EP2414496A1

EP2414496A1 - Fluid bleaching agent composition

Info

Publication number: EP2414496A1
Application number: EP10707306A
Authority: EP
Inventors: Fabian Sieben; Tatiana Schymitzek
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2009-03-30
Filing date: 2010-03-11
Publication date: 2012-02-08
Anticipated expiration: 2030-03-11
Also published as: EP2414496B1; WO2010112312A1; US20120015859A1; DE102009001973A1

Abstract

The invention relates to an aqueous, fluid washing or cleaning agent comprising bleaching agent, comprising hydrogen peroxide and non-ionic tenside in the form of an alkoxylated alcohol and anionic tenside, wherein the weight ratio of alkoxylated alcohol to anionic tenside is in the range from 1:1 to 5:1, in particular 2:1 to 4:1, and the agent comprises a paraffin hydrocarbon.

Description

Liquid bleach composition

The present invention relates to liquid bleaching compositions which can be used as agents for cleaning textile and hard surfaces.

Liquid bleach compositions are known in the art as detergents, detergent additives and also as laundry pretreatment agents, as well as hard surface cleaners such as tiles, tiles or kitchen countertops.

In the laundry pretreatment, such bleach-containing compositions are used to improve the removal of caked-on dirt or stains or "problem spots" such as grease, coffee, tea, grass, grime and clay soils which are difficult to wash by washing with conventional laundry detergents Another field of application of such agents is the removal of local soiling of otherwise clean surfaces of textile fabrics, so that a more complex washing or cleaning process of the corresponding overall structure, be it a piece of clothing or a carpet or a piece of furniture upholstery, can be avoided The corresponding treatment with bleach-containing liquid agents are usually sour formulations are used when the bleaching agent is a peroxygen compound such as H ₂ O ₂ , as this remains longer shelf stable under acidic conditions Under acidic conditions has hydrogen However, peroxide has a lower bleaching power than under alkaline conditions. In order to achieve the best possible bleaching result, it is therefore generally desirable to work at pH values in the alkaline range.

In order to improve the washing performance or stain removal performance of hydrogen peroxide-containing formulations, these can be combined with nonaqueous solvents. Such solvent-containing preparations are particularly suitable for direct stain pretreatment and also as a detergent additive and in particular have an effect on greasy and pigment-containing stains. However, non-water-soluble solvents usually can not be readily hydrolyzed

Hydrogen peroxide preparations are incorporated, since it comes due to demixing tendencies, especially during prolonged storage, phase separations.

The present invention shows that this problem can be solved by considering the selection of the surfactants contributing to the achievement of a good cleaning result and therefore desirable. The present invention accordingly provides a bleach-containing aqueous liquid washing or cleaning agent which contains hydrogen peroxide and nonionic surfactant in the form of an alkoxylated alcohol and anionic surfactant, wherein the weight ratio of alkoxylated alcohol to anionic surfactant in the range from 1: 1 to 10: 1, in particular 2: 1 to 4: 1, and the agent contains a paraffinic hydrocarbon.

The alkoxylated alcohols used are preferably ethoxylated, propoxylated and / or butoxylated, advantageously ethoxylated, especially primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of alkylene oxide per mole of alcohol, in which the alcohol radical is linear or branched, including in particular 2-position may be methyl-branched or may contain linear and branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, alcohol ethoxylates having linear radicals of alcohols of native origin having 12 to 18 C atoms, for example coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 ethylene oxide (EO) per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C- ₂ - ₁₄ -alcohols with 3 EO, 4 EO or 7 EO, C ₉ .n-alcohol with 7 EO, C-ms alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -is-alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₁₂ - ₁₄ - alcohol having 3 EO and C | ₂ - ₁₈ alcohol with 7 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE). It is also possible to use fatty alcohols with more than 12 EO. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Alkoxylated alcohols which contain EO and PO groups together in the molecule can also be used according to the invention. Here, block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers. It is also mixed alkoxylated alcohols can be used in which EO and PO units are not block wise, but statistically distributed. Such products are available by the simultaneous action of ethylene and propylene oxide on fatty alcohols. Also suitable are mixtures of branched ethoxylated fatty alcohols and unbranched ethoxylated fatty alcohols, such as a mixture of a Ci ₆ -i ₈ fatty alcohol with 7 EO and 2-propylheptanol with 7 EO.

Compositions according to the invention preferably comprise from 3% by weight to 20% by weight, in particular from 5% by weight to 12% by weight, of alkoxylated alcohol, the statement of% by weight here and hereinafter referring to the total amount of washing or detergent refers. In addition to the alkoxylated alcohol, the agent according to the invention also necessarily contains an anionic surfactant. The anionic surfactant used is preferably sulfonates, sulfates, soaps and mixtures thereof.

Suitable surfactants of the sulfonate type are preferably C ₉ .i ₃ -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and also disulfonates, as are known for example from C 1 _{_2-18} monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products into consideration. Also suitable are alkanesulfonates, from C ₂ - ₁₈ are obtained, for example, alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization. Likewise suitable are the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Suitable alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric acid semiesters of the C ₁₂ -C ₁₈ FeKaIkOhoIs, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂ o- Oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. 2,3-alkyl sulfates, which can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

Also, the sulfuric acid monoesters of straight-chain or branched C ₇ ethoxylated with 1 to 6 moles of ethylene oxide. ₂₁ -alcohols, such as 2-methyl-branched C ^ -π-alcohols having an average of 3.5 moles of ethylene oxide (EO) or C ₁₂ . _18- fatty alcohols containing 1 to 4 EO are suitable and are used in preferred embodiments of the invention.

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ --i ₈ -fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which by themselves are nonionic surfactants. Again, sulfosuccinates, their fatty alcohol radicals derived from ethoxylated fatty alcohols with restricted homolog distribution, particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Also suitable anionic surfactants are soaps, in particular saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and in particular from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids, derived soap mixtures.

The anionic surfactants may be in the form of their sodium, potassium or magnesium salts. Preferably, the anionic surfactants are in the form of their sodium salts. Another preferred counterion for anionic surfactants is choline.

The content of an anionic surfactant according to the invention is preferably from 1% by weight to 15% by weight, in particular from 1.5% by weight to 7% by weight.

The paraffinic hydrocarbons contained in the agent according to the invention are liquid at room temperature. Typically, they are mixtures of hydrocarbon chains of different lengths, which may be linear or branched. They usually do not contain hydrocarbons with more than 17 carbon atoms. Preferably, the compositions of the invention contain branched-chain isoparaffins, with C ₁₂ -i ₄ -lsoparaffins being particularly preferred. An agent according to the invention preferably contains from 0.1% by weight to 2.5% by weight, in particular from 0.5% by weight to 1.5% by weight, of paraffinic hydrocarbon.

The content of hydrogen peroxide in the composition according to the invention is preferably 0.5 wt .-% to 5 wt .-%, in particular 1 wt .-% to 3 wt .-%.

It is possible that an agent according to the invention, apart from the surface-active ingredients mentioned, the paraffin and hydrogen peroxide, consists only of water. If appropriate, however, it is also possible to use further customary ingredients of detergents or cleaners, in particular additional surfactants, complexing agents, hydrotropes, radical scavengers, foam inhibitors, foam boosters, soil release agents, dyes and / or fragrances, but also dye transfer inhibitors and / or so-called fiber care agents. be included.

Other suitable surfactants are those of the type of alkylamine oxides which carry an alkyl group which corresponds to those in the abovementioned alkoxylated alcohols, and two shorter ones Carry alkyl groups such as methyl, ethyl or propyl. ₂₂ - - Under the alkylamine oxides are C _8, in particular C preferably ₂ -i ₄ -Alkyldinnethylanninoxide. Amine oxide is preferably present in the composition according to the invention in amounts of up to 2% by weight, in particular from 0.2% by weight to 1% by weight.

Further suitable surfactants also include N-alkylpyrrolidones whose alkyl group preferably has 6 to 22 C atoms, in particular 8 to 12 C atoms, and may be branched or preferably linear. N-alkylpyrrolidone is preferably present in the composition according to the invention in amounts of up to 2% by weight, in particular from 0.5% by weight to 1.5% by weight.

Hydrotropes which can be used in compositions according to the invention preferably originate from the group of monohydric or polyhydric alcohols, alkanolamines, ketones, ethers, esters or glycol ethers which are miscible at room temperature at least partially, more preferably unrestrictedly with water. The hydrotropes are preferably selected from ethanol, n- or i-propanol, the butanols, ethylene glycol, the propylene and butylene glycols, acetone, methyl acetate, ethyl acetate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, Diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, diisopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these. Hydrotropes may optionally be used in the compositions according to the invention in amounts of up to 1% by weight, preferably up to 0.8% by weight and in particular from 0.1% by weight to 0.5% by weight become.

To adjust the viscosity, one or more thickeners or thickening systems can be added to the composition according to the invention. The viscosity of the compositions of the invention can be measured using standard methods (for example Brookfield viscometer RVD-VII at 20 U / min and 2O ⁰ C, spindle 3) and is preferably in the range 200 mPa.s to 1200 mPa.s, especially 400 mPa.s to 900 mPa.s Suitable thickeners are usually polymeric compounds. These also called swelling (ungs) agent, mostly organic high molecular weight substances that absorb liquids, thereby swelling and eventually go into viscous real or colloidal solutions come from the groups of natural polymers, the modified natural polymers and fully synthetic polymers. Natural-derived polymers used as thickening agents include agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, gellan, diutan, guar flour, locust bean gum, starch, dextrins, gelatin and casein. Modified natural products come mainly from the group of modified starches and celluloses, examples being carboxymethylcellulose. Methyl cellulose and other cellulose ethers, hydroxyethyl and propyl cellulose and Kernmehlether called. A large group of thickeners, which find wide use in a variety of applications, are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes. Also suitable are so-called swelling clays, such as sodium magnesium silicates.

To increase the storage stability, complexing agents may additionally be used in the compositions according to the invention. Examples of complexing agents are low molecular weight hydroxycarboxylic acids such as citric acid, tartaric acid, malic acid, or gluconic acid or their salts, with citric acid or sodium citrate being particularly preferred. In order to avoid the catalyzed by heavy metals decomposition of certain detergent ingredients, especially the hydrogen peroxide, substances can be used that complex heavy metals. Suitable heavy metal complexing agents are, for example, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA) or N, N-biscarboxymethylalanine in the form of the free acids or as alkali metal salts and derivatives thereof and the alkali metal salts of anionic polyelectrolytes, such as polymaleates and polysulfonates. A preferred class of complexing agents are the phosphonates. These preferred compounds include in particular organophosphonates such as 1-hydroxyethane-1, 1-diphosphonic acid (HEDP), aminotri (methylene phosphonic acid) (ATMP), diethylenetriamine penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1 , 2,4-tricarboxylic acid (PBS-AM), which are mostly used in the form of their ammonium or alkali metal salts. Complexing agents are contained in agents according to the invention preferably in amounts of from 0.01% by weight to 2.0% by weight, in particular from 0.05 to 0.5% by weight.

Suitable soil release agents are, for example, the polymers of phthalic acid and / or terephthalic acid known from the prior art or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Also, polyacrylates may optionally be used.

Active ingredients which are known to function as radical scavengers, which are preferably present in the compositions according to the invention in amounts of from 0.01% by weight to 0.1% by weight, include phenols, such as 1,6-di-tert-butyl-4 methylphenol (butylhydroxytoluene, BHT), hydroquinones such as di-tert-butyl-hydroquinone, catechols such as allylcatechol, alkylated diphenylamines or N-phenyl-α-naphthylamines and dihydroquinolines. BHT is used as the preferred radical scavenger. Around It has been found useful to incorporate such normally poorly water-soluble substances into compositions according to the invention, in the form of a solution in a water-miscible solvent, for example a lower alcohol such as ethanol or isopropanol.

Optionally, optical brighteners may be added to the compositions of the present invention to eliminate graying and yellowing of the treated fabrics. These fabrics impinge on the fiber and cause whitening and bleaching by transforming invisible ultraviolet radiation into visible longer wavelength light, emitting the ultraviolet light absorbed from the sunlight as faint bluish fluorescence, and pure with the yellowness of the grayed or yellowed wash White results. Suitable compounds for example, originate from the substance classes of the 4,4 ^'2,2 -Diamino- ^{stilbenedisulfonic} acids (flavonic), ^{4,4'-biphenylene} -Distyryl, Methylumbelliferone, coumarins, dihydroquinolinones, 1, 3-diaryl pyrazolines, naphthalimides, benzoxazole , Benzisoxazole and benzimidazole systems as well as heterocyclic substituted pyrene derivatives. The optical brighteners are usually used in amounts between 0.01 and 0.3 wt .-%, based on the finished composition, but can, especially if the means for cleaning sensitive and / or colored surfaces are to be used, even completely absent ,

The compositions may contain color transfer inhibitor which in a preferred embodiment is a polymer of vinylpyrrolidone, vinylimidazole, vinylpyridine-N-oxide or a copolymer thereof. Among the copolymers, those of vinylpyrrolidone and vinylimidazole in a molar ratio of 5: 1 to 1: 1 having an average molecular weight in the range of 5,000 to 50,000, especially 10,000 to 20,000 are preferred.

Since textile fabrics, in particular of rayon, rayon, cotton and their mixtures, may be creasing because the individual fibers are sensitive to bending, buckling, pressing and squeezing transversely to the fiber direction, the compositions according to the invention may contain synthetic crease inhibitors. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, -alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.

The preparation of the compositions according to the invention is carried out continuously or batchwise by simply mixing the constituents, with water, solvent and surfactant (s) being suitably initially introduced and the further constituents being added in portions. Separate heating during production is not required if desired is, the temperature of the mixture 8O ⁰ C should not exceed. The compositions according to the invention can be filled into customary bottles, if appropriate into those with gas-permeable closure systems, from which they can be poured out or, if appropriate, sprayed via nozzle openings onto the surface to be cleaned.

Preferably, an agent according to the invention has a pH in the range from pH 4 to pH 6, in particular in the range from pH 5 to pH 5.5. By adding conventional system-compatible acids, in particular citric acid, lactic acid or malic acid, pH values in these ranges can be easily adjusted if they do not already result from the composition of the other ingredients.

The compositions according to the invention are preferably used for cleaning soiled surfaces of textile fabrics which may be washable, in particular a garment, or non-washable home textiles, in particular a textile upholstery material or a carpet, or as a washing additive or for cleaning soiled hard surfaces. However, they can also be used as a heavy-duty detergent or as a washing power booster. Their use as household cleaners, for example in wet rooms and in the kitchen, as a dishwashing detergent or for upholstery or carpet cleaning is possible.

For cleaning soiled surfaces of textile fabrics, it is preferable to apply the agent according to the invention to the textile or at least to the soiled parts of the textile, leave it to act there and then remove it by treatment with water. This treatment step with water can take place in the context of a customary manual or automatic textile washing process, so that the treatment according to the invention then corresponds to a conventional pretreatment step.

An agent according to the invention is usually applied to the fabric for a treatment of the textile surface over a period of up to 24 hours, in particular from 30 seconds to one hour and particularly preferably from 1 minute to 30 minutes. The same applies to the treatment of hard surfaces, but here preferably periods at the lower end of the specified ranges are more suitable. The period should be chosen so that the liquid composition does not dry on the surface. Usually, the surfaces to be cleaned are contaminated with dried-on stains or dirt, which are generally very difficult to remove. The liquid agents can simply be applied to the surface and left there and then rinsed off, but the soil removal can also be assisted by mechanical support, for example by rubbing or by treating with a sponge or a brush. Likewise, the removal by Treat with water using a moistened sponge or cloth. The latter is except for hard surfaces, especially in sensitive non-washable home textiles, such as textile upholstery materials or carpets on.

As a rule, the compositions according to the invention are applied in undiluted form to the textiles or to the substrate to be treated. If necessary, they can also be diluted with water before use. They can also be used as an additive in a conventional washing process, in particular a mechanical washing process, together with a commercial detergent.

Examples

Detergents of the following total composition (% by weight) were prepared:

E1 E2

C ₁₂ -i ₄ fatty alcohol with 7 EO 6 10

C ₁₂ -i ₆ fatty alcohol with 2 EO sulfate, Na salt 1, 5 1, 5

N-Laurylpyrrolidone 1 -

C ₁₂ -i ₄ -alkyl-dimethylamine oxide - 0.6

Hydrogen peroxide 6,5 4,5

C ₁₂ -i ₄ iso-paraffin 1 1

Xanthan 0.4 0.1

Etidic acid 0.05 0.05

N, N-Biscarboxymethylalanine, Na Sa 0.1 0.1

Ethanol 0.1 0.1

BHT 0.03 0.03

Soil-Release-Polyester 0,5 -

Dye + -

Perfume + +

Water Ad 100 Ad 100

Both compositions had a pH of about 5 to 5.5; E1 had a viscosity of about 850 mPa.s, E2 of about 450 mPa.s.

Claims

claims

A bleach-containing aqueous liquid washing or cleaning composition containing hydrogen peroxide and nonionic surfactant in the form of an alkoxylated alcohol and anionic surfactant, wherein the weight ratio of alkoxylated alcohol to anionic surfactant in the range of 1: 1 to 10: 1, especially 2: 1 to 4: 1, and the agent contains a paraffinic hydrocarbon.

2. Composition according to claim 1, characterized in that it contains 3 wt .-% to 20 wt .-%, in particular 5 wt .-% to 12 wt .-% alkoxylated alcohol.

3. Composition according to claim 1 or 2, characterized in that the alkoxylated alcohol is selected from ethoxylated, propoxylated and / or butoxylated alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of alkylene oxide per mole of alcohol.

4. Composition according to one of claims 1 to 3, characterized in that it contains 1 wt .-% to 15 wt .-%, in particular 1, 5 wt .-% to 7 wt .-% anionic surfactant.

5. Composition according to one of claims 1 to 4, characterized in that the anionic surfactant is a sulfuric acid monoester of ethoxylated with 1 to 6 moles of ethylene oxide straight-chain or branched C _7th _{2 is} i-alcohols.

6. Composition according to one of claims 1 to 5, characterized in that it is 0.1 wt .-% to 2.5 wt .-%, in particular 0.5 wt .-% to 1, 5 wt .-% paraffinic hydrocarbon contains.

7. Composition according to one of claims 1 to 6, characterized in that it contains 0.5 wt .-% to 5 wt .-%, in particular 1 wt .-% to 3 wt .-% hydrogen peroxide.

8. Composition according to one of claims 1 to 7, characterized in that it contains additional surfactants, complexing agents, hydrotropes, radical scavengers, foam inhibitors, foam boosters, soil release agents, dyes and / or fragrances, but also color transfer inhibitors and / or so-called contains fiber care agents.

9. Use of a composition according to any one of claims 1 to 8 for cleaning soiled textile surfaces.

10. Use according to claim 9, characterized in that applying the composition, optionally after dilution with water, on the textile or at least on the soiled parts of the textile, there to act and then removed by treatment with water.

11. Use according to claim 9 or 10, characterized in that the textile is washable, in particular a garment, or that the textile is a non-washable home textile, in particular a textile padding material or a carpet.

12. Use of a composition according to any one of claims 1 to 8 for cleaning soiled hard surfaces.