EP0009193A1 - Liquid cleanser for hard surfaces - Google Patents

Abstract

1. A liquid cleaning agent for hard surfaces based on aqueous solutions of surfactants, builders and organic polymers, characterized in that it contains as organic polymers from 0.05 to 0.5 % by weight and preferably from 0.08 to 0.4 % by weight of water-soluble polyethylene glycols having a molecular weight of from 300,000 to 4,000,000 and preferably from 500,000 to 1,000,000.

Description

Modern prefabricated construction methods, easy-care kitchen, bathroom and cellar furnishings, plastic-veneered furniture, the increasing equipment of households with freezers, refrigerators, washing machines and dishwashers, i.e. devices with enamelled or plastic-coated large-area metal walls have the demand for liquid all-purpose cleaning agents for use in the household in have increased significantly in recent years. But the use of such agents has also become increasingly important in commercial enterprises. It is required that it be as simple and problem-free as possible to use. The agents are usually marketed as preferably aqueous concentrates. They can be applied diluted or undiluted to a damp, absorbent cloth of any nature or a sponge, which is then used to wipe the hard surfaces made of metal, lacquered wood, plastic, ceramic products such as porcelain, tiles, tiles and the like, thereby causing dust, grease and stains be removed. It is desired that this surface treatment does not have any detergent stains and streaks leaves behind and does not require post-treatment with a damp cloth soaked in clear water.

Numerous cleaning agents of this type are already known from the market and from the literature. In addition, it is also known from the patent literature to add different polymers to these cleaning agents to increase their cleaning power.

DE-AS 10 51 440 discloses liquid cleaning agents which are used for all purposes, but especially for washing textiles, and to increase the dirt-carrying capacity, inter alia, water-soluble cellulose or starch derivatives or else water-soluble or colloidally soluble polymers, such as polyvinylpyrrolidone. can contain.

AT-PS 2 78 216 discloses liquid cleaning agents which can also contain water-soluble high-molecular substances as dirt carriers. Water-soluble salts of polyacrylic acid and also water-soluble derivatives of cellulose such as carboxymethyl cellulose are mentioned as examples.

From US-PS 35 91 509 liquid all-purpose cleaners are known which, in addition to water-soluble synthetic surface-active substances, organic solvents and optionally water-soluble builders, a small amount of a special water-soluble carboxymethyl cellulose, namely one with a degree of substitution of about 1 to about 2 and a degree of polymerization of contain about 1000 to about 3000 as well as water. From DE-OS 26 10 995 liquid builder-containing cleaning agents for hard surfaces with small amounts of surfactants in combination with small amounts of a mixture of polyvinyl alcohol and / or polyvinyl pyrrolidone and polysaccharide salt are known, which should also have an improved dirt removal capacity.

Finally, from DE-AS 27 09 690 liquid cleaning agents for hard surfaces are known, which can also contain cleaning-enhancing additives to water-soluble high-molecular substances, such as polyvinyl alcohol, polyvinyl pyrrolidone and carboxymethyl cellulose.

None of the above-mentioned polymeric cleaning enhancers fully meets the demands that the consumer places today on a liquid cleaning agent for hard surfaces. This also explains why these polymers, some of which have been known for a long time, have no significant significance as additives to household cleaners used in large quantities. Some disadvantages of these known polymers are e.g. B. insufficient solubility, excessive thickening or residue, d. H. Streaking or film formation when using the agents, if they contain polymers in the amounts necessary to enhance cleaning.

Surprisingly, it has now been found that a completely unexpected increase in the cleaning performance of liquid cleaning agents for hard surfaces can be achieved if, instead of the known additions of dirt-bearing compounds, substantially smaller amounts of polyethylene glycols with a certain molecular weight are added.

The present invention therefore relates to a liquid detergent for hard surfaces in the form of dilute, preferably aqueous solutions containing anionic, nonionic or cationic surfactants or suitable mixtures thereof, organic and / or inorganic builders, optionally water-soluble solvents or solubilizers and other customary components of such Detergent and organic polymers, which is characterized in that 0.05 to 0.5, preferably 0.08 to 0.4% by weight of water-soluble polyethylene glycols with a molecular weight between 300,000 and 4,000,000, preferably between 500,000, are used as organic polymers and deploys 1,000,000. With these amounts of use, which bring about an unexpected cleaning enhancement, none of the above-mentioned disadvantages of the known polymers can be observed.

The polyethylene glycols mentioned are prepared in a known manner by subjecting ethylene glycols to a polycondensation process in a known manner. They can also be considered as condensation polymers of ethylene oxide with ethylene glycol or water. They have the general formula FO (-CH ₂ -CH ₂ -O) _n H, where n can vary between 4800 and 64,600 in the case of the polyethylene glycols used according to the invention.

Such polymers are also commercially available and are sold by Union Carbon Carbide Corporation (UCC) under the name "POLYOX.

Practically all conventional surfactants and mixtures of surfactants can be used which contain at least one hydrophobic organic residue and one water-solubilizing anionic, nonionic or cationic residue in the molecule. The hydrophobic residue is usually an aliphatic hydrocarbon residue with 8-26, preferably 10-22 and in particular 12-18 C atoms or an alkyl aromatic radical having 6 to 18, preferably 8 to 16 aliphatic C atoms. In the case of the surfactant mixtures, the known incompatibility of most anionic and cationic surfactants would have to be taken into account.

Preferably, amounts of 1-30% by weight of surfactants from the group of synthetic anionic surfactants, soaps and nonionic surfactants and mixtures thereof are used. Surfactant combinations of anionic surfactants from the group of the sulfonate and sulfate surfactants and the nonionic surfactants of the ethoxylated alkanols, alkenols and alkylphenols type are particularly preferred. A soap can be included as a further component.

Because of the small amount of the polymers used according to the invention, the weight ratio of the total amount of surfactant to the polymer is at least 10: 1, in particular at least 20: 1.

As anionic surfactants such. B. Soaps from natural or synthetic, preferably saturated fatty acids, optionally also from resin or naphthenic acids. Suitable synthetic anionic surfactants are those of the sulfonate, sulfate and synthetic carboxylate type.

Suitable surfactants of the sulfonate type are alkylbenzenesulfonates (C _9-15 -alkyl), mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonating group , into consideration. Also suitable are alkanesulfonates which can be obtained from alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins. Other useful surfactants of the sulfonate type are the esters of d-sulfo fatty acids, e.g. B. the d-sulfonic acids from hydrogenated methyl or ethyl esters of coconut, palm kernel or tallow fatty acid.

Suitable sulfate-type surfactants are the sulfuric acid monoesters of primary alcohols (for example from coconut fatty alcohols, tallow fatty alcohols or oleyl alcohol) and those of secondary alcohols. Sulfated fatty acid alkanolamides, fatty acid monoglycerides or reaction products of 1-4 moles of ethylene oxide with primary or secondary fatty alcohols or alkylphenols are also suitable.

Other suitable anionic surfactants are the fatty acid esters or amides of hydroxy or amino carboxylic acids or sulfonic acids, such as. B. the fatty acid sarcosides, glycolates, lactates, taurides or isethionates.

The anionic surfactants can be present in the form of their alkali, alkaline earth and ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The sodium salts are mostly preferred for cost reasons.

Addition products of 4-40, preferably 4-20 moles of ethylene oxide or ethylene oxide and propylene oxide with 1 mole of fatty alcohol, alkanediol, alkylphenol, fatty acid, fatty amine, fatty acid amide or alkanesulfonamide can be used as nonionic surfactants. The addition products of 5-16 moles of ethylene oxide or ethylene and propylene oxide with coconut oil or tallow fatty alcohols, with oleyl alcohol or with secondary alcohols with 8-18, preferably 12-18, carbon atoms, and with mono- or dialkylphenols with 6-, 14 carbon atoms in the alkyl radicals. In addition to these water-soluble nonionics, non-fully or not fully water-soluble polyglycol ethers with 1-4 ethylene glycol ether residues in the molecule are also of interest, in particular if they are used together with water-soluble nonionic or anionic surfactants.

Furthermore, the non-ionic surfactants which can be used are the water-soluble adducts of ethylene oxide with polypropylene oxide, alkylene diamine polypropylene glycol and alkyl polypropylene glycols with 1-10 C atoms in the alkyl chain, in which the polypropylene glycol chain functions as a hydrophobic residue, containing polypropylene oxide, alkylene diamine polypropylene glycol and 10-100 propylene glycol ether groups.

Nonionic surfactants of the amine oxide type can also be used. Typical representatives are, for example, the compounds N-dodecyl-N, N-dimethylamine oxide, N-tetradecyl-N, N-dihydroxyethylamine oxide, N-hexadecyl-N, N-bis (2,3-dihydroxypropyl) amine oxide.

The cationic surfactants contain at least one hydrophobic and at least one basic group, which may be in the form of a salt and which makes water soluble. The hydrophobic group is an aliphatic or cycloaliphatic hydrocarbon group with preferably 10-22 carbon atoms or an alkyl or cycloalkylaromatic group with preferably 8-16 aliphatic carbon atoms. As basic groups, primarily basic nitrogen atoms come into question, which can also be present several times in a surfactant molecule; it is preferably quaternary ammonium compounds such as N-dodecyl-N, N, N-trimethylammonium methosulfate, N-hexadecyl or N-octadecyl-N, N, N-trimethylammonium chloride, N, N-dicocosalkyl-ti, N -dimethylammonium, - chloride, N-dodecyl-N, N-dimethyl-N-benzylammonium bromide, the reaction product of 1 mol of tallow alkylamine with 10 mol of ethylene oxide, N-dodecyl-N, N ', N'-trimethyl-1,3-diaminopropane , N-hexadecylpyridinium chloride.

The nitrogen compounds mentioned can be replaced by corresponding compounds with a quaternary phosphorus atom or with a tertiary sulfur atom.

For the liquid cleaning agents according to the invention, alkaline organic or inorganic compounds, in particular inorganic or organic complexing agents, are used as framework substances in their entirety, which are preferably present in the form of their alkali metal or amine salts, in particular the potassium salts. The framework substances here also include the alkali metal hydroxides, of which the potassium hydroxide is preferably used. The alkaline polyphosphates, in particular the tripolyphosphates and the pyrophosphates, are particularly suitable as inorganic complex-forming framework substances. They can be replaced in whole or in part by organic complexing agents. Further inorganic builder substances which can be used according to the invention are, for example, dicarbonates, carbonates, borates, silicates or orthophosphates of the alkalis.

The organic complexing agents of the aminopolycarboxylic acid type include, among others, nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethylethylene diamine triacetic acid and polyalkylene polyamine N-polycarboxylic acids. Examples of di- and polyphosphonic acids are: methylenediphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, propane-1,2,3-triphosphonic acid, butane-1,2,3,4-tetraphonic acid, polyvinylphosphonic acid, copolymers of vinylphosphonic acid and Acrylic acid, ethane-1,2, dicarboxy-1,2-diphosphonic acid, ethane-1,2-dicarboxy-1,2-dihydroxy-diphosphonic acid, phosphonosuccinic acid, 1-aminoethane-1,1-diphosphonic acid, aminotri- (me - Thylenephosphonic acid), methylamino- or ethylamino-di- (methylenephosphonic acid) and ethylenediamine-tetra- (methylenephosphonic acid).

A wide variety of, mostly N- or P-free polycarboxylic acids have recently been proposed as builders in the literature, many, if not exclusively, of polymers containing carboxyl groups. A large number of these polycarboxylic acids have a complexing ability for calcium. These include e.g. As citric acid, tartaric acid, benzene hexacarboxylic acid, tetrahydrofuran tetracarboxylic acid, etc.

Since household cleaning agents are generally almost neutral to slightly alkaline, i. H. their aqueous working solutions at application concentrations of 2 - 20, preferably 5 - 15 g / 1 water or aqueous solution have a pH in the range of 7.0 - 10.5, preferably 7.5 - 9.5 Regulation of the pH may require the addition of acidic or alkaline components.

Suitable acidic substances are customary inorganic or organic acids or acidic salts, such as, for example, hydrochloric acid, sulfuric acid, bisulfates of alkalis, aminosulfonic acid, phosphoric acid or other acids of phosphorus, in particular the anhydrous acids of phosphorus or their acidic salts or their acid-reacting solid compounds with urea or other lower carboxylic acid amides, partial amides of phosphoric acids or anhydrous phosphoric acid, citric acid, tartaric acid, lactic acid and the like.

If the content of alkaline builders is not sufficient to regulate the pH, organic or inorganic compounds such as alkanolamines, namely mono-, di- or triethanolamine or ammonia, can also be added.

In addition, known solubilizers can be incorporated, which in addition to the water-soluble organic solvents such as, in particular, low-molecular aliphatic alcohols with 1-4 carbon atoms, also include the so-called hydrotropic substances of the lower alkylarylsulfonate type, for example toluene, xylene or cumene sulfonate. They can also be in the form of their sodium and / or potassium and / or alkylamino salts. Water-soluble organic solvents can also be used as solubilizers, in particular those with boiling points above 75 ° C., for example the ethers from the same or different types of polyhydric alcohols or the partial ethers from polyhydric alcohols. These include, for example, di- or triethylene glycol polyglycerols and the partial ethers of ethylene glycol, propylene glycol, butylene glycol or glycerol with aliphatic monohydric alcohols containing 1 to 4 carbon atoms in the molecule.

Suitable water-soluble or water-emulsifiable organic solvents are also ketones, such as acetone, methyl ethyl ketone and aliphatic, cycloaliphatic, aromatic and chlorinated hydrocarbons, and also the terpene alcohols.

To regulate the viscosity, it may be advisable to add higher polyglycol ethers with molecular weights up to about 600 or polyglycerol. It is also recommended to add sodium chloride and / or urea to regulate the viscosity.

In addition, the claimed agents can contain additives of colorants and fragrances, preservatives and, if desired, antimicrobial agents of any kind.

Suitable antimicrobial agents to be used are those compounds which are stable and effective in the liquid agents according to the invention. These are phenolic compounds of the halogenated phenol type with 1-5 halogen substituents, in particular chlorinated phenols; Alkyl, cycloalkyl, aralkyl and phenylphenols with 1-12 carbon atoms in the alkyl radicals and with 1-4 halogen substituents, in particular chlorine and bromine in the molecule; Alkylene bisphenols, in particular derivatives substituted by 2-6 halogen atoms and optionally lower alkyl or trifluoromethyl groups, with an alkylene bridge member having 1-10 carbon atoms; Hydroxybenzoic acids or their esters and amido, in particular anilides, which can be substituted in the benzoic acid and / or _A nilinrest, in particular also 2 or 3-halogen atoms and / or trifluoromethyl groups; Orthophenoxyphenols, which can be substituted by 1 7, preferably 2- 5 halogen atoms and / or the hydroxyl, cyano, methoxycarbonyl and carboxyl group or lower alkyl. Particularly preferred antimicrobial agents of the phenyl type are e.g. B. O-phenylphenol, 2-phenylphenol, 2-hydroxy-2 ', 4,4'-trichlorodiphenyl ether, 3,4', 5-tribromosalicylanilide and 3,3 ', 5,5', 6,6'-hexachloro- 2,2'-dihydroxy-diphenylmethane.

Other useful antimicrobial agents are the lower alcohols or diols having 3 to 5 carbon atoms, such as those substituted by bromine or by the nitro group. B. the compounds 2-bromo-2-nitro-propanediol-1,3, 1-bromo-1-nitro-3,3,3-trichloropropanol, 2,2-bromo-2-nitro-butanol-1.

Bis-diguanides such as, for. B. the 1,6-bis (p-chlorophenyldiguanido) hexane in the form of the hydrochloride, acetate or gluconate and also N, N'-disubstituted 2-thione-tetrahydro-1,3,5-thiadinazines such as. B, the 3,5-dimethyl-, 3,5-diallyl-, 3-benzl-5-methyl- and especially the 3-benzyl-5-carboxymethyl-tetrahydro-1,3,5-thiadiazine as additional anticrobial agents.

Formaldehyde-amino alcohol condensation products can preferably be used. The products are obtained by reacting an aqueous solution of formaldehyde with amino alcohols, e.g. B. 2-aminoethanol, 1-amino-2-propanol 2- Aminoiso-butanol, 2 (2'-aminoethyl) aminoethanol.

In addition, it may be advantageous for other areas of application to additionally add further antimicrobial substances, for example of the quaternary ammonium compound type, for example a benzylalkyldimethylammonium chloride.

Tries

To demonstrate the advantages of the cleaning agents according to the invention over the known cleaning agents for hard surfaces, comparisons were made with regard to their cleaning ability and their residue formation.

The test method described below was used to test the cleaning ability and provides very reproducible results. Furthermore, the cleaning agents according to the invention and a comparison product each were handed over to housewives for several weeks for use testing. After the test period, these test persons were asked about their experiences with regard to cleaning effect and residue behavior.

In addition, the residue behavior was checked in laboratory tests on mirrors, black tiles and plastic surfaces. Here, adjacent areas were treated with the diluted solutions of the agents according to the invention and with a comparative product. The test areas were allowed to air dry without wiping and the appearance of the dry areas was assessed by several test persons.

Testing the cleaning effect

The cleaning agent to be tested is placed on an artificially soiled plastic surface. A mixture of carbon black, machine oil, triglyceride, saturated fatty acids and low-boiling aliphatic hydrocarbon is used as artificial soiling. The test area of 26 x 28 cm is evenly coated with 2 g of the artificial soiling with the help of a surface coater.

A plastic sponge is soaked with 1 _" 2 ml of the detergent solution to be tested and moved mechanically on the test surface. After 6 wiping movements, the cleaned test surface is kept under running water and the loose dirt is removed. The cleaning effect, ie, the whiteness of the plastic surface cleaned in this way is measured with a photoelectric color measuring device LF 90 (Dr. B. Lange) The clean white plastic surface serves as the white standard.

Since the measurement of the clean surface is set to 100% and the soiled area is shown with O, the read values for the cleaned plastic surfaces are to be equated with the percentage cleaning capacity (% RV). In the tests below, the% RV values given are the values determined by this method for the cleaning ability of the investigated cleaning agents. They represent mean values from fourfold determinations.

Example: 1 e example 1

The all-purpose cleaner shows an RV of 85% when used as a 1% aqueous solution. The comparative product without POLYOX an RV of 64%. If 0.3% by weight of polyvinyl alcohol was added to the comparison product, only a value of 63% RV was likewise obtained. If its proportion was increased to 0.5% by weight, there was still no increase in cleaning performance. In addition, the product became so highly viscous that a further increase in the proportion of polyvinyl alcohol no longer made sense for this reason alone.

When testing the residue behavior, a black tile wall was wiped half with the 1% solution of the cleaning agent according to Example 1 and half with the comparison sample with 0.3% by weight polyvinyl alcohol. After drying in air, the surface treated with the agent according to the invention showed no visible residue, while the comparison surface had clear plaster strips.

Example 2

RV of the undiluted product: 98% RV of the undiluted comparison product without polymer: 75%.

Example 3

No visible residue was visible after use on mirrors, black tiles and plastic surfaces.

Example 4

RV of the 1% solution: 84% RV of the 1% solution of the comparison sample without POLYOX: 60%.

The residue behavior was perfect as in the previous examples.

Example 5

RV of the 2% solution: 64% RV of the 2% solution of the comparative product without polymer: 42%.

Trying to include other known polymers in this formulation instead of POLYOX, e.g. B. to incorporate polyvinyl alcohol, polyacrylates or copolymers of acrylic and methacrylic acid failed because of their lack of solubility in this agent.

Example 6

It was not possible to increase the polymers known as cleaning enhancers in comparison samples 4) and 5), since the amounts used here were no longer clearly soluble.

Claims (10)

1. Liquid cleaning agent for hard surfaces, based on aqueous solutions of surfactants, builders and organic polymers, characterized in that it is 0.05 to 0.5, preferably 0.08 to 0.4% by weight of water-soluble polyethylene glycols as organic polymers with a molecular weight between 300,000 and 4,000,000, preferably between 500,000 and 1,000,000. 2. Composition according to claim 1, characterized in that it contains synthetic anionic surfactants, soaps or nonionic surfactants, or their mixtures in amounts of 1 - 30 wt .-%, based on the total formulation. 3. Composition according to claim 1 and 2, characterized in that it contains a surfactant combination of anionic surfactants from the group of sulfonate and sulfate surfactants and nonionic surfactants of the type of ethoxylated alkanols, alkenols and alkylphenols, optionally together with a soap. 4. Composition according to claim 1 to 3, characterized in that it further contains solubilizers, preferably toluene, xylene or cumene sulfonate. 5. Composition according to claim 1 to 4, characterized in that it contains as a solubilizer ether from the same or different types of polyhydric alcohols with 1-4 carbon atoms. 6. Composition according to claim 1 to 5, characterized in that it further contains antimicrobial agents. 7. Composition according to claim 1 to 6, characterized in that it contains aldehyde condensation products as antimicrobial agents. 8. Composition according to claim 1 to 7, characterized in that it contains quaternary ammonium compounds as antimicrobial agents. 9. Composition according to claim 1 to 8, characterized in that it further contains nitrogen compounds such as ammonium hydroxide or mono-, di- or trialkanolamine as pH regulating agent. 10.Means according to claim 1 to 9, characterized in that it further contains dyes and fragrances and preservatives.