SK115597A3 - Laundry pretreatment with peroxide bleaches containing chelators for iron, copper or manganese for reduced fabric damage - Google Patents

Abstract

The present invention relates to the use of a liquid composition comprising a peroxygen bleach and a compound chelating copper and/or iron and/or manganese, for pretreating fabrics before said fabrics are washed, whereby the loss of tensile strength in said fabrics is reduced. The present invention further encompasses a process for pretreating soiled fabrics as well as compositions suitable to be used in said process.

Description

Pre-treatment before washing with peroxide bleaches containing iron, copper or manganese chelators to reduce tissue damage.

Technical field

The present invention is concerned with soiled fabrics, compositions for pretreatment, and a pretreatment method suitable for treatment.

adjusting usage

BACKGROUND OF THE INVENTION In detail, peroxygen bleach additives have been laundry such as laundry pre-treatment detergents, such compositions which contain pre-laundry detergents for which tea, grass, are found; A long time before stains / dirt are oil, coffee, like. But the means

Compositions containing the compositions described in the compositions on or even compositions

It is known to use peroxide bleach to improve the removal of dried otherwise difficult to remove as mud / clay containing impurities, and the disadvantage of using such peroxide bleach is that, when pretreated when applied directly to fabrics and treated during washing, the fabrics may damage the fabrics.

It is an object of the present invention to provide improved protection of fabrics in pretreatment using means. which contain a peroxygen bleach, especially where said compositions remain in contact with the fabric for a long time before washing.

When pretreating fabrics with compositions containing a peroxygen bleach such as hydrogen peroxide, it has been found that the presence of metal ions such as copper and / or iron and / or manganese on the surface of the fabrics results in fabric damage resulting in loss of strength on the fabric fibers. in turn. It is believed that the presence of metal ions such as copper and / or iron and / or manganese on the surface of fabrics, in particular on cellulose fibers, catalyses the radical decomposition of peroxide bleaches such as hydrogen peroxide. Thus, a free radical reaction occurs on the surface of the fibers, resulting in a loss of tensile strength.

It is therefore necessary to pre-treat this surface radical reaction and thereby increase the resistance of the fabrics.

It has been found that this can be achieved by preparing a composition comprising a peroxide bleach further comprising a copper and / or iron and / or manganese chelating compound. More specifically, it has been found that the use of a compound for chelating copper and / or iron and / or manganese and preferably diethylenetriaminepentamethylene phosphoric acid (DTPMP), hydroxyethanediphosphoric acid (HEDP), ethylenediamine-N, N'dijuccinic acid (EDDS), methylglycine ditacetic acid diethylenetriaminepentaacetic acid (DTPA), propylenediaminetetraacetic acid (PDTA), 2-hydroxypyridine-noxide (HPNO) or ethylenedinitrilotetrakis (methylenephosphonic acid) N, N-dioxide in a fabric bleaching composition comprising a peroxygen bleaching agent.

An advantage associated with the use of a composition comprising a peroxygen bleach further comprising a copper and / or iron and / or manganese chelating compound in pretreatment prior to washing is that there will also be less deterioration of the color.

Another advantage of the present invention is the excellent bleaching of stains, including the removal of greasy stains.

A further advantage of the present invention is that the composition of the present invention gives excellent results as well for other uses such as laundry detergent, laundry additive or even hard surface cleaning.

In one embodiment of the present invention, it has also been found that the use of a chelating agent such as ethylenedinitriltetrakis (methylene phosphoric acid) N, N-dioxide, hydroxyethanediphosphoric acid (HEDP) and / or a chelating agent having two electron donor groups capable of occupying adjacent coordination sites by coordinating the metal ion sphere by complexing with metal ions in which each metal is complexed with 3 chelating agent molecules such as 2-hydroxypyridine-N-oxide, it makes it possible to prepare acidic liquid compositions suitable for pretreating fabrics that exhibit improved chemical stability and with longer storage time.

Compositions containing a peroxygen bleach have been extensively described in the art. EP-A-629691 describes emulsions of non-ionic surfactants containing a silicon compound which contain as an optional component hydrogen peroxide or a water-soluble source thereof and a chelating agent. The only chelating agent mentioned is S, S-ethylenediaminodisuccinic acid (see examples). Although the compositions of EP-A-629691 have been described for use in pretreatment, the use of compositions containing a peroxide bleach and further comprising a copper and / or iron and / or manganese chelating compound in pretreating fabrics where loss is reduced the tensile strength of these fabrics is not described anywhere.

EP-A-629690 discloses emulsions of non-ionic surfactants comprising a terephthalate-based polymer comprising as an optional component hydrogen peroxide or a water-soluble source thereof and a chelating agent. The only chelating agent mentioned is S, S-ethylenediaminodisuccinic acid (see examples). Although the compositions of EP-A-629690 have been described for use in pretreatment, the use of compositions containing a peroxygen bleach further comprising a copper and / or iron and / or manganese chelating compound in pretreating fabrics when the loss of strength is reduced tensile strength of these fabrics is not described anywhere.

EP-B-209228 discloses compositions comprising a peroxide source such as hydrogen peroxide and an aminopolyphosphonate chelating agent and a radical scavenger. In particular, diethylenepentamethylene phosphorous acid is disclosed. Likewise, EP-B-209228 discloses that compositions comprising hydrogen peroxide can be used as pre-staining agents. However, nowhere is it disclosed that compositions comprising a peroxygen bleach, which further comprise a copper and / or iron and / or manganese chelating compound, in pretreating fabrics, make it possible to reduce the tensile strength loss of the fabrics used.

SUMMARY OF THE INVENTION

Summary of the Invention

The present invention includes the use of a liquid composition comprising a peroxygen bleach further comprising a copper and / or iron and / or manganese chelating compound for pretreating soiled fabrics prior to washing, while reducing the tensile strength loss of the fabrics used.

The present invention further comprises a method of pretreating soiled fabrics with a composition comprising a peroxygen bleach further comprising a copper and / or iron and / or manganese chelating compound, the process comprising the steps of applying the composition in undiluted form to the fabric and allowing the composition to act that it does not dry on the fabric before washing.

The present invention further includes a liquid detergent composition comprising a peroxygen bleach, further comprising a copper and / or iron and / or manganese chelating compound, methyl glycine diacetic acid, propylenediaminetetraacetic acid, 2-hydroxypyridine-N-oxide, ethylenedinitriltetrakos (N), N-dioxide, hydroxyethanediphosphoric acid or mixtures thereof.

DETAILED DESCRIPTION OF THE INVENTION

In its broadest aspect, the present invention encompasses the use of a liquid composition comprising a peroxygen bleach further comprising a copper and / or iron and / or manganese chelating compound for pretreating soiled fabrics prior to washing, while reducing the tensile strength loss of the fabrics used.

The present invention is based on the fact that fabric damage resulting in reduced tensile strength is reduced when the compositions containing the peroxygen bleach and the copper and / or iron and / or manganese chelating compound of the present invention are used for pretreating soiled fabrics as compared to using the same means, but without the copper and / or iron and / or manganese chelating compound, for pretreating said fabrics.

By combining the pretreatment of soiled fabrics, it is meant that the liquid composition is applied undiluted to the soiled fabric and is allowed to act until the fabric is washed as described below by the pretreatment method of the soiled fabrics of the present invention.

In other words, the use of a composition comprising a peroxygen bleach further comprising a copper and / or iron and / or manganese chelating compound according to the present invention allows a noticeable reduction in the tensile strength loss caused by the presence of copper and / or iron and / or manganese on the fabric surface. even if the composition is left on the pretreated fabric for a long time before washing, e.g. 24 hours, and even if the fabric is contaminated with large amounts of copper and / or iron and / or manganese.

The tensile strength loss can be measured using the tensile strength method described in the Examples below. This method is based on measuring the tensile strength of a given fabric by stretching until it breaks. The force, expressed in kg, necessary to rupture the fabric is the tensile strength and can be measured with The Stress-Strain INSTRON Machine. By tensile strength loss is meant the difference when comparing the tensile strength of the fabric taken as a reference, i. a fabric which has not been pretreated and the tensile strength of the same fabric after the pretreatment of the present invention. A loss in tensile strength of zero means that no fabric damage has been observed.

An advantage of the present invention is that color damage is also reduced. The observed change in color and / or discoloration in pretreating soiled colored fabrics with a peroxygen bleach-containing composition further comprising a copper and / or iron and / or manganese chelating compound according to the present invention is less than the color change and / or or by discolouration observed using the same compositions, but without the copper and / or iron and / or manganese chelating compound, and even if the composition is allowed to act on the fabric for a longer period before washing. Thus, the present invention also encompasses the use of a liquid composition comprising a peroxygen bleach and a copper and / or iron and / or manganese chelating compound for pretreating soiled colored fabrics prior to washing, while reducing color damage to the fabric.

Reducing the loss of tensile strength and / or deterioration of fabric color achieved by the use of liquid compositions comprising a peroxygen bleach and a copper and / or iron chelating compound chelating compound will not reduce bleaching performance or stain removal performance.

The present invention further encompasses a method of pretreating soiled fabrics with a liquid composition comprising a peroxygen bleach and a copper and / or iron and / or manganese chelating compound, and comprising the steps of applying the composition in undiluted form to the fabric and allowing the composition to act the fabric does not dry before washing. The composition is applied to the fabric, usually 1 minute to 24 hours, preferably 1 minute to 1 hour, and more preferably 5 minutes to 30 minutes. Optionally, if the fabric is contaminated with dried spots / impurities that are otherwise relatively difficult to remove, the compositions of the present invention may be soaped and / or rubbed, for example, with a sponge or brush or more simply by soaping two pieces of fabric against each other. By washing is meant herein a simple rinse of fabrics with water or the fabrics can be washed by conventional means containing at least one surfactant, in a washing machine or simply by hand.

In its undiluted form, the compositions described herein are applied to the fabrics in the pretreatment without dilution, i. they are applied as described herein.

In the pretreatment process of the soiled fabrics of the present invention, the liquid process used should not be found that evaporation of the compositions that are allowed to dry on the fabrics, water, contributes to increasing the free radical concentration on the fabric surface and, consequently, the chain speed. reactions. It is also contemplated that an auto-oxidation reaction occurs when water is evaporated when the composition is allowed to dry on the fabric. This autooxidation reaction generates peroxide radicals that contribute to cellulose degradation. Therefore, not letting the liquid compositions of the present invention, upon pretreating the soiled fabrics of the present invention, dry on the fabric contributes to the improvement of the present invention, ie. reducing the tensile strength loss in pretreating fabrics with liquid compositions containing a peroxygen bleach.

An essential component of the compositions suitable for use in the present invention is a peroxygen bleach. A preferred peroxygen bleach is hydrogen peroxide or a water-soluble source thereof or a mixture thereof. Hydrogen peroxide is most preferred for use in the compositions of the present invention. A source of hydrogen peroxide herein is any compound that produces hydrogen peroxide upon contact with water.

Suitable water-soluble hydrogen peroxide sources for use in the present invention include perborates, persulfates include percarbonates such as monoperoxosulfate, perborates and peracids such as diperoxododecanoic acid (DPDA), magnesium perphthalic acid, and mixtures thereof.

Conventional compositions suitable for use in the present invention comprise from 0.5% to 20% by weight of the total composition of said peroxygen bleach, preferably from 2% to% by weight and most preferably from 3% to 10% by weight. The presence of a peroxygen bleach, preferably hydrogen peroxide, confers a great cleaning benefit, which is particularly noticeable during washing.

The second essential component of a composition suitable for use in the present invention is a copper and / or iron and / or manganese chelating compound. Conventional compositions suitable for use in the present invention comprise from 0.005% to 2% by weight of the total composition of the copper and / or iron and / or manganese chelating compound, or mixtures thereof, preferably 0.01% to 1% by weight and most preferably 0.01% to 1% by weight. 0.5% by weight.

Copper and / or iron and / or manganese chelating compounds may be any compound capable of binding copper and / or iron and / or manganese, and / or manganese from phosphonate

Such copper and / or iron chelating compounds may be selected from the group consisting of chelating agents, aminocarboxylate chelating agents, polyfunctionally substituted aromatic chelating agents or polycarboxylic acids pyridine and the like, or mixtures thereof.

The phosphonate chelating agents may be ethydronic acid, hydroxyethane diphosphoric acid (HEDP) and ethylenedinitriltetrakis (methylene phosphoric acid) -N, N-oxide as well as aminophosphonate aminoalkylene polyols (alkylene phosphonate), alkane metal salts of methanesulfonate such as methanediamine phosphonate nitri trimethylene phosphonates, and diethylene triamine pentamethylene phosphonates. The phosphonate compounds may be present or in the form of an acid or as salts of different cations on some or all of their acid groups. Phosphonate chelating agents are commercially available from Monsanto under the trade name DEQUEST ^R. Preferred phosphonate chelating agents for use in the present invention are diethylenetriamine pentamethylene phosphonates, hydroxyethane diphosphoric acid (HEDP) and ethylenedinitriltetrakis (methylene phosphoric) acid-N, N-oxide.

Hydroxyethanediphosphoric acid and ethylenedinitrile tetrakis (methylene phosphoric) acid-N, N-oxide have been found to be particularly resistant to protonation and oxidation. Accordingly, the hydroxyethane diphosphonic acid and ethylenedinitriltetrakis (methylene phosphoric acid) N, N-oxide are particularly suitable for use in acidic liquid compositions as the copper and / or iron and / or manganese chelating compound of the present invention, while improving fabric protection. Hydroxyethane diphosphonic acid and / or ethylenedinitriltetrakis (methylene phosphoric acid) N, N-oxide make it possible to prepare liquid acid compositions containing a peroxygen bleach with improved chemical stability compared to the same compositions without a chelating agent or compared to the same but with a different chelating agent with an agent, e.g. diethylenetriamine pentamethylene phosphoric acid, instead of the chelating agents mentioned. Thus, a further aspect of the present invention is the use of hydroxyethanediphosphoric acid and ethylenedinitriltetrakis (methylenephosphonic acid) N, N-oxide in an acidic liquid composition, wherein the chemical stability of said composition is enhanced, i. the bleach decomposition rate is reduced for a longer shelf life of the composition.

Polyfunctionally substituted aromatic chelating agents can also be used in the compositions of the present invention. See U.S. Pat. No. 3,812,044, issued May 21, 1974, to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelating agent for use in the present invention is ethylenediamine-N-N'-disuccinic acid or its alkali metal, alkaline earth metal, ammonia or substituted amine salts or mixtures thereof. Ethylenediamine-N-N'-disuccinic acid, in particular the (S, S) isomer has been described in detail in U.S. Patent 4,704,233, Nov. 3, 1987 to Hartman and Perkins. Ethylenediamine-N-N'-disuccinic acid is commercially available, for example, under the trade name ssEDDS ^R from Palmer Research Laboratories.

Amino carboxylates useful as compounds chelating copper and / or iron and / or manganese include ethylene diamine tetra acetates, dietyléntriamínpentoacetát (DTPA), N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine, triethylenetetraamine, ethanoldiglycines, propylene acid (PDTA) and methyl glycine diacetic acid (MGDA), both in in acid form and in the form of alkali metal salts, ammonia and substituted amines. Particularly suitable for use in the present invention are diethylenetriaminepentaacetic acid (DTPA), propylenediaminetetraacetic acid (PDTA), which is, for example, commercially available from BASF under the trade name Trilon FS ^R , and methylglycine diacetic acid (MGDA).

Suitable pyridine polycarboxylic acids useful in the present invention include dipicolinic acid. According to the present invention, it is preferred to use dipicolinic acid in admixture with another copper and / or iron and / or manganese chelating compound of the present invention. The dipicolinic acid is preferably added to the other chelating agents in the liquid compositions of the present invention to improve the chemical stability of the composition.

Other chelating agents suitable for use in the present invention as copper and / or iron and / or manganese chelating compounds include chelating agents having two electron donor groups capable of occupying adjacent coordination sites in the metal ion coordination sphere to form metal ion complexes, in wherein each metal is complexed with 3 chelating agent molecules, (stoichiometry chelating agent: metal, 3: 1). In other words, chelating agents by occupying the coordinating sphere of the metal ion will cause the ion to be catalytically inactive. Chelating agents have been found to be particularly resistant to protonation and / or oxidation. Thus, chelating agents are particularly suitable for use in acidic liquid compositions such as the copper and / or iron and / or manganese chelating compounds of the present invention, while fabric protection is improved.

- ii Chelating agents having two electron donor groups capable of occupying adjacent coordination sites in the metal ion coordination sphere make it possible to prepare acid compositions containing a peroxygen bleach with improved chemical stability compared to the same compositions without a chelating agent or compared to the same compositions but with another chelating agent, e.g. diethylenetriamine pentamethylene phosphoric acid, instead of the chelating agents mentioned. Another aspect of the present invention is the use of chelating agents having two electron donor groups capable of occupying adjacent coordination sites in the metal ion coordination sphere by forming complexes with metal ions in which each metal is complexed with 3 chelating agent molecules, in acidic liquid compositions which contain a peroxide bleach, whereby chemical stability is improved, i. the bleach decomposition rate is lower for longer storage periods of the composition.

Chelating agents having two electron donor groups capable of occupying adjacent coordination sites in the metal ion ion coordination sphere include chelating agents having an ionized carboxyl group directly adjacent to one of the following: an unionized carboxyl group, a hydroxyl group, an amino group, or an N-oxide group. Particularly suitable for use in the present invention are malonic acid, 2-hydroxypyridine-N-oxide or mixtures thereof.

2-hydroxypyridine-N-oxide is commercially available, for example, from Pyrion Chemie (Germany) under the trade name 2-hydroxypyridine-N-oxide.

According to the present invention, liquid compositions comprising a peroxygen bleach and, as a copper and / or iron and / or manganese chelating compound, propylenediaminetetraacetic acid (PDTA), methylglycine diamine acetic acid (MGDA), diethylenetriaminepentamethylene phosphonate (DTPMPosediamine), N'-disuccinic acid (EDDS), 2-hydroxypyridine-N-oxide (HPNO) and / or ethylenedinitriltetrakis (methylene phosphorous) N-N-oxide, apparently no tensile strength loss in fabrics pretreated by the method of the present invention, i.e. the fabric resistance is not reduced, even after prolonged contact of the fabrics with the compositions, e.g. 24 hours.

The present invention further encompasses liquid compositions comprising a peroxygen bleach and, as a copper and / or iron and / or manganese chelating compound, propylenediaminetetraacetic acid (PDTA), methylglycine di-acetic acid (MGDA), 2-hydroxypyridine-N-oxide, ethylenedinitriltetrinphosphine (methenylenitrile tetris). N, N-oxide, hydroxyethanediphosphoric acid or mixtures thereof. The following description of the compositions relates to the compositions of the present invention which are claimed in themselves, the compositions used according to the present invention for pretreating soiled fabrics, and the compositions applied to the fabrics by the fabric pretreatment method of the present invention.

The compositions of the present invention are aqueous liquid cleaners. These compositions have a pH of from 1 to 9, preferably from 2 to 6, and more preferably from 3 to 5. The pH of the compositions can be adjusted with organic or inorganic acids or bases.

The compositions of the present invention further comprise a wide variety of optional ingredients such as radical scavengers, surfactants, fillers, stabilizers, other chelating agents, soil suspending agents, color transfer agents, solvents, brighteners, fragrances, antioxidants, foam suppressors and dyes.

A preferred optional component of the compositions of the present invention is a radical scavenger or a mixture thereof. Suitable radical scavengers suitable for use in the present invention include the well-known substituted mono and dihydroxybenzenes and analogs thereof, alkyl and aryl carboxylates, and mixtures thereof. Preferred radical scavengers suitable for use in the present invention are butylhydroxytoluene, hydroquinone, ditert-butylhydroquinone, monotert-butylhydroquinone, tert-butylhydroxyanisole, benzoic acid, toluic acid, catechol, tert-butylcatechol, benzylamine, 1,1,3- tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, commercially available under the tradename Topanol CA ^R from ICI, as well as n-propyl gallate. In use, the radical scavengers are present in amounts of 0.001% to 2% by weight of the total composition, and preferably 0.001% to 0.05% by weight.

The compositions of the present invention further comprise any surfactant known to those skilled in the art, including nonionic, anionic, cationic, zwitterionic or amphoteric surfactants. The compositions of the present invention preferably comprise any nonionic surfactants or mixtures thereof described herein and / or any anionic surfactants or mixtures thereof described herein. Typically, the compositions of the present invention contain up to 50% by weight of the total surfactant composition or mixture thereof.

The compositions of the present invention further comprise a liquid hydrophobic bleach activator as a highly preferred component. A bleach activator refers to a compound that reacts with peroxide to form a peracid. The resulting peracid is an activated bleach. A hydrophobic bleach activator is an activator that is not substantially and permanently miscible with water. Typically, hydrophobic bleach activators have an HLB of less than 11. Suitable liquid hydrophobic bleach activators belong to the group of esters, amides, imides, or anhydrides. A particular class of bleach activators of interest in the present invention has been described in EP 624 154 and acetyltriethyl citrate (ATC) is particularly preferred. ATC has the additional advantage of being environmentally friendly because it degrades into citric acid and alcohol. ATC is also sufficiently stable against hydrolysis in the compositions of the present invention and is an effective bleach activator. Finally, it also has a good capacity as a filler. A mixture of liquid hydrophobic bleach activators may also be used in the present invention. The compositions of the present invention contain up to 20% by weight of the total bleach activator composition or mixtures thereof, preferably% to 10% by weight, even more preferably 3% to 7% by weight.

If the composition comprising a peroxygen bleach according to the present invention further comprises a liquid hydrophobic bleach activator, it is for reasons of formulations or in a form comprising a liquid microemulsion of a liquid matrix comprising a hydrophilic surfactant system which is a non-ionic surfactant. In an embodiment wherein the peroxide-containing compositions contain bleaching stability of a highly desirable aqueous surfactant emulsion, bleach activator or bleach activator of the peroxygen bleach consists of the anionic of the present invention, the bleach, according to the activator, and are hydrophobic hydrophobic from water, in

of the present invention further in the form of aqueous emulsions, emulsions comprising a peroxygen bleach comprise an emulsifying surfactant system of at least two different surfactants, i. at least a hydrophobic surfactant having an HLB of up to 9 and a hydrophilic surfactant having an HLB of greater than 10 to emulsify the liquid hydrophobic bleach activator. In order to form an emulsion, it must have two different surfactants with different HLBs (hydrophilic-lipophilic balance) and preferably the difference in HLB values of the two surfactants is at least 1, even more preferably 3. In other words, due to a suitable combination of at least two surfactants with different HLBs water-stable emulsions, i. emulsions which do not divide into two different layers on standing for at least two weeks at 50 ° C.

The emulsions of the present invention comprise 2% to 50% by weight of the total composition of a hydrophilic and hydrophobic surfactant, preferably 5% to 40% by weight, and even more preferably 8% to 30% by weight. The emulsions of the present invention comprise at least 0.1% by weight of the total hydrophobic surfactant emulsion or mixtures thereof, preferably at least 3% by weight, and even more preferably at least 5% by weight, and at least 0.1% by weight of the total hydrophilic surfactant emulsion or mixtures thereof, with preferably at least% by weight and even more preferably at least 6% by weight.

Hydrophobic nonionic surfactants and hydrophilic nonionic surfactants are preferred for use in the present invention. Hydrophobic nonionic surfactants suitable for use in the present invention have an HLB of up to 9, preferably less than 9, even more preferably less than 8, and hydrophilic surfactants have an HLB of greater than 10, preferably greater than 11 and even more preferably greater than 12. Hydrophobic nonionic surfactants suitable for use according to the present invention have excellent grease removal properties, i. have a solvent effect which contributes to the removal of hydrophobic impurities. The hydrophobic surfactants act as a carrier for hydrophobic brighteners to the fabric, allowing the brighteners to act near the fabric surface from the start of the wash.

Nonionic surfactants suitable for use in the present invention are alkoxylated fatty alcohols, preferably fatty alcohol ethoxylates and / or propoxylates. A wide variety of such alkoxylated fatty alcohols having very different HLB (hydrophilic-lipophilic) values are commercially available. The HLB values of such alkoxylated nonionic surfactants depend on the basis of the fatty alcohol chain length, the nature of the alkoxylation and the degree of alkoxylation. Hydrophilic nonionic surfactants have a high degree of alkoxylation and a short chain fatty alcohol, while hydrophobic surfactants have a low degree of alkoxylation and a long chain fatty alcohol. There are surfactant catalogs in which many surfactants, including nonionic ones, are listed along with their HLB value.

A suitable chemical process for the preparation of nonionic surfactants suitable for use in the present invention is by condensation of the corresponding alcohols with alkylene oxide in a suitable ratio. This procedure is well known to those skilled in the art and has been described in detail in the art. As an alternative, a large number of alkoxylated alcohols suitable for use in the present invention are commercially available from various suppliers.

Preferred hydrophobic nonionic surfactants suitable for use in the present invention are surfactants having HLB up to 9 and are compounds of formula (I):

R 0 - (C H) (C H 0) H

4 n 3 β m.

(I) wherein R is a C _e to C ₂₂ alkyl or C ₂ to C _g alkyl benzene and n + m is from 0.5 to 5 and n is from 0 to 5 amje0až5as preferably n + m is from 0.5 to 4, and m are from 0 to 4 . the preferred R chains for use herein are C _e to C ₂₂ alkyl groups. Suitable hydrophobic nonionic surfactants for use herein are Dobanol ^R 91-2.5 (HLB = 8.1; R is a mixture _of C ₉ to C _xi alkyl chains, n is

2.5 and m is 0), or Lutensol ^R T03 (HLB = 8; R is a mixture of C to C alkyl chains _{X 3,} n is 3amje0), or Tergitol ^R 25L3 (HLB = 7.7; R is a mixture of C to C alkyl, (HLB = R is a mixture of C _x2 Dobanol ^R 23-2 (HLB = 6.2;

is 0) or mixtures thereof. 23-2, Lutesol ^R available from BASF.

n is 3 and m is up to C 1 alkyl,

R is a mixture of C 12 Preferred ^J

0) or Dobanol ^R 23-3 n is 3 and m is 0)

C alkyl,

Dobanol ^R 23-3

The Dobanol ^R surfactants are ^R are commercially or n is or until they are

T03 or mixtures thereof.

SHELL. Lutesol surfactants and Tergitol ^R surfactants are commercially available from Others suitable according to am

Dobanol ^R commercially available from UNION CARBIDE. suitable for use with non-alkoxylated surfactants. An example

Preferred hydrophilic non-ionic uses of the present invention above 10 a are

C 1-6 alkyl for ¹ to 11 am

HLB to 11 and n is 0 m are 0 to hydrophobic nonionic surfactants of the present invention is Dobanol ^R 23 (HLB <3).

surfactants suitable are those having the compounds of formula (I) wherein R is C or (ζ to C _2a alkylbenzene) and n + m is 5 to 0 to 11 and preferably n + m is 6 to 10, at

10. Throughout the present invention they refer to the average degree of ethoxylation / propoxylation. The preferred R chains for use herein are the _C, to C ₂₂ alkyl groups. Suitable hydrophilic

17 non-ionic surfactants for use in the present invention are Dobanol ^R 23-6.5 (HLB = 11.9; R is a mixture of C 2 to C alkyl, n is 6.5 and m is 0), Dobanol ^R 25-7 (HLB = 12; R is a mixture of C to C alkyl chains, n is 7 and m is 0), Dobanol ^R 45-7 (HLB = 11.6; R is a mixture of C to C alkyl chains, n is 7 and m is 0), Dobanol ^R 91- 5 (HLB = 11.6; R is a mixture of Cg to Cxi alkyl chains, n is 5 and m is 0), Dobanol ^R 91-6 (HLB = 12.5; R is a mixture of CQ to C _xx alkyl chains, n is 6 and m is 0), Dobanol ^R 91-8 (HLB = 13, 7 R is a mixture of _Cg to C alkyl chains, n is

8 m is 0), Dobanol ^R 91-10 (HLB = 14.2; R is a mixture of _Cg to C _ix alkyl chains, n is 10 and m is 0), or mixtures thereof. Dobanol ^R 91-10, Dobanol ^R 45-7, Dobanol ^R 23-6.5 or mixtures thereof are preferred for use in the present invention. Dobanol ^R surfactants are commercially available from SHELL. In addition to the nonionic surfactants, other hydrophilic surfactants, such as the anionic surfactants described below, can be used in the emulsions of the present invention.

The emulsions of the present invention further comprise other surfactants which should not appreciably change the weighted average HLB values of the total emulsion.

In a preferred embodiment of the emulsion of the present invention wherein the emulsion comprises acetyl triethyl citrate as a bleach activator, a suitable nonionic surfactant system should comprise a hydrophobic nonionic surfactant with HLB, for example, 6 such as Dobanol ^R 23-2 and a hydrophilic nonionic surfactant such as Dobanol ^R 91- 10th Other suitable nonionic surfactant systems include, for example, Dobanol ^R 23-6.5 (HLB = 12) and Dobanol ^R 23 (HLB less than 6) or Dobanol ^R 45-7 (HLB = 11.6) and Lutensol ^R T03 (HLB) = 8).

In an embodiment of the present invention wherein the peroxygen bleach-containing compositions of the present invention comprise a bleach activator and are in the form of microemulsions, the peroxygen bleach-containing microemulsions of the present invention comprise a hydrophilic surfactant system comprising an anionic surfactant and a nonionic surfactant. A key factor for stabilizing the inclusion of a hydrophobic activator is that at least one of the surfactants must have an HLB value different from the hydrophobic activator. If all the surfactants had the same value

HLB as a hydrophobic activator, one continuous phase would be formed and thus the chemical stability of the bleach / bleach activator system would be reduced. Preferably, at least one of the surfactants has an HLB value that differs from the bleach activator by at least 1.0 HLB, preferably 2.0 HLB.

Suitable anionic include water-soluble (II): surfactants of the present invention salts or acids of the general formula

ROSO M to C wherein R is preferably C _1-10 hydroxyalkyl having alkyl C ₂₀ , even more preferably CH or potassium, ammonium and quaternary and dimethylpiperidinium derived from alkylamines and mixtures thereof, and the like). alkyl chains of C to (e.g., below 50 ° C) and at higher temperatures (e.g., above 50 ° C).

Other anionic surfactants suitable for the invention are water-soluble salts or formula (III):

cation, lithium) a cation (e.g., an ammonium (II) hydrocarbon, preferably an alkyl or a component consisting of a C to 10 alkyl or hydroxyalkyl and M is an alkali metal (e.g., sodium, cation to C)

X 2 18 eg. an alkali metal cation or an ammonium cation or a substituted methyl-, dimethyl- and trimethylammonium cation such as tetramethylammonium and quaternary ammonium cations is ethylamine, diethylamine, triethylamine Typically, C to x alkyl chains of C _{x 6} to lower temperatures are preferred than washing

C _xe for laundering use according to the acids of the present invention. RO (A) with M m 3 (III) wherein R is an unsubstituted alkyl C _xo to _C24 or hydroxyalkyl having an alkyl component consisting of C _xo to C _2o, preferably C _{X2-C xe} alkyl or hydroxyalkyl, A is an ethoxy or propoxy group, m is greater than zero, typically m is 0.5 to 6, more preferably 0.5 to 3, and M is H or a cation such as a metal cation (e.g. sodium, potassium, lithium) , calcium, magnesium, etc.), an ammonium cation or a substituted ammonium cation. Alkyl ethoxylated sulphates as well as alkyl propoxylated sulphates are considered in the present invention. Specific examples of substituted ammonium cations include methyl, dimethyl and trimethylammonium cations and quaternary ammonium cations such as tetramethylammonium cation, dimethylpiperidinium cation and alkanolamine derived cations such as ethylamine, diethylamine, triethylamine, mixtures thereof, and mixtures thereof. Exemplary surfactants are C _i2 to C _s alkyl polyethoxylate (1, 0) sulfate (C _{X2-C xe} E (1) M), C to C alkyl polyethoxylate (2, 25) sulfate, (C _x2 and _Ό χβ E (2 , 25) M),

C to C alkylpolyethoxylate (3,0) sulfate (C to CE (3,0)), C to C _xs alkylpolyethoxylate (4,0) sulfate (C _x2 to C _xe E (4,0) M), where M is commonly selected from sodium and potassium.

Other anionic surfactants may also be used in the present invention. Such surfactants can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, _{Cg-C 2o} linear alkylbenzenesulfonates, _Cg alkane, and C _e to C ₂₂ primary or secondary

C ₂₄ olefin sulfonates, sulfonated polycarboxylic acids prepared by sulfonating pyrolyzed alkaline earth metal citrate products, e.g. as described in British patent application no. alkyl polyglycol ether sulfates (containing

1,082,179, and C. C. to 10 moles of ethylene oxide), alkyl ester sulfonates such as C and _{X 4} acyl glycerol sulfonates, fatty

The C _xg methyl ester sulfonates, acyl glycerol sulfates, alkylphenolethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as and sulfosuccinates, and unsaturated C _{x 2} (especially saturated acyl isethionates, N-acyltaurates, alkyl succinamates, such as unsaturated sulfonates such as the mono-ester sulfates. primary alkyl, a compound which has the monoesters) diesters sulfone, C _g and C _{X 4} diesters), sulfates of alkylpolyglucoside (r as described below), and alkyl polyethoxy formula (IV):

RO (CH CH) CH COOM *

2 K 2 (IV) wherein R is a C _e to C ₂₂ alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin and resin acids, and hydrogenated resin acids present or derived from tall oil. Further examples are provided in the book Surface Active Agents and Detergents (Vol. I and II, Schwartz, Perry and Berch). Many such surfactants are also described in U.S. Patent 3,929,678, issued Dec. 30, 1975 to Laughlin, et al., At column 23, line 58 through column 29, line 23 (herein incorporated by reference).

Nonionic surfactants suitable for use in the microemulsions of the present invention are hydrophilic nonionic surfactants as defined above.

A preferred preparation of the microemulsions of the present invention which contain a liquid hydrophobic bleach activator comprises premixing the surfactants with water and subsequently adding other ingredients including hydrogen peroxide and a hydrophobic bleach activator. Regardless of this preferred order of addition, it is important that during mixing of the components the microemulsion is still mixed with a relatively high mixing energy, preferably 30 minutes at 750 rpm, most preferably 30 minutes at 1000 rpm.

In an embodiment of the present invention in which the compositions in the form of transparent testing did not show microemulsions are in the absence of centrifugation, there was no phase separation for these opalescence and staining compositions. When observed, the composition was 15 minutes at 6000 rpm.

macroscopic discoloration.

that

Under the microscope, the compositions appear as a dispersion of droplets in the matrix. The matrix is the hydrophilic matrix described above, and the droplets consist of a liquid hydrophobic bleach activator.

We observed that the particles were typically sized, on average microns.

The composition suitable for use in the present invention further comprises as a highly preferred optional component a foam suppressor such as 2-alkyl alkanol or mixtures thereof. Particularly suitable for use in the present invention are

2-alkyl alkanols having; carbon atoms, preferably 8 hydroxyl groups, wherein in position they are alkyl, preferably 2 to 8 carbon atoms. Such suitable compounds are alkyl of up to 12, consisting of 6 to 16, and still of 1 to carbon alkyl, and terminal is substituted with carbon atoms, more preferably 3 to 6 atoms commercially available, for example, as an Isofol ^R series, particularly Isofol ^R 12 (2-butyloctanol) or IsofoT * 16 (2-hexyldecanol). Typically, compositions suitable for use in the present invention comprise 0.05% to 2% by weight of the total 2-alkylalkanol composition or mixtures thereof, preferably 0.1% to 1.5% by weight, and most preferably 0.1% to 0.8%. % by weight.

Although the preferred use of the compositions of the present invention is pretreatment prior to washing, the compositions of the present invention can also be used for washing or as a detergency-enhancing detergent as well as a household detergent for bathrooms and kitchens. When used as a cleaning agent for cleaning solid surfaces, they are easy to flush and give good shine to the cleaned surface.

The present invention is further illustrated by the following examples.

DETAILED DESCRIPTION OF THE INVENTION

Experimental data

The following compositions were made by mixing said ingredients in the indicated proportions (% by weight unless otherwise stated).

means 1 2 3 4 5 6 alkyl sulfate 1.2 1.2 1.2 1.2 1.2 1 2 Dobanol ^R 91-10 1.6 1.6 1.6 1.6 1.6 1 6 Dobanol ^R 23.3 1.1 1.1 1.1 1.1 1.1 1 1 H 0 2 2 7 7 7 7 7 7 BHT 0.03 0.03 0.03 0.03 0.03 0 003 Fragrance 0.1 0.1 0.1 0.1 0.1 0 1 S, S-EDDS - 0.5 - - - - DTPMP - - 0.5 - - - MGDA ---. - - 0.5 - - DTPA - - - ---. 0.5 - - HEDP - - - - - 0 5 Water and minority ry 1 ry Iz 'r - Rest to 100 £ -L LJ Z Λ. IN • about H 2 SO 4 added to to pH 4 Loss of tensile strength 60 0 0 2 4 0

ppm copper per gram of fabric

Pre-treatment for 24 hours.

S, S EDDS is ethylenediamine-N, N'-disuccinic acid (S, S isomer). DTPMP is diethylene triamine pentamethylene phosphonate sold by Monsanto under the trade name DEQUEST ^R.

MGDA is methylglycine diacetic acid.

PDTA is propylenediaminetetraacetic acid sold by BASF under the trade name Trilon FS ^R.

Formulation 1 contains only hydrogen peroxide and does not contain any compounds chelating copper and / or iron and / or manganese. Formulations 2 to 6 are representative formulations of the present invention comprising hydrogen peroxide and a copper and / or iron and / or manganese chelating compound.

The following tests were performed:

The tensile strength test was performed with the above compositions. This test method was applied to fabrics contaminated with metals.

Cotton ribbons (12.5 x 5 cm ² ) with a copper concentration of 50 ppm per gram of cotton were pretreated according to the present invention. The cotton ribbons were each pre-treated with 2 ml of liquid composition. The compositions were allowed to act for 24 hours and then washed with water. Then, the fabric damage, i. cotton ribbons, determined by stretching the ribbons until they burst. The force necessary to tear ribbons, ie. the ultimate tensile strength was measured using the The Stress-Strain INSTRON Machine. The lower the force required to rupture cotton ribbons, the more serious the damage to fabrics. Good credibility (standard deviation = 2-5 kg) of the results was determined using five samples for each test.

The tensile strength loss reported above for the various compositions tested is expressed as a percentage and was determined by comparing the tensile strength of the fabric as a reference, ie. a fabric which has not undergone pretreatment having a tensile strength of the same fabric measured after pretreating the fabric according to the method described.

The results clearly show an unexpected improvement in safety; a reduction in the tensile strength loss that occurs with the liquid compositions of the present invention comprising a peroxygen bleach and a copper and / or iron and / or manganese chelating compound compared to using the same composition but without any copper chelating compound and / or iron and / or manganese (composition 1). Apparently, there is no loss of tensile strength as long as the pretreatment of the fabrics by the compositions of the present invention has been carried out (see compositions 2 to 6), even after a prolonged period of action, i. 24 hours and in the presence of high concentrations of copper on the fabric surface, i. 50 ppm per gram of cotton fabric.

Examples

The following compositions were made by mixing said ingredients in the indicated proportions (% by weight unless otherwise stated).

means 1 2 3 4 5 6 7 8 H 0 2 2 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 Alkyl sulfate (1) 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 Dobanol ^R 91-10 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 Dobanol * 23-3 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 BHT 0.03 0.03 0.03 0.03 - - 0.09 0.09 2-butyl 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 S, S-EDDS 0.5 - - - - - - - PDTA - 0.5 - - - - - - DTPMP - - 0.5 - 0.18 - - --- MGDA - - - 0.5 - - - - HPNO - - - - - 0.1 - - HEDP - - - - - - 0.18 - DTPA - - - - - - - 0.1 Water and minority folders ---- Rest to 100 1% ---

(Color)

H 2 SO 4 added until pH 4

S, S EDDS is ethylenediamine-N, N'-disuccinic acid (S, S isomer). DTPMP is diethylene triamine pentamethylene phosphonate sold by Monsanto under the trade name DEQUEST ^R.

MGDA is methylglycine diacetic acid.

PDTA is propylenediaminetetraacetic acid sold by the company

BASF under the trade name Trilon FS ^R.

HPNO is 2-hydroxypyridine-N-oxide.

HEDP is hydroxyethane diphosphoric acid.

DTPA is ethylenetriaminepentaacetic acid.

means 9 10 11 12 13 H 0 7.0 7.0 7.0 4.0 6.0 2 2 Alkyl sulfate (1) 1.2 1.2 1.2 2.0 - AES 25-3 - - - - 12.0 Dobanol ^R 45-7 - - - 6.4 6.0 Dobanol ^R 91-10 1.6 1.6 1.6 - - Dobanol ^R 23-3 1.1 1.1 1.1 8.6 - Dobanol ^R 23-6.5 - - - - 6.0 Activator (ATC) - - - 3.5 3.5 BHT 0.03 0.03 0.03 0.05 0.05 S, S EDDS 0.1 - - - - PDTA - 0.1 - - - DTPMP - - 0.1 - - HEDP - - - 0.1 0.1 Dipicolinic acid 0.05 0.05 0.05 - Water and Minority ----- -the rest to 100% ---

The compositions in Examples 1 to 13 are according to the present invention. The pretreatment was carried out according to the present invention by means of compositions 1 to 13 seemingly without loss of tensile strength of the treated fabrics, even if the composition was allowed to act on the fabrics for 24 hours prior to washing.

Industrial usability

The compositions of the present invention are suitable for the industrial production of detergent compositions.

Claims (15)

PATENT CLAIMS Use of a liquid composition comprising a peroxygen bleach and a copper and / or iron and / or manganese chelating compound for pretreating a soiled fabric prior to washing, reducing the tensile strength loss of the fabric. A method of pretreating soiled fabrics with a liquid composition comprising a peroxygen bleach and a copper and / or iron and / or manganese chelating compound, the method comprising the steps of: applying the composition in undiluted form to the fabric and leaving the composition in contact with the fabric before washing so that the fabric does not dry. The use according to claim 1 or the method according to claim 2, wherein the copper and / or iron and / or manganese chelating compound is selected from the group consisting of phosphonate chelating agents, aminocarboxylate chelating agents, polyfunctionally substituted aromatic chelating agents, polycarboxylic acids. pyridine chelating agents having two electron donor groups capable of occupying adjacent coordination sites in the metal coordination sphere by forming complexes with metal ions in which the metal ion is complexed with three chelating agents, and mixtures thereof. Use according to any one of the preceding claims, wherein the chelating compound of copper and / or iron and / or manganese is N, N ¹ -disuccinic acid or an alkali metal or alkaline earth metal salt, ammonia or substituted ammonia or diethylenetriaminepentaacetic acid or methylglycine diacetic acid. acid or. diethylenetriaminepentamethylenephosphonic acid or hydroxyethanediphosphoric acid or propylenediaminetetraacetic acid or 2-hydroxypyridine-N-oxide or ethylenedinitriltetrakis (methylene phosphoric acid) -N, N-oxide or mixtures thereof. Use or method according to any one of the preceding claims, wherein the liquid composition comprises 0.005% to 2% by weight of the total composition of a copper and / or iron and / or manganese chelating compound or mixtures thereof, preferably 0.01% to 1% by weight, and even more preferably 0.01% to 0.5% by weight. Use or method according to any one of the preceding claims, wherein the peroxygen bleach is hydrogen peroxide or a water-soluble source thereof, preferably hydrogen peroxide. The use or method of the preceding claims, wherein it comprises 0.5% to 20% by weight of a peroxide bleach or mixtures thereof, by weight and more preferably The use or the preceding claims, wherein the surfactant is present in an amount of the composition. 9th characterized in that the bleaching agent is 2% to 15% by weight of the composition, and is preferably a liquid total preferably% by weight. according to any A 3% to 10 process wherein the liquid composition further comprises up to 50% by weight of the total detergent composition, comprising a peroxide compound chelating copper and / or iron and / or Liquid effects include manganese, methylglycine diacetic acid, propylenediaminetetraacetic acid, 2-hydroxypyridine-N-oxide, ethylenedinitriltetrakis (methylene phosphoric acid) -N, N-oxide, hydroxyethanediphosphoric acid or mixtures thereof. Composition according to claim 9, characterized in that the peroxygen bleach is hydrogen peroxide or a water-soluble source thereof, preferably hydrogen peroxide, and the composition comprises 0.5% to 20% by weight of the total composition of the peroxygen bleach, preferably 2% to 15% by weight and even more preferably 3% to 10% 11th It also contains compound mixtures,% by weight. according to any one of the claims, characterized in that it is liquid 2% by weight of total copper and / or iron and / or manganese or% to 1% by weight, and more preferably 9 or 10, the composition of the composition 0.01% to 0.5% by weight. Composition according to any one of claims 9 to 11, characterized in that the composition is aqueous and has a pH of 1 to 9, preferably 2 to 6 and even more preferably 3 to 5. Composition according to any one of claims 9 to 12, characterized in that the composition further comprises a surfactant or a mixture thereof in an amount of up to 50% by weight of the total composition, preferably a non-ionic surfactant or mixtures thereof and / or an anionic surfactant or mixtures thereof. Use of a liquid composition comprising a peroxygen bleach and a copper and / or iron and / or manganese chelating compound, preferably according to claim 1, for pretreating a soiled colored fabric prior to washing, whereby color damage is reduced for the fabric. 15. Use of a chelating agent having two electron donor groups capable of occupying adjacent coordination sites in the metal coordination sphere by forming complexes with metal ions in which the metal ion is complexed with three chelating agents and / or ethylenedinitriltetrakis (methylene phosphoric acid) and / or hydroxyethane diphosphonic acid in a liquid acid composition comprising a peroxygen bleach, wherein the chemical stability of the composition is increased.