ES2276418T3 - PROCEDURE FOR WHITENING FABRICS. - Google Patents

Abstract

THE PRESENT INVENTION REFERS TO TISSUE WHITENING PROCESSES, IN WHICH THESE FABRICS ARE CONTACTED WITH A LIQUID WHITENING COMPOSITION THAT INCLUDES A WHITENING HYPOHALITE, BETWEEN 0.1 AND 20% BY WEIGHT OF THE TOTAL COMPOSITION OF A TOTAL COMPOSITION TENSIOACTIVE AND BETWEEN 0.001 AND 10% BY WEIGHT OF A STABILIZING AGENT SELECTED FROM THE GROUP FORMED BY A RADICAL RECEIVER, A COMPLAINANT AGENT AND A MIXTURE OF THE SAME, IN ITS DILUTED OR PURE FORM. ADVANTAGES, AFTER THE AGING OF THE COMPOSITION, EFFICIENCY OF ELIMINATION OF THE STAINS IS IMPROVED, WHEN USED IN ANY APPLICATION OF COLADA.

Description

Procedures for bleaching tissues.

Field of the Invention

The present invention relates to the bleaching of fabrics, including methods of handwashing and machine with compositions containing bleach type liquid hypohalite

Background of the invention

The bleaching compositions are fine known in the art. Among the different compositions bleachers on the market, often preferred those that base bleaching on hypohalite based bleaches such as hypochlorite, mainly due to its performance, especially at low temperatures.

However, there are some limitations to the convenience of use of compositions containing bleach hypohalite type, especially when you want to have a good performance in the ability to remove stains on the treated tissues in addition to bleaching performance. This is even a problem when using aged compositions, that is, when compositions are used in a laundry application after prolonged periods of storage after manufacturing.

It has now been observed that when desired incorporate surfactants in a bleach type composition liquid hypohalite, the resulting composition generally shows poor chemical stability when the composition ages, which results in a low stain removal capacity of The composition when used in any washing application clothing after prolonged periods of storage. Indeed, With prolonged periods of storage, surfactants will they can decompose by action of the hypohalite bleach present in said hypohalite bleach composition liquid, thus losing its potential to eliminate spots This decomposition of the surfactant can be accelerated. by exposure of the product to high temperatures or by impurities in the raw material.

It is therefore an object of the invention address the problem of poor stain removal ability on the tissues when they are bleached with aged compositions containing hypohalite bleach.

The applicant has now discovered surprisingly that this problem can be treated efficiently when the liquid bleaching composition used to bleach tissues comprises a hypohalite bleach, a surfactant and a stabilizing agent selected from the group that it consists of a radical inactivator, a chelating agent and a mixture thereof. Indeed, it has been discovered that the presence of a stabilizing agent of this type in a composition liquid bleach comprising a hypohalite bleach  and a surfactant, provides an ability to remove Improved spots on various spots including spots greasy like sebum, makeup or lipstick, spots enzymatic such as blood, grass or coconut, as well as spots bleachable as wine, coffee or tea, in any washing application of clothing during the aging of the composition, that is, when used after prolonged periods of storage after its manufacture, compared to the ability to stain removal provided by the same composition but without such a stabilizing agent, during aging of the composition. Also, use in a composition that contains liquid hypohalite bleach comprising a surfactant, of such a stabilizing agent, provides an improved surfactant stability in said composition for prolonged periods of storage.

Another advantage of tissue bleaching processes according to the present invention is that they are suitable for bleaching different types of fabrics including natural fabrics (e.g., fabrics made of cotton, viscose, linen, silk and wool), fabrics synthetics, such as those made from polymeric fibers of synthetic origin, as well as those made from both natural and synthetic fibers. Indeed, synthetic fibers can be bleached according to the present invention despite the prejudice against the use of hypohalite based bleaches, especially hypochlorite based bleaches, on synthetic fibers, as evidenced in the warning of bleach labels based on commercialized hypochlorite and garments. Advantageously, the compositions used according to the bleaching processes of the present invention are not only safe per se for the bleached fabrics therewith, but also for the colors of the fabrics.

Advantageously, the compositions liquid bleaches used according to the present invention can  get in touch with the tissues you want to bleach, in diluted conditions, e.g. ex. when used as an additive of detergent or alone as a detergent composition for washing clothes or in their purest form, p. e.g., when used as a pretractant liquid (pretreatment).

Prior art

Application EP-A-668 345 describes compositions containing hypochlorite that comprise a source of alkalinity strong, a buffering medium of pH (silicate / carbonate) and radical inactivator. Surfactants are described as Optional ingredients without mentioning any or levels of same.

Application EP-A-0 867 501 (relevant for its novel character according to Art. 54 EPC) describes compositions bleaches comprising a hypohalite bleach, a pH buffering medium and an effective amount of a anionic surfactant. Radical inactivators and agents chelators are mentioned as optional unspecified ingredients None or their levels.

Application EP-A-0 812 904 and EP-A-0 834 549 (both relevant by its novel character according to Art. 54 EPC) describes compositions based on hypochlorite with surfactants and optionally radical inactivators. Chelators are mentioned as Optional ingredients without specifying any or levels of the same. It does not describe any laundry application.

Application EP-A-317 066 describes compositions thickened aqueous cleaners comprising an ingredient active cleanser (hypochlorite, acids, bases [NaoH, carbonate, silicate]), a quaternary ammonium compound and a counterion organic (eg benzoic acid). It does not describe any application of laundry

US-5384 061 describes thickened compositions comprising hypochlorite, a polymer of cross-linked polycarboxylate, phytic acid, an inactivator of radicals, a rheology stabilizing agent, an agent alkaline buffer to provide said composition with a pH greater than 10. Various surfactants are described. Does not describe No laundry application.

Summary of the invention

The present invention encompasses a process of tissue bleaching comprising the steps of:

-

put on contacting said tissues with a liquid bleaching composition comprising a hypohalite bleach, from 0.1% to 20%, in weight of the total composition of a surfactant and from 0.001% to 10%, by weight of a stabilizing agent that is an inactivator of radicals or a mixture thereof, alone or together with an agent chelator or a mixture thereof, in its diluted form or pure,

-

leave said tissues in contact with said bleaching composition for a period of time sufficient to bleach said tissues,

-

already then rinse said tissues with water.

In a preferred embodiment the compositions used in the present invention further comprise a component pH buffer. The presence of a pH buffer component in the compositions of the present invention it also contributes to the effective bleaching capacity of these compositions, as well as to its safety for tissue, when used to bleach tissues. In fact, the pH buffer component allows controlling the alkalinity in the bleaching solution, that is, maintaining the pH of the bleaching solution at a pH of at least 7.5, preferably at least 8.5, and more preferably at least 9.5 over a period of more prolonged time starting from the moment in which completes the dilution (eg when the bleaching composition of The present invention is diluted in the bleaching solution to a 200: 1 dilution level [water: composition]). This action pH buffer component buffer reduces conversion of hypochlorite in hypochlorous acid, one of the species that are more responsible for the yellowing of the tissues and / or damage in the tissues.

Detailed description of the invention

The present invention encompasses a process of bleaching of tissues with a bleaching composition as described below.

By "tissues", any type is understood. of fabrics including eg clothing, curtains, curtains, bedding, towels, tablecloths, sleeping bags, stores, furniture upholstery and the like.

The process of bleaching tissues of the present invention is suitable for both natural fabrics and for synthetic fabrics "Natural" fabrics means fabrics. Made of cotton, viscose, linen, silk and / or wool. By tissues "synthetic" means those made of synthetic fibers as polymeric fibers (polyamide, polyester, lycra® and elasthane®), and those made of both natural fibers and synthetic fibers.

The process of bleaching of tissues according to the The present invention comprises the steps of contacting said fabrics with a liquid bleaching composition comprising a hypohalite bleach, a surfactant (0.1% -20%) and a stabilizing agent as defined herein (0.001% -10%). In a preferred embodiment, the compositions used in the fabric bleaching process of the present invention they are compositions that contain liquid hypochlorite that can further comprising a pH buffer component as defined by continuation. Said bleaching process according to the present invention provides effective stain removal ability during The aging of the compositions.

Liquid compositions according to the present invention come into contact with the tissues in their pure form or diluted

The compositions according to the present invention are typically used in diluted form in an operation of laundry Hereby "in diluted form" It is understood that tissue bleaching compositions according to The present invention can be diluted by the user, preferably with water. Said dilution can be made, by example, in laundry applications by hand or by others procedures such as p. eg, in a clothes washer. These compositions can be diluted up to 500 times, preferably 5 200 times and more preferably 10 to 80 times.

More specifically, the bleaching process of fabrics according to the present invention comprise the steps of putting first contacting said tissues with a bleaching composition liquid as described herein, in its form diluted, then leave said tissues in contact with said composition, for a period of time sufficient to bleach said tissues, typically 1 to 60 minutes, preferably 5 to 30 minutes, then rinse said tissues in water. When such fabrics have to be washed, namely with a conventional composition comprising at least one agent surfactant, said washing can be carried out together with the bleaching of said tissues by putting said tissues simultaneously in contact with a bleaching composition according to the present invention and with said detergent composition, or it can also said washing be performed before or after bleaching said tissues. Therefore, the process according to the present invention allows bleaching fabrics and optionally wash fabrics with a detergent composition  comprising at least one surfactant before the step of contacting said tissues with the bleaching composition liquid as described herein and / or the stage in where said tissues come in contact with the composition bleach and / or after the stage where said tissues are put in contact with the bleaching composition and before washing stage and / or after the washing stage.

In another embodiment of the present invention the tissue bleaching process comprises the step of putting in contact tissues with a liquid bleaching composition as described below, in its pure form, allow such tissues remain in contact with said bleaching composition for a period of time sufficient to bleach said tissues, typically 5 seconds to 30 minutes, preferably 1 minute to 10 minutes and then rinse these tissues in Water. When such fabrics have to be washed, e.g. eg with a conventional composition comprising at least one agent surfactant, said washing can be done before or after bleach said tissues. In the embodiment of the present invention wherein the liquid bleaching composition used according to the In the present invention, it contacts the tissues in their form pure, it is preferred that the level of hypohalite bleach be from 0.01% to 5%, preferably from 0.1% to 3.5%, more preferably from 0.2% to 2% and most preferably from 0.2% to 1%. So advantageously, the present invention provides a bleaching process of fabrics where the bleach containing compositions of Liquid hypohalite type are applied in pure form on a tissue to bleach, despite the existing prejudice against the use of compositions containing hypochlorite in pure form in tissues.

It is preferred to carry out the processes of bleaching of the present invention before washing said fabrics. In effect, it has been observed that the bleaching of said tissues with the Compositions of the present invention (dilute bleaching methods or pure) before washing them with a detergent composition provides superior whiteness and less stain removal energy and detergent that if these fabrics were washed first and bleached later.

Alternatively, instead of the process bleaching in pure form as described above in the present memory (pretractant application) follow a stage of rinsed with water or a conventional wash stage with a conventional liquid or powder detergent, the operation of bleaching pretreatment can also be followed by the process of diluted bleach as described hereinbefore memory in a bucket (manual operation) or in a washing machine.

The temperatures at which the bleaching process of the present invention, have an influence on the stain removal capacity provided. Plus specifically, an increase in temperature accelerates the process of bleaching, that is, decreases the time required to bleach a given dirt. Typically, bleaching solutions that are produced in the bleaching processes according to the present invention where the bleaching compositions of the present invention are use in its diluted form have a temperature of 4ºC to 60ºC, preferably from 10 ° C to 50 ° C and most preferably from 20 ° C to 40 ° C

The compositions of use in these processes of Bleaching are in liquid form. Preferably you are Compositions are in liquid aqueous form. More preferably, the compositions comprise water in an amount of 60% to 98% in weight, more preferably from 80% to 97% and most preferably 85% to 97%, by weight of the aqueous liquid bleaching composition total.

Hypohalite based bleach

An essential component of the invention is a hypohalite bleach. Bleaches based on hypohalite can come from several sources, including bleaches that are oxidizing and therefore lead to formation of positive halide ions as well as bleaches that are organic sources of halides such as chloroisocyanurates.

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Hypohalite based bleaches Suitable for use in the present invention include the hypochlorites, hypobromites and hypoiodites of alkali metals and alkaline earth metals, chlorinated trisodium phosphates dodecahydrates, potassium and sodium dichloroisocyanurates, potassium and sodium trichlorocyanurates as well as N-chloroimides, N-chloroamides, N-chloroamines and chlorohydantoins.

For the liquid compositions herein invention, the preferred hypohalite bleach from those described above are alkali metal hypochlorites and / or alkaline earth metals selected from the group consisting of sodium, potassium, magnesium, lithium and calcium hypochlorites and mixtures thereof, more preferably the metal hypochlorite sodium alkaline

Preferably, the liquid compositions used according to the present invention comprise said bleach hypohalite type so that the active halide content in the composition is from 0.1% to 20%, by weight, more preferably 0.25% at 8%, by weight, most preferably from 0.5% to 6%, by weight of the composition.

The surfactant

An essential component of the invention is a surfactant or mixture thereof. Said surfactant is present in the compositions used according to the present invention in amounts of 0.1% to 20%, by weight, of the total composition, preferably from 0.1% to 15%, more preferably from 1% to 10% and with highest preference from 2% to 8%.

The surfactants used herein invention include anionic surfactants, non-surfactants ionic, cationic surfactants, amphoteric surfactants, hybrid ion surfactants and mixtures thereof. Evidently,  For the purposes of the invention, the surfactants have to be stable in the hypohalite bleach.

Surfactants are essential ingredients in the present invention because they provide the ability to desired stain removal on bleached tissues.

Suitable anionic surfactants for use in The present invention includes salts or water-soluble acids of formula ROSO 3 M where R is preferably a hydrocarbyl C 4 -C 24, preferably a linear alkyl or branched that has an alkyl component C 6 -C 20, more preferably an alkyl C 8 -C 18 linear or branched and M is H or a cation, p. e.g., an alkali metal cation (e.g., sodium, potassium, lithium), or substituted ammonium or ammonium (e.g., cations methylammonium, dimethylammonium and trimethylammonium and ammonium cations quaternary, such as tetratamethylammonium cations and dimethylpiperidinium and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).

Other anionic surfactants for use in the present invention are salts or water-soluble acids of formula
RO (A) m SO 3 M wherein R is a linear or branched alkyl group having a C 4 -C 24 alkyl component, preferably a C 8 -C 20 alkyl linear or branched, more preferably linear or branched C 10 -C 18 alkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 30, more preferably between about 0.5 and about 5, and M is H or a cation, which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or ammonium cation replaced. In the present invention both ethoxylated alkyl sulfates and propoxylated alkyl sulfates are contemplated. Specific examples of substituted ammonium cations include methylammonium, dimethylammonium, trimethylammonium and quaternary ammonium cations, such as tetramethylammonium or dimethyl piperidinium, and alkylamine derived cations, such as ethylamine, diethylamine or triethylamine, mixtures thereof and the like. Illustrative surfactants are C 12 -C 18 alkyl polyethoxylated sulfate (1.0), C 12 -C 18 E sulfate (1.0), C 12 -C 18 alkyl polyethoxylated sulfate (2.25), C 12 -C 18 E sulfate (2.25), C 12 -C 18 alkyl polyethoxylated sulfate (3.0), C 12 -C 18 sulfate E (3.0) and C 12 -C 18 alkyl polyethoxylated sulfate (4.0), C 12 -C 18 sulfate E (4.0), wherein the counterion is conveniently selected of sodium and potassium.

They can also be used here. invention other anionic surfactants useful for detersive purposes.  These may include salts (including, for example, sodium salts, potassium, ammonium and substituted ammonium such as salts of soap monoethanolamine, diethanolamine and triethanolamine), alkyl C 4 -C 24 linear benzenesulfonates, alkane C 8 -C 22 primary or secondary sulfonates, C 8 -C 24 olefin sulfonates, acids sulfonated polycarboxylic acids prepared by sulfonation of pyrolized product of alkaline earth metal citrates such as, e.g. eg, that described in GB-1,082,179, alkyl C 8 -C 24 polyglycol ether sulfates (which contain up to 10 moles of ethylene oxide); esters alkyl sulfonates such as esters of C 14-16 methylsulfonate; acylglycerol sulfonates, oleyl glycerol fatty sulfates, alkylphenol ether ethylene oxide sulfates, paraffin sulphonates, alkyl phosphates, isethionates such as acyl isethionates, N-acyl taurates, alkyl succinamates and sulphosuccinates, monoesters of sulfosuccinate (especially saturated monoesters or C 12 -C 18 unsaturated diesters of sulfosuccinate (especially saturated or unsaturated diesters of C 6 -C 14), alkylpolysaccharide sulfates such as alkyl polyglucoside sulfates (the compounds not non-sulfated ionics are described below), alkyl sulfates branched primaries, alkyl polyethoxy carboxylates such like the formula ones RO (CH 2 CH 2 O) k CH 2 COO-M + wherein R is a C 8 -C 22 alkyl group, k is an integer from 0 to 10 and M is a soluble cation-forming cation of you go out. Resin acids and acids are also suitable hydrogenated resins such as rosin, hydrogenated rosin and hydrogenated resin acids present in coniferous oil or derivatives thereof. Other examples are described in "Surface Active Agents and Detergents "(vol. I and II of Schwartz, Perry and Berch). Different surfactants of this type are generally described. also in US Patent 3,929,678, issued on 30 December 1975 to Laughlin et al., from column 23, line 58, to column 29, line 23.

Other anionic surfactants suitable for Use in the present invention also include acylsarcosinate or mixtures thereof, in its acid and / or salt form, preferably the Long chain acylsarcosinates of formula:

one

where M is hydrogen or a cationic portion and where R is an alkyl group of 11 to 15 atoms carbon, preferably 11 to 13 carbon atoms. For M se prefers hydrogen and alkali metal salts, especially sodium and potassium Said acylsarcosinate type surfactants they come from natural fatty acids and the amino acid sarcosine (N-methyl glycine). They are suitable to be used as an aqueous solution of its salt or in its acid form as a powder. To the be derived from natural fatty acids, said acylsarcosinates they are quickly and completely biodegraded and have a good compatibility with skin.

Therefore, long chain acylsarcosinates suitable for use in the present invention include acyl C 12 sarcosinate (ie, an acylsarcosinate according to the formula above where M is hydrogen and R is an alkyl group of 11 carbon atoms) and C 14 acyl sarcosinate (i.e. a acylsarcosinate according to the above formula wherein M is hydrogen and R is an alkyl group of 13 carbon atoms). C 12 acyl Sarcosinate is marketed, for example, as Hamposyl L-30® by Hampshire. The C 14 acyl sarcosinate is marketed, for example, as Hamposyl M-30® by Hampshire

In a preferred embodiment of the present invention the compositions for use in the bleaching process of The present invention comprises at least one anionic surfactant, especially an alkyl benzene sulfonate, alkyl sulfate, alkylalkoxy (preferably ethoxy) sulfate or a alkylethoxycarboxylate with an alkyl chain containing from 4 to 24 carbon atoms, preferably from 8 to 18, with maximum preference from 8 to 16. Indeed, it has been seen that such anionic surfactants provide a good ability to stain removal as well as improve the whiteness of tissues when treated according to the process of the present invention, with a bleaching composition that comprises them.

The bleaching effect, that is, the effect of yellowish color inhibition, can be determined by both visual and instrumental score. Visually, the yellowish difference between the samples treated with different compositions can be determined by a team of experts Instrumental assessment can be done with the help of colorimeters such as Ganz Griesser® instruments (e.g., Datacolor® Spectraflash® SF 500, Machbet White-eye® 500) ZEISS ELREPHO® or others, marketed p. e.g., by Hunterlab® or Gardner®.

In a particular embodiment of the present invention the surfactant system used in a system anionic surfactant, namely alkylalkoxy (preferably ethoxy) sulfate as alkyl (ethoxy) 3 sulfate alone or together with a auxiliary surfactant, preferably an alkyl sulfate C4-C18 or a C8-C18 alkyl or aryl sulfonate such as benzene C8-C18 sulfonate and / or other alkylalkoxysulfate other than ethoxylated. Indeed, the presence of said alkyl (ethoxy) 3 sulfate alone or together with a auxiliary surfactant provides the desired viscosity at compositions suitable for use according to the bleaching process of the present invention and provides excellent properties of stain removal to said compositions when used in Any laundry application of this invention.

Typically, such suitable compositions for use in the present invention have a viscosity between 0.025 Pa.s (25 cps) and 1.5 Pa.s (1500 cps), preferably between 0.05 Pa.s (50 cps) and 1.1 Pa.s (1100 cps), depending on the relationship between AE 3 S and the auxiliary surfactant, when measured using the following viscosity parameter: angle: 1 ° 58, hollow: 60, diameter: 4.0 cm and iner: 63.60 at a temperature of 25ºC and a shear rate of 30 1 / sec.

Also suitable in the present invention is a mixture of anionic surfactants and other surfactants especially hybrid ion surfactants as surfactants of betaine type

Nonionic surfactants for use herein invention include a class of compounds that can be defined in general lines as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with a organic hydrophobic compound, which can be branched aliphatic or linear (eg Guerbet or secondary alcohol) or nature aromatic alkyl. The length of the hydrophilic radical or polyoxyalkylene that condenses with any hydrophobic group can be easily adjusted to obtain a water soluble compound having the desired balance between hydrophilic elements and hydrophobic elements

Therefore, non-ionic synthetic surfactants Suitable include:

(i)

The condensates of poly (ethylene oxide) of alkyl phenols, e.g. eg the condensation products of alkyl phenols having a group alkyl containing 6 to 20 carbon atoms in a linear chain or branched chain configuration, preferably from 8 to 12 carbon atoms, with ethylene oxide being present, in amounts equal to 10 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds may derived from propylene, diisobutylene, octane, and nonane polymerized;

(ii)

Those derived from condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine products that can vary in composition depending on the desired balance between the hydrophobic and hydrophilic elements. Examples constitute them compounds containing 40% to 80% polyoxyethylene by weight and with a molecular weight of 5,000 to 11,000 resulting from the reaction of ethylene oxide groups with a hydrophobic base constituted by the reaction product of ethylenediamine and excess oxide of propylene, said base having a molecular weight of the order of 2,500 to 3,000;

(iii)

He condensation product of aliphatic alcohols having 6 to 22 carbon atoms, in linear chain or chain configuration branched, preferably from 8 to 18 carbon atoms, with from 2 to 35 moles of ethylene oxide, preferably 4 to 25 and more preferably from 5 to 18. Examples of this type of material are a condensate of coconut alcohol and ethylene oxide that is 5 to 18 moles of ethylene oxide per mole of coconut alcohol, the fraction Coconut alcohol has 9 to 14 carbon atoms;

(iv)

Trialkylamine oxides and oxides of trialkyl phosphine wherein an alkyl group ranges from 10 to 18 atoms  carbon and two alkyl groups range from 1 to 3 carbon atoms; a specific example is tetradecyl dimethyl oxide phosphine;

(v)

The condensation products of ethylene oxide with a base hydrophobic formed by the condensation of propylene oxide with propylene glycol; the hydrophobic fraction of these compounds will have preferably a molecular weight of 1,500 to 1,800 and will have insolubility in water. The addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retains so far when the polyoxyethylene oxide is of 50% of the total weight of the condensation product, which corresponds a condensation with up to 40 moles of oxide ethylene.

Especially suitable nonionic surfactants of use in the present invention are ethoxylated surfactants not Terminal protected ionics according to the formula:

R 1 (OR 2) n OR 3

in where

R1 is an alkyl or alkenyl group C 8 -C 18 linear or branched, a group aryl, an alkylaryl group, preferably R1 is a group C 10 -C 15 alkyl or alkenyl and more preferably an alkyl group C 10 -C 15;

R2 is an alkyl or alkenyl group C 2 -C 10 linear or branched, preferably a C4 group;

R_ {3} is a group C 1 -C 10 alkyl or alkenyl, preferably a C1-C5 alkyl group, Y

n is an integer from 1 to 20, preferably from 1 to 10 and more preferably from 1 to 5;

or mixtures of same.

These surfactants are marketed by BASF with the trade name Plurafac®, by HOECHST with the name trade name Genapol® or by ICI under the trade name Symperonic®. Terminal-protected non-ionic ethoxylated surfactants Preferred of the above formula are those marketed with the trade name Genapol® L 2.5 NR from Hoechst and Symperonic® LF / CS 1100 of ICI.

Other non-ionic surfactants for use in the The present invention includes the amine oxides corresponding to the formula:

R \ R '\ R' '\ N \ rightarrow OR

where R is an alkyl group primary containing 6 to 24 carbons and preferably 10 to 18 carbons, and R 'and R' 'are, each independently of each other, an alkyl group with 1 to 6 carbon atoms. The arrow in the Formula is a conventional representation of a semipolar link. Preferred amine oxides are those in which the group Primary alkyl has a linear chain in at least most of the molecules, usually at least 70% and preferably in at least 90% of the molecule, and amine oxides Especially preferred are those in which R contains from 10 to 18 carbons and R 'and R' 'are both methyl. Examples of oxides of Preferred amine are the oxide of N-hexyldimethylamine oxide N-octyldimethylamine oxide N-decyldimethylamine oxide N-dodecyldimethylamine oxide N-tetradecyldimethylamine oxide N-hexadecyldimethylamine oxide N-octadecyldimethylamine oxide N-eicosyldimethylamine oxide N-docosyldimethylamine oxide N-tetracosyldimethylamine, the corresponding amine oxides in which one or both methyl groups are substituted with ethyl or 2-hydroxyethyl groups, and mixtures thereof. The most preferred amine oxide for use in the present invention is the oxide of N-decyldimethylamine.

Other non-ionic surfactants for the purpose of invention are phosphine or sulfoxide surfactants of formula:

R \ R '\ R' '\ A \ rightarrow OR

where A is a phosphorus atom or sulfur, R is a primary alkyl group containing from 6 to 24 carbons and preferably 10 to 18 carbons, and in which R 'and R '' each is selected, independently of each other, from among methyl, ethyl and 2-hydroxyethyl. The arrow in the formula is a conventional representation of a link semipolar

Detergents suitable for use herein invention comprise betaine and betaine type detergents where the molecule contains both groups contains both groups basic and acids that form an internal salt contributing to the molecule both cationic and anionic groups in a wide range of values pH Some common examples of these detergents are described in patents US-2,082,275, US-2,702,279 and US-2,255,082. The preferred hybrid ion detergent compounds have the formula:

2

where R1 is an alkyl radical which has 8 to 22 carbon atoms, R2 and R3 contain 1 to 3 carbon atoms, R4 is an alkylene chain containing 1 to 3 carbon atoms, X is selected from the group consisting of hydrogen and a hydroxyl radical, and is selected from the group that consists of carboxyl and sulfonyl radicals and where the sum of the radicals R1, R2 and R3 is from 14 to 24 atoms of carbon.

Amphoteric and ampholytic detergents that they can be cationic or anionic depending on the pH of the system are represented by detergents such as dodecilbeta-alanine, N-alkyltaurines, such as the one prepared by the reaction of dodecylamine with sodium isethionate according to Patent teachings US-2,658,072, acids N-alkyl aspartic higher, such as produced according to the teachings of the patent US 2,438,091 and products sold under the name "Miranol" and described in the patent US 2,528,378.

Additional synthetic detergents and listings of Your commercial sources can be found at McCutcheon's Detergents and Emulsifiers, American Ed. 1980, incorporated as a reference herein.

The cationic surfactants suitable for use in the compositions of the present invention are those that They have a long chain hydrocarbyl group. Examples of cationic surfactants of this type include surfactants of ammonium such as alkyltrimethylammonium halides and surfactants with the formula:

[R 2 (OR 3) y] [R 4 (OR 3) y] 2 R 5 N + X -

where R2 is a group alkyl or alkylbenzyl having 8 to 18 carbon atoms in the alkyl chain, each R3 is selected from the group consisting in -CH2CH2-, -CH2CH (CH3) -, -CH 2 CH 2 CH 2 -, and mixtures thereof; every R 4 is selected from the group consisting of alkyl structures C 1 -C 4, benzyl ring formed by the union of two R 4 groups and hydrogen when y is not 0; R 5 is the same as R 4 or is an alkyl chain where the number Total carbon atoms of R2 plus R5 is not more than 18; each y is from 0 to 10 and the sum of the values and is from 0 to 15; and X is any anion compatible.

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A suitable quaternary ammonium surfactant For the present invention it has the formula (I):

3

where

R1 is a (C6-C10) alkyl of short chain

and is 2-4, preferably 3.

where R2 is H or an alkyl C1-C3,

where x is 0-4, preferably 0-2, most preferably 0,

whereby R3, R4 and R5 are the same or different and can be an alkyl chain (C1-C3) or alkoxylated alkyl of formula II,

where X - is a counterion, preferably a halide, for example chloride, or methylsulfate.

4

R6 is C 1 -C 4 and z is 1 or 2.

Quaternary ammonium surfactants Preferred are those defined by formula I where

R 1 is C 8, C 10 or mixtures of the themselves, x = o,

R 3, R 4, R 5 = CH 3.

Very preferred cationic surfactants are those water-soluble quaternary ammonium compounds that have the formula:

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

in where

R1 is alkyl C_ {8} -C_ {16}, each of R2, R3 and R4 is independently C 1 -C 4 alkyl, benzyl, and - (C 2 H 40) x H where x has a value of 2 to 5 and X is a union. No more than one of the R 2, R 3 or R 4 It should be benzyl.

The preferred alkyl chain length for R 1 is C 12 -C 15, particularly when the alkyl group is a mixture of chain lengths derived from coconut or palm kernel oil or is derived by synthesis of accumulation of olefins or synthesis of OXO alcohols. Groups preferred for R 2 R 3 and R 4 are methyl and the anion X is you can select from halide, methosulfate, acetate and phosphate.

Examples of quaternary ammonium compounds suitable with the formulas (i) of use in the present invention They are:

chloride or coconut trimethylammonium bromide;

chloride decyltriethylammonium;

chloride or trimethyl C 12-15 ammonium bromide;

methylsulfate myristyltrimethylammonium;

chloride or lauryl dimethylbenzylammonium bromide;

chloride or lauryl dimethyl (ethenoxy) 4 ammonium bromide;

choline esters (compounds of formula (i) wherein R 1 is alkyl CH 2 -CH 2 -

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

-C-C 12-14 and R 2 R 3 R 4 are methyl) di-alkylimidazolines.

Other cationic surfactants useful in the The present invention is also described in the patent US 4,228,044, issued October 14, 1980 to Change, and in the European patent application EP 000.224.

Stabilizing agent

An essential component of the invention is a stabilizing agent that is a radical inactivator or a mixture thereof alone or together with a chelating agent or mixture of the same. Naturally, for the purposes of the invention, the stabilizing agents have to be stable in the bleach based on hypohalite.

Radical inactivators suitable for use in the present invention include radical inactivators aromatics comprising a ring system of 3 to 20 atoms of carbon, preferably from 3 to 18 and more preferably from 5 to 14 and that have a group of double bonds that comprise a total of 4n + 2 electrons, where n is an integer from 0 to 4, preferably from 1 to 3. Indeed, said inactivators of aromatic radicals include benzene derivatives, derivatives of naphthalene, anulene derivatives, cyclopentadiene derivatives, cyclopropene derivatives and the like, especially carboxylates of aryl and / or aryl sulfonates.

Radical inactivators (carboxylates of aryl, aryl sulfonate and derivatives thereof) for use in the The present invention has one of the following formulas:

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5

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7

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8

where each X, Y, and Z are -H, -COO-M +, -Cl, -Br, -SO 3 -M +, -NO 2, -OCH 3, or groups C 1 to C 10 alkyl primary or secondary and M is H or a alkali metal, or mixtures thereof. The examples of these components include pyromellitic acid, that is, when X, Y and Z are -COO-H +; hemimelitic acid and the trimellitic acid, that is, when X and Y are -COO-H + and Z is H. The inactivators of Preferred radicals for use in the present invention are acidic. phthalic; sulfophthalic acid; other monosubstituted phthalic acids; disubstituted benzoic acids; alkylbenzoic acids, chlorobenzoic, bromobenzoic, sulfobenzoic, nitrobenzoic or alkoxybenzoic, that is, where Y and Z are -H and X are alkyl groups C 1 to C 10 primary and secondary, -Cl, -Br, -SO 3 -H +, -NO 2 or -OCH 3 (acid anisic) respectively and substituted sulfonic acids. Examples highly preferred radical scavengers useful in the Present invention are benzoic acid, methoxybenzoic acid, acid toluic, 4-toluenesulfonic acid, acid 3-nitrobenzoic acid 2 n-octylbenzoic acid, 2 n-octyl acid sulfonic acid, anisic acid or mixtures thereof. Most preferred  in the present invention are benzoic acid, the acid methoxybenzoic acid 3-nitrobenzoic.

All described radical inactivators they are the acid form of the species, that is, that M is H. This provided that the present invention also covers derivatives in salt form of these species, that is, M is an alkali metal, preferably sodium or potassium. In fact, since the pH of the compositions of the present invention are in the range alkaline, the radical inactivators of the present invention They are found mainly as the ionized salt in the composition aqueous of the present invention. The anhydrous derivatives of certain species described above herein they can also be used in the present invention, e.g. eg the pyromellitic dianhydride, phthalic anhydride, anhydride sulfophthalic and the like.

Chelating agents suitable for use in The present invention may be any of those known to those skilled in the art, such as those selected from the group that comprises phosphonate type chelating agents, chelating agents of phosphate type, substituted aromatic type chelating agents polyfunctionally, acids ethylenediamino-N, N'-disuccinics, or mixtures thereof.

Suitable phosphonate type chelating agents of use in the present invention may include ethane 1-hydroxy diphosphonates (HEDP) of alkali metals, alkyl poly (alkylene phosphonate), as well as compounds of aminophosphonate, including acid amino-aminotri (methylene phosphonic) (ATMP), nitrile-trimethylene phosphonates (NTP), ethylenediamine tetra methylene phosphonates, and diethylene triamino pentamethylene phosphonates (DTPMP). Phosphonate type compounds may be present in its acid form or as salts of different cations in some or all its acid functions. Phosphonate type chelating agents Preferred for use in the present invention are diethylene triamino pentamethylene phosphonate  (DTPMP) and ethane 1-hydroxy diphosphonate (HEDP). These phosphonate type chelating agents are marketed by Monsanto with the trade name DEQUEST®.

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Suitable phosphate chelating agents they are as follows: phosphonic acid can condense on the reaction

9

The reaction can be repeated with any of the reactive OH groups and phosphate ingredients are obtained which They may be:

-

linear or branched polyphosphates of structure

10

-

when R is M or

eleven

-

when M is a counterion, preferably of an alkali metal;

-

when O? N + m <500 (if n + m = 0, the compound is acidic phosphonic)

-

cyclic polyphosphates (also called metaphosphates), of the structure

12

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-

when R is M or

13

-

yes R is

14

the compound of phosphate contains cycles and branched chain and can be called ultraphosphate).

-

in where M is a counterion, preferably an alkali metal

-

in where O \ n n + m <500.

All these phosphate ingredients are suitable for use in the present invention, and the linear phosphate ingredients (i.e., R is M) where n is 1 (pyrophosphate) and n is 2 (tripolyphosphate [STPP]), with maximum preference where n is 2. The most common commercialized form of These phosphates is where M is sodium.

Phytic acid, which is a chelating agent particularly suitable for use in the present invention, it is a hexa-phosphoric acid found in seeds of many cereals, usually in the form of salt Insoluble calcium-magnesium. Can also be obtained from macerated corn solution. Quality phytic acid Commercial is marketed by J. T. Baker Co., p. eg, as 40% aqueous solution. It is intended that the present invention cover the acidic form of phytic acid as well as its derivatives in form of alkali metal salts, particularly sodium or potassium. Sodium phytate is marketed by Jonas Chemical Co (Brooklyn, N.Y.). In fact, since the characteristic pH of the compositions of the present invention is in the alkaline range, the Phytic acid component is found in liquid compositions of the present invention primarily in the form of ionized salt, even when added in its acidic form. The mixtures of said Phytic acid salts are also covered by the invention.

Aromatic chelating agents polyfunctionally substituted may also be useful in the present invention See US Patent 3,812,044, granted on May 21, 1974 to Connor et al. The compounds Preferred of this type in acidic form are dihydroxydisulfobenzenes, such as the 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelating agent for its use in the present invention is acid ethylene diamino-N, N'-disuccinic,  or salts of alkali metals, or alkaline earth metals, of ammonium or of substituted ammonium or mixtures thereof. Acids ethylene diamino-N, N'-disuccinics, especially isomers (S, S) have been described extensively in the US Patent 4,704,233, issued November 3, 1987 to Hartman and Perkins. Acids ethylenediamine-N, N'-disuccinics are marketed, for example, under the trade name ssEDDS®por Palmer Research Laboratories.

Particularly preferred chelating agents of use in the present invention are chelating agents of type phosphate such as sodium tripolyphosphate, sodium pyrophosphate, phytic acid and mixtures thereof. Indeed, it has been discovered that when these chelating agents are present in the bleaching compositions used to bleach tissues of the The present invention also contributes to the excellent ability to stain removal provided by these compositions during The aging of the compositions.

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Typically, the compositions used in the The present invention comprises from 0.01% to 10%, by weight, of the total composition of a stabilizing agent, or mixtures of the same, preferably from 0.01% to 8%, by weight, more preferably from 0.1% to 5%, and most preferably from 0.2% to 3%.

The present invention is based on the finding that the addition of a stabilizing agent, preferably a radical inactivator alone or together with a chelating agent, at a liquid bleaching composition comprising a bleach of hypohalite type and a surfactant results in a capacity Effective stain removal of the aged composition when used in any laundry application.

For stain removal ability "effective" means that the ability to eliminate stains provided on bleached tissues with a aged composition according to the present invention is better in comparison with stain removal ability provided by the same composition, but without an agent stabilizer as mentioned above herein memory in the same state of aging. In other words, the This invention allows to maintain an excellent ability to stain removal after periods of time prolonged storage compared to the same composition, but without said stabilizing agent.

The ability to remove stains during the aging of the composition in the bleaching process according to the present invention can be measured by comparison with it bleaching process where the composition used is exempt of said stabilizing agent (eg after 3 months of storage at room temperature [approximately 25 ° C] from manufacture of these compositions).

Stain removal ability can be determine by visual score on a scale of for example four points This can be done on stained items. commercials (e.g. from WFK Germany or EMPA Switzerland) or in real stained items.

pH

The pH of the liquid compositions used according to the present invention, as is, typically 12 to 14 measured at 25 ° C. Liquid compositions for use according to bleaching processes of the invention have a pH of 7.5 to 13, preferably from 8 to 12, more preferably from 8.5 to 11.5, when They are diluted in 1 to 500 times their water weight. In this interval of alkalinity you get the stability and optimal performance of hypohalite, as well as the whiteness of the tissue and / or the safety of the same. The pH range is adequately provided by the hypohalite bleach mentioned above in the present memory and optionally the pH buffer component when present, which are alkalis. However, in addition to these components can optionally be used a source of strong alkalinity

Suitable sources of strong alkalinity are Caustic alkalis such as sodium hydroxide, potassium hydroxide and / or lithium hydroxide and / or alkali metal oxides such as sodium oxide and / or potassium oxide. A source of alkalinity strong preferred is a caustic alkali, more preferably sodium hydroxide and / or potassium hydroxide. Concentrations typical of such caustic alkalis, when present, are of 0.1% to 1.5% by weight, preferably 0.5% to 1.5% by weight of the composition.

Optional pH buffer components

In the compositions used according to the present invention, the presence of a pH buffer component It is not mandatory, but it is very preferred.

The pH buffer component ensures that the The pH of the composition is buffered at a pH value of 7.5 to 13, preferably from 8 to 12 and more preferably from 8.5 to 11.5, after diluting the composition 1 to 500 times its weight in water.

The appropriate pH buffer components for use in the present invention are selected from the group that It consists of alkali metal salts such as carbonates, polycarbonates, sesquicarbonates, silicates, polysilicates, salts of boron, phosphates, stannates, aluminates and mixtures thereof. Preferred alkali metal salts for use herein invention are those of sodium and potassium.

Boron salts or mixtures thereof suitable for use in the present invention include borates and alkali metal alkylborates or mixtures thereof. Examples of boron salts include boric acid, alkali metal salts of metaborate, tetraborate, octoborate, pentaborate, dodecaboro, boron trifluoride and alkylborate containing 1 to 12 atoms carbon, preferably 1 to 4. Suitable alkylborates include methylborate, ethylborate and propylborate. Boron salts Particularly preferred in the present invention are the alkali metal metaborates, such as sodium metaborate or potassium metaborate, and alkali metal borates such as sodium borate, or mixtures thereof. Boron salts as Sodium Metaborate and Sodium Tetraborate are marketed by Borax and Societa Chimica Larderello with the name of metaborate of sodium and Borax®.

PH buffer components particularly preferred are selected from the group consisting of sodium carbonate, sodium silicate, sodium borate, sodium metaborate and mixtures thereof.

The raw materials involved in the Preparation of hypohalite based bleaches contain usually secondary products, e.g. eg calcium carbonate in an amount of up to 0.4% by weight of by-product contained in the hypohalite composition. However, in this amount the by-product will not present the defined buffering action previously.

Liquid bleaching compositions for use in the present invention they will typically contain an amount of pH buffer component from 0.5% to 9%, by weight, preferably from 0.5% to 5%, by weight, and more preferably in an amount of 0.6% to 3%, by weight of the composition.

The compositions according to the invention can comprise other optional components such as organic alkalis  or inorganic, detergency builders, thickeners, polymers, pigments, dyes, solvents, perfumes, brighteners and mixtures thereof.

Optional brighteners

Any invention can be used in the present invention brightener known by those skilled in the art including both hydrophobic and hydrophilic brighteners and mixtures thereof. Naturally, for purposes of the invention, the brightener must be stable against bleach type hypohalite The presence of brighteners may be desirable. in the present invention to enhance the bleaching capacity of the compositions of the present invention.

Brighteners are compounds that have the ability to fluoresce when absorbing wavelengths corresponding to the ultraviolet and send the visible light. The brighteners, also called bleaching agents Fluorescent (FWA), have been widely described in the art as, for example, in EP-A-0 265 041, EP-A-0 322 564, EP-A-0 317 979 or "Fluorescent whitening agents "by A.K. Sarkar, published by MERROW, particularly pages 71-72.

Commercial optical brighteners that can be useful in the present invention can be classified in subgroups that include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinacyanines, dibenzothiophene-5,5-dioxide, azoles, heterocycles with 5 and 6 member rings and other agents miscellaneous. Examples of such brighteners are described in "The Production and Application of Fluorescent Brightening Agents ", M. Zahradnik, published by John Wiley & Sons, New York (1982). Other optical brighteners that can be used in The present invention include naphthylimide, benzoxazole, benzofuran,  benzimidazole and any mixture thereof.

Examples of optical brighteners that are useful in the present compositions are those identified in US Patent 4,790,856. These brighteners include the PHORWHITE® series of brighteners from Verona. Others brighteners described in this reference include: Tinopal-UNPA®, Tinopal CBS® and Tinopal 5BM® marketed by Ciba-Geigy; Artic White CC® and Artic White CWD®; the 2- (4-styrene-phenyl) -2H-naphtho [1,2-d] triazoles; 4,4'-bis (1,2,3-triazol-2-yl) -stilbenes;  4,4'-bis (stretch) bisphenyls; and the amino coumarins

Specific examples of brighteners useful in the present invention include 4-methyl-7-diethyl-amino coumarin; 1,2-bis (-benzimidazol-2-yl) ethylene; 1,3-diphenyl-pyrazolines; 2,5-bis (benzoxazol-2-yl) thiophene; 2-styrene-naphtho- [1,2-d] oxazole; 2- (stilben-4-yl) -2H-naphtho [1,2-d] triazole, 3-phenyl-7- (isoindolinyl) coumarin; 3-methyl-7- (isoindolinyl) coumarin; 3-chloro-7- (isoindolinyl) coumarin; 4- (isoindolinyl) -4'-methyl ethylbeno; 4- (isoindolinyl) -4'-methoxystilbene; 4- (isoindoly-
nil) sodium -4'-stilbenesulfonate; 4- (isoindolinyl) -4'-phenyl ethylbeno; 4- (isoindolinyl) -3-methoxy-4'-methyl ethylbeno; 4- (2-Chloroisoindolinyl) -4 '- (2-methylisoindolinyl) -2,2'-stilbendiisosulfonic acid; Disodium 4,4'-diisoindolinyl-2,2'-stilbene disulfonate; 4,4'-diisoindolinyl-2,2'-stilbene disulfonamide; 4,4 '- (7,8-dichloro-1-isoindolinyl) -2,2-stilbene disulphonate disodium; 4,4 '- (7-chloro-1-isoindolinyl) -2,2-stilbene disulfonate disodium; 4,4 '- (6-isopropoxy-1-isoindolinyl) -2,2-stilbene disulphonate disodium; 4,4 '- (7,8-diisopropyl-1-isoindolinyl) -2,2-stilbene disulphonate disodium; 4,4 '- (7-Butoxy-1-isoindolinyl) -2,2-stilbene disulphonate disodium; 4,4 '- (6-trifluoromethyl-1-isoindolinyl) -2,2-stilbene disulphonate disodium; 4,4 '- [6- (1,4,7-trioxanonyl) -1-isoindolinyl)] - 2,2-stylobenzene disulfonate disodium; 4,4 '- (7-methoxymethyl-1-isoindolinyl) -2,2-stilbene disulphonate disodium; 4,4 '- (6-phenyl-1-isoindolinyl) -2,2-stilbene disulfonate disodium; 4,4 '- (6-naphthyl-1-isoindolinyl) -2,2-stilbene disulfonate; 4,4 '- (6-methylsulfonyl-1-isoindolinyl) -2,2-stilbene disulfonate disodium; 4,4 '- (7-cyano-1-isoindolinyl) -2,2-stilbene disulfonate disodium; and 4,4 '- [7- (1,2,3-trihydroxypropyl) -1-isoindolinyl)] -2,2-stilbene disodium disodium; Disodium 4-isoindolinyl-4'-ethoxy-2,2'-stilbene disulfonate; Disodium 4-isoindolinyl-4'-methoxy-2,2'-stilbene disulfonate; Disodium 4-isoindolinyl-4'-ethoxy-2,2'-stilbene disulfonamide; Disodium 4-isoindolinyl-4'-methyl-2,2'-stilbene disulfonamide; 4,4'-bis (4-phenyl-2H-1,2,3-triazol-2-yl) -2,2'-stilbendisulfonic acid and mixtures thereof. For more examples of brighteners useful in the present invention, see patents US-3,646,015, US-3,346,502 and US-3,393,153.

Indeed, one of the salts with functionality acid-derived equivalent 4,4'-bis (4-phenyl-2H-1,2,3-triazol-2-yl) -2,2'-stilbendisulfonic acid,  namely its sodium salt, is marketed by Mobay Chemical Corporation, a subsidiary of Bayer AG, with the name Phorwite® CAN. The amino salt is marketed by Molay under the name Phorwite® CL solution. Potassium salt is marketed under the name of Phorwite® BHC 766.

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Specific examples of optical brighteners hydrophilic useful in the present invention are those that have the structural formula:

fifteen

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-methyl-amino, morpholino, chlorine and amino; and M is a salt-forming cation, such 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-triacin-2-yl) amino] -2,2'-stilbenedisulfonic acid  and the disodium salt. This particular type of brightener is marketed under the trade name Tinopal UNPA-GX by Ciba-Geigy Corporation. Tinopal UNPA-GX is the hydrophilic optical brightener preferred useful in detergent compositions herein invention.

When, in the above formula, R_ {1} is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is salt acid disodium 4,4'-bis [(4-anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triacin-2-yl) amino] -2,2'-stilbenedisulfonic acid.  This type of brightener in particular is marketed with the name Tinopal 5BM-GX by Ciba-Geigy Corporation.

When, in the previous formula R_ {1} is anilino, R2 is morpholino and M is a cation such as sodium, the brightener is the acidic sodium salt 4,4'-bis [(4-anilino-6-morfilino-s-triacín-2-yl) amino] -2,2'-stilbenedisulfonic acid.  This type of brightener in particular is marketed with the Trade name Tinopal AMS-GX by Ciba-Geigy Corporation.

Other derivatives of stilbene acid 2,2'-disulfonic substituted also include 4-4'-bis (2-2 ' styryl sulfonate) biphenyl, marketed by Ciba-Geigy with the trade name Brightener 49® u other hydrophilic brighteners such as Brightener 3® or Brightener 47®, also marketed by Ciba-Geigy.

Specific examples of brighteners hydrophobes useful in the present invention include derivatives of polycyclic oxazol such as derivatives benzo-oxazole, or mixtures thereof, being Especially preferred herein are derivatives of benzo-oxazole. An example of a brightener from this type is benzoxazol-2,2 '- (thiophenyldil) bis which has the following formula C18H10N2O2S, marketed by Ciba-Geigy with the trade name Tinopal SOP®. This brightener is practically insoluble in water, that is, It has a solubility that is less than 1 gram per liter. Other example of such a brightener is bis (sulfobenzofuranyl) biphenyl, marketed by Ciba-Geigy with the trade name Tinopal PLC®.

By "hydrophobic brighteners", it understand herein any brightener whose Water solubility is less than 10 grams per liter at 25 ° C. By "solubility" of a given compound, is understood herein memory the amount of said compound dissolved in deionized water at 25 ° C. Therefore, a compound that has a solubility that is less than 10 grams per liter means that at least 10 grams of said given compound are incorporated into deionized water at 25 ° C, said compound dissolves completely in said water, is that is, a transparent and stable solution is obtained. In others words, the incorporation of 10 grams per liter or more of said compound given to water will result in precipitation of said compound in said medium. Therefore, by "brighteners hydrophilic "is understood herein as any brightener whose water solubility is greater than or equal to 10 grams per liter at 25 ° C.

Typically the compositions used according to the present invention comprise up to 1.0%, by weight of the total composition of a brightener or a mixture thereof, preferably from 0.005% to 0.5%, more preferably from 0.005% to 0.3% and most preferably from 0.008% to 0.1%.

When hydrophobic brighteners are present in the compositions used according to the present invention these may be dissolved or suspended in the compositions containing hypohalite bleach of the present invention This solution of the brighteners can achieved for example by a surfactant or a mixture of the Same as described below. For this purpose you can use various surfactants such as alkylaryl C8-C20 sulfonates as described for example in US 4,623,476 or amine oxides as those described for example in the application EP-A-186386. Surfactants Preferred also called "auxiliary surfactants" for dissolving and / or suspending such a hydrophobic brightener are anionic surfactants including alkyl sulfates or alkylalkoxysulfates having 4 to 30 carbon atoms in the alkyl chain, or alkylethoxycarboxylates having 6 to 30 carbon atoms in the alkyl chain such as Akyposoft® 100 NV from Chemy or Sandosan LNCS from Sandoz. Alkylethoxy are preferred C12-C14 sulfates. Said auxiliary surfactants of The present invention should be used in quantities required for dissolve the hydrophobic brightener that needs it.

In general, when a surfactant is used auxiliary, the liquid compositions for use in the present invention  they are prepared in a process where the hydrophobic brightener and the auxiliary surfactant are mixed first to form a premix, the premix is then mixed with the rest of the composition that has been prepared separately.

Alternatively the hydrophobic brightener it can be suspended by a specific suspending agent, such as polymers and silicates in the form of colloidal particles. Any polymer known to those skilled in the art as those have suspending properties are suitable for use in the present invention including those described for example in the application EP-A- 206718.

Optional polymers

An optional component of the compositions of The present invention is a polymer. It has been found, surprisingly, that this polymer also reduces the color yellowing of the tissues treated with it, that is, it improves the Whiteness and tissue safety. Naturally, for the purpose of invention the polymer has to be stable against bleach of hypohalite.

Polymers suitable for use in the The present invention are polymers comprising monomer units  selected from the group consisting of carboxylic acids unsaturated, polycarboxylic acids, sulfonic acids, acids phosphonic and mixtures thereof. The copolymerization of the previous monomer units with each other or with other comonomers such as styrene sulfonic acid.

Preferred examples of such polymers are the polymers and copolymers of monomer units selected from group consisting of acrylic acid, maleic acid, acid vinyl sulfonic and mixtures thereof. They are also suitable for their use in the present invention polymers and copolymers previously mentioned modified to contain other groups functional as aminophosphonic and / or phosphonic units. The Most preferred polymers are selected from the group consisting of polyacrylate polymers, acrylic acid and acid copolymers maleic, copolymers of styrene sulfonic acid and maleic acid and mixtures thereof, preferably modified with groups aminophosphonic and / or phosphonic.

The molecular weight of these polymers and copolymers is preferably less than 100,000, with maximum preference between 500 and 50,000. The most polymers and copolymers suitable for use in the present invention will be soluble in a amount of up to 0.1% by weight, in an aqueous composition that It comprises 5% by weight of sodium hypochlorite with its pH adjusted to 13 with sodium hydroxide.

Polymers suitable for use in the present invention and commercially available are those of BF Good-Rite® brand name polyacrylate Goodrich, Acrysol® by Rohm & Haas, Sokalan® by BASF, Norasol® by Norso Haas They are also suitable for use herein invention the copolymers of styrene sulfonic acid and acid maleic, marketed under the trade name Versaflex® of National Starch as Versaflex 157, as well as terpolymers Acumer® by Rohm and Haas, particularly the Acumer® 3100. They are preferred commercial polymers polyacrylate polymers, especially Norasol® polyacrylate polymers, and they are more preferred the Norasol® 410N polyacrylate polymer (PM 10,000) and the polyacrylate polymer modified with phosphonic groups Norasol® 440N (PM 4000) and its corresponding acidic form Norasol® QR 784 (PM 4000).

A preferred polymer for use herein invention is a polyacrylate polymer modified with groups Phosphonics sold under the trade name Norasol® 440N (PM 4000), and its corresponding acidic form Norasol® QR 784 (PM 4000), by Norso-Haas.

They can also be used in the present invention. polymer blends as described herein memory.

The polymers in the present invention are preferably found in low amounts, that is, in amounts up to 10% by weight, preferably up to 1%, more preferably from 0.001% to 0.5%, by weight, with maximum preference of 0.005% to 0.2%, by weight, of the composition liquid

Examples

The invention is illustrated by the following examples, which do not exclude other possible ones. The percentages are Express by weight, unless otherwise indicated.

16

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18

19

twenty

Tinopal PLC® is bis (sulfobencenofuranyl) biphenyl marketed by Ciba Geigy.

Na C12-C14 E3S is an alkyl C12-C14 (ethoxy) 3 sulfate marketed by Rhone Poulenc and Albright & Wilson.

Benzoic acid is marketed by Elf Atochem, Enichem, or Albright & Wilson.

Methoxybenzoate is marketed by Aldrich

Norasol 440N® is a polyacrylate polymer modified with phosphonic groups (PM 4000) from Norso Haas.

Betaine ** is lauryl dimethyl aminobetaine marketed by Albright & Wilson.

The non-ionic surfactant *** is Plurafac® marketed by BASF.

These compositions provide excellent ability to remove stains on various stains including greasy spots, enzymatic spots and bleachable spots when used in a laundry application in its pure form or diluted, e.g. ex. 200 times its water weight, after periods of extended storage time, e.g. eg, after 3 months of storage at room temperature (25 ° C) since they have been prepared

Claims (14)

1. A tissue bleaching process that It comprises the stages of:

-

put on contacting said tissues with a liquid bleaching composition comprising a hypohalite bleach, from 0.1% to 20%, in weight, of the total composition of a surfactant and from 0.001% to 10%, by weight, of a stabilizing system that is an inactivator of radicals or a mixture thereof, alone or together with an agent chelator or a mixture thereof, in its diluted form or pure,

-

leave said tissues in contact with said bleaching composition for a period of time sufficient to bleach said tissues,

-

to then rinse said tissues with water,

where said radical inactivator has one of the following formulas;

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twenty-one

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22

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2. 3

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24 where each X, Y, and Z are -H, -COO-M +, -Cl, -Br, -SO_ {-3} -M <+>, -NO_ {2}, -OCH_ {3}, or groups C 1 to C 10 alkyl primary and secondary and M is H or a alkali metal, or mixtures of same. 2. A bleaching process according to the claim 1, wherein the composition is diluted with water to a dilution level of up to 500 times its weight, preferably 5 200 times and more preferably 10 to 80 times. 3. A process according to any of the claims 1 or 2, wherein said fabrics are washed with a detergent composition comprising at least one agent surfactant before the step of contacting said tissues with the bleaching composition and / or at the stage where said tissues are contacted with the bleaching composition in diluted form and / or after the stage where said tissues are put in contact with the bleaching composition and before rinse stage and / or after the rinse stage. 4. A process according to any of the previous claims, wherein in said composition bleach said hypohalite bleach is a hypochlorite of the alkali metal sodium. 5. A process according to any one of the previous claims, wherein said hypohalite, based on active halide, of said bleaching composition, is present in an amount of 0.1% to 20%, by weight, preferably 0.25% to 8%, by weight, of the total liquid composition. 6. A process according to any of the previous claims, wherein said radical inactivator  it is phthalic acid; sulfophthalic acid; other phthalic acid monosubstituted; disubstituted benzoic acid; an acid alkylbenzoic, chlorobenzoic, bromobenzoic, sulfobenzoic, nitrobenzoic or alkoxybenzoic, that is, where Y and Z are -H and X is a primary and secondary C 1 to C 10 alkyl group, -Cl, -Br, -SO 3 -H +, -NO 2 or -OCH 3, respectively, or a substituted sulfonic acid, even more preferably it is benzoic acid, methoxybenzoic acid, acid toluic, 4-toluenesulfonic acid, 2 acid n-octylbenzoic acid 3-nitrobenzoic acid 2 n-octylsulfonic acid, anisic acid or mixtures of themselves and most preferably it is benzoic acid and / or acid methoxybenzoic and / or 3-nitrobenzoic acid. 7. A process according to any of the previous claims, wherein said chelating agent of said  bleaching composition is a phosphonate-type chelating agent, phosphate chelating agent, aromatic chelating agent polyfunctionally substituted acids ethylenediamino-N, N'-disuccinics, or mixtures thereof, more preferably sodium pyrophosphate, sodium tripolyphosphate and / or phytic acid. 8. A process according to any one of the previous claims, wherein in said composition the agent  stabilizer or the mixture thereof is present in an amount from 0.01% to 8%, by weight, more preferably from 0.1% to 5% and with maximum preference of 0.2% to 3%, by weight, of the liquid composition total. 9. A process according to any one of the previous claims, wherein in said composition the surfactant is an anionic surfactant, a non-surfactant ionic, a hybrid ion surfactant, an amphoteric surfactant and / or a cationic surfactant, preferably at least one anionic surfactant, more preferably at least one alkylbenzenesulfonate, alkylsulfate, alkylalkoxysulfate or alkylethoxycarboxylate with an alkyl chain containing from 4 to 24 carbon atoms, preferably from 8 to 18, with maximum preference of 8 to 16, or mixtures thereof alone or with another type of surfactant. 10. A process according to any one of the previous claims, wherein in said composition the surfactant or a mixture thereof is present in an amount from 0.1% to 15%, more preferably from 1% to 10% and with maximum preference of 2% to 8%, by weight, of the liquid composition total. 11. A process according to any of the previous claims, wherein said composition comprises in addition a pH buffer component typically in a amount from 0.5% to 9%, by weight of the total composition, preferably from 0.5% to 5%, by weight. 12. A process according to claim 11, in wherein said pH buffer component is selected from the group consisting of alkali metal carbonate salts, polycarbonates, sesquicarbonates, silicates, polysilicates, salts of boron, phosphates, stannates, aluminates, and mixtures of same. 13. A process according to any of the previous claims, wherein said composition comprises also a source of strong alkalinity. 14. A process according to any of the previous claims, wherein said composition comprises also an optional ingredient selected from the group consisting in detergency builders, thickeners, polymers, pigments, dyes, solvents, perfumes, brighteners and mixtures thereof.