WO2007025642A1

WO2007025642A1 - Liquid hypohalite bleach

Info

Publication number: WO2007025642A1
Application number: PCT/EP2006/007954
Authority: WO
Inventors: Belén Garcia; Carlos Malet; Miguel Osset
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2005-08-31
Filing date: 2006-08-11
Publication date: 2007-03-08
Also published as: DE102005041436A1

Abstract

An aqueous liquid bleach composition is proposed, comprising hypohalite bleach, a surfactant mixture containing ether sulphate, alkanesulphonate and amine oxide, in an amount of 0.1% to 20% by weight of the total composition, foam regulator in an amount of 0.5% to 10% by weight of the total composition, up to 2% by weight of alkali metal silicate, and up to 10% by weight of stabilizer selected from the group encompassing free-radical scavengers, complexing agents and mixtures thereof.

Description

Liquid hypohalite-containing bleach

The present invention relates to the bleaching of fabrics, including hand and machine laundering, with liquid hypohalite-containing bleaches.

Bleaching agents are well known in the art. Of the various bleaches available, those which are often due to performance reasons, especially at low temperatures, are often those whose bleaching effect is due to hypohalite bleach, such as hypochlorite.

There are nevertheless limits to the applicability of hypohalite-containing bleaches, particularly when good stain removal performance is sought in textiles treated therewith in addition to achieving good whiteness of the fabric. This is an even greater problem when used with aged compositions, that is, when detergents employ means that have been stored for a longer time after their preparation.

It has often been observed that when surfactants are incorporated into liquid hypohalite-based compositions, the resulting composition generally exhibits a rather limited chemical stability on aging, resulting in only a small stain removal performance of the composition when used after a prolonged storage period in a washing process starts. Surfactants may decompose at longer storage times, possibly due to the hypohalite oxidizing agent contained in such liquid agents, so that their stain removal potential may be lost. The decomposition of the surfactants can even accelerate if the product is exposed to higher temperatures or light. Although a chemically more stable composition should be found, it may have the disadvantage of lack of phase stability, that is, the components of the liquid product may separate into several distinct phases upon storage. It is therefore an object of the invention to provide a stable hypohalite-containing bleach having good stain removal performance.

Surprisingly, it has now been found that this can be achieved if the liquid bleaching agent contains hypohalite, a surfactant mixture specified below in greater detail and a defoaming agent. Stabilizers selected from the group comprising radical scavengers, complexing agents and mixtures thereof may additionally be present. The presence of such stabilizers in liquid, surfactant and hypohalite-containing bleaching agents results in improved stain removal performance over a variety of stains in laundry applications, including greasy stains such as sebum, makeup or lipstick, enzymatically removable stains such as blood, grass or cocoa, but also bleachable Stains such as wine, coffee or tea, even after aging of the composition, that is, if it has been stored for a long time after their preparation.

Another advantage of bleaches according to the present invention is that they are suitable for bleaching textiles of various materials, including those of natural fibers such as cotton or linen, but also those of synthetic material, such as synthetic polymer fibers, and also of corresponding ones mixed fabrics.

A liquid agent according to the present invention is advantageously applied to the textiles to be cleaned in dilute form, for example when it is used as a washing additive or alone as a detergent, but it can additionally or alternatively be applied undiluted to the textile, for example as a liquid pretreatment agent or stain remover.

European Patent Application EP-A-668 345 discloses hypochlorite-containing compositions containing a strong alkalinity source, a pH buffer (silicate / carbonate) and radical scavengers. Surfactants are mentioned as optional ingredients without specifying specific surfactants or their amounts. European Patent Application EP-A-317 066 discloses thickened aqueous compositions containing hypochlorite, bases such as NaOH, carbonate and silicate, an organic counterion quaternary ammonium compound such as benzoate.

The present invention relates to an aqueous liquid bleaching composition containing hypohalite bleach, a surfactant mixture comprising at least 2 of the constituents ether sulfate, alkanesulfonate and amine oxide, in an amount of from 0.1% to 20% by weight of the total composition, foam regulator in an amount of from 0.5% to 10% by weight of the total composition, up to 2% by weight of alkali silicate, and up to 10% by weight of stabilizer selected from the group consisting of free radical scavengers, complexing agents and mixtures thereof.

A mandatory component of the compositions of the invention is a hypohalite bleach. Hypohalite can be provided by a variety of sources, including the oxidation of halogens and organic sources such as chloroisocyanurates. The hypohalite bleaches useful in this invention include the alkali and alkaline earth hypochlorites, hypobromites, hypoiodites, chlorinated trisodium phosphate dodecahydrate, potassium and sodium dichloroisocyanurates, potassium and sodium trichlorocyanurates, N-chloroimides, N-chloroamides, N-chloroamines and chlorohydantoins. The preferred hypohalite bleaches in the liquid compositions of the invention are the alkali and / or alkaline earth hypochlorites, especially selected from the group of sodium, potassium, magnesium, lithium and calcium hypochlorite, and mixtures thereof, particularly preferably sodium hypochlorite.

Preferably, the hypohalite bleach, based on the active substance, in an amount of 0.1 wt .-% to 20 wt .-%, in particular from 0.25 wt .-% to 8 wt .-% in the inventive compositions.

Another compelling component of the invention is a binary or ternary surfactant mixture. This is in compositions according to the invention in amounts of 0.1 wt .-% to 20 wt .-% of the total composition, preferably from 0.1 wt .-% to 15 wt .-%, in particular from 1 wt .-% to 10 wt .-% and more preferably of 2 wt .-% to 8 wt .-% included. The surfactant mixture preferably comprises both ether sulfate and alkanesulfonate as well as amine oxide.

Ethersulfaten should here water-soluble salts or acids of the formula RO (A) _n SO ₃ M, in which R is a linear or branched C ₈ -C ₂₄ alkyl group, preferably a linear or branched Cio-C ₂ o-alkyl group, in particular a linear or branched Ci ₂ -Ci ₈ alkyl group, A is an ethoxy or propoxy moiety, n is a number greater than zero, typically from about 0.5 to about 30, preferably from about 0.5 to about 5, and MH or a Cation, which may be, for example, a metal ion such as sodium, potassium, lithium, calcium, magnesium, an ammonium or substituted ammonium cation is understood. Both ethoxylated and propoxylated alkyl ether sulfates are included therein. Specific examples of substituted ammonium cations are methyl-, dimethyl-, trimethyl-ammonium cations and quaternary ammonium cations, such as tetramethylammonium, dimethylpiperidinium cations derived from alkanolamines such as ethanolamine, diethanolamine, triethanolamine, and mixtures thereof. Examples of ether sulfate surfactants are C] _{_2-Ci8} alkyl polyethoxylate (l, 0) sulfate, C ₂ -C ₈ alkyl polyethoxylate sulfate (2.0), C ₂ - C ₈ alkyl polyethoxylate (2, 25) sulfate, Ci ₂ -Ci ₈ -Alkylpolyethoxylat- (3,0) sulfate, and Ci ₂ - Ci ₈ -Alkylpolyethoxylat- (4,0) sulfates, wherein the number in parentheses indicates the average degree of ethoxylation, and in where the counter cation is expediently selected from sodium and / or potassium. Ether sulfate is preferably contained in an amount of from 0.1% to 15% by weight, and more preferably from 2% to 10% by weight in the total composition.

Alkanesulfonates are obtainable by, for example, sulfochlorination or sulfoxidation and subsequent hydrolysis and neutralization of C ₂ -C ₈ alkanes. The sulfonate group substituent is usually randomly distributed throughout the carbon chain, with secondary alkanesulfonates predominating. For the Gengenion, which usually comes from the neutralization of intermediately occurring alkanesulfonic acid, the above for the ether sulfates said. Alkanesulfonate is preferably included in an amount of from 0.1% to 15%, more preferably from 2% to 10% by weight of the total composition. Among the useful amine oxides are in particular those having an alkyl group having 10 to 18 carbon atoms and two alkyl groups each having 1 to 3 carbon atoms, such as dimethyl-C ₆ alkyl-amine oxide. Preferably, amine oxide is included in an amount of from 0.1% to 15%, more preferably from 2% to 10%, by weight of the total composition.

Useful foam control agents are, for example, saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, in particular soap mixtures, which are accessible from natural fatty acid sources, such as, for example, coconut oil, palm kernel oil or tallow. Soap mixtures which consist of 50 to 100 wt .-% of Ci ₂ -Ci ₈ fatty acid soaps and 0 to 50 wt .-% of oleic acid soap, are particularly preferred. In addition to, or in place of, other bleach-stable foam regulators may be used, such as low molecular weight alkyl carbonates, for example bis (2-ethylhexyl) carbonate, available under the tradename Tego® Antifoam 626 from Degussa-Goldschmidt. Foam regulators are preferably included in an amount of from 0.1% to 15%, and more preferably from 2% to 10%, by weight of the total composition.

The radical scavenger used according to the invention is preferably a benzene derivative, naphthalene derivative, annulene derivative, cyclopentadiene derivative, cyclopropane derivative, arylcarboxylate, arylsulfonate or a mixture thereof, in particular benzoic acid, methoxybenzoic acid, methylbenzoic acid, 4-toluenesulfonic acid, 2-N-octylbenzoic acid, 3-nitrobenzoic acid, anisic acid, Benzyl alcohol, methoxybenzyl alcohol, optionally substituted hydroxytoluene, 2-N-octylbenzyl alcohol, 3-nitrobenzyl alcohol, anisalcohol, or a mixture of these. Among the most preferred radical scavengers are BHT and aniseed alcohol.

Complexing agents which can be used in agents according to the invention are chelating agents known to the person skilled in the art, in particular a phosphonate, phosphate, polyfunctional-substituted aromatic, ethylenediamine-N, N'-disuccinic acid or a mixture of these. Useful phosphonates include alkylene polyphosphonates as well as amino phosphonates such as aminotrimethylene phosphonic acid (ATMP), nitrilotrimethylene phosphonate (NTP), ethylenediamine tetramethylene phosphonate, and Diethylene triamine pentamethylene phosphonate (DTPMP). The nitrogen atom in the amino phosphonates may also be present in oxidized form, that is, as N-oxide. Phosphonates can be present in either acid or salt form. Preferred phosphonate complexing agents for use in compositions and processes according to the invention are diethylenetriaminepentamethylenephosphonate and aminotrimethylenephosphonic acid N-oxide, available commercially under the trade name Sequion® CLR.

The compositions according to the invention are in aqueous liquid form. They preferably contain 60 wt .-% to 98 wt .-%, in particular 80 wt .-% to 97 wt .-% and particularly preferably 85 wt .-% to 97 wt .-% water, each based on the total aqueous liquid bleaching composition.

In a preferred embodiment of the invention, the compositions additionally contain a pH buffering ingredient. Its presence contributes to the whiteness as well as the textile safety of the compositions according to the invention when used for bleaching textiles. The pH buffering ingredient permits control of the alkalinity of the bleaching agent and the bleaching liquor optionally produced therefrom by dilution with water, the pH of which is at least pH 7.5, preferably at least pH 8.5 and more preferably at least pH 9.5 should be kept, beginning with the completion of the dilution with water, for example in the ratio of about 1: 200. The buffering effect of hypochlorite-containing agents reduces the formation of hypochlorous acid, presumably one of the species responsible for textile yellowing and the onset of textile damage.

The pH of liquid compositions of the present invention is normally in the range of 12 to 14, neat at 25 ° C. Dilute aqueous bleach liquors, if desired, used in the inventive processes described below and prepared by blending with, for example, 1 to 500 times the weight of water preferably have a pH of 7.5 to 13, especially 8 to 12, more preferred from 8.5 to 1 1.5. In this alkaline range, the optimum stability of the hypohalite, as well as the best textile whiteness and a high textile safety in the application of the agent is usually achieved. Of the said pH range is normally established by the presence of the alkaline hypohalite bleach and, optionally, the pH buffering agent. Optionally, however, a strong source of alkalinity may additionally be used, for example sodium hydroxide, potassium hydroxide and / or lithium hydroxide, and / or sodium and / or potassium oxide being useful. Preference is given to sodium hydroxide and / or potassium hydroxide. Typically, if present, they will be present in amounts of from 0.1% to 1.5%, more preferably from 0.5% to 1.5% by weight, based on the total composition of the composition used.

Useful pH buffering ingredients are preferably selected from the alkali carbonates, polycarbonates, sesquicarbonates, silicates, polysilicates, borates, phosphates, stannates, aluminates, and mixtures thereof, the preferred alkali metals being sodium and potassium. The starting materials for the preparation of, for example, the hypohalite bleach may contain by-products, for example, carbonate, which may result in a content of such by-product in the inventive compositions of optionally up to 0.4% by weight.

If desired, the compositions according to the invention may also contain other ingredients such as, for example, organic or inorganic alkali carriers, builders, thickeners, polymers, pigments, dyes, solvents, perfume and / or optical brighteners.

Compositions according to the invention normally have viscosities in the range from about 25 mPa.s to 1500 mPa.s, in particular from 50 mPa.s to 1100 mPa.s.

A composition of the invention may be used, in dilute or undiluted form, to remove stains and stains from fabrics by allowing the composition and fabric to contact one another over a period of time sufficient to bleach the test piece and then rinse the fabric rinsed with water. Alternatively, or alternatively to rinsing with water, the textile can also be washed using an agent according to the invention by hand or in a mechanical washing process in which an agent according to the invention is metered into a conventional washing machine. The present invention therefore also relates to a process for bleaching textiles having a composition as described herein. Textiles are understood to mean all types of textiles, for example garments, curtains, curtains, bed linen, towels, tablecloths, sleeping bags, tents, and furniture upholstery, as well as carpets and tapestries or textile wallcoverings. The erfϊndungsgemäße method can be used for both natural and synthetic textiles. Natural textiles are understood to mean, for example, cotton and / or linen, synthetic synthetic materials such as polyamide, polyester, Lycra® and Elasthane®, and those containing natural and synthetic material. By a diluted form of an agent according to the invention is meant that the compositions described herein can be diluted by the user with water. Such dilutions can occur, for example, in manual washing applications as well as in washing machines. If desired, the compositions may be diluted up to 500 times, preferably 5 times to 200 times and in particular 10 times to 80 times diluted.

An embodiment of the method according to the invention comprises the step of contacting the test-piece with the composition according to the invention in diluted form, then leaving the textile in contact with the composition for a period of time, normally from about 1 minute to 60 minutes, sufficient for bleaching the textile. in particular 5 minutes to 30 minutes, and then rinsing the textile with water. If the textiles are to be washed with a conventional detergent containing at least one surfactant, this may be done simultaneously with one of the first two cuts, or the washing may be carried out before or after these steps. The process of the invention accordingly permits bleaching and optionally additionally washing with a conventional detergent containing at least one surfactant prior to the step of contacting the fabric with the bleaching composition, and / or during the step of contacting with the bleaching composition, and / or after the step of contacting the bleaching composition and before the step of rinsing with water, and / or after the step of rinsing with water Another embodiment of the method of the invention comprises the step of contacting the fabric with a composition of the invention, in neat form, the further step of leaving the fabric in contact with the bleaching composition for a sufficient time for bleaching, typically about 5 seconds to 30 minutes , in particular about 1 minute can be up to 10 minutes, and the further step of rinsing the textile with water. Thus, the present invention advantageously provides a process for bleaching textiles in which liquid compositions containing hypohalite bleach are applied undiluted to the fabric to be bleached.

Alternatively, instead of the step of rinsing with water and / or washing with a conventional liquid or powder detergent after the undiluted pretreatment, the bleaching pretreatment step may also be followed by a washing step, manually or by means of a washing machine, in which an agent according to the invention is diluted with water is used, followed.

The temperature at which the bleaching process of the present invention is carried out normally has an influence on stain removal performance, with an elevated temperature accelerating the bleaching process. Dilute aqueous systems which can be prepared by mixing erfϊndungsgemäßer compositions with water, are usually at temperatures of 5 ° C to 60 ° C, preferably from 10 ⁰ C to 50 ° C and particularly preferably from 20 ⁰ C to 40 ° C. applied.

Examples

In the following examples, all quantities are wt .-%.

These compositions showed excellent stain removal performance on various stains, including greasy, enzyme-degenerate and bleachable soils, especially when used in wash applications neat or diluted with 200 times the amount of water, and lost these good Properties even after storage for example 3 months at room temperature (20 to 25 ⁰ C).

Claims

claims

An aqueous liquid bleaching composition containing hypohalite bleaching agent, a surfactant mixture comprising at least 2 of the constituents ether sulfate, alkanesulfonate and amine oxide, in an amount of 0.1% by weight to 20% by weight of the total composition, foam regulator in an amount from 0.5% to 10% by weight of the total composition, up to 2% by weight of alkali silicate, and up to 10% by weight of stabilizer selected from the group consisting of free radical scavengers, complexing agents and mixtures thereof.

2. Composition according to claim 1, characterized in that the hypohalite bleach, based on the active substance, in an amount of 0.1 wt .-% to 20 wt .-%, in particular from 0.25 wt .-% to 8 wt .-% is included.

3. Composition according to claim 1 or 2, characterized in that the hypohalogenite bleaching agent is an alkali metal hypochlorite, in particular sodium hypochlorite.

4. Composition according to one of claims 1 to 3, characterized in that the ether sulfate in an amount of 0.1 wt .-% to 15 wt .-%, in particular from 2 wt .-% to 10 wt .-% in the Total composition is included.

5. Composition according to one of claims 1 to 4, characterized in that the alkanesulfonate in an amount of 0.1 wt .-% to 15 wt .-%, in particular from 2 wt .-% to 10 wt .-% in the Total composition is included.

6. Composition according to one of claims 1 to 5, characterized in that the amine oxide in an amount of 0.1 wt .-% to 15 wt .-%, in particular from 2 wt .-% to 10 wt .-% in the Total composition is included.

7. Composition according to one of claims 1 to 6, characterized in that the foam regulator in an amount of 0.1 wt .-% to 15 wt .-%, in particular from 2 wt .-% to 10 wt .-% in the Total composition is included.

8. Composition according to one of claims 1 to 7, characterized in that the radical scavenger is a benzene derivative, naphthalene derivative, Annulenderivat, cyclopentadiene derivative, cyclopropane derivative, aryl carboxylate, arylsulfonate or a mixture of these, in particular benzoic acid, methoxybenzoic acid, methylbenzoic acid, 4-toluenesulfonic acid, 2nd N-octylbenzoic acid, 3-nitrobenzoic acid, anisic acid, benzyl alcohol, methoxybenzyl alcohol, optionally substituted hydroxytoluene, 2-N-octylbenzyl alcohol, 3-nitrobenzyl alcohol, anisalcohol, or a mixture of these.

9. Composition according to one of claims 1 to 8, characterized in that the complexing agent is a phosphonate, phosphate, polyfunctional-substituted aromatic, ethylenediamine-N, N'-disuccinic acid or a mixture of these.

A method of bleaching textiles, comprising the steps of contacting the fabric with a liquid bleaching composition according to any one of claims 1 to 9 in diluted or undiluted form, leaving the fabric in contact with the bleaching composition for a time sufficient for bleaching, and rinsing the textile with water.

11. The method according to claim 10, characterized in that the textiles with a detergent containing at least one surfactant, before contacting the textile with the bleaching composition, and / or during the step of contacting with the bleaching composition, and / or after the step contacting with the bleaching composition and before the step of rinsing with water, and / or after the step of rinsing with water.