EP0295590A2 - Liquid cleaning composition for hard surfaces - Google Patents

Abstract

To improve the cleaning and dirt-dispersing ability of liquid cleaning agents, 0.01-1% by weight of a cleaning amplifier mixture in a weight ratio of polyacrylamide: highly polyethoxylated alkanols of 1: 3 to 3: 1 are added. Preferred polyacrylamides are polymers or copolymers of acrylamide with molecular weights of preferably from 2,000,000 to 1,200,000. The highly polyethoxylated mono- or polyvalent alkanols are addition products of 30-150 mol ethylene oxide onto terminal or internal hydroxyalkanols with 12-22 carbon atoms or addition products of 40- 90 moles of ethylene oxide in stearyl or 12-hydroxystearyl alcohol.

Description

DE-AS 10 51 440 discloses liquid cleaning agents which are used for all purposes, but especially for washing textiles, and which, in addition to anionic and nonionic surfactants to increase the dirt-carrying capacity, include small amounts of water-soluble cellulose or starch derivatives or else of water-soluble or colloidally soluble polymers, such as polyvinylpyrrolidone.

AT-PS 278 216 discloses liquid cleaning agents which can also contain water-soluble high-molecular substances as dirt carriers. Examples include water-soluble salts of polyacrylic acid and also water-soluble derivatives of cellulose such as carboxymethyl cellulose. Mixtures of anionic and nonionic surfactants are also preferably used here.

US Pat. No. 3,591,509 discloses liquid all-purpose cleaners which, in addition to water-soluble synthetic surface-active substances, organic solvents and optionally water-soluble builders, contain 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 about 1000 to about 3000 as well Contain water. This product has a thickening effect and is said to improve the adhesive strength of the cleaning agents on dirty surfaces.

From DE-OS 26 10 995 liquid builder-containing cleaning agents for hard surfaces with small amounts of preferably anionic 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.

German patent specification 27 09 690 describes liquid detergents for hard surfaces which essentially consist of a mixture of anionic and nonionic surfactants and, if appropriate, other conventional constituents of such agents, such as, for example, framework substances, adducts of ethylene oxide with aliphatic vicinal diols being used as nonionic surfactants or partially etherified diols with a linear alkyl chain of 10 to 20 carbon atoms. They 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 met the demands that the consumer places on a liquid cleaning agent for hard surfaces today.

So it was described in German Offenlegungsschrift 28 40 463 that you get a completely unexpected increase in the cleaning performance of such liquid cleaning agents for hard surfaces if, instead of the known additions of dirt-bearing compounds, significantly smaller amounts of polyethylene glycols with a molecular weight between 500,000 and 4,000,000 adds.

And German Offenlegungsschrift 29 13 049 shows that one can even dispense with the proportion of anionic surfactants and still achieve comparable good cleaning results if instead of them water-soluble nonionic, weakly anionic or cationic polymers from the group of polyethylene glycols, polyvinyl alcohols , Polyvinylpyrrolidones, cellulose ethers, polysaccharides, proteins and polyacrylamides with average molecular weights of 5,000 to 10,000,000, preferably 20,000 to 2,000,000, or mixtures of these polymers.

It has now been found that both the cleaning ability (RV) and the dirt dispersing power of liquid cleaning agents for hard surfaces based on surfactants, cleaning agents, possibly with a content of builders, and other conventional components of such agents can be surprisingly greatly increased if they contain a mixture of polyacrylamides and highly polyethoxylated mono- or polyhydric alkanols as cleaning enhancers.

The liquid detergents contain approximately
0.5 to 40, preferably 5 to 20 percent by weight of surfactants or surfactant mixtures,
0 to 6, preferably 1.0 to 6 percent by weight of organic or inorganic builders,
0.01 to 1, preferably 0.05 to 0.5 percent by weight of cleaning boosters,
as well as up to a total of 100% by weight of water, solvents, hydrotropes, preservatives, antimicrobial agents, viscosity regulators, pH regulators, perfume and dyes.

Practically all known surfactants and mixtures of surfactants that are commonly used in the claimed cleaning agent type can be used. These are generally those which contain at least one hydrophobic organic radical and one water-solubilizing anionic, nonionic or cationic radical in the molecule. The hydrophobic radical is usually an aliphatic hydrocarbon radical with 8 to 26, preferably 10 to 22 and in particular 12 to 18 carbon atoms or an alkyl aromatic radical with 6 to 18, preferably 8 to 16 aliphatic carbon atoms. In the case of the surfactant mixtures, the known incompatibility of many anionic and cationic surfactants would have to be taken into account.

Surfactants from the group of nonionic and synthetic anionic surfactants, soaps and mixtures thereof are preferably used. Surfactant combinations of the nonionic surfactants of the ethoxylated alkanediols, alkanols, alkenols and alkylphenols type and the synthetic anionic surfactants from the group of the sulfonate and sulfate surfactants are particularly preferred. A soap can be included as a further component.

Addition products of 4 to 40, preferably 4 to 20 moles of ethylene oxide or ethylene oxide and propylene oxide with 1 mole of fatty alcohols, preferably terminal or vicinal internal alkanediols, alkylphenols, fatty acids, fatty amines, fatty acid amides or alkanesulfonamides, can be used as nonionic surfactants. These include the adducts of 5 to 16 moles of ethylene oxide or ethylene and propylene oxide with coconut or tallow fatty alcohols, with oleyl alcohol or with secondary alcohols with 8 to 18, preferably 12 to 18 carbons as well as with mono- or dialkylphenols with 6 to 14 carbon atoms in the Alkyl residues. The addition products of ethylene oxide with aliphatic vicinal terminal or internal alkane diols are particularly important linear alkyl chain with 10 to 20 carbon atoms, which are known from German patent specification 27 09 690. In addition to these water-soluble nonionics, polyglycol ethers with 1 to 4 ethylene glycol ether residues in the molecule, which are not or not completely water-soluble, are also of interest, in particular if they are used together with other water-soluble nonionic or anionic surfactants.

Furthermore, the non-ionic surfactants that can be used are the water-soluble adducts of ethylene oxide with polypropylene oxide, alkylene diamine polypropylene glycol and alkyl polypropylene glycols with 1 to 10 carbon atoms in the alkyl chain, in which the polypropylene glycol chain acts as a hydrophobic residue, containing polypropylene oxide, alkylene diamine polypropylene glycol and 10 to 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 and N-hexadecyl-N, N-bis- (2,3-dihydroxypropyl) amine oxide. Alkyl glucosides with 10 to 18, preferably 12 to 14 carbon atoms in the alkyl radical and 1 to 10, preferably 1 to 2, glucose units in the molecule are also suitable as nonionic surfactants.

Synthetic anionic surfactants of the sulfonate type include alkylbenzenesulfonates (C _9-15 -alkyl), mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained from monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis Sulfonating group. Also suitable are alkanesulfonates which are obtained from alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins receives. Other useful surfactants of the sulfonate type are the esters of alpha-sulfo fatty acids, for example the alpha-sulfonic acids from hydrogenated methyl or ethyl esters of coconut, palm kernel or tallow fatty acid.

Suitable synthetic anionic surfactants of the sulfate type are the sulfuric acid monoesters of primary alcohols (e.g. 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 to 4 moles of ethylene oxide with primary or secondary fatty alcohols or alkylphenols are also suitable.

Other suitable synthetic anionic surfactants are the fatty acid esters or amides of hydroxy or aminocarboxylic acids or sulfonic acids, e.g. the fatty acid sarcosides, glycolates, lactates, taurides or isethionates.

Soaps from natural or synthetic, preferably saturated fatty acids, optionally also from resin or naphthenic acids, can also be used as anionic surfactants.

All 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 preferred for cost reasons.

If cationic surfactants are used, they contain at least one hydrophobic and at least one basic group, which may be in the form of a salt and make water soluble. The hydrophobic group is an aliphatic or cycloaliphatic hydrocarbon group with preferably 10 to 22 carbon atoms or an alkyl or cycloalkyl aromatic group with preferably 8 to 16 aliphatic carbon atoms. As basic groups come primarily basic nitrogen atoms in question, which can also be present more than once 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-N, N-dimethylammonium chloride, N-cocoalkyl-N, N-dimethyl-N-benzylammonium 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, 0 to 6, preferably 1.0 to 6, percent by weight of inorganic or organic compounds which are alkaline in their entirety, in particular inorganic or organic complexing agents, preferably in the form of their alkali metal or amine salts, in particular the Potassium salts are present.

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 inorganic builders also include the alkali hydroxides, of which the potassium hydroxide is preferably used.

Organic complexing agents of the aminopolycarboxylic acid type include nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethyl ethylene diamine triacetic acid and polyalkylene polyamine N polycarboxylic acids. Examples of di- and polyphosphonic acids are: methylenediphosphonic acid, 1-hydroxy-ethane-1,1-diphosphonic acid, propane-1,2,3-triphosphonic acid, butane-1,2,3,4-tetraphosphonic acid, polyvinylphosphonic acid, copolymers 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- (methylenephosphonic acid ), Methyl-amino- or ethylamino-di- (methylenephosphonic acid) and ethylenediamine-tetra- (methylenephosphonic acid).

Various, mostly N- or P-free polycarboxylic acids can also be used as builders, 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. Citric acid, tartaric acid, gluconic acid, benzene hexacarboxylic acid, tetrahydrofuran tetracarboxylic acid etc. and their mixtures.

The cleaning booster mixture consists of polyacrylamides and highly polyethoxylated mono- or polyhydric alkanols. Their weight ratio is 1: 3 to 3: 1, preferably 1: 2 to 2: 1.

The polyacrylamides are polymers and copolymers of acrylamide of the general formula (-CH₂-CH (CONH₂) -) _n with molecular weights of 300,000 to 15,000,000, preferably 2,000,000 to 12,000,000 the companies Dow (Separan® MG 205; Separan® NP 10), Stockhausen (Praestol® 2850; Praestol® 2935/73; Praestol® 114/73) BASF (Sedipur® AF 200; Sedipur® AF 400, Sedipur® NF 100) and Henkel (P3-ferrocryl® 8720; P3-ferrocryl® 8721®; P3-ferrocryl® 8723; P3-ferrocryl® 8740).

The highly polyethoxylated mono- or poly-, preferably mono- or dihydric alkanols are addition products of 30 to 150, preferably 40 to 90 mol ethylene oxide onto terminal or internal hydroxyalkanols with 12 to 22, preferably 14 to 20 carbon atoms in the molecule, such as stearyl or 12-hydroxystearyl alcohol.

Since household cleaning agents are generally almost neutral to slightly alkaline, i.e. their aqueous working solutions at application concentrations of 2 to 20, preferably from 5 to 15 g / l of water or aqueous solution have a pH in the range from 7.0 to 10.5, preferably 7.5 to 9.5, can for 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 Urea or other lower carboxylic acid amides, partial amides of phosphoric acids or anhydrous phosphoric acid, adipic acid, glutaric acid, succinic acid, citric acid, tartaric acid, lactic acid and the like, some of which additionally have complex-forming properties.

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, which have an alkaline action, 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 having 1 to 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 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 various terpene alcohols as individual substances or in a mixture. Terpene alcohols also have a fragrance effect.

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 those in the invention liquid funds are stable and effective. These are phenolic compounds of the halogenated phenol type with 1 to 5 halogen substituents, in particular chlorinated phenols, alkyl, cycloalkyl, aralkyl and phenylphenols with 1 to 12 carbon atoms in the alkyl radicals and with 1 to 4 halogen substituents, in particular chlorine and Bromine in the molecule, alkylene bisphenols, in particular derivatives substituted by 2 to 6 halogen atoms and optionally lower alkyl or trifluoromethyl groups, with an alkylene bridge member having 1 to 10 carbon atoms, hydroxybenzoic acids or their esters and amides, especially anilides, in particular in the benzoic acid and / or aniline residue can be substituted by 2 or 3 halogen atoms and / or trifluoromethyl groups; Orthophenoxyphenols, which can be substituted by 1 to 7, preferably 2 to 5 halogen atoms and / or the hydroxyl, cyano, methoxycarbonyl and carboxyl group or lower alkyl. Particularly preferred antimicrobial agents of the phenyl type are, for example, 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 with 3 to 5 carbon atoms substituted by both bromine and by the nitro group, such as e.g. the compounds 2-bromo-2-nitropropanediol-1,3, 1-bromo-1-nitro-3,3,3-trichloropropanol, 2,2-bromo-2-nitro-butanol-1.

Also suitable are bis-diguanides such as 1,6-bis (p-chlorophenyldiguanido) hexane in the form of the hydrochloride, acetate or gluconate and also N, N'-disubstituted 2-thiontetrahydro-1,3,5-thiadiazines such as 3,5-dimethyl-, 3,5-diallyl-, 3-benzyl-5-methyl- and especially 3-benzyl-5-carboxymethyl-tetrahydro-1,3,5-thiadiazine as additional antimicrobial agents.

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

tries

The following tests were carried out to demonstrate the surprising cleaning-enhancing effect of the combination of the claimed compounds:

1. Check the cleaning ability for greasy soiling

The formulation to be tested for its cleaning ability was applied to an artificially soiled white PVC plastic surface. A mixture of carbon black, machine oil, a trigylceride of saturated fatty acids and low-boiling aliphatic hydrocarbons was used as artificial soiling.

The test area of 26 x 4.0 cm was coated evenly with 0.3 or 0.6 g (diluted or undiluted product application) of the artificial soiling and stored for one hour at room temperature before the start of the test. Subsequently, a plastic sponge with 10 ml (6 ml in the undiluted application) of the cleaning agent solution to be tested was soaked and mechanically moved back and forth on the test surface, the sponge covering both the soiled central area and the non-soiled edge zones. After 10 wiping movements under precisely defined contact pressure conditions of 2 kp, the cleaned test area was rinsed with 400 ml tap water and the loosened dirt was thereby removed. The cleaning ability, ie the degree of whiteness of the plastic surface cleaned in this way, was measured with a photoelectric reflection measuring device LF 90 (from Dr. B. Lange), the whiteness of the part of the test surface which was originally soiled used to determine the cleaning ability. The clean, white PVC plastic surface was used as the white standard. There When measuring the clean surface, the deflection of the measuring device was set to 100 percent and for the soiled area to 0 percent, the readings on the cleaned plastic surfaces could be regarded as "percent cleaning ability" (% RV). The specified delta RV values (increase in cleaning performance) are average values from a quadruple determination.

example 1

• a) To a commercially available all-purpose cleaning agent for hard surfaces with the following composition in percent by weight:
  0.5% sodium C₁₂-C₁₄ alkyl benzene sulfonate
  2.0% nonylphenol, reacted with 9 moles of ethylene oxide
  0.8% ethylenediaminetetraacetate
  2.0% butyl glycol
  Rest to 100%: demineralized water
  0.5 percent by weight of a mixture of 12-hydroxysteayl alcohol reacted with 73 moles of ethylene oxide (= EO) and polyacrylamide with a molecular weight of 5 × 10⁶ (weight ratio 2: 1) was added. When using 6 ml of this undiluted product, an increase in cleaning performance by delta-RV = 34% was determined.
• b) By removing the anionic surfactant according to the teaching of DE 29 13 049, delta RV = 43% was obtained under otherwise the same conditions as in a). Was the cleaning amplifier mixture based on the invention replaced by one that would be theoretically possible according to DE 29 13 049, namely by a polyethylene glycol with a molecular weight of 600,000 (Polyox® WSR 205 from Union Carbide Corporation) and the polyacrylamide used under a) in a weight ratio 2: 1, delta-RV was only 30%.

Example 2

For a commercial, general purpose-built, all-purpose cleaning agent with the composition:
2% C₁₂-C₁₄ alkanediol · 10 EO
8% sodium C₁₂-C₁₄ alkyl benzosulfonate
Balance to 100%: demineralized water,
0.2% of the cleaning booster mixture specified in Example 1 was added. The application was also carried out with the undiluted mixture. Delta RV was 36%. When adding the same amount of cleaning amplifier mixture theoretically possible according to the prior art (cf. Example 1), delta-RV was only 26%.

The table below gives examples of mixtures of different, predominantly anionic and nonionic surfactants and different or no builder substances that have been mixed with significantly smaller amounts of polymer mixtures based on the invention than in Examples 1 and 2 and their cleaning performance at 25 ° C. and 16 ° d determined. The results from delta-RV show that even then significant improvements could be achieved. (In Examples 3 to 7, diluted (10 g product per liter tap water from 25 ° C with 16 ° d) and in Examples 8 to 10 undiluted (6 g product) detergent mixtures were used.)

Claims (6)

1. cleaning agents for hard surfaces based on surfactants, cleaning reinforcements, possibly containing structural substances, and other conventional components of such agents, characterized in that they contain a mixture of polyacrylamides and highly polyethoxylated mono- or polyhydric alkanols as cleaning enhancers. 2. Cleaning agent according to claim 1, d. that is, the cleaning booster consists of a mixture of polyacrylamides and highly polyethoxylated mono- or polyhydric alkanols in a weight ratio of 1: 3 to 3: 1, preferably 1: 2 to 2: 1. 3. Detergent according to claim 1 and 2, ie that they
0.5 to 40, preferably 5 to 20 percent by weight of surfactants or surfactant mixtures,
0 to 6, preferably 1.0 to 6 percent by weight of organic or inorganic builders,
0.01 to 1, preferably 0.05 to 0.5 percent by weight of cleaning boosters,
as well as up to a total of 100 weight percent total weight of water, and as other common components of such agents, solvents, hydrotropes, preservatives, antimicrobial agents, viscosity regulators, pH regulators, perfume and dyes. 4. Cleaning agent according to claim 1 to 3, ie that they are polyacrylamides polymers or copolymers of acrylamide of the general formula (-CH₂-CH (CO NH₂) -) _n with molecular weights of 300,000 to 15,000,000, preferably 2,000,000 to 12,000,000 included. 5. Cleaning agent according to claim 1 to 4, ie that it as contain highly polyethoxylated mono- or poly-, preferably mono- or dihydric alkanols adducts from 30 to 150, preferably from 40 to 90 mol ethylene oxide onto terminal or internal hydroxyalkanols with 12 to 22, preferably 14 to 20 carbon atoms in the molecule. 6. Cleaning agent according to claim 1 to 5, d. that is, they contain adducts of 40 to 90 moles of ethylene oxide with stearyl or 12-hydroxystearyl alcohol as highly polyethoxylated mono- or divalent alkanols.