassware, plates and cutlery, and mixtures of them with an aqueous liquid that has dissolved or dispersed an amount effective of a composition for automatic dishwashing of according to the invention. By effective amount of the composition for automatic dishwashing, typically understood from 8 g to 60 g of product dissolved or dispersed in a volume of 3 to 10 liters of wash solution, which are typical product doses and the wash solution volumes commonly used in Conventional methods of automatic dishwashing.

Methods of automatic laundry

The automatic laundry methods of the present invention typically comprise treating dirty clothes with an aqueous washing solution in an automatic washing machine, solution that carries an effective amount of a dissolved or dispersed detergent composition for automatic washing of clothes according with the invention The detergent can be added to the solution of wash either through the washing machine's dosing box automatically or using a dosing device. By quantity Effective detergent composition is typically understood as 40 g to 300 g of product dissolved or dispersed in a volume of wash solution of 5 to 65 liters, which are the typical doses of product and wash solution volumes commonly used in conventional methods of automatic laundry.

In a preferred washing method herein invention, a dosing device is introduced, which contains a effective amount of detergent product, in the drum of a automatic washing machine, preferably front loading, before Start the wash cycle.

The dosing device is a container for contain detergent product, which is used to discharge the product directly in the drum of the automatic washing machine. his volume capacity should be such that it can contain so much detergent product such as would normally be used in the washing method

Once the washing machine has been loaded with the clothes, the dosing device containing the product is placed detergent inside the drum. When the wash cycle begins the washing machine, water is introduced into the drum and the drum rotate periodically. The design of the dosing device should be such that it allows the containment of the dry detergent product but which then allows the release of this product during the cycle wash 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 certain number of openings through which the product can pass. Alternatively, the device may be made of a material. that is liquid permeable but impervious to solid product, what  which will allow the release of the dissolved product. Preferably, the detergent product will be released quickly at the beginning of wash cycle, thus providing high concentrations located passenger components such as the component water soluble and component detergency builder heavy metal ion sequestrant in the machine drum washing machine in this phase of the wash cycle.

Preferred dosing devices are reusable and are designated in such a way that the integrity of the container is kept both in its dry state and during the wash cycle Dosing devices have been described especially preferred for use according to the invention in the Patents mentioned below: 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 dosing devices especially preferred for use with granulated products for wash clothes, which are the type commonly known as "granuleta".

Dosing devices are described especially preferred in European Patent Applications with Publication numbers 0343069 and 0343070. This last request describes a device comprising a flexible envelope in shape of a bag that extends from a support ring that defines a hole, the hole being intended to enter enough product in the bag for a wash cycle in a washing process. A part of the washing medium flows through the hole entering the bag, dissolves the product, and then the solution passes through the hole to the washing medium. Ring support is provided with a masking arrangement for prevent the outflow of wet but not dissolved product, and this arrangement typically comprises walls that extend in radial direction from a central enhancement in a configuration of wheel with spokes, or a similar structure in which the walls They have a helical shape.

Pretreatment washing method

In a pretreatment washing method, which constitutes an aspect of the invention, a dirty / stained substrate is deals with an effective amount of a pretreatment solution that contains a heavy metal ion sequestrant, but exempt of bleaching components. The solution could contain optionally other non-bleaching detergent components such as surfactants, detergency builders, enzymes and detergent polymers. Preferably the solution also contains a water soluble detergency builder.

The level of the metal ion sequestrant heavy in said pretreatment solution is typically of 0.0005% to 1%, and preferably is greater than 0.05%.

The pretreatment solution is left in contact with the dirty substrate for a period of time effective. Said time interval will typically be 10 seconds at 1800 seconds, more preferably from 60 seconds to 600 seconds.

Then, the dirty substrate is washed using a suitable washing method in which a product is used detergent containing bleach. The washing method can be, for example, any of the automatic washing methods of the crockery or automatic washing of the clothes described here.

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

 XYAS

: Rent C 1X-C 1Y sodium sulfate

 24EY

: A predominantly linear primary alcohol C_ {12-14} condensed with an average of Y moles of ethylene oxide

 XYEZ

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

 XYEZS

: A C 1X-C 1Y alkyl condensed sodium sulfate with an average of Z moles of ethylene oxide per mole

 TFAA

: rent C 16 -C 18 N-methyl glucamide

 Silicate

: Amorphous sodium silicate (SiO2 ratio: Na2O = 2.0)

 NaSKS-6

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

 Carbonate

: Anhydrous sodium carbonate

 Polycarboxylate

: 1: 4 maleic / acrylic acid copolymer, weight Average molecular approximately 80,000.

 Zeolite A

: Hydrated sodium aluminosilicate of formula Na 12 (AIO 2 SiO 2) 12. 27H2 O with a main particle size in the range of 1 to 10 micrometers

 Citrate

: Trisodium citrate dihydrate

 Percarbonate (release particles fast)

: Whitening based on anhydrous sodium percarbonate with the empirical formula 2Na2CO3 .3H2O2 coated with a mixed salt of formula Na2 {SO4} .n.Na_ {2} CO3 {where n is 0.29 and where The weight ratio of percarbonate to mixed salt is 39: 1

 Percarbonate (release particles slow)

: Whitening based on anhydrous sodium percarbonate coated with a coating of sodium silicate (Si2O: Na2O = 2: 1 ratio) at a weight ratio of percarbonate to sodium silicate of 39: 1

 TAED

: Tetraacetylethylenediamine

 TAED (release particles slow)

: Particles formed by agglomerating TAED with citric acid and polyethylene glycol (PEG) of Pm = 4,000 with a weight ratio of TAED components: citric acid: PEG of 75:10:15, coated with an outer coating of citric acid to a weight ratio of agglomerate coating: citric acid 95: 5

 Benzoil Caprolactam (particles of slow release)

: Particles formed by agglomeration of benzoyl caprolactam (BzCl) with citric acid and polyethylene glycol (PRG) of Pm = 4,000, with a weight ratio of BzCl components: citric acid: PEG of 63:21:16, coated with a external coating of citric acid at a weight ratio of chipboard coating: 95: 5 citric acid

 TAED (release particles fast)

: Particles formed by TAED agglomeration with partially neutralized polycarboxylate at a ratio of TAED: 93: 7 polycarboxylate, coated with a external polycarboxylate coating in a weight ratio of 96: 4 chipboard coating

 EDDS (quick release particles)

: Particle formed by drying by EDDS spray with MgSO4 at a weight ratio of 26:74

 Protease

: Proteolytic enzyme sold by the trade name Savinase by Novo Industries A / S with an activity of 13 KNPU / g

 Amylase

: Proteolytic enzyme sold by the trade name Termamyl 60T by Novo Industries A / S with an activity of 300 KNU / g

 Cellulase

: Cellulosic enzyme sold by Novo Industries A / S with an activity of 1,000 CEVU / g

 Lipase

: Lipolytic enzyme sold by the trade name Lipolase by Novo Industries A / S with an activity of 165 KLU / g

 CMC

: Sodium carboxymethylcellulose

 HEDP

: acid 1,1-hydroxyethane diphosphonic

 EDDS

: Acid ethylenediamino-N, N'-disuccinic, isomer (S, S), in the form of sodium salt

 PVNO

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

 Granular foam suppressor

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

 Nonionic

: Mixed ethoxylated / propoxylated fatty alcohol C 13 -C 15 with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5, sold by the trade name Plurafac LF404 by BASF Gmbh (poor training of foam)

 Metasilicate

: Sodium Metasilicate (ratio SiO2: Na2O = 1.0)

 Phosphate

: Sodium tripolyphosphate

 480N

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

 GDP

: Sodium perborate monohydrate anhydrous-shaped compacted particles to retard peroxide release from hydrogen

 Cationic lactam

: Precursor salt of peroxyacid bleach trialkyl ammonium methylene alkyl-C5 cationic caprolactam with tosylate

 DETPMP

: Diethylenetriaminopenta (methylene phosphonic acid), placed on the market by Monsanto under the trade name Dequest 2060

 Bismuth nitrate

: Bismuth nitrate salt

 Paraffin

: Paraffin oil sold by the trade name Winog 70 by Wintershall

 BSA

: Enzyme amylolytic sold by the trade name LE17 by Novo Industries A / S (approximately 1% enzymatic activity)

 Sulfate

: Anhydrous sodium sulfate

 PH

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

Example 1

The following compositions were prepared laundry detergents, expressing values as weight percentages of the compositions: Composition A is a comparative composition, compositions B to E agree with the invention:

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18

19

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

twenty

Test comparative

Test-stain removal method Preparation of test cloths

Three white cotton sheets were pre-washed with a high performance detergent, free of bleach and not biological. Sets of six 6 cm x 6 test cloths were cut cm of each sheet. Stains were applied evenly over each set of cloths (eg painting on top).

In addition, prepared cloths of beforehand, obtained from the EMPA institute.

In summary, the following games of cloths:

Stains enzymatic Grass; Stains bleachable Blood of EMPA; Blood, milk and ink of EMPA; Stains greasy Motor oil dirty; Shoe cream;

The cloth cloth sets underwent a Washing cycle in an automatic washing machine. Then the cloths were evaluated for the removal of stains by a expert committee using a four-point Scheffe scale. The combined results of averaged pairs for each of the Comparisons are the ones shown below, using as common reference the composition A of the prior art.

In more detail, a washing machine was used automatic Miele 698 WM and the short cycle program was chosen to 40 ° C Water of 12º of German hardness was used (Ca: Mg = 3: 1). 75 g of detergent were used, dosed in the cutlet that placed in the middle of the load of clothes. A cloth of each type was washed together with a ballast load composed of 2.7 kg of little sheets dirty (domestic use for 1 week).

Comparative test-stain removal

The elimination test method of spots described above to compare the effectiveness of the Composition B with reference Composition A of the technique above, in the removal of different types of spots.

The results obtained were the following:

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Stain type Disposal benefit of spots (PSU) Blood of EMPA + 1.8 * BMI of EMPA +0.6 Grass +0.7 Oil of dirty engine +0.6 Cream shoes +0.7 * significant to a confidence limit of 95%

Example 2

The following compositions of according to the invention containing bleach for washing Automatic tableware (parts by weight).

twenty-one

Example 3

The following test method was carried out. representative in beaker to determine if the order sequential exposure of stained tissue to the sequestrant of heavy metal ions and bleaching solution based on hydrogen peroxide would lead to differences in the profile of stain removal.

The previously stained cotton cloths are They prepared by dipping them in a concentrated solution of tea. The Tea stains contain high levels of manganese and it is recognized that It is difficult to remove them from stained / dirty tea substrates.

Beakers were charged individually 1,000 ml capacity with solutions containing individually concentrations of 0.5% by weight of EDDS, and a hydrogen peroxide solution equivalent to 2% AvO. Each of heavy metal ion sequestrant solutions and of bleach was buffered to pH 10.5, which is a typical wash pH that It is in a method of washing clothes.

The previously stained cloth sets are put to soak in any one of the solutions, or sequentially in both. The soak time in each solution was 20 minutes Each soak was followed by a rinse with solution diluted NaOH.

In detail, the following were used Soaking and washing protocols:

Game Protocol TO Alone soak in bleaching solution B Only soak in EDDS solution C Soak in bleaching solution followed by soak in EDDS solution D Soak in EDDS solution followed by soaking in bleaching solution

Separation results of stains obtained for each wash / soak protocol using a Macbeth spectrometer, measuring yellowing, whiteness and values a, b and l, for comparison with a white cotton cloth Clear.

The following results were obtained:

Cloth stained TO B C D Yellowing 55.1 35.7 36.7 29.4 19.3 Whiteness -141.2 -92.1 -94.1 -75.0 -50.1 I -9.7 -5.8 -8.6 -4.5 -3.4 TO 3.5 -0.3 2.3 0.0 -0.7 B 23.8 16.1 15.5 13.4 8.9

Yellowing values are desirable, a and b less positive. Whiteness and more positive values are desirable.

Therefore, it is observed that the results of stain removal for the D-cloth set are better than obtained for cloths A-C. This is how the enhanced stain removal power that is obtained with the sequential exposure of a stained tissue to a solution that contains a heavy metal ion sequestrant and then at a solution containing bleach.

Example 4

The following representative test method demonstrates that significant elimination power is obtained from bleachable spots when stained cloths are treated with a solution containing a heavy metal ion sequestrant before washing them in a detergent product that contains whitening with fast release speed (i.e. speed uncontrolled release of bleach).

The previously stained cotton cloths are They prepared by dipping them in a concentrated solution of tea. The Tea stains contain high levels of manganese and it is recognized that It is difficult to remove them from stained / dirty tea substrates.

Beakers were charged individually 1,000 ml capacity with solutions containing a concentration of 0.005% by weight of EDDS buffered to pH 10.5, which it is a typical wash pH found in a wash method of clothing.

The previously stained cloth sets are They were rinsed in the EDDS solutions and then washed in a full-scale method of laundry washing, using a detergent product containing bleach. Rinsing time in the EDDS solution it was set in 2 or 5 minutes. The method of washing clothes included a main wash in a washing machine Automatic Miele at 40ºC using soft water. The product detergent used in this washing method had fast speed release of the bleach and its composition was that of the formulation A of Example 1.

The effect of pre-rinsing on the heavy metal ion sequestrant solution before washing was estimated with reference to cloth sets pre-stained subjected only to the washing method to real scale.

Bleachable stain removal was estimated both with the naked eye, using the well-known Scheffé scale of 4 points that apply expert scoring units (PSU), as using the Macbeth spectrometer to calculate a value Stain removal percentage.

The following results were obtained:

Rinse / Wash Protocol % from elimination PSU (Scheffé) from stains VS only washed Alone washed 87 - Cleared up for 2 minutes in solution of EDDS 92 + 3 * followed by washed Cleared up for 5 minutes in solution of EDDS 97 + 3 * followed by washed * significant at the level of confidence of 95%

Marked elimination benefits of bleachable spots for cloths exposed to the solution heavy metal ion sequestrant before washing in the detergent product containing bleach.

Example 5

The wash / rinse protocol was repeated Example 3, but with the following variations:

1. The 0.005% EDDS solution was replaced by a solution containing 0.005% EDDS and sodium citrate at 0.05%, which was also buffered at pH 10.5.

2. The rinse time was set to 3 minutes

3. Stained (cotton) cloths were used individually with the following spots:

(to)

Blood (EMPA)

(b)

Coffee

(c)

Wine red

(d)

Cocoa

(and)

Blood, milk and ink (EMPA)

Cloths (a) and (e) were obtained from the EMPA organization. Cloths (b) to (d) were obtained by painting the stains on 15 cm x 15 cm samples of white cotton sheet previously washed.

Using this modified test protocol, estimated the effect of cloth pre-rinse stained in solution containing metal ion sequestrant heavy / detergency builder before washing, by comparison with the results obtained for the same cloths stains exposed only to the laundry method, without No pre-cleared stage.

Stain removal results are estimated using the Macbeth spectrometer to calculate a value Stain removal percentage.

The following results were obtained:

22

According to the above, it can be seen that a improved stain removal power when the rinse stage in the improver solution of the heavy metal ion detergency / sequestrant before washing stage

Claims (16)

1. A detergent composition, which contains (a) a heavy metal ion sequestrant; Y (b) a peroxyacid bleaching system organic where a means is provided to delay the release of said organic peroxyacid in a wash solution regarding the release of said metal ion sequestrant heavy, so that in the T50 test method described here, the difference between the time to obtain a concentration that is 50% of the final concentration of the metal ion sequestrant heavy is less than 120 seconds and the time to get a concentration that is 50% of the final peroxyacid concentration organic is more than 180 seconds, where the medium comprises a coating that delays the release of the peracid and optionally it also comprises one or more of (1) a coating on the heavy metal ion sequestrant that accelerates release of the heavy metal ion sequestrant, (2) selection of particle sizes of the heavy metal ion sequestrant and / or the bleaching system, and (3) selection of solubilities of the heavy metal ion sequestrant and / or system bleaching 2. A detergent composition according to the claim 1, wherein the time to obtain a concentration that is 50% of the final concentration of organic peroxyacid is 180 at 480 seconds 3. A detergent composition, which contains (a) a heavy metal ion sequestrant; Y (b) a peroxyacid bleaching system organic where a means is provided to delay the release of said organic peroxyacid in a wash solution with respect to said heavy metal ion sequestrant so that in the T50 test method described here the time to obtain a concentration that is 50% of the final concentration of said heavy metal ion sequestrant is at least 100 seconds less than the time to obtain a concentration that is 50% of the final concentration of said organic peroxyacid, where the medium it comprises a coating that delays the release of the peracid and optionally it also comprises one or more of (1) a coating about the heavy metal ion sequestrant that accelerates the release of heavy metal ion sequestrant, (2) particle size selection of the ion sequestrant from heavy metals and / or the bleaching system, and (3) selection of solubilities of the heavy metal ion sequestrant and / or the bleaching system 4. A detergent composition according to any of claims 1 to 3, further containing: (c) a soluble detergency builder in Water where a means is provided to delay the release of said organic peroxyacid in a wash solution regarding the release of said detergency builder water soluble so that in the T50 test method described here the time to get a concentration that is 50% of the final concentration of said soluble detergency builder in Water is less than 120 seconds. 5. A detergent composition according to any of claims 1-4, wherein said system organic peroxyacid-based bleach comprises, in combination (i) a source of hydrogen peroxide; Y (ii) a bleaching precursor compound organic peroxyacid. 6. A detergent composition according to the claim 5, wherein said bleach precursor compound peroxyacid is selected from a bleach precursor compound peroxyacid which, when perhydrolyzed, provides a peroxyacid that it is (i) a perbenzoic acid or a substituted derivative non-cationic thereof; or (ii) a cationic peroxyacid. 7. A detergent composition according to claim 6, wherein said bleach precursor compound Organic peroxyacid is selected from the group consisting of a) a bleach precursor substituted with Amide, of general formula: R1 ---

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

---

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

--- R2 ---

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

--- L,

 \ hskip1cm 

or

 \ hskip1cm 

R1 ---

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

---

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

--- R2 ---

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

--- L where R 1 is an aryl or alkylaryl group that Contains from 1 to 14 carbon atoms, R2 is an arylene group or alkarylene containing from 1 to 14 carbon atoms, R 5 is H or an alkyl, aryl, or alkylaryl group containing 1 to 10 atoms of carbon, and L is a group outgoing; b) a precursor of bleaching lactam N-acylated, of formula: 2. 3 where n is 0 to 8, preferably 0 to 2, and R 6 is an aryl, alkoxyaryl or alkaryl group containing 1 at 12 carbon atoms, or a substituted phenyl group containing 6 to 18 atoms of carbon; and mixtures of a) and b). 8. A detergent composition according to the claim 5, wherein the precursor compound of said bleach peroxy acid is 24 where R 1 is H, alkyl, alkylaryl, aryl, arylalkyl and where R2, R3, R4 and R5 can be the same or different substituents, selected among functions H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxy, amino, alkylamino, COOR 6 in which R 6 is H or an alkyl group and carbonyl 9. A detergent composition according to the claim 5, wherein the precursor compound of said bleach peroxyacid is tetraacetylethylenediamine. 10. A detergent composition according to any of claims 5 to 9, wherein said source of peroxide of Hydrogen is a perhydrated inorganic salt. 11. A detergent composition according to claim 10, wherein said perhydrated inorganic salt is a alkali metal percarbonate. 12. A detergent composition according to any of claims 1-11, which contains additionally a catalyst for the bleach. 13. A detergent composition according to claim 12, wherein said bleach catalyst is selected from the group consisting of Mn IV 2 (uO) 3 (1,4,7-trimethyl-1,4, 7-triazacyclononane) 2 (PF 6) 2, Mn III 2 (uO) 1 (u-OAc) 2 (1,4,7 -trimethyl-1,4,7-triazacyclononane) 2 - (ClO 4) 2; Mn IV 4 (uO) 6 (1,4,7-triazacyclononane) 4 (ClO 4) 4; Mn III Mn IV 4 (uO) 1 (u-OAc) 2 - (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (ClO 4) 3; Mn IV (1,4,7-trimethyl-1,4,7-triazacyclononane) - (OCH 3) 3 (PF 6); Co
(2,2'-bispyridyl amine) Cl2; Di- (isothiocyanate) -bispyridylamine-cobalt (II); trisdipyridylamine-cobalt (II) perchlorate; Co (2,2-bispyridylamine) 2 -O 2 ClO 4; bis- (2,2'-bispyridylamine) copper (II) perchlorate; tris (di-2-pyridylamine) iron (II) perchlorate; Mn gluconate; Mn (CF 3 SO 3) 2; Co (NH 3) 5 Cl; Binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including N 4 Mn III (uO) 2 Mn IV N 4) + and [ Bipy 2 Mn III (uO) 2 Mn IV bipy 2] - (ClO 4) 3 and mixtures thereof. 14. A detergent composition according to any of claims 1 to 13, which is free of bleach chlorine. 15. The use of a detergent composition according to any one of claims 1 to 14 in a method of washing clothes, where the detergent composition is discharged into the solution washing by means of a dosing device introduced in the drum of an automatic washing machine before starting the wash. 16. A washing method comprising the steps from:

(one)

apply a solution, free of bleach, of a composition containing a heavy metal ion sequestrant to a dirty substrate;

(two)

let bliss solution remains in contact with said dirty substrate for a effective time interval;

(3)

wash said dirty substrate using a washing method that involves the use of a detergent composition containing bleach.