KR19980702566A - Laundry pretreatment with peroxide bleach containing chelating agents for iron, copper or manganese for reduced crop damage - Google Patents

Abstract

The present invention relates to the use of a liquid composition comprising a peroxygen bleach and a compound that chelates copper and / or iron and / or manganese in which the loss of tensile strength of the fabric is reduced by pretreatment of the fabric before the fabric is washed. The present invention further includes a method suitable for use in the method as well as a method of pretreating contaminated fabric.

Description

Laundry pretreatment with peroxide bleach containing chelating agents for iron, copper or manganese for reduced fabric damage

Percoral bleach-containing compositions have been widely described for use in laundry as detergents, laundry additives or even laundry pretreatments.

In fact, it is known to use such peroxygen bleach-containing compositions in laundry pretreatment to increase the removal of covered stains / dirts, which are particularly difficult to remove lubricants, coffee, tea, grass, mud / clay containing dirt and the like. However, a disadvantage associated with such peroxygen bleach containing compositions has been found to be damaging to the fabric when the composition is used in pretreatment applications, ie, applied directly to the fabric and acting on the fabric for a long time before cleaning the fabric. ought.

Accordingly, it is an object of the present invention to provide improved fabric safety when pretreating a fabric with a peroxygen bleach containing composition, especially in applications where the composition will be in contact with the fabric for a long time before cleaning the fabric.

When pretreatment of the fabric with a composition comprising a peroxygen bleach such as hydrogen peroxide, the presence of metal ions such as copper and / or iron and / or manganese on the surface of the fabric causes loss of tensile strength of the fabric fiber resulting in fabric damage. It is found to produce. The presence of metal ions such as copper and / or iron and / or manganese on the surface of the fabric, in particular cellulose fibers, is considered to promote radical decomposition of peroxygen bleach such as hydrogen peroxide. Thus, the radical reaction occurs on the surface of the fabric with the generation of free radicals, which causes a loss of tensile force.

Thus, it has been found necessary to provide improved stability to fabrics by controlling surface radical reactions in a pretreatment environment.

It has been found that this can be obtained by combining a peroxygen bleach containing composition comprising a compound for chelate copper and / or iron and / or manganese. More particularly, compounds for chelate copper and / or iron and / or manganese in a composition containing peroxygen bleach, preferably diethylene triamine penta methylene phosphonic acid (DTPMP), hydroxy-ethane diphosphonic acid (HEDP), ethylene Diamine N, N'-disuccinic acid (EDDS), methyl glycine diacetic acid (MGDA), diethylene triamine penta acetic acid (DTPA), propylene diamine tetraacetic acid (PDTA), 2-hydroxypyridine-N-oxide (HPNO ) Or the use of ethylenedinitrotetrakis (methylenephosphonic acid) N, N'-dioxide has been found to significantly reduce damage on fabrics pretreated with such compositions.

An advantage associated with the use of peroxygen bleach containing compositions, including compounds for chelate copper and / or iron and / or manganese, during laundry pretreatment applications, is that color loss is also reduced.

A further advantage of the present invention is that excellent laundry performance is provided to remove not only bleachable stains but also lubricious stains.

Another advantage of the present invention is that it provides excellent performance when a composition suitable for use according to the present invention is also used as a detergent or detergent additive in a separate application apart from other laundry applications or even hard surface cleaning applications such as hard surface cleaning applications. Is that.

In one embodiment of the invention, chelating agents such as ethylenedinitrotetrakis (methylenephosphonic acid) N, N'-dioxide, hydroxy-ethane diphosphonic acid (HEDP) and / or 2-hydroxypyridine-N It is also possible to use chelating agents having two electron donating groups which can occupy adjacent coordination positions in the metal ion coordination spheres to form complexes with metal ions each complexed by three molecules of chelating agents, such as oxides. It has been found that acidic liquid compositions suitable for pretreatment of fabrics exhibiting improved chemical stability with prolonged storage can be formulated.

Peroxygen bleach containing compositions are widely described in the art. EP-A-629691 discloses an emulsion of a nonionic surfactant, comprising a silicone compound and, optionally, hydrogen peroxide or a water soluble source thereof, and a chelating agent. The chelating agents disclosed are only S, S-ethylene diamino disuccinic acid (see Examples). Pretreatment applications for the compositions of EP-A-629691 are disclosed, but include compounds that chelate copper and / or iron and / or manganese for pretreatment of fabrics (the loss of tensile strength of the fabrics is reduced). The peroxygen bleach-containing composition to be disclosed is not disclosed anywhere.

EP-A-No. 629690 discloses an emulsion of a nonionic surfactant comprising a tetephthalate-based polymer and, optionally, hydrogen peroxide or a water soluble source thereof, and a chelating agent. The chelating agents disclosed are only S, S-ethylene diamino disuccinic acid (see Examples). Although pretreatment applications for the compositions of EP-A-No. 629690 are disclosed, include compounds that chelate copper and / or iron and / or manganese for pretreatment of fabrics (the loss of tensile strength of the fabrics is reduced). The peroxygen bleach-containing composition to be disclosed is not disclosed anywhere.

EP-B-209 228 discloses a composition comprising a peroxide source such as hydrogen peroxide, an amino polyphosphonate chelating agent and a radical scavenger. Diethylene triamine pentamethylene phosphonic acid is particularly disclosed. EP-B-209 228 also discloses that a hydrogen peroxide containing composition can be used as a prespotter. However, it is not mentioned anywhere that a peroxygen bleach containing composition comprising a compound that chelates copper and / or iron and / or manganese to pretreat the fabric can reduce the loss of tensile strength of the fabric.

[Overview of invention]

The present invention reduces the loss of tensile strength of the fabric by using a liquid composition comprising a peroxygen bleach and a compound that chelates copper and / or iron and / or manganese to pretreat the fabric before the contaminated fabric is washed. It includes being.

The invention also includes a method of pretreatment of a contaminated fabric with a liquid composition comprising a peroxygen bleach and a compound that chelates copper and / or iron and / or manganese, the method comprising the above in its pure form on the fabric. Applying the composition and allowing the composition to contact the fabric without drying on the fabric before the fabric is washed.

The present invention also relates to compounds of chelating peroxygen bleach and copper and / or iron and / or manganese, such as methyl glycine diacetic acid, propylene diamine tetraacetic acid, 2-hydroxypyridine-N-oxide, ethylenedinitrotetrakis ( Methylenephosphonic acid) N, N-dioxide, hydroxy-ethane diphosphonic acid or mixtures thereof.

The present invention relates to pretreatment of contaminated fabrics, compositions suitable for use as pretreatment agents and methods of pretreatment.

In a broad aspect, the present invention uses a liquid composition comprising a peroxygen bleach and a compound that chelates copper and / or iron and / or manganese to pretreat the fabric before the contaminated fabric is washed. Reducing the loss of tensile force.

The present invention compares the use of the same composition except for the absence of any compound that chelates copper and / or iron and / or manganese to pretreat contaminated fabrics, and the peroxygen bleach and copper according to the invention and And / or a composition comprising a compound that chelates iron and / or manganese is found to reduce the loss of tensile force causing fabric damage when used to pretreat contaminated fabric.

In a method for pretreatment of a contaminated fabric in accordance with the present invention, as described herein below, the Iranian liquid composition for pretreatment of contaminated material is applied in pure form onto the contaminated fabric and the fabric is washed. It is understood to leave it on the fabric before.

In other words, the use of a peroxygen bleach-containing composition comprising a compound that chelates copper and / or iron and / or manganese according to the present invention may even be used for a long time (eg 24 hours) before the composition has washed the fabric. Tensile forces caused by the presence of copper and / or iron and / or manganese on the fabric surface, even though the fabric is left on the fabric to be pretreated over, even if the fabric is contaminated by high amounts of copper and / or iron and / or manganese. The loss can be significantly reduced.

Tensile loss of fabric can be measured using the tensile method, as can be seen in the examples below. This method consists in measuring the tensile force of a given fabric by stretching the fabric until it is cut. The force, expressed in Kg, is the maximum tensile stress required to cut the fabric and can be measured with a stress-strain Instron machine. Tensile force loss is understood as the difference when comparing the tensile force of a fabric taken by reference, ie a fabric that has not been pretreated, with the tensile force of the same fabric after being pretreated according to the invention. A tensile loss of zero means no fabric damage was observed.

An advantage associated with the present invention is that color damage is also reduced. In fact, the color change or / and discoloration observed when pretreating colored fabrics contaminated with a peroxygen bleach containing composition comprising a compound that chelates copper and / or iron and / or manganese according to the present invention, even the composition Compared to the color change and / or discoloration observed when using the same composition without any such compound to chelate copper and / or iron and / or manganese, even if left on the fabric for a long time before washing the fabric. Is reduced. Accordingly, the present invention also provides a color of the fabric by using a liquid composition comprising a peroxygen bleach and a compound that chelates copper and / or iron and / or manganese to pretreat the stained colored fabric prior to washing of the fabric. Damage is reduced.

In addition, reduced fabric tension loss and / or reduced fabric color damage can include compounds that chelate peroxygen bleach and copper and / or iron and / or manganese without compromising the bleaching or decontamination performance delivered by the composition. Obtained as a liquid composition.

The invention also includes a method of pretreatment of a contaminated fabric with a liquid composition comprising a peroxygen bleach and a compound that chelates copper and / or iron and / or manganese, wherein the method is in its pure form on the fabric. Applying the composition and causing the composition to contact the fabric without the composition drying on the fabric before the fabric is washed. The composition can typically be contacted with the fabric for 1 minute to 24 hours, preferably 1 minute to 1 hour and more preferably 5 minutes to 30 minutes. Optionally, when the fabric is contaminated with covered stains / contaminations that are relatively difficult to remove separately, the compositions according to the invention may be slightly rubbed and / or rubbed, for example by means of sponges or brushes, or simply by rubbing the two parts of the fabric against each other, respectively. Or brushed. Washing is understood herein as simply rinsing the fabric with water, or the fabric may be washed with a washing machine or simply by hand with a conventional composition comprising one or more surfactants.

Its pure form is understood that the compositions described herein are applied on a pretreated fabric without performing any dilution, ie as described herein.

In the method for pretreatment of the contaminated fabric of the present invention, the liquid composition used in the method should not be left dry on the fabric. In fact, water vapor evaporation increases the concentration of free radicals on the surface of the fabric, thus contributing to the rapid increase in chain reaction. It is also contemplated that auto-oxidation reactions occur based on the evaporation of water vapor when the liquid composition is left dry on the fabric. The self oxidation produces peroxy-radicals that can contribute to the decomposition of cellulose. Thus, in the method of pretreating contaminated fabric according to the invention, the separation of the liquid composition for drying of the fabric as described herein is an advantage according to the invention, namely the preparation of the fabric with a liquid peroxygen bleach containing composition. It contributes to reducing the tension loss during processing.

Compositions suitable for use according to the invention as essential elements include peroxygen bleach. Preferred peroxygen bleach is hydrogen peroxide or its water-soluble source or mixtures thereof. Hydrogen peroxide is most preferred for use in the compositions according to the invention. As used herein, a hydrogen peroxide source refers to any compound that produces hydrogen peroxide when the compound is in contact with water.

Water-soluble sources of peroxides suitable for use herein include percarbonates, persulfates, persulfates such as monosulfates, perborates, and peroxyacids such as diperoxidodedecanedioic acid (DPDA), magnesium perphthalate, and mixtures thereof. Include.

Typically, compositions suitable for use herein are from 0.9 to 20% by weight, preferably from 2 to 15% and most preferably from 3 to 10% by weight of the total composition of the peroxygen bleach. In fact, the presence of peroxygen bleach, preferably hydrogen peroxide, provides a particularly strong cleaning benefit that is particularly noticeable for laundry applications.

As a second essential ingredient, compositions suitable for use in accordance with the present invention include compounds that chelate copper and / or iron and / or manganese. Typically, compositions suitable for use herein comprise 0.005 to 2% by weight, preferably 0.01 to 1% by weight and most preferably 0.01 to 0.5% by weight of a compound or mixture thereof that chelates copper and / or iron and / or manganese. It includes.

The compound that chelates copper and / or iron and / or manganese may be any compound capable of bonding copper and / or iron and / or manganese. Such compounds that chelate copper and / or iron and / or manganese are from the group comprising phosphonate chelating agents, amino carboxylate chelating agents, polyfunctionally substituted aromatic chelating agents or polycarboxylic acids of pyridine, or mixtures thereof. Can be selected.

Such phosphonate chelating agents include ethydronic acid, hydroxy-ethane diphosphonic acid (HEDP) and ethylenedinitrotetrakis (methylenephosphonic acid) N, N'-oxides as well as amino ankylene poly (alkylene phosphates). Amino phosphonate compounds such as phosphates), alkali metal-ethane 1-hydroxy diphosphonates, nitrilo trimethylene phosphonate, ethylene diamine tetra methylene phosphonate and diethylene triamine pentamethylene phosphonate can do. Phosphonate compounds may exist as salts of other cations in their acid form or on some or all of their acid functional groups. Phosphonate chelating agents are commercially available from Monsanto under the trade name DEQUEST ^@ . Preferred phosphonate chelating agents as used herein are diethylene triamine penta methylene phosphonate, hydroxy-ethane diphosphonic acid (HEDP) and ethylenedinitriletetrakis (methylenephosphonic acid) N, N-oxide .

Hydroxy-ethane diphosphonic acid and ethylenedinitrilotetrakis (methylenephosphonic acid) N, N-oxides have been found to be particularly resistant to protonation and oxidation. Thus hydroxy-ethane diphosphonic acid and ethylenedinitrilotetrakis (methylenephosphonic acid) N, N-oxides are the application of acidic liquid compositions as compounds which chelate copper and / or iron and / or manganese according to the invention. Particularly suitable for this, the fabric safety is improved. In fact, hydroxy-ethane diphosphonic acid and / or ethylenedinitrilotetrakis (methylenephosphonic acid) N, N-oxides are compared with the same composition without the chelating agent, or instead of the chelating agent, Yes, it is possible to formulate liquid acidic peroxygen bleach containing compositions with improved chemical safety compared to the same composition without diethylene triamine penta methylene phosphonic acid). Thus another aspect of the present invention is the use of hydroxy-ethane diphosphonic acid and / or ethylenedinitrotetrakis (methylenephosphonic acid) N, N-oxide in an acidic liquid peroxygen bleach-containing composition, and thus Chemical stability is improved, ie the rate of degradation of the bleach decreases with prolonged storage of the composition.

Multifunctionally substituted aromatic chelating agents may also be useful in the compositions herein. See US Pat. No. 3,812,044, issued May 21, 1974 to Connor et al. Preferred forms of the compound in acidic form are dihydroxysulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

Preferred biodegradable chelating agents for use herein are ethylene diamine N, N'-disuccinic acid, alkali metals, alkaline earth metals, ammonium or substituted ammonium salts or mixtures thereof. Ethylenediamine N, N'-disuccinic acid, especially the (S, S) isomer, is described extensively in US Pat. No. 4,704,233, issued November 3, 1987 to Hartman and Perkins. Ethylenediamine N, N'-disuccinic acid is commercially available, for example, under the trade name ssEDDS ^@ from Palmer Research Laboratories.

Such carboxylates useful as compounds that chelate copper and / or iron and / or manganese include ethylene diamine tetra acetate, diethylene triamine pentaacetate, diethylene triamine pentoacetate (DTPA), N-hydroxyethylethylenediamine triacetate Nitrilotriacetate, ethylenediamine tetraproprionate, triethylenetetraaminehexaacetate, ethanoldiglycine, propylene dimine tetraacetic acid (PDTA) and methyl glycine diacetic acid (MGDA) in their acid form or their alkali metal ammonium and In the form of substituted ammonium salts. Particularly suitable for use herein are diethylene triamine penta acetic acid (DTPA), propylene diamine tetraacetic acid (PDTA) (eg, commercially available from BASF under the trade name Trilon FS ^@ ) and methyl glycine diacetic acid (MGDA).

Suitable polycarboxylic acids of pyridine as used herein include dipicolinic acid. Preferred dipicolinic acid is used herein in admixture with other compounds that chelate copper and / or iron and / or manganese according to the invention. In fact, dipicolinic acid is preferably added on top of other chelating agents herein in the liquid composition according to the invention to improve the chemical stability of the composition.

Other chelating agents suitable for use herein as compounds that chelate copper and / or iron and / or manganese are complexes with metal ions complexed by trimolecular chelating agents, respectively (3: 1, chelating agent: metal ion stoichiometry). Chelating agents having two electron donating groups that can occupy adjacent coordination positions in the metal ion coordination sphere to form. In other words, the chelating agent is made catalytically inert by occupying a coordination sphere of metal ions. The chelating agents have been found to be particularly resistant to protonation and / or oxidation. The chelating agent is therefore particularly suitable for use in acidic liquid compositions as a compound for chelating copper and / or iron and / or manganese according to the invention, thereby improving fabric safety. Indeed, the chelating agent having two electron donating groups which may occupy adjacent coordination positions in the metal ion coordination sphere is compared to the same composition without the chelating agent or in place of the chelating agent, instead of another chelating agent (eg diethylene Acidic peroxygen bleach containing compositions can be formulated with improved chemical safety compared to the same composition with triamine menta methylene phosphonic acid). Accordingly, another aspect of the present invention provides two electrons that may occupy a coordination position adjacent to the metal ion coordination sphere to form a complex with a metal ion complexed with each of the three chelating agents in the acidic liquid peroxygen bleach containing composition. It relates to the use of chelating agents with donor groups, so that the chemical stability of the composition is improved, ie the rate of degradation of the bleach is reduced based on long term storage of the composition.

The chelating agent having two electron donating groups which may occupy adjacent coordination positions in the metal ion coordination sphere comprises a chelating agent having one or more ionized carboxylates immediately adjacent to one of the following groups: unionized Carboxylate, hydroxyl group, amino group or N-oxide group. Especially suitable for use herein are malonic acid, 2-hydroxypyridine-N-oxide or mixtures thereof.

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

According to the present invention, propylene dimine tetraacetic acid (PDTA), methyl glycine diacetic acid (MGDA), diethylene triamine pentamethylene phosphonate as peroxygen bleach, and compounds that chelate copper and / or iron and / or manganese (DTPMP), hydroxy-ethane diphosphonic acid (HEDP), ethylenediamine N, N'-disuccinic acid (EDDS), 2-hydroxypyridine-N-oxide (HPNO), and / or ethylenedinirototetra Liquid compositions comprising a kiss (methylenephosphonic acid) N, N-oxide do not substantially provide a tensile loss in the pretreated fabric. That is, even after prolonged contact (eg, 24 hours) of the composition on the fabric, the fabric resistance is not reduced.

In accordance with the present invention, as a compound which further chelates peroxygen bleach and copper and / or iron and / or manganese as already described herein, prepropylene diaminetetraacetic acid (PDTA), methyl glycine diacetic acid (MGDA), 2- Hydroxypyridine-N-oxide, ethylenedinitrotetrakis (methylenephosphonic acid) N, N-oxide, hydroxy-ethane diphosphonic acid or mixtures thereof. The following description of the composition is applied on the fabric according to the claimed composition of the invention, the composition used according to the invention for pretreatment of the contaminated fabric and the method of pretreatment of the contaminated fabric of the invention. To a composition.

The composition according to the invention is an aqueous liquid cleaning composition. The aqueous composition has a pH of 1 to 9, preferably 2 to 6 and more preferably 3 to 5. The pH of the composition can be adjusted using organic or inorganic acids or alkalizing agents.

The compositions according to the invention are also suitable for various optional agents such as radical scavengers, surfactants, structuring agents, stabilizers, other chelating agents, fouling suspending agents, dye transfer agents, solvents, varnishes, flavorings, antioxidants, foaming inhibitors and dyes. Contains ingredients.

Preferably optional components of the composition according to the invention are radical scavengers or mixtures thereof. Suitable radical scavengers for use herein include well known substituted mono and dihydroxy benzenes and their analogs, alkyl and aryl carboxylates and mixtures thereof. Preferred radical scavengers for use herein are butyl hydroxy toluene, hydroquinone, di-tert-butyl hydroquinone, mono-tert-butyl hydroquinone, tert-butyl-hydroxy anisole, benzoic acid, toluic acid , Catechol, t-butyl catechol, benzylamine, as well as 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane under the tradename Topanol CA ^@ ex ICI But not n-propyl-gallate. When a radical scavenger is used, it is typically present in an amount of 0.001 to 2% by weight and preferably 0.001 to 0.5% by weight of the total composition.

The composition according to the invention comprises any surfactant known in the art, including nonionic, anionic, cationic, bipolar or amphoteric surfactants. The composition according to the invention preferably comprises any nonionic surfactant or mixtures thereof described herein below and / or any anionic surfactant or mixtures thereof described herein below. Typically the compositions according to the invention may comprise up to 50% by weight of the total composition of the surfactant or mixtures thereof.

The composition of the present invention also includes a liquid hydrophobic bleach activator as any component that is highly preferred. Bleach activator means herein a compound that reacts with hydrogen peroxide to form peracid. The peracids thus formed constitute an activated bleach. Hydrophobic bleach activator is not substantial herein and means an active agent that is stably miscible with water. Typically such hydrophobic bleach activators have an HLB of 11 or less. Such suitable liquid hydrophobic bleach activators typically belong to the class of esters, amides, imides or anhydrides. A particular group of beneficial bleach activators is described in EP 624 154, with particular preference in this group being acetyl triethyl citrate (ATC). ATC has other environmentally friendly advantages in that it substantially degrades to citric acid and alcohol. In addition, ATC has good hydrolytic stability and is an effective bleach activator in the compositions herein. Eventually, the composition provides good reinforcement. It is also possible here to use mixtures of liquid hydrophobic bleach activators. The compositions herein may comprise up to 20%, preferably 2 to 10%, most preferably 3 to 7% by weight of the total composition of the bleach activator or mixtures thereof.

When the peroxygen bleach-containing composition according to the invention also comprises a liquid hydrophobic bleach activator, as an aqueous emulsion of a surfactant comprising said liquid hydrophobic bleach activator, or as water, peroxygen bleach and anionic and nonionic interfaces It is highly preferred herein for stability purposes to formulate the composition as a microemulsion of said liquid hydrophobic bleach in a matrix comprising a hydrophilic surfactant system comprising an active agent.

In an embodiment of the invention wherein the peroxygen bleach-containing composition further comprises the bleach activator and is formulated as an aqueous emulsion, the peroxygen bleach-containing emulsion is formulated with at least two other Emulsifying surfactant systems of surfactants, that is, at least one hydrophobic surfactant having an HLB of 9 or less and at least one hydrophilic surfactant having at least 10 HLBs. In fact, in order to form a stable emulsion, the two different surfactants must have different HLB values (hydrophilic lipophilic equilibrium values), preferably the difference in the value of the HLB of the two surfactants is at least 1, preferably at least 3 to be. That is, by mixing appropriately two or more surfactants and other HLB in water, a stable emulsion will be formed, i.e. an emulsion that does not substantially separate into individual layers as it is left at 50 ° C. for at least two weeks.

The emulsions according to the invention comprise from 2 to 50% by weight, preferably from 5 to 40% and more preferably from 8 to 30% by weight of the total composition of said hydrophilic and hydrophobic surfactants. The emulsion according to the invention is at least 0.1% by weight, preferably at least 3% and more preferably at least 5% by weight of the total emulsion of the hydrophobic surfactant or mixtures thereof, and 0.1 of the total fluid of the hydrophilic surfactant or mixtures thereof. At least% by weight, preferably at least 3% by weight and more preferably at least 6% by weight.

Preferred for use herein are hydrophobic nonionic surfactants and hydrophilic nonionic surfactants. As used herein, the hydrophobic nonionic surfactant has an HLB of 9 or less, preferably less than 9, more preferably less than 8, and the hydrophilic surfactant has an HLB of 10 or more, preferably 11 or more, more preferably 12 or more. . In fact, the hydrophobic nonionic surfactants used herein have good lubricating oil cutting properties; That is, they have a solvent effect that contributes to hydrophobic decontamination. The hydrophobic surfactant acts as a carrier of the hydrophobic varnish on the fabric so that the varnish acts closest to the fabric surface after the start of cleaning.

Suitable nonionic surfactants for use herein include alkoxylated fatty alcohols, preferably fatty alcohol ethoxylates and / or propoxylates. In fact, a wide variety of these alkoxylated fatty alcohols can use commercially available ones having very different HLB values (hydrophilic lipophilic equilibrium values). The HLB value of these alkoxylated nonionic surfactants depends essentially on the chain length of the fatty alcohol, the nature of the alkoxylation and the degree of alkoxylation. Hydrophilic nonionic surfactants tend to have low levels of alkoxylated and short chain fatty alcohols, while hydrophobic surfactants tend to have low levels of alkoxylated and long chain fatty alcohols. The surfactant list is available to describe multiple surfactants along with their individual HLB values.

Suitable chemical methods for preparing nonionic surfactants for use herein include the condensation of alkylene oxides with the corresponding alcohols in the desired proportions. Such methods are well known to those skilled in the art and are extensively described in the art. In addition, various alkoxylated alkoxys suitable for use herein may utilize those available from a variety of suppliers.

Preferred hydrophobic nonionic surfactants used according to the invention have an HLB of 9 or less, and the formula RO- (C ₂ H ₄ O) _n (C ₃ H ₆ O) _m H, wherein R is C ₆ to C ₂₂ Alkyl chain or C ₆ to C ₂₈ alkyl benzene chain, n + m is 0.5 to 5, n is 0 to 5, m is 0 to 5, preferably n + m is 0.5 to 4, n and m Is 0 to 4). Preferred R chains for use herein are C ₈ to C ₂₂ alkyl chains. Thus, suitable hydrophobic nonionic surfactants for use herein are Dobanol ^@ 91-2.5 (HLB = 8.1; R is a mixture of C ₉ and C ₁₁ alkyl chains, n is 2.5, m is 0) or ruten brush ^{(Lutensol) @ T03 (HLB =} 8; R is C ₁₃ and C a mixture of ₁₅ alkyl chains, n is 3, m is 0), or Terre gitol ^{(Tergitol) @ 25L3 (HLB =} 7.7; R ranges from C ₁₂ to C ₁₅ alkyl chain length, n is 3, m is 0, or Dobanol ^@ 23-3 (HLB = 8.1; R is C ₁₂ and C ₁₃ alkyl chain) Mixture, n is 3, m is 0, or Dobanol ^@ 23-2 (HLB = 6.2; R is a mixture of C ₁₂ and C ₁₃ alkyl chains, n is 2, m is 0 ), Or a mixture thereof. Preferred herein are Dobanol ^@ 23-3, Dobanol ^@ 23-2, Lutensol ^@ T03 or mixtures thereof. These Dobanol ^@ surfactants are commercially available from SHELL. These Lutensol ^@ surfactants are commercially available from BASF, and these Tergitol ^@ surfactants are commercially available from UNION CARBIDE. Other suitable hydrophobic nonionic surfactants used herein are nonalkoxylated surfactants. An example is Dobanol ^@ 23 (HLB3).

Preferred hydrophilic nonionic surfactants used according to the invention have a HLB of at least 10, and the formula RO- (C ₂ H ₄ O) _n (C ₃ H ₆ O) _m H, wherein R is C ₆ to C ₂₂ alkyl Chain or C ₆ to C ₂₈ alkyl benzene chain, n + m is 5 to 11, n is 0 to 11, m is 0 to 11, preferably n + m is 6 to 10, n and m are 0 to 10). N and m in this description refer to the average degree of ethoxylation / propoxylation. Preferred R chains for use herein are C ₈ to C ₂₂ alkyl chains. Thus, suitable hydrophilic nonionic surfactants for use herein are Dobanol ^@ 23-6.5 (HLB = 11.9; R is a mixture of C ₁₂ and C ₁₃ alkyl chains, n is 6.5 and m is 0) Or Dobanol ^@ 25-7 (HLB = 12; R is a mixture of C ₁₂ and C ₁₅ alkyl chains, n is 7 and m is 0) or Dobanol ^@ 45-7 (HLB R 1 is a mixture of C ₁₄ and C ₁₅ alkyl chains, n is 7 and m is 0, or Dobanol ^@ 91-5 (HLB = 11.6; R is C ₉ and C ₁₁ alkyl) Chain is a mixture, n is 5, m is 0, or Dobanol ^@ 91-6 (HLB = 12.5; R is a mixture of C ₉ and C ₁₁ alkyl chains, n is 6, m Is 0), or Dobanol ^@ 91-8 (HLB = 13.7; R is a mixture of C ₉ and C ₁₁ alkyl chains, n is 8, m is 0), or Dobanol ^@ 91-10 (HLB = 14.2; R is a mixture of C ₉ and C ₁₁ alkyl chains, n is 10 and m is 0) or mixtures thereof. Preferred herein are Dobanol ^@ 91-10, Dobanol ^@ 45-7, Dobanol ^@ 23-6.5 or mixtures thereof. These Dobanol ^@ surfactants are commercially available from SHELL. Apart from hydrophilic nonionic surfactants, other hydrophilic surfactants may also be used as emulsions of the invention, such as the anionic surfactants described herein below.

The emulsions according to the invention may also comprise other surfactants, but do not significantly alter the weighted average HLB value of the total emulsion.

In a particularly preferred embodiment of the emulsion of the present invention, where the emulsion comprises acetyl triethyl straight as the bleach activator, suitable nonionic surfactant systems use HLB 6, such as, for example, Dobanol ^@ 23-2. Hydrophobic nonionic surfactant with and hydrophilic nonionic surfactant with HLB 15, such as Dobanol ^@ 91-10. Other suitable nonionic surfactant systems include, for example, Dobanol ^@ 23-6.5 (HLB about 12) and Dobanol ^@ 23 (HLB 6 or less) or Dobanol ^@ 45-7 ( HLB = 11.6) and Lutensol ^@ T03 (HLB = 8).

In an embodiment of the invention wherein the peroxygen bleach-containing composition of the invention comprises the bleach activator and is formulated as a microemulsion, the peroxygen bleach-containing microemulsion according to the invention comprises anionic surfactants and nonionic surfactants. Hydrophilic surfactant systems. The main factor for the stable incorporation of hydrophobic activators is that at least one of the surfactants should have a different HLB value than the hydrophobic activators. In fact, if all of the above surfactants have the same HLB value as the hydrophobic activator, a continuous single phase is formed, thereby lowering the chemical stability of the bleach / bleach activator system. Preferably, at least one of the surfactants has a HLB value that differs from that of the bleach activator in units of at least 1.0 HLB, preferably 2.0.

Suitable anionic surfactants herein are of formula ROSO ₃ M, wherein R is preferably C ₁₀ -C ₂₄ hydrocarbyl, preferably alkyl or hydroxyalkyl with a C ₁₀ -C ₂₀ alkyl component, more preferably C _12- C ₁₈ alkyl or hydroxyalkyl, M is H or a cation (e.g., an alkali metal cation (e.g. sodium, potassium, lithium) or ammonium or a substituted ammonium (e.g. methyl-, dimethyl-, and trimethyl ammonium cation) And quaternary ammonium cations such as tetramethyl ammonium and dimethyl piperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof). Typically alkyl chains of C ₁₂ -C ₁₆ are preferred for low wash temperatures (eg, below about 50 ° C.), and C ₁₆ -C ₁₈ alkyl chains are preferred for high wash temperatures (eg, above about 50 ° C.). Do.

Other suitable anionic surfactants for use herein are water soluble salts or acids of formula RO (A) _m SO ₃ M, wherein R has an unsubstituted C ₁₀ -C ₂₄ alkyl or C ₁₀ -C ₂₄ alkyl component A hydroxyalkyl group, preferably C ₁₂ -C ₂₀ alkyl or hydroxyalkyl, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is at least 0, typically From about 0.5 to about 6, more preferably from about 0.5 to about 3, M may be H or metal ions (e.g. sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted ammonium cations Is a cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include quaternary ammonium cations such as methylammonium, dimethylammonium, trimethylammonium and tetramethylammonium, dimethyl piperidinium and alkylols such as ethylamine, diethylamine, triethylamine, mixtures thereof Cations derived from amines; Exemplary surfactants include C ₁₂ -C ₁₈ alkyl polyethoxylate (1.0) sulfate, C ₁₂ -C ₁₈ E (1.0) M, C ₁₂ -C ₁₈ alkyl polyethoxylates (2.25) sulfate, C ₁₂ -C ₁₈ E (2.25) M, C ₁₂ -C ₁₈ alkyl polyethoxylate (3.0) sulfate, C ₁₂ -C ₁₈ E (3.0) and C ₁₂ -C ₁₈ alkyl polyethoxylate (4.0) sulfate, C _12- C ₁₈ E (4.0) M, wherein M is commonly selected from sodium and potassium.

Other anionic surfactants useful for cleaning agents can also be used herein. These include soap salts (e.g., substituted ammonium salts such as sodium, potassium, ammonium and monoethanolamine salts, diethanolamine salts and triethanolamine salts), C ₉ -C ₂₀ linear alkylbenzenesulfonates, C ₈ -C Sulfonated polycarboxylic acids (e.g., British Patent No. 1,082,179), C ₈ -C prepared by sulfonation of pyrolysis products of ₂₂ primary or secondary alkanesulfonates, C ₈ -C ₂₄ olefinsulfonates, alkyl earth metal citrates ₂₄ alkylpolyglycol ether sulfate (contains less than 10 moles of ethylene oxide), alkyl ester sulfonates such as C ₁₄ -C ₁₆ methyl ester sulfonate, acyl glycerol sulfonate, fatty oleyl glycerol sulfate, alkyl phenol ethylene oxide Ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as acyl isethionates, N-acyl taurates, alkyl succinates and sulfosuccines Agent, monoesters of sulphoxide succinate (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters), diesters of succinic sulfoxide carbonate (especially saturated and unsaturated C ₆ -C ₁₄ diesters), sulfates of alkyl poly glucoside Sulfates of alkylpolysaccharides such as the nonionic nonsulfate compounds described below branched primary alkyl sulfates, formula RO (CH ₂ CH ₂ O) _k CH ₂ COO-M ⁺ , wherein R is C ₈ -C ₂₂ Alkyl, k is an integer from 0 to 10, and M is a soluble salting cation). Resin acids such as rosin, hydrogenated rosin and hydrogenated resin acids are also suitable, and the resin acids and hydrogenated resin acids are present in or derived from tall oil. Further examples are given in Surface Active Agents and Detergents (Vol. I and II by Schwartz, Perry and Berch) A wide range of such surfactants are also generally given to Laughlin, issued December 30, 1975. US Pat. No. 3,929,678, line 23, line 58 to line 29, line 23 (incorporated herein by reference).

Suitable nonionic surfactants for use in the microemulsions herein include hydrophilic nonionic surfactants as already defined herein.

Preferred preparations of the microemulsions of the present invention comprising liquid hydrophobic bleach activators include premixing water and surfactant, followed by addition of hydrogen peroxide and the remaining ingredients including the hydrophobic bleach activator. Regardless of the order of addition desired, during the mixing of the components, it is important that the microemulsion is kept constant by stirring under a relatively high stirring energy, preferably at 30 minutes at 750 rpm, most preferably at 1,000 rpm.

In an embodiment of the invention wherein the composition is formulated as a microemulsion, the composition is macroscopically transparent in the absence of opaques and dyes. In the centrifugation test, the microemulsion herein showed no phase separation after 15 minutes at 6,000 RPM. In microscopic testing, the microemulsion appeared to be the dispersion of droplets in the matrix. The matrix is the hydrophilic matrix already described herein, and the droplets are constituted by a liquid hydrophobic bleach activator. The particles are typically observed to have a size of less than 3 microns in diameter.

Compositions suitable for use according to the invention may also comprise foam inhibitors, such as 2-alkyl alkanols or mixtures thereof, as highly preferred optional components. Particularly suitable for use in the present invention include 6 to 16, preferably 8 to 12 carbon atoms and terminal hydroxy groups, and 1 to 10, preferably 2 to 8 and more preferably 3 to 6 carbon sources 2-alkyl alkanol having an alkyl chain substituted at the α-position by an alkyl chain including a hexa. Such suitable compounds are commercially available in the Isofol ^@ series such as, for example, Isofol ^@ 12 (2-butyl octanol) or Isofol ^@ 16 (2-hexyl decanol). It is available. Typically, compositions suitable for use herein comprise from 0.05 to 2% by weight, preferably from 0.1 to 1.5% and most preferably from 0.1 to 0.8% by weight of 2-alkyl alkanols, based on the total composition or mixtures thereof.

While the preferred application of the compositions described herein is laundry pretreatment, the compositions according to the invention can also be used as detergents or detergent promoters as well as bathroom cleaners or household cleaners. When used as a hard surface cleaner, these compositions are easy to rinse and provide good gloss characteristics on the cleaned surface.

The invention will be further illustrated by the following examples.

A) Experimental Data

The following compositions were prepared by mixing the stated ingredients in the stated proportions (% by weight unless otherwise specified).

Table 1

Composition I only contains hydrogen peroxide and is free of compounds that chelate copper and / or iron and / or manganese. Compositions II to VI are representative of the present invention, but they include compounds that chelate hydrogen peroxide and copper and / or iron and / or manganese.

The following tests were run:

Tensile test methods were performed on the compositions already described above. The test method was run on metal contaminated fabric.

Cotton ribbons (size 12.5 x 5 cm 2) with a copper concentration of 50 ppm per gram of cotton were pretreated according to the present invention. In fact, the cotton ribbon was pretreated with 2 ml of each liquid composition already described herein. The composition was in contact with the ribbon for 24 hours before rinsing with water. Thereafter, the ribbon was stretched until it was cut to assess the damage on the fabric, ie cotton ribbon. The force required to cut the ribbon, ie the maximum tensile stress, was measured in the wet state with a stress-straining Instron machine. The lower the force required to cut the cotton ribbon, the more severe the damage that occurs on the fabric. Good confidence in the results (standard deviation = 2 ÷ 5 Kg) was obtained using five iterations for each test.

The aforementioned loss of tensile strength for the other compositions tested is expressed in% and is taken as a reference, that is, the tensile strength of a given fabric taken as a reference, i.e. the untreated fabric and the same fabric measured after the fabric has been pretreated as already mentioned herein. Obtained by comparing the tensile force of.

The result is a compound that chelates peroxygen bleach and copper and / or iron and / or manganese as compared to the use of the same composition (composition I) except that no compound chelates copper and / or iron and / or manganese. The unexpected safety improvement obtained using the liquid composition according to the present invention, i.e., the reduction in tensile force loss, is clearly shown. In fact, even in the presence of long contact times, i.e. 24 hours and high concentrations of copper on the surface of the fabric, i.e. 50 ppm of copper per gram of cotton, the tensile loss observed when pretreating the fabric with the composition according to the invention is substantially (See compositions II to VI).

B) Example

The following compositions were prepared by mixing the stated ingredients in the stated proportions)% by weight unless otherwise specified.

[Table 2]

Table 3

The compositions of Examples 1 to XIII are in accordance with the present invention. The pretreatment process was carried out in accordance with the present invention with compositions I to III without substantially losing the tensile force of the treated fabric even when the composition was applied to the fabric for 24 hours prior to washing the fabric.

No content.

Claims (15)

Use of a liquid composition comprising a peroxygen bleach and a compound that chelates copper and / or iron and / or manganese, which reduces the loss of tensile force in the contaminated fabric by pretreating the contaminated fabric before cleaning the contaminated fabric. . A method of pretreatment of a contaminated fabric with a liquid composition comprising a peroxygen bleach and a compound that chelates copper and / or iron and / or manganese, the method comprising applying the liquid composition onto the fabric in its pure form, and Allowing the fabric to contact without drying the composition on the fabric before it is washed. The method according to claim 1 or 2, The compounds that chelate copper and / or iron and / or manganese are complexed by phosphonate chelating agents, amino carboxylate chelating agents, polyfunctionally substituted aromatic chelating agents, polycarboxylic acids of pyridine, chelating agents of three molecules, respectively. Use or method selected from the group consisting of chelating agents or mixtures thereof having two electron donating groups which can be positioned adjacent to the coordination position in the metal ion coordination sphere to form a complex with a metal ion. The method according to any one of claims 1 to 3, Compounds that chelate the copper and / or iron and / or manganese include ethylene diamine, N, N'-disuccinic acid, alkali metals, alkaline earth metals, ammonium or substituent ammonium salts thereof, diethylene triamine pentaacetic acid, methyl glycine diacetic acid Or diethylene triamine penta methylene phosphonic acid, hydroxyethane diphosphonic acid or propylene tetraacetic acid, 2-hydroxypyridine-N-oxide, ethylenedinitrotetrakis (methylenephosphonic acid) N, N'-oxide Or a mixture thereof. The method according to any one of claims 1 to 4, Or the liquid composition comprises from 0.005 to 2% by weight, preferably 0.01 to 1% by weight and more preferably 0.01 to 0.5% by weight of the compound or mixture thereof chelating copper and / or iron and / or manganese. The method according to any one of claims 1 to 5, Or the peroxygen bleach is hydrogen peroxide or a water soluble source thereof, preferably hydrogen peroxide. The method according to any one of claims 1 to 6, Or the composition comprises from 0.5 to 20% by weight, preferably from 2 to 15% by weight and more preferably from 3 to 10% by weight of the peroxygen bleach or mixture thereof, based on the total composition. The method according to any one of claims 1 to 7, Use or method wherein the composition further comprises up to 50% by weight of surfactant, based on the total composition. As peroxygen bleach and compounds that chelate copper and / or iron and / or manganese, methyl glycine diacetic acid, propylene dimine tetraacetic acid, 2-hydroxypyridine-N-oxide, ethylenedinitrotetrakis (methylenephosphonic acid ), N, N'-oxide, hydroxy-ethane diphosphonic acid or mixtures thereof. The method of claim 9, The peroxygen bleach is hydrogen peroxide or a water soluble source thereof, preferably hydrogen peroxide, and the composition is 0.5 to 20% by weight, preferably 2 to 15% by weight and more preferably 3 to 10% by weight, based on the total composition. Composition comprising. The method according to claim 9 or 10, 0.005 to 2% by weight, preferably 0.01 to 1% by weight and more preferably 0.01 to 0.5% by weight of said compound or mixture thereof, wherein said liquid composition chelates copper and / or iron and / or manganese based on the total composition Composition comprising. The method according to any one of claims 9 to 11, The composition is aqueous and has a pH of 1 to 9, preferably 2 to 6 and more preferably 3 to 5. The method according to any one of claims 9 to 12, Wherein said composition further comprises a surfactant or mixture thereof, preferably a nonionic surfactant or mixture thereof and / or an anionic surfactant or mixture thereof up to 50% by weight of the total composition. A peroxygen bleach and a compound that chelates copper and / or iron and / or manganese, the color damage of which is reduced by pretreatment of the contaminated colored fabric before the contaminated colored fabric is washed, preferably with claim 1 Use of a liquid composition according to. Metals complexed with three chelating agents and / or ethylene dinitrotetrakis (methylenephosphonic acid) N, N'-oxide and / or hydroxyethane diphosphonic acid, respectively, in a liquid acidic composition comprising a peroxygen bleach Use of a chelating agent, wherein the chemical stability of the composition is improved by having two electron donating groups which can occupy adjacent coordination positions in the metal ion coordination sphere to form complexes with ions.