EP0017149A1 - Use of a liquid composition for cleaning hard surfaces - Google Patents

Use of a liquid composition for cleaning hard surfaces Download PDF

Info

Publication number
EP0017149A1
EP0017149A1 EP80101581A EP80101581A EP0017149A1 EP 0017149 A1 EP0017149 A1 EP 0017149A1 EP 80101581 A EP80101581 A EP 80101581A EP 80101581 A EP80101581 A EP 80101581A EP 0017149 A1 EP0017149 A1 EP 0017149A1
Authority
EP
European Patent Office
Prior art keywords
water
weight
mixtures
polymers
soluble
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP80101581A
Other languages
German (de)
French (fr)
Other versions
EP0017149B1 (en
Inventor
Jürgen Dr. Wegener
Frank Weber
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT80101581T priority Critical patent/ATE6268T1/en
Publication of EP0017149A1 publication Critical patent/EP0017149A1/en
Application granted granted Critical
Publication of EP0017149B1 publication Critical patent/EP0017149B1/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3753—Polyvinylalcohol; Ethers or esters thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam

Definitions

  • customary liquid, so-called all-purpose cleaning agents consist of anionic and / or nonionic surfactants, preferably of the combination of both classes of surfactants, usually additionally combined with soluble inorganic or organic builders, such as sodium and potassium pyrophosphate, tripolyphosphate, and citrate , Nitrilotriacetate, ethylenediaminetetraacetate, and additions of solvents, primarily ethylene and / or butyl glycol, ethanol or isopropanol.
  • anionic and / or nonionic surfactants preferably of the combination of both classes of surfactants, usually additionally combined with soluble inorganic or organic builders, such as sodium and potassium pyrophosphate, tripolyphosphate, and citrate , Nitrilotriacetate, ethylenediaminetetraacetate, and additions of solvents, primarily ethylene and / or butyl glycol, ethanol or isopropanol.
  • DE-AS 10 51 440 discloses liquid cleaning agents which are used for all purposes, but especially for washing textiles, and in addition to anionic and nonionic surfactants to increase the dirt-carrying capacity, including small amounts of water-soluble cellulose or starch derivatives or else 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.
  • 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.
  • liquid cleaning agents for hard surfaces which, in addition to a combination of anionic and very specific nonionic surfactants, can also contain cleaning-enhancing additives in water-soluble high-molecular substances, such as polyvinyl alcohol, polyvinylpyrrolidone and carboxymethyl cellulose.
  • Addition products of 4-40, preferably 4-20 moles of ethylene oxide or ethylene oxide and propylene oxide with 1 mole of fatty alcohols, alkanediols or their C 1 -C 4 -monoalkyl ethers, alkylphenols, fatty acids, fatty amines, fatty acid amides or alkanesulfonamides can be used as nonionic surfactants.
  • polyglycol ethers with 1-4 ethylene glycol ether residues in the molecule that are not or not completely water-soluble are also of interest, in particular if they are used together with water-soluble nonionic surfactants.
  • nonionic surfactants are the readily water-soluble addition products of about 20-100 ethylene glycol ether groups and about 10-65 propylene glycol ether groups of ethylene oxide with polypropylene oxide, alkylenediamine polypropylene glycol and alkylpolypropylene glycols with 1-10 carbon atoms in the alkyl chain, in which the polypropylene glycol chain acts as a hydrophobic agent Rest acts.
  • the average molecular weight of these nonionic surfactants is preferably less than 5000.
  • 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.
  • Fatty acid alkanolamides are also useful nonionic surfactants.
  • the water-soluble nonionic polymers include the polyethylene glycols, the polyvinyl alcohols and the polyvinyl pyrrolidones.
  • Cellulose ethers, polysaccharides, proteins and polyacrylamides are water-soluble, weakly anionic polymers, depending on the degree of substitution or conversion. These are understood to mean those polymers whose charge density is greater than O, but not greater than 0.5, preferably greater than O, but not greater than 0.2 and in particular greater than O, but not greater than 0.01.
  • the definition for the charge density corresponds to the following formula:
  • the polyethylene glycols mentioned are prepared in a known manner by subjecting ethylene glycols to a polycondensation process. They can also be considered as condensation polymers of ethylene oxide with ethylene glycol or water. They generally have the formula HO (-CH 2 -CH 2 -O-) n H, the degree of polymerization n in the case of the polyethylene glycols used according to the invention varying between 4,800 and 64,600. Such polymers are also commercially available and are marketed by the company, Union Carbon Carbide Corporation (UCC) under the name "P OLYO X ®".
  • UCC Union Carbon Carbide Corporation
  • Polyvinyl alcohols can be produced by hydrolysis of polyvinyl acetate. They have the general formula (-CH 2 -CH (OH) -) n and molecular weights of about 13,400 to 250,000, preferably 80,000 to 100,000. They can still contain small amounts of acetyl radicals from the hydrolysis reaction, but these should be less than 40, preferably less than 15 and in particular less than 2 and preferably 0%. Polyvinyl alcohols are traded, for example, by Wacker-Chemie under the name "Polyviol®” or by Nippon Gohsei under the name "Gohsenole®”.
  • Polyvinylpyrrolidones of the general formula are also commercially available polymers. They are marketed by the company BASF, among others, under the name "Luviskole®”. Their degree of polymerization for use according to the invention is between 100 and 9000, preferably between 350 and 7500, the molecular weights between approximately 10,000 and 1,000,000, preferably between approximately 30,000 and 850,000.
  • the cellulose ethers with a charge density greater than O, but not greater than 0.5, preferably greater than O, but not greater than 0.2 include, in particular, those whose 2% aqueous solution has a viscosity of> 50 at 20 ° C. m Pa.S, preferably of> 100 m Pa.S.
  • These include the methylcelluloses (MC), methylhydrocyethylcelluloses (MHEC), methylhydroxypropylcelluloses (MHPC), carboxymethylmethylcellulose (CMMC) and hydroxyethylcelluloses (HEC), also methylhydroxybutylcellulose (MHBC), which are traded by the Henkel company under the type collective name "Culminal®". as they are traded by Dow Chemicals under the brand name Methocel®.
  • Polysaccharides are particularly suitable in derivative form, for example as starch ethers (for example Solvitose® from W.A. Scholtens, Holland), the charge density of 0.5 to ⁇ 0.2 also being decisive here.
  • Alginates (“Algipon®” from Henkel) also belong to this class of polymers.
  • the proteins which can be used according to the invention are, for example, sodium caseinate and gelatin, both of which are sold, inter alia, by the company Milac, Hamburg.
  • Polyacrylamides ie polymers and copolymers of acrylamide with the general formula (-CH 2 -CH (CONH 2 ) -) n with molecular weights of 300,000 to 6,000,000, preferably 500,000 to 2,000,000, are marketed by Schuchardt, among others and are also suitable for use in accordance with the invention.
  • cleaning agents claimed can also be observed if they are used in the form of their aqueous solutions without any further addition. However, they are advantageously used together with other constituents customary for such cleaning agents, as indicated below by way of example.
  • 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 also include the alkali 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 usable according to the invention.
  • Inorganic builders are, for example, the bicarbonates, 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-hydroxyethyl-ethylenediamine triacetic acid, polyalkylene-polyamine-N-polycarboxylic acids.
  • di- and polyphosphonic acids examples include: methylene diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, propane-1,2,3-triphosphonic acid, butane-1,2,3,4-tetraphosphonic 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-di-phosphonic acid, phosphonosuccinic acid, 1-aminoethane-1,1-diphosphonic acid, aminotri- (methylenephos - Phonic acid), methylamino- or ethylamino-di- (methylenephosphonic acid), and ethylenediamine-tetra- (methylenephosphonic acid).
  • 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, for example, citric acid, tartaric acid, 'benzenehexacarboxylic, tetrahydrofurantetracarboxylic etc.
  • Suitable acidic substances are customary inorganic or organic acids or acidic salts, such as, for example, hydrochloric acid, sulfuric acid, bisulfates or 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 carboxamides, partial amides of phosphoric acid. or anhydrous phosphoric acid, citric acid, tartaric acid, lactic acid and the like.
  • alkaline builders If the content of alkaline builders is not sufficient to regulate the pH, organic or inorganic compounds such as alkanolamides, namely mono-, di- or triethanolamine or ammonia, can also be added.
  • alkanolamides namely mono-, di- or triethanolamine or ammonia
  • Suitable water-soluble or water-emulsifiable organic solvents are ketones, such as acetone, methyl ethyl ketone and aliphatic, cycloaliphatic, aromatic and chlorinated hydrocarbons, and also the terpene alcohols.
  • water-soluble organic solvents can be used, in particular those with boiling points above 75 ° C., such as, for example, the ethers from identical or different polyhydric alcohols or the partial ethers from polyhydric and monohydric alcohols.
  • di- or triethylene glycol polyglycerols include, for example, di- or triethylene glycol polyglycerols and the partial ethers of ethylene glycol, propylene glycol, butyl glycol or glycerol with aliphatic monohydric alcohols containing 1-4 carbon atoms in the molecule. Isopropanol, butyl glycol, acetone or mixtures of these solvents are preferred.
  • solubilizers can be incorporated, which include, in addition to the water-soluble organic solvents such as, in particular, low molecular weight aliphatic hydrotropic substances of the lower aryl sulfonate type, for example toluene, xylene or cumene sulfonate. You can their sodium and / or potassium and / or alkylolamaine vorlie- g s in the form ..
  • 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 type of the halogenated phenols with 1-5 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 2-6 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 amides, especially anilides, which can be substituted in the benzoic acid and / or aniline residue, in particular by 2 or 3 halogen atoms and / or trifluoromethyl groups; O rthophenoxyphenols, which can be substituted by 1
  • 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'-dihydroxydiphenylmethane.
  • Other useful antimicrobial agents are the lower alcohols or diols with 3 to 5 carbon atoms substituted by both bromine and the nitro group, such as the compounds 2-bromo-2-nitropropanediol-1,3,1-bromo-1-nitro-3 , 3,3-trichloropropanol-2, 2-bromo-2-nitro-butanol-1 ..
  • bis-diguanides such as, for example, 1,6-bis- (p-chlorophenyldiguanido) hexane in the form of the hydrochloride, acetate or gluconate, and also N, N'-disubstituted 2-thioenetrahydro-1,3 , 5-thiadizines 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.
  • bis-diguanides such as, for example, 1,6-bis- (p-chlorophenyldiguanido) hexane in the form of the hydrochloride, acetate or gluconate
  • N, N'-disubstituted 2-thioenetrahydro-1,3 , 5-thiadizines such as 3,5-dimethyl, 3,5-diallyl, 3-benzyl-5-
  • Formaldehyde-amino alcohol condensation products can preferably be used.
  • the products are prepared by reacting an aqueous solution of formaldehyde with amino alcohols, for example 2-aminoethanol, 1-amino-2-propanol, 2-amino-iso-butanol, 2 (2'-aminoethyl) aminoethanol.
  • amino alcohols for example 2-aminoethanol, 1-amino-2-propanol, 2-amino-iso-butanol, 2 (2'-aminoethyl) aminoethanol.
  • 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 triglyceride of saturated fatty acids and low-boiling aliphatic hydrocarbons was used as artificial soiling.
  • the test area of 24 x 4.6 cm was evenly coated with 0.1 g of the artificial soiling in the central part to about 30 cm 2 and stored for one hour at room temperature before the start of the test. Then a plastic sponge was impregnated with 12 ml of the cleaning agent solution to be tested and moved mechanically 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, i.e. the degree of whiteness of the plastic surface cleaned in this way, was measured with a photoelectric reflection measuring device LF 90 (Dr. B.
  • a 2-year-old, naturally soiled truck tarpaulin was used as the test area, which was divided into 20 x 10 cm pieces and was independently assessed by 3 test persons by treating it evenly with a product-soaked sponge, then rinsing the area under running water and visual grading (Grade 1: residual pollution corresponds to the effect of water, Grade 3: complete dirt removal).
  • nonionic or weakly ionic polymers to a disinfectant cleaner formulation of the composition has a particularly favorable effect Remainder to 100%: polymer additive and demineralized water, since in such a formulation the use of anionic surfactants is prohibited because of the known incompatibility with quaternary ammonium compounds and the cleaning power of such products is therefore generally relatively low.
  • Table 5 show the cleaning ability against greasy soiling:
  • the disinfectant effect is not affected by the addition of polymer.
  • Example 4 an aqueous solution of worked.
  • numerous advantageous all-purpose cleaning agents can be produced.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Abstract

1. The use of a liquid composition for cleaning hard surfaces, the composition containing in aqueous or solventcontaining aqueous solution non-ionic surfactants, builders showing an alkaline reaction and water-soluble polymers and essentially consisting of : a) from 0.1 to 10% by weight of the non-ionic surfactants, b) from 0.01 to 2% by weight of the water-soluble polymers which comprise non-ionic, weakly anionic or cationic polymers from the group including polyvinyl alcohols, polyvinyl pyrrolidones, cellulose ethers, polysaccharides, proteins and polyacrylamides with average molecular weights of from 5000 to 10,000,000 and preferably from 20,000 to 2,000,000, or mixtures of these polymers, the quantity in which the polymer b) is present always being below that in which the non-ionic surfactant a) is present, and c) from 0.1 to 10% by weight of the alkaline-reacting inorganic or organic builders, and, in addition, being in the form of a solution in demineralized water or in mixtures of demineralized water and water-miscible organic solvents, with the proviso that no protection is claimed for the use of compositions containing (a) from about 0.05 to about 15% by weight of an anionic, non-ionic, ampholytic or zwitterionic surfactant or mixtures thereof ; (b) from about 0.5 to about 99% by weight of an organic or inorganic builder or mixtures thereof and (c) from about 0.03 to about 5% by weight of a mixture for the improved removal of dirt containing (1) a watersoluble or dispersible non-ionizing primary polymer material, namely (i) polyvinyl alcohols having a degree of hydrolysis of from about 60 to about 100% and a degree of polymerization of from about 100 to about 7000 or (ii) polyvinyl pyrrolidones having a degree of polymerization of from about 50 to about 6000 or (iii) mixtures thereof and (2) an ionizing polysaccharide salt, namely seaweed extracts, plant exudates, seed gums, plant extracts, animal extracts or biosynthetic gums, the ratio by weight of primary polymer material to polysaccharide salt amounting to between about 4:1 and 1:4.

Description

Moderne Fertigbauweisen, pflegeleichte Küchen-, Badezimmer- und Kellereinrichtungen, kunststoffurnierte Möbel, die zunehmende Ausstattung der Haushalte mit Tiefkühltruhen, Kühlschränken, Wasch- und Geschirrspülmaschinen, d.h. Geräten mit emaillierten oder kunststoffbeschichteten großflächigen Metallwänden haben die Nachfrage nach flüssigen Allzweckreinigungsmitteln für Haushaltszwecke in den letzten Jahren stark steigen lassen. Aber auch in Gewerbebetrieben hat die Anwendung derartiger Mittel zunehmend an Bedeutung gewonnen. Dabei wird eine möglichst einfache und problemlose Anwendbarkeit gefordert. Meist werden die Mittel als vorzugsweise wäßrige Konzentrate in den Handel gebracht. Sie lassen sich verdünnt oder unverdünnt auf ein feuchtes saugfähiges Tuch beliebiger Beschaffenheit oder einen Schwamm aufbringen, mit dem dann die harten Oberflächen aus Metall, lackiertem Holz, Kunststoff, keramischen Erzeugnissen wie Porzellan, Fliesen, Kacheln, Glas und dergleichen abgewischt werden, wodurch Staub, Fettschmutz und Flecken entfernt werden. Dabei wird gewünscht, daß diese Oberflächenbehandlung keine Reinigungsmittelflecken und -streifen zurückläßt und keine Nachbehandlung mit einem mit klarem Wasser getränkten, feuchten Tuch erfordert.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. Appliances with enamelled or plastic-coated large-area metal walls have increased the demand for liquid all-purpose cleaning agents for household purposes 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, painted wood, plastic, ceramic products such as porcelain, tiles, tiles, glass and the like, causing dust, Grease dirt and stains are removed. It is desired that this surface treatment does not leave any detergent stains and strips, and does not require any post-treatment with a damp cloth soaked in clear water.

übliche flüssige, sogenannte Allzweckreinigungsmittel be- 'stehen bekanntlich aus anionischen und/oder nichtionischen Tensiden, vorzugsweise aus der Kombination beider Tensidklassen, meist zusätzlich kombiniert mit löslichen anorganischen oder organischen Gerüstsubstanzen, wie zum Beispiel Natrium- und Kalium-Pyrophosphat, -Tripolyphosphat, -Citrat, -Nitrilotriacetat, Ethylendiamintetraacetat, sowie Zusätzen von Lösungsmitteln, vornehmlich Ethylen-und/oder Butylglycol, Ethanol oder Isopropanol.As is known, customary liquid, so-called all-purpose cleaning agents consist of anionic and / or nonionic surfactants, preferably of the combination of both classes of surfactants, usually additionally combined with soluble inorganic or organic builders, such as sodium and potassium pyrophosphate, tripolyphosphate, and citrate , Nitrilotriacetate, ethylenediaminetetraacetate, and additions of solvents, primarily ethylene and / or butyl glycol, ethanol or isopropanol.

Ihre Reinigungswirkung gegen ölige und fetthaltige Anschmutzungen verdanken sie den anionischen und/oder nichtionischen Tensiden, die häufig noch durch Lösungsmittelzusatz unterstützt werden; gegen Pigmentschmutz wirkt der zumeist hohe Anteil an Gerüstsubstanzen.They owe their cleaning effect against oily and greasy soiling to the anionic and / or nonionic surfactants, which are often supported by the addition of solvents; the mostly high proportion of framework substances works against pigment dirt.

Vom Markt her und aus der Literatur sind bereits zahlreiche derartige Reinigungsmittel bekannt. Darüber hinaus ist auch aus der Patentliteratur bekannt, diesen Reinigungsmitteln zur Verstärkung ihrer Reinigungskraft verschiedene Polymere zuzusetzen.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.

Aus der DE-AS 10 51 440 sind flüssige Reinigungsmittel bekannt, die für alle Zwecke, insbesondere jedoch zum Waschen von Textilien, eingesetzt werden und neben anionischen und nichtionischen Tensiden zur Steigerung des Schmutztragevermögens unter anderem kleine Mengen an wasserlöslichen Cellulose- oder Stärkederivaten oder auch an wasserlöslichen oder kolloidal löslichen Polymerisaten, wie Polyvinylpyrrolidon, enthalten können.DE-AS 10 51 440 discloses liquid cleaning agents which are used for all purposes, but especially for washing textiles, and in addition to anionic and nonionic surfactants to increase the dirt-carrying capacity, including small amounts of water-soluble cellulose or starch derivatives or else water-soluble or colloidally soluble polymers, such as polyvinylpyrrolidone.

Aus der AT-PS 278 216 sind flüssige Reinigungsmittel bekannt, die ebenfalls wasserlösliche hochmolekulare Substanzen als Schmutzträger enthalten können. Als Beispiele werden wasserlösliche Salze der Polyacrylsäure und auch wasserlösliche Derivate der Cellulose wie Carboxymethylcellulose genannt. Auch hier werden bevorzugt Gemische anionischer und nichtionischer Tenside eingesetzt.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.

Aus der US-PS 3 591 509 sind flüssige Allzweckreiniger bekannt, die neben wasserlöslichen synthetischen oberflächenaktiven Substanzen, organischen Lösungsmitteln und gegebenenfalls wasserlöslichen Gerüstsubstanzen eine geringe Menge einer speziellen wasserlöslichen Carboxymethylcellulose, nämlich einer solchen mit einem Substitutionsgrad von etwa 1 bis etwa 2 und einem Polymerisationsgrad von etwa 1000 bis etwa 3000 sowie Wasser enthalten. Dieses Produkt wirkt verdickend und soll die Haftfestigkeit der Reinigungsmittel auf den schmutzigen Flächen verbessern.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 contain about 1000 to about 3000 as well as water. This product has a thickening effect and is said to improve the adhesive strength of the cleaning agents on dirty surfaces.

Aus der DE-OS 26 10 995 sind flüssige gerüststoffhaltige Reinigungsmittel für harte Oberflächen mit geringen Mengen an vorzugsweise anionischen Tensiden in Kombination mit geringen Mengen eines Gemisches aus Polyvinylalkohol und/ oder Polyvinylpyrrolidon und Polysaccharidsalz bekannt, die ebenfalls ein verbessertes Schmutzentfernungsvermögen aufweisen sollen.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.

.Schließlich sind noch aus der DE-AS 27 09 690 flüssige Reinigungsmittel für harte Oberflächen bekannt, die neben einer Kombination aus anionischen und ganz bestimmten nichtionischen Tensiden ebenfalls reinigungsverstärkende Zusätze an wasserlöslichen hochmolekularen Substanzen, wie Polyvinylalkohol, Polyvinylpyrrolidon und Carboxymethylcellulose, enthalten können.Finally, from DE-AS 27 09 690 liquid cleaning agents for hard surfaces are known which, in addition to a combination of anionic and very specific nonionic surfactants, can also contain cleaning-enhancing additives in water-soluble high-molecular substances, such as polyvinyl alcohol, polyvinylpyrrolidone and carboxymethyl cellulose.

Keinem der genannten Hinweise auf den Stand der Technik ist zu entnehmen, daß geringe Mengen zahlreicher verschiedener organischer Polymerer, die jedoch gemeinsam bestimmte, weiter unten angegebene Bedingungen erfüllen, geeignet sind, die Reinigungswirksamkeit ebenfalls geringer Mengen nichtionischer Tenside in Allzweckreinigungsmitteln synergistisch zu steigern, so daß nicht nur die Mitverwendung anionischer Tenside überflüssig wird, sondern sogar eine bessere Reinigungswirkung erzielt wird, als mit entsprechenden bekannten polymerhaltigen Kombinationen aus nichtionischen und anionischen Tensiden.None of the cited references to the prior art indicate that small amounts of numerous different organic polymers, which, however, together meet certain conditions specified below, are suitable for synergistically increasing the cleaning effectiveness of likewise small amounts of nonionic surfactants in all-purpose cleaning agents, so that not only is the use of anionic surfactants superfluous, but even a better cleaning effect is achieved than with corresponding known polymer-containing combinations of nonionic and anionic surfactants.

Die vorliegende Erfindung betrifft daher flüssige Reinigungsmittel für harte Oberflächen aus wäßrigen oder wäßrigen, lösungsmittelhaltigen Lösungen nichtionischer Tenside und wasserlöslicher Polymerer, dadurch gekennzeichnet, daß sie entmineralisiertes Wasser und

  • a) 0,001 bis 35, vorzugsweise-0,1 bis 10 Gewichtsprozent eines nichtionischen Tensids,
  • b) 0,005 bis 15, vorzugsweise 0,01 bis 2 Gewichtsprozent eines wasserlöslichen nicht- ; ionischen, schwach anionischen oder ; kationischen Polymers aus der Gruppe der Polyethylenglycole, Polyvinylalkohole, Polyvinylpyrrolidone, Celluloseether, Polysaccharide, Proteine und Polyacrylamide mit mittleren Molgewichten von 5000 bis 10 000 000, vorzugsweise von 20 000 bis 2 000 000 oder Gemische dieser Polymeren,
  • c) 0,01 bis 20, vorzugsweise 0,1 bis 10 Gewichts- prozent alkalisch reagierende anorganische oder organische Gerüstsubstanzen,
  • j d) O bis 40, vorzugsweise 0,5 bis 15 Gewichtsprozent eines wasserlöslichen oder in Wasser emulgierbaren organischen Lösungsmittels und
  • e) O bis 20, vorzugsweise 0,5 bis 2 Gewichtsprozent anorganische Neutralsalze, Harnstoff, Farbstoffe, Duftstoffe, Konservierungsmittel sowie antimikrobiell wirksame Mittel enthalten.
The present invention therefore relates to liquid cleaning agents for hard surfaces made from aqueous or aqueous, solvent-containing solutions of nonionic surfactants and water-soluble polymers, characterized in that they contain demineralized water and
  • a) 0.001 to 35, preferably 0.1 to 10 percent by weight of a nonionic surfactant,
  • b) 0.005 to 15, preferably 0.01 to 2 percent by weight of a water-soluble non-; ionic, weakly anionic or ; cationic polymers from the group of polyethylene glycols, polyvinyl alcohols, polyvinyl pyrrolidones, 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,
  • c) 0.01 to 20, preferably 0.1 to 10 percent by weight of alkaline inorganic or organic framework substances,
  • jd) 0 to 40, preferably 0.5 to 15 percent by weight of a water-soluble or water-emulsifiable organic solvent and
  • e) O to 20, preferably 0.5 to 2 percent by weight of inorganic neutral salts, urea, dyes, fragrances, preservatives and antimicrobial agents.

Als nichtionische Tenside sind Anlagerungsprodukte von 4 - 40, vorzugsweise 4 - 20 Mol Ethylenoxid oder Ethylenoxid und Propylenoxid an 1 Mol Fettalkohole, Alkandiole beziehungsweise deren C1-C4-Monoalkylether, Alkylphenole, Fettsäuren, Fettamine, Fettsäureamide oder Alkansulfonamide verwendbar. Besonders wichtig sind die Anlagerungsprodukte von 5 - 16 Mol Ethylenoxid oder Ethylen- und Propylenoxid an Cocos- oder Talgfettalkohole, an Oleylalkohol oder an sekundäre Alkohole mit 8 - 18, vorzugsweise 12 - 18 C-Atomen, sowie an Mono- oder Dialkylphenole mit 6 - 14 C-Atomen in den Alkylresten. Neben diesen wasserlöslichen Nonionics sind aber auch nicht, beziehungsweise nicht vollständig wasserlösliche Polyglycolether mit 1 - 4 Ethylenglycoletherresten im Molekül von Interesse, insbesondere, wenn sie zusammen mit wasserlöslichen nichtionischen Tensiden eingesetzt werden.Addition products of 4-40, preferably 4-20 moles of ethylene oxide or ethylene oxide and propylene oxide with 1 mole of fatty alcohols, alkanediols or their C 1 -C 4 -monoalkyl ethers, alkylphenols, fatty acids, fatty amines, fatty acid amides or alkanesulfonamides 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, however, polyglycol ethers with 1-4 ethylene glycol ether residues in the molecule that are not or not completely water-soluble are also of interest, in particular if they are used together with water-soluble nonionic surfactants.

Weiterhin sind als nichtionische Tenside die leicht wasserlöslichen, etwa 20 - 100 Ethylenglycolethergruppen und etwa 10 - 65 Propylenglycolethergruppen enthaltenden Anlagerungsprodukte von Ethylenoxid an Polypropylenoxid, Alkylendiaminpoly-propylenglycol und Alkylpolypropylenglycole mit 1 - 10 C-Atomen in der Alkylkette brauchbar, in denen die Polypropylenglycolkette als hydrophober Rest fungiert. Das mittlere Molgewicht dieser nichtionischen Tenside liegt vorzugsweise unter 5000.Also useful as nonionic surfactants are the readily water-soluble addition products of about 20-100 ethylene glycol ether groups and about 10-65 propylene glycol ether groups of ethylene oxide with polypropylene oxide, alkylenediamine polypropylene glycol and alkylpolypropylene glycols with 1-10 carbon atoms in the alkyl chain, in which the polypropylene glycol chain acts as a hydrophobic agent Rest acts. The average molecular weight of these nonionic surfactants is preferably less than 5000.

Auch nichtionische Tenside vom Typ der Aminoxide sind verwendbar. Typische Vertreter sind beispielsweise die Verbindungen N-Dodecyl-N,N-dimethylaminoxid, N-Tetradecyl-N,N-dihydroxyethylaminoxid, N-Hexadecyl-N,N-bis-(2,3-dihydroxypropyl)-aminoxid.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.

Fettsäurealkanolamide sind ebenfalls brauchbare nichtionische Tenside.Fatty acid alkanolamides are also useful nonionic surfactants.

Zu den wasserlöslichen nichtionischen Polymeren gehören die Polyethylenglycole, die Polyvinylalkohole und die Polyvinylpyrrolidone.The water-soluble nonionic polymers include the polyethylene glycols, the polyvinyl alcohols and the polyvinyl pyrrolidones.

Celluloseether, Polysaccharide, Proteine und Polyacrylamide stellen dagegen je nach Substitutions- beziehungsweise Umsetzungsgrad wasserlösliche sogenannte schwach anionische Polymere dar. Darunter versteht man solche Polymere, deren Ladungsdichte größer als O, aber nicht größer als 0,5, vorzugsweise größer als O, aber nicht größer als 0,2 und insbesondere größer als O, aber nicht größer als 0,01 ist. Die Definition für die Ladungsdichte entspricht dabei folgender Formel:

Figure imgb0001
Cellulose ethers, polysaccharides, proteins and polyacrylamides, on the other hand, are water-soluble, weakly anionic polymers, depending on the degree of substitution or conversion. These are understood to mean those polymers whose charge density is greater than O, but not greater than 0.5, preferably greater than O, but not greater than 0.2 and in particular greater than O, but not greater than 0.01. The definition for the charge density corresponds to the following formula:
Figure imgb0001

Die genannten Polyethylenglycole werden in bekannter Weise dadurch hergestellt, daß man Ethylenglycole einem Polykondensationsprozeß unterwirft. Man kann sie auch als Kondensationspolymere des Ethylenoxids mit Ethylenglycol oder Wasser auffassen. Sie besitzen im allgemeinen die Formel HO(-CH2-CH2-O-)nH, wobei der Polymerisationsgrad n im Falle der erfindungsgemäß eingesetzten Polyethylenglycole zwischen 4.800 und 64.600 variieren kann. Derartige Polymere sind auch im Handel erhältlich und werden von der Firma, Union Carbon Carbide Corporation (UCC) unter dem Namen "POLYOX ® " vertrieben.The polyethylene glycols mentioned are prepared in a known manner by subjecting ethylene glycols to a polycondensation process. They can also be considered as condensation polymers of ethylene oxide with ethylene glycol or water. They generally have the formula HO (-CH 2 -CH 2 -O-) n H, the degree of polymerization n in the case of the polyethylene glycols used according to the invention varying between 4,800 and 64,600. Such polymers are also commercially available and are marketed by the company, Union Carbon Carbide Corporation (UCC) under the name "P OLYO X ®".

Polyvinylalkohole können durch Hydrolyse von Polyvinylacetat hergestellt werden. Sie besitzen die allgemeine Formel (-CH2-CH(OH)-)n und Molgewichte von etwa 13 400 bis 250 000, vorzugsweise 80 000 bis 100 000. Sie können von der Hydrolysereaktion noch geringe Anteile an Acetylresten enthalten, diese sollen jedoch weniger als 40, vorzugsweise weniger als 15 und insbesondere weniger als 2 und möglichst O % betragen. Polyvinylalkohole werden beispielsweise von der Firma Wacker-Chemie unter der Bezeichnung "Polyviol®" oder von der Firma Nippon Gohsei unter der Bezeichnung "Gohsenole®" gehandelt.Polyvinyl alcohols can be produced by hydrolysis of polyvinyl acetate. They have the general formula (-CH 2 -CH (OH) -) n and molecular weights of about 13,400 to 250,000, preferably 80,000 to 100,000. They can still contain small amounts of acetyl radicals from the hydrolysis reaction, but these should be less than 40, preferably less than 15 and in particular less than 2 and preferably 0%. Polyvinyl alcohols are traded, for example, by Wacker-Chemie under the name "Polyviol®" or by Nippon Gohsei under the name "Gohsenole®".

i Polyvinylpyrrolidone der allgemeinen Formel

Figure imgb0002
sind ebenfalls handelsübliche Polymere. Sie werden unter anderem von der Firma BASF unter dem Namen "Luviskole®" vertrieben. Ihr Polymerisationsgrad liegt für den erfin- .dungsgemäßen Einsatz zwischen 100 und 9000, vorzugsweise zwischen 350 und 7500, die Molgewichte zwischen etwa 10 000 und 1 000 000, vorzugsweise zwischen etwa 30 000 und 850 000.i Polyvinylpyrrolidones of the general formula
Figure imgb0002
 are also commercially available polymers. They are marketed by the company BASF, among others, under the name "Luviskole®". Their degree of polymerization for use according to the invention is between 100 and 9000, preferably between 350 and 7500, the molecular weights between approximately 10,000 and 1,000,000, preferably between approximately 30,000 and 850,000.

Zu den Celluloseethern mit einer Ladungsdichte größer als O, aber nicht größer als 0,5, vorzugsweise größer als O, aber nicht größer als 0,2 gehören vor allem solche, deren 2-prozentige wäßrige Lösung bei 20 °C eine Viskosität von >50 m Pa.S, vorzugsweise von>100 m Pa.S aufweist. Hierzu gehören die von der Firma Henkel unter der Typensammel- bezeichnung "Culminal®" gehandelten Methylcellulosen (MC), Methylhydrocyethylcellulosen (MHEC), Methylhydroxypropylcellulosen (MHPC), Carboxymethylmethylcellulose (CMMC) und Hydroxyethylcellulosen (HEC), außerdem Methylhydroxybutylcellulose (MHBC) und Hydroxybutylcellulose, wie sie von der Dow Chemicals unter dem Markennamen Methocel® gehandelt werden.The cellulose ethers with a charge density greater than O, but not greater than 0.5, preferably greater than O, but not greater than 0.2 include, in particular, those whose 2% aqueous solution has a viscosity of> 50 at 20 ° C. m Pa.S, preferably of> 100 m Pa.S. These include the methylcelluloses (MC), methylhydrocyethylcelluloses (MHEC), methylhydroxypropylcelluloses (MHPC), carboxymethylmethylcellulose (CMMC) and hydroxyethylcelluloses (HEC), also methylhydroxybutylcellulose (MHBC), which are traded by the Henkel company under the type collective name "Culminal®". as they are traded by Dow Chemicals under the brand name Methocel®.

Polysaccharide kommen insbesondere in Derivatform zum Beispiel als Stärkeether (zum Beispiel Solvitose®der Firma W.A. Scholtens, Holland) in Betracht, wobei auch hier die Ladungsdichte von 0,5 bis <0,2 ausschlaggebend ist. Ebenso gehören Alginate ("Algipon®" der Firma Henkel) zu dieser Polymerenklasse.Polysaccharides are particularly suitable in derivative form, for example as starch ethers (for example Solvitose® from W.A. Scholtens, Holland), the charge density of 0.5 to <0.2 also being decisive here. Alginates ("Algipon®" from Henkel) also belong to this class of polymers.

Bei den erfindungsgemäß einsetzbaren Proteinen handelt es sich beispielsweise um Natriumcaseinat und Gelatine, die beide unter anderem von der Firma Milac, Hamburg vertrieben werden.The proteins which can be used according to the invention are, for example, sodium caseinate and gelatin, both of which are sold, inter alia, by the company Milac, Hamburg.

Polyacrylamide, d.h. Polymere und Copolymere des Acrylamids mit der allgemeinen Formel (-CH2-CH(CONH2)-)n mit Molgewichten von 300 000 bis 6 000 000, vorzugsweise 500 000 bis 2 000 000 werden unter anderem von der Firma Schuchardt vertrieben und eignen sich ebenfalls für den erfindungsgemäßen Einsatz.Polyacrylamides, ie polymers and copolymers of acrylamide with the general formula (-CH 2 -CH (CONH 2 ) -) n with molecular weights of 300,000 to 6,000,000, preferably 500,000 to 2,000,000, are marketed by Schuchardt, among others and are also suitable for use in accordance with the invention.

Die vorteilhaften Eigenschaften der beanspruchten Reinigungsmittel sind zwar auch dann zu beobachten, wenn sie in Form ihrer wäßrigen Lösungen ohne jeden weiteren Zusatz verwendet werden. Man verwendet sie jedoch vorteilhaft zusammen mit sonstigen für derartige Reinigungsmittel üblichen Bestandteilen wie nachfolgend beispielhaft angegeben.The advantageous properties of the cleaning agents claimed can also be observed if they are used in the form of their aqueous solutions without any further addition. However, they are advantageously used together with other constituents customary for such cleaning agents, as indicated below by way of example.

Für die erfindungsgemäßen flüssigen Reinigungsmittel werden als Gerüstsubstanzen in ihrer Gesamtheit alkalisch reagierende anorganische oder organische Verbindungen, insbesondere anorganische oder organische Komplexbildner verwendet, die bevorzugt in Form ihrer Alkali- oder Aminsalze, insbesondere der Kaliumsalze vorliegen. Zu den Gerüstsubstanzen zählen auch die Alkalihydroxide, von denen bevorzugt das Kaliumhydroxid eingesetzt wird.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 also include the alkali hydroxides, of which the potassium hydroxide is preferably used.

Als anorganische komplexbildende Gerüstsubstanzen eignen sich besonders die alkalisch reagierenden Polyphosphate, insbesondere die Tripolyphosphate sowie die Pyrophosphate. Sie können ganz oder teilweise durch organische Komplexbildner ersetzt werden. Weitere erfindungsgemäß brauchbare . anorganische Gerüstsubstanzen sind beispielsweise die Bicarbonate, Carbonate, Borate, Silikate oder Orthophosphate der Alkalien.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 usable according to the invention. Inorganic builders are, for example, the bicarbonates, carbonates, borates, silicates or orthophosphates of the alkalis.

Zu den organischen Komplexbildnern vom Typ der Aminopolycarbonsäuren gehören unter anderem die Nitrilotriessigsäure, Ethylendiamintetraessigsäure, N-Hydroxyethyl-ethylendiamintriessigsäure, Polyalkylen-polyamin-N-polycarbonsäuren. Als Beispiele für Di- und Polyphosphonsäuren seien genannt: Methylendiphosphonsäure, 1-Hydroxyethan-1,1-diphosphonsäure, Propan-1,2,3-triphosphonsäure, Butan-1,2,3,4-tetraphosphonsäure, Polyvinylphosphonsäure, Mischpolymerisate aus Vinylphosphonsäure und Acrylsäure, Ethan-1,2-dicarboxy-1,2-diphosphonsäure, Ethan-1,2-dicarboxy-1,2-dihydroxy-di-phosphonsäure, Phosphonobernsteinsäure, 1-Aminoethan-1,1-diphosphonsäure, Aminotri-(methylenphos- phonsäure), Methylamino- oder Ethylamino-di-(methylenphos- phonsäure), sowie Ethylendiamin-tetra-(methylenphosphon- säure).The organic complexing agents of the aminopolycarboxylic acid type include, among others, nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethyl-ethylenediamine triacetic acid, polyalkylene-polyamine-N-polycarboxylic acids. Examples of di- and polyphosphonic acids are: methylene diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, propane-1,2,3-triphosphonic acid, butane-1,2,3,4-tetraphosphonic 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-di-phosphonic acid, phosphonosuccinic acid, 1-aminoethane-1,1-diphosphonic acid, aminotri- (methylenephos - Phonic acid), methylamino- or ethylamino-di- (methylenephosphonic acid), and ethylenediamine-tetra- (methylenephosphonic acid).

In jüngerer Zeit sind in der Literatur verschiedenste, meist N- oder P-freie Polycarbonsäuren als Gerüstsubstanzen vorgeschlagen worden, wobei es sich vielfach, wenn auch nicht ausschließlich, um Carboxylgruppen enthaltende Polymerisate handelt. Eine große Zahl dieser Polycarbonsäuren besitzen ein Komplexbildungsvermögen für Calcium. Hierzu gehören zum Beispiel Citronensäure, Weinsäure, 'Benzolhexacarbonsäure, Tetrahydrofurantetracarbonsäure usw.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, for example, citric acid, tartaric acid, 'benzenehexacarboxylic, tetrahydrofurantetracarboxylic etc.

Da Allzweckreinigungsmittel für den Haushalt im allgemeinen fast neutral bis schwach alkalisch eingestellt sind, d.h. ihre wäßrigen Gebrauchslösungen bei Anwendungskonzentrationen von 2 - 20, vorzugsweise von 5 - 15 g/1 Wasser oder wäßriger Lösung einen pH-Wert im Bereich von 7,0 bis 10,5, vorzugsweise 7,5 - 9,5, besitzen, kann zur Regulierung des pH-Wertes ein Zusatz saurer oder alkalischer Komponenten erforderlich sein.Since all-purpose household cleaning agents are generally almost neutral to slightly alkaline, i.e. 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 to 10.5, preferably 7.5 - 9.5 Regulation of the pH may require the addition of acidic or alkaline components.

Als saure Substanzen eignen sich übliche anorganische oder organische Säuren oder saure Salze, wie beispielsweise Salzsäure, Schwefelsäure, Bisulfate oder Alkalien, Aminosulfonsäure, Phosphorsäure oder andere Säuren des Phosphors, insbesondere die anhydrischen Säuren des Phosphors beziehungsweise deren saure Salze oder deren sauer reagierende feste Verbindungen mit Harnstoff oder anderen niederen Carbonsäureamiden, Teilamide der Phosphorsäure . oder der anhydrischen Phosphorsäure, Citronensäure, Weinsäure, Milchsäure und dergleichen.Suitable acidic substances are customary inorganic or organic acids or acidic salts, such as, for example, hydrochloric acid, sulfuric acid, bisulfates or 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 carboxamides, partial amides of phosphoric acid. or anhydrous phosphoric acid, citric acid, tartaric acid, lactic acid and the like.

Sofern der Gehalt an alkalischen Gerüstsubstanzen nicht zur Regulierung des pH-Wertes ausreicht, können auch noch alkalisch wirkende organische oder anorganische Verbindungen wie die Alkanolamide, nämlich Mono-, Di- oder Triethanolamin oder Ammoniak zugesetzt werden.If the content of alkaline builders is not sufficient to regulate the pH, organic or inorganic compounds such as alkanolamides, namely mono-, di- or triethanolamine or ammonia, can also be added.

Als wasserlösliche oder mit Wasser emulgierbare organische Lösungsmittel kommen Ketone, wie Aceton, Methylethylketon sowie aliphatische, cycloaliphatische, aromatische und chlorierte Kohlenwasserstoffe, ferner die Terpenalkohole in Betracht. Weiterhin sind wasserlösliche organische Lösungsmittel verwendbar, insbesondere solche mit Siedepunkten oberhalb von 75 °C wie beispielsweise die Ether aus gleich- oder verschiedenartigen mehrwertigen Alkoholen oder die Teilether aus mehrwertigen und einwertigen Alkoholen. Hierzu gehören beispielsweise Di- oder Triethylenglycolpolyglycerine sowie die Teilether aus Ethylenglycol, Propylenglycol, Butylglycol oder Glycerin mit aliphatischen, 1 - 4.Kohlenstoffatome im Molekül enthaltenden einwertigen Alkoholen. Bevorzugt werden Isopropanol, Butylglycol, Aceton oder Gemische dieser Lösungsmittel.Suitable water-soluble or water-emulsifiable organic solvents are ketones, such as acetone, methyl ethyl ketone and aliphatic, cycloaliphatic, aromatic and chlorinated hydrocarbons, and also the terpene alcohols. Furthermore, water-soluble organic solvents can be used, in particular those with boiling points above 75 ° C., such as, for example, the ethers from identical or different polyhydric alcohols or the partial ethers from polyhydric and monohydric alcohols. These include, for example, di- or triethylene glycol polyglycerols and the partial ethers of ethylene glycol, propylene glycol, butyl glycol or glycerol with aliphatic monohydric alcohols containing 1-4 carbon atoms in the molecule. Isopropanol, butyl glycol, acetone or mixtures of these solvents are preferred.

Außerdem kann man, falls erforderlich, an sich bekannte Lösungsvermittler einarbeiten, wozu außer den wasserlöslichen organischen Lösungsmitteln wie insbesondere niedermolekularen aliphatischen hydrotropen Stoffe vom Typ der niederen Arylsulfonate beispielsweise Toluol-, Xylol- oder Cumolsulfonat gehören. Sie können auch in Form ihrer Natrium- und/oder Kalium- und/oder Alkylolaminsalze vorlie- gen..In addition, if necessary, known solubilizers can be incorporated, which include, in addition to the water-soluble organic solvents such as, in particular, low molecular weight aliphatic hydrotropic substances of the lower aryl sulfonate type, for example toluene, xylene or cumene sulfonate. You can their sodium and / or potassium and / or alkylolamaine vorlie- g s in the form ..

Zur Regulierung der Viskosität empfiehlt sich gegebenenfalls zusätzlich zu den erfindungsgemäß eingesetzten Polymeren nach b) ein weiterer Zusatz von Polyglycerin oder Sorbit oder von anderen wasserlöslichen hochmolekularen Stoffen. Weiterhin kann sich zur Regulierung der Viskosität bzw. Lösungsvermittlung ein Zusatz von Neutralsalzen, vorzugsweise von NaCl, Na2S04 und/oder Harnstoff empfehlen.To regulate the viscosity, in addition to the polymers according to the invention according to b), a further addition of polyglycerol or sorbitol or of other water-soluble high-molecular substances is recommended. Furthermore, the addition of neutral salts, preferably NaCl, Na 2 S0 4 and / or urea, can be recommended to regulate the viscosity or to impart a solution.

Weiterhin können die beanspruchten Mittel Zusätze an Farb-und Riechstoffen, Konservierungsmitteln und gewünschtenfalls auch antimikrobiell wirksamen Mitteln beliebiger Art enthalten.Furthermore, the claimed agents can contain additives of colorants and fragrances, preservatives and, if desired, antimicrobial agents of any kind.

Als zu verwendende antimikrobielle Wirkstoffe kommen solche Verbindungen in Betracht, die in den erfindungsgemäßen flüssigen Mitteln stabil und wirksam sind. Dabei handelt es sich um phenolische Verbindungen vom Typ der i halogenierten Phenole mit 1 - 5 Halogensubstituenten, insbesondere chlorierte Phenole; Alkyl-, Cycloalkyl-, Aralkyl- und Phenylphenole mit 1 - 12 Kohlenstoffatomen in den Alkylresten und mit 1 - 4 Halogensubstituenten, insbesondere Chlor und Brom im Molekül; Alkylen-bisphenole, insbesondere durch 2 - 6 Halogenatome und gegebenenfalls niedere Alkyl- oder Trifluormethylgruppen substituierte Derivate, mit einem Alkylenbrückenglied mit 1 - 10 Kohlenstoffatomen; Hydroxybenzoesäuren beziehungsweise deren Ester und Amide, insbesondere Anilide, die im Benzoesäure-und/oder Anilinrest, insbesondere durch 2 oder 3 Halogenatome und/oder Trifluormethylgruppen substituiert sein können; Orthophenoxyphenole, die durch 1 - 7, vorzugsweise 2 - 5 Halogenatome und/oder die Hydroxyl-, Cyano-, Methoxycarbonyl- und Carboxylgruppe oder niederes Alkyl substituiert sein können. Besonders bevorzugte antimikrobielle Wirkstoffe vom Phenyltyp sind zum Beispiel O-Phenylphenol, 2-Phenylphenol, 2-Hydroxy-2',4,4'-trichlor- diphenylether, 3,4',5-Tribromsalicylanilid und 3,3',5,5', 6,6'-Hexachloro-2,2'-dihydroxydiphenylmethan.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 type of the halogenated phenols with 1-5 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 2-6 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 amides, especially anilides, which can be substituted in the benzoic acid and / or aniline residue, in particular by 2 or 3 halogen atoms and / or trifluoromethyl groups; O rthophenoxyphenols, 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, 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'-dihydroxydiphenylmethane.

Weitere brauchbare antimikrobielle Wirkstoffe sind die sowohl durch Brom als auch durch die Nitrogruppe substituierten niederen Alkohole beziehungsweise Diole mit 3 - 5 Kohlenstoffatomen wie zum Beispiel die Verbindungen 2-Brom-2-nitropropandiol-1,3,1-Brom-1-nitro-3,3,3-trichlor- propanol-2, 2-Brom-2-nitro-butanol-1..Other useful antimicrobial agents are the lower alcohols or diols with 3 to 5 carbon atoms substituted by both bromine and the nitro group, such as the compounds 2-bromo-2-nitropropanediol-1,3,1-bromo-1-nitro-3 , 3,3-trichloropropanol-2, 2-bromo-2-nitro-butanol-1 ..

Ferner eignen sich auch Bis-diguanide wie zum Beispiel das 1,6-Bis-(p-chlorphenyldiguanido)-hexan in der Form des Hydrochlorids, Acetats oder Glukonats sowie auch N,N'- disubstituierte 2-Thiön-tetrahydro-1,3,5-thiadizine wie zum Beispiel das 3,5-Dimethyl, 3,5-Diallyl-, 3-Benzyl-5-methyl- und insbesondere das 3-Benzyl-5-carboxymethyl- tetrahydro-1,3,5-thiadiazin als zusätzliche antimikrobielle Wirkstoffe.Also suitable are bis-diguanides such as, for example, 1,6-bis- (p-chlorophenyldiguanido) hexane in the form of the hydrochloride, acetate or gluconate, and also N, N'-disubstituted 2-thioenetrahydro-1,3 , 5-thiadizines 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.

Bevorzugt können Formaldehyd-Aminoalkohol-Kondensationsprodukte zum Einsatz kommen. Die Produkte werden durch Umsetzung einer wäßrigen Lösung von Formaldehyd mit Aminoalkoholen, zum Beispiel 2-Aminoethanol, 1-Amino-2-Propanol, 2-Amino-iso-butanol, 2(2'-Aminoethyl)-aminoethanol hergestellt.Formaldehyde-amino alcohol condensation products can preferably be used. The products are prepared by reacting an aqueous solution of formaldehyde with amino alcohols, for example 2-aminoethanol, 1-amino-2-propanol, 2-amino-iso-butanol, 2 (2'-aminoethyl) aminoethanol.

Darüber hinaus kann es für weitere Anwendungsbereiche vorteilhaft sein, allein oder zusätzlich zu anderen als weitere antimikrobiell wirksame Substanzen solche vom Typ der quaternären Ammoniumverbindungen, beispielsweise ein Benzylalkyldimethylammoniumchlorid zuzusetzen.In addition, it can be advantageous for other areas of application, alone or in addition to other substances having other antimicrobial activity, to add those of the quaternary ammonium compound type, for example a benzylalkyldimethylammonium chloride.

V e r s u c h eTries

Zum Nachweis des überraschenden reinigungsverstärkenden Effektes der Kombination der beanspruchten Verbindungen wurden folgende Versuche durchgeführt:The following tests were carried out to demonstrate the surprising cleaning-enhancing effect of the combination of the claimed compounds:

1. Prüfung des Reinigungsvermögens bei fetthaltigen Anschmutzungen1. Check the cleaning ability for greasy soiling

Auf einer künstlich angeschmutzten weißen PVC-Kunststoffoberfläche wurde die auf ihr Reinigungsvermögen zu prüfende Formulierung gegeben. Als künstliche Anschmutzung wurde ein Gemisch aus Ruß, Maschinenöl, einem Triglycerid gesättigter Fettsäuren und niedrigsiedenden aliphatischen Kohlenwasserstoffen verwendet.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 triglyceride of saturated fatty acids and low-boiling aliphatic hydrocarbons was used as artificial soiling.

Die Testfläche von 24 x 4,6 cm wurde im mittleren Teil auf ca. 30 cm2 gleichmäßig mit 0,1 g der künstlichen Anschmutzung beschichtet und vor Versuchsbeginn eine Stunde lang bei Raumtemperatur gelagert. Anschließend wurde ein Kunststoffschwamm mit jeweils 12 ml der zu prüfenden Reinigungsmittellösung getränkt und maschinell auf der Testfläche hin und her bewegt, wobei der Schwamm sowohl den angeschmutzten, mittleren Bereich erfaßt, als auch die nicht beschmutzten Randzonen. Nach 10 Wischbewegungen unter genau definierten Anpreßdruckbedingungen von 2 kp wurde die gereinigte Testfläche mit 400 ml Leitungswasser gespült und dadurch der gelockerte Schmutz entfernt. Das Reinigungsvermögen, d.h. der Weißgrad der so gereinigten Kunststoffoberfläche wurde mit einem photoelektrischen Reflektionsmeßgerät LF 90 (Firma Dr. B. Lange) gemessen, wobei der Weißgrad des ursprünglich angeschmutzten Teils der Testfläche der Ermittlung des Reinigungsvermögens, der Weißgrad des nicht angeschmutzten, vom Kunststoffschwamm aber miterfaßten Teils der Testfläche der Ermittlung des Schmutztragevermögens (SV) diente. Als Weiß-Standard wurde die saubere, weiße PVC-Kunststoffoberfläche zugrunde gelegt. Da bei der Messung der sauberen Oberfläche der Ausschlag des Meßgerätes auf 100 Prozent und bei der angeschmutzten Fläche auf O Prozent eingestellt wurde, konnten die abgelesenen Werte an den gereinigten Kunststoff-Flächen als "Prozent Reinigungsvermögen" (% RV) beziehungsweise als "Prozent Schmutztragevermögen" (% SV) angesehen werden. Die angegebenen % RV- beziehungsweise % SV-Werte sind gemittelte Werte aus einer 4-fach-Bestimmung.The test area of 24 x 4.6 cm was evenly coated with 0.1 g of the artificial soiling in the central part to about 30 cm 2 and stored for one hour at room temperature before the start of the test. Then a plastic sponge was impregnated with 12 ml of the cleaning agent solution to be tested and moved mechanically 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, i.e. the degree of whiteness of the plastic surface cleaned in this way, was measured with a photoelectric reflection measuring device LF 90 (Dr. B. Lange), the whiteness of the originally soiled part of the test area determining the cleaning ability, the whiteness of the non-soiled, of the plastic sponge, however recorded part of the test area of the Determination of dirt carrying capacity (SV) served. The clean, white PVC plastic surface was used as the white standard. Since the deflection of the measuring device was set to 100 percent for the measurement of the clean surface and to 0 percent for the soiled surface, the readings on the cleaned plastic surfaces could be expressed as "percent cleaning capacity" (% RV) or as "percent dirt carrying capacity" (% SV) can be viewed. The% RV or% SV values given are averages from a 4-fold determination.

2. Prüfung der Reinigungsleistung bei stark pigmenthaltigen Anschmutzungen2. Checking the cleaning performance for soiling with a high pigment content

Als Testfläche diente eine 2 Jahre alte, natürlich verschmutzte LKW-Plane, die in 20 x 10 cm große Stücke aufgeteilt und unabhängig voneinander von 3 Testpersonen durch gleichmäßiges Behandeln mit einem produktgetränkten Schwamm, anschließendes Abspülen der Fläche unter fließendem Wasser und.visuelle Benotung beurteilt wurde (Note 1: Restverschmutzung entspricht der Wirkung von Wasser, Note 3: vollständige Schmutzentfernung).A 2-year-old, naturally soiled truck tarpaulin was used as the test area, which was divided into 20 x 10 cm pieces and was independently assessed by 3 test persons by treating it evenly with a product-soaked sponge, then rinsing the area under running water and visual grading (Grade 1: residual pollution corresponds to the effect of water, Grade 3: complete dirt removal).

Beispiel 1example 1

a) Mit einem üblichen Allzweck-Reinigungsmittel für harte Oberflächen der Zusammensetzung

Figure imgb0003
Rest auf 100 %: entmineralisiertes Wasser
wurde geprüft, in welchem Maße sich Reinigungs- und : Schmutztragevermögen beziehungsweise Reinigungsleistung gegenüber fetthaltigen Anschmutzungen und Pigmentschmutz durch Zugabe von je 0,5 % eines Polymeren zur vorstehend angegebenen Rezeptur steigern läßt. Wie der nachfolgenden Tabelle 1 zu entnehmen ist, ergab sich bei unverdünnter Anwendung erwartungsgemäß gegenüber Fettschmutz ein geringfügiger Anstieg, nicht jedoch gegenüber Pigmentschmutz.a) With a common all-purpose cleaner for hard surfaces of the composition
Figure imgb0003
 Rest to 100%: demineralized water
The extent to which cleaning and: dirt-carrying capacity or cleaning performance compared to greasy soiling and pigment soiling can be increased by adding 0.5% of a polymer to the above-mentioned formulation was examined. As can be seen in the following Table 1, when used undiluted, there was, as expected, a slight increase over grease soiling, but not over pigment soiling.

b) Durch Herausnahme des Aniontensids und Ersatz durch Wasser in der vorstehend genannten Rezeptur wurde erfindungsgemäß in Kombination mit den beanspruchten Polymeren eine erhebliche Steigerung des Reinigungs-und des Schmutztragevermögens gegenüber Fettschmutz, sowie eine Steigerung der Reinigungsleistung gegenüber Pigmentschmutz erzielt; vergleiche Tabelle 2.

Figure imgb0004
b) By removing the anionic surfactant and replacing it with water in the above-mentioned formulation, in combination with the claimed polymers, a considerable increase in cleaning and dirt-carrying capacity compared to greasy dirt, as well as an increase in cleaning performance compared to pigmented dirt was achieved; see table 2.
Figure imgb0004

Beispiel 2Example 2

a) Mit einem üblichen Allzweck-Reinigungsmittel der Zusammensetzung

Figure imgb0005
Rest auf 100 %: entmineralisiertes Wasser
wurde entsprechend Beispiel 1 untersucht, in welcher Weise sich das Reinigungs- und Schmutztragevermögen sowie die Reinigungsleistung dieser alkalischen Formulierung durch Polymerzusätze steigern läßt. Auch hier wurde erwartungsgemäß eine Steigerung erzielt, wie die nachfolgende Tabelle 3 zeigt.a) With a common all-purpose detergent of the composition
Figure imgb0005
 Rest to 100%: demineralized water
was examined according to Example 1, in which way the cleaning and dirt-carrying capacity and the cleaning performance of this alkaline formulation can be increased by polymer additives. As expected, an increase was also achieved here, as shown in Table 3 below.

b) Auch hier führte der Zusatz von nicht- oder schwachionogenen Polymeren bei gleichzeitigem Ersatz das Aniontensidanteils durch Wasser zu ausgeprägten Steigerungseffekten von Reinigungs- und Schmutztragevermögen und Reinigungsleistung; vergleiche Tabelle 4.

Figure imgb0006
b) Here, too, the addition of non-ionic or weakly ionic polymers with simultaneous replacement of the anionic surfactant component by water led to pronounced increases in cleaning and dirt-carrying capacity and cleaning performance; see Table 4.
Figure imgb0006

Beispiel 3Example 3

Besonders günstig wirkt sich der erfindungsgemäße Zusatz von nicht- oder schwachionogenen Polymeren zu einer Desinfektionsreiniger-Formulierung der Zusammensetzung

Figure imgb0007
Rest auf 100 %: Polymerzusatz und entmineralisiertes Wasser aus, da sich bei einer derartigen Formulierung der Einsatz von Aniontensiden wegen der hierbei auftretenden bekannten Unverträglichkeit mit quartären Ammoniumverbindungen verbietet und das Reinigungsvermögen derartiger Produkte daher im allgemeinen relativ niedrig ist. Die nachfolgend angegebenen Versuchsergebnisse in Tabelle 5 geben das .Reinigungsvermögen gegenüber fetthaltigen Anschmutzungen wieder:
Figure imgb0008
 The addition of nonionic or weakly ionic polymers to a disinfectant cleaner formulation of the composition has a particularly favorable effect
Figure imgb0007
 Remainder to 100%: polymer additive and demineralized water, since in such a formulation the use of anionic surfactants is prohibited because of the known incompatibility with quaternary ammonium compounds and the cleaning power of such products is therefore generally relatively low. The test results given in Table 5 below show the cleaning ability against greasy soiling:
Figure imgb0008

Beispiel 3 / Tabelle 5Example 3 / Table 5

Die Desinfektionswirkung wird durch den Polymerzusatz nicht beeinträchtigt.The disinfectant effect is not affected by the addition of polymer.

Beispiel 4Example 4

Mit einem wäßrigen Allzweck-Reinigungsmittel mit einem Gehalt an

Figure imgb0009
wurde ebenfalls eine bedeutende Steigerung der Reinigungsleistung gegenüber bekannten Allzweck-Reinigungsmitteln erzielt.With an aqueous all-purpose detergent containing
Figure imgb0009
 a significant increase in cleaning performance over known general-purpose cleaning agents was also achieved.

Beispiel 5Example 5

Wie in Beispiel 4 wurde mit entsprechend gutem Ergebnis mit einer wäßrigen Lösung von

Figure imgb0010
gearbeitet. Im Rahmen der eingesetzten Mengen der Bestandteile und unter Einsatz verschiedener erfindungsgemäßer Polymerer lassen sich zahlreiche vorteilhafte Allzweck- Reinigungsmittel herstellen.As in Example 4, an aqueous solution of
Figure imgb0010
 worked. Within the scope of the amounts of the components used and using various polymers according to the invention, numerous advantageous all-purpose cleaning agents can be produced.

Claims (6)

1. Flüssiges Reinigungsmittel für harte Oberflächen aus wäßrigen oder wäßrigen, lösungsmittelhaltigen Lösungen nichtionischer Tenside und wasserlöslicher Polymerer, dadurch gekennzeichnet, daß sie entmineralisiertes Wasser und a) 0,001 bis 35, vorzugsweise 0,1 bis 10 Gewichtsprozent eines nichtionischen Tensids, b) 0,005 bis 15, vorzugsweise 0,01 bis 2 Gewichtsprozent eines wasserlöslichen nicht- ionischen, schwach anionischen oder kationischen Polymers aus der Gruppe der Polyethylenglycole, Polyvinylalkohole, Polyvinylpyrrolidone, Celluloseether, Polysaccharide, Proteine und Polyacrylamide mit mittleren Molgewichten von 5000 bis 10 000 000, vorzugsweise von 20 000 bis 2 000 000 oder Gemische dieser Polymeren, c) 0,01 bis 20, vorzugsweise 0,1 bis 10 Gewichtsprozent alkalisch reagierende anorganische oder organische Gerüstsubstanzen, d) O bis 40, vorzugsweise 0,5 bis 15 Gewichtsprozent eines wasserlöslichen oder in Wasser emulgierbaren organischen Lösungsmittels und e) O bis 20, vorzugsweise 0,5 bis 2 Gewichtsprozent anorganische Neutralsalze, Harnstoff, Farbstoffe, Duftstoffe, Konservierungsmittel sowie antimikrobiell wirksame Mittel enthalten. 1. Liquid cleaning agent for hard surfaces from aqueous or aqueous, solvent-containing solutions of nonionic surfactants and water-soluble polymers, characterized in that they contain demineralized water and a) 0.001 to 35, preferably 0.1 to 10 percent by weight of a nonionic surfactant, b) 0.005 to 15, preferably 0.01 to 2 percent by weight of a water-soluble, non-ionic, weakly anionic or cationic polymer from the group of polyethylene glycols, polyvinyl alcohols, polyvinyl pyrrolidones, cellulose ethers, polysaccharides, proteins and polyacrylamides with average molecular weights of 5,000 to 10,000,000 , preferably from 20,000 to 2,000,000 or mixtures of these polymers, c) 0.01 to 20, preferably 0.1 to 10 percent by weight alkaline inorganic or organic framework substances, d) 0 to 40, preferably 0.5 to 15 percent by weight of a water-soluble or water-emulsifiable organic solvent and e) O to 20, preferably 0.5 to 2 percent by weight of inorganic neutral salts, urea, dyes, fragrances, preservatives and antimicrobial agents. 2. Reinigungsmittel nach Anspruch 1, dadurch gekennzeichnet, daß als schwach anionische Polymere solche eingesetzt werden, deren Ladungsdichte, d.h. das Verhältnis der Anzahl dissoziierbarer Gruppen pro Makromolekül zum Polymerisationsgrad n größer als O, aber nicht größer als 0,5, vorzugsweise größer als O, aber nicht größer als 0,2 und insbesondere größer als O, aber nicht größer als 0,01 ist.2. Cleaning agent according to claim 1, characterized in that those are used as weakly anionic polymers whose charge density, i.e. the ratio of the number of dissociable groups per macromolecule to the degree of polymerization n is greater than O, but not greater than 0.5, preferably greater than O, but not greater than 0.2, and in particular greater than O, but not greater than 0.01. 3. Reinigungsmittel nach Anspruch 1 und 2, dadurch gekennzeichnet, daß sie als wasserlösliche oder in Wasser emulgierbare organische Lösungsmittel Isopropanol, Butylglycol, Aceton oder Gemische dieser Lösungsmittel enthalten.3. Cleaning agents according to claim 1 and 2, characterized in that they contain isopropanol, butyl glycol, acetone or mixtures of these solvents as water-soluble or water-emulsifiable organic solvents. 4. Reinigungsmittel nach Anspruch 1 bis 3, dadurch gekennzeichnet, daß sie als antimikrobiell wirksame Mittel Aldehyd-Kondensationsprodukte und/oder quartäre Ammoniumverbindungen enthalten.4. Cleaning agents according to claims 1 to 3, characterized in that they contain aldehyde condensation products and / or quaternary ammonium compounds as antimicrobial agents. 5. Reinigungsmittel nach Anspruch 1 bis 4, dadurch gekennzeichnet, daß die mittleren Molgewichte der nichtionischen Tenside unterhalb von 5000 liegen.5. Cleaning agent according to claim 1 to 4, characterized in that the average molecular weights of the nonionic surfactants are below 5000. 6. Reinigungsmittel nach Anspruch 1 bis 5, dadurch gekennzeichnet, daß sie als nichtionische Tenside Trialkylaminoxide enthalten.6. Cleaning agents according to claim 1 to 5, characterized in that they contain trialkylamine oxides as nonionic surfactants.
EP80101581A 1979-03-31 1980-03-26 Use of a liquid composition for cleaning hard surfaces Expired EP0017149B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80101581T ATE6268T1 (en) 1979-03-31 1980-03-26 USING A LIQUID AGENT TO CLEAN HARD SURFACES.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19792913049 DE2913049A1 (en) 1979-03-31 1979-03-31 LIQUID DETERGENT
DE2913049 1979-03-31

Publications (2)

Publication Number Publication Date
EP0017149A1 true EP0017149A1 (en) 1980-10-15
EP0017149B1 EP0017149B1 (en) 1984-02-15

Family

ID=6067140

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80101581A Expired EP0017149B1 (en) 1979-03-31 1980-03-26 Use of a liquid composition for cleaning hard surfaces

Country Status (3)

Country Link
EP (1) EP0017149B1 (en)
AT (1) ATE6268T1 (en)
DE (2) DE2913049A1 (en)

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2544329A1 (en) * 1983-04-15 1984-10-19 Oreal WASHING AND FOAMING COMPOSITION BASED ON NON-IONIC SURFACTANTS AND ANIONIC POLYMERS
GB2172009A (en) * 1985-03-05 1986-09-10 Drew Chem Corp Rinse water additive
EP0244006A1 (en) * 1986-04-22 1987-11-04 Unilever N.V. General-purpose cleaning composition
EP0262358A1 (en) * 1986-08-21 1988-04-06 Henkel Kommanditgesellschaft auf Aktien Glass cleaning agent in tablet form
EP0268064A2 (en) * 1986-10-18 1988-05-25 Henkel Kommanditgesellschaft auf Aktien Aqueous composition for the pretreatment of dishes
EP0295590A2 (en) * 1987-06-19 1988-12-21 Henkel Kommanditgesellschaft auf Aktien Liquid cleaning composition for hard surfaces
EP0353408A2 (en) * 1988-08-01 1990-02-07 Ecolab Inc. Non-filming high performance solid floor cleaner
EP0359492A2 (en) * 1988-09-12 1990-03-21 Unilever Plc Thickened liquids
EP0359491A2 (en) * 1988-09-12 1990-03-21 Unilever Plc Liquid cleaning products
EP0408279A2 (en) * 1989-07-11 1991-01-16 Unilever Plc Fabric softening composition
EP0420802A2 (en) * 1989-09-26 1991-04-03 Ciba-Geigy Ag Aqueous, storage stable, low foaming wetting agent
WO1991008283A2 (en) * 1989-11-28 1991-06-13 Unilever N.V. Thickened composition
EP0467472A2 (en) * 1990-07-16 1992-01-22 Colgate-Palmolive Company Hard surface liquid cleaning composition with anti-soiling polymer
EP0607529A2 (en) * 1993-01-20 1994-07-27 Hüls Aktiengesellschaft Aqeous softeners for the treatment of textiles
EP0957156A1 (en) * 1998-05-15 1999-11-17 The Procter & Gamble Company Liquid acidic hard surface cleaning composition
EP0982394A1 (en) * 1998-08-27 2000-03-01 The Procter & Gamble Company Liquid neutral or alkaline hard-surface cleaning composition
WO2001085889A1 (en) * 2000-05-12 2001-11-15 Unilever N.V. Process and composition for providing shine to a hard surface
US6718992B1 (en) 1998-08-27 2004-04-13 Sergio Cardola Liquid neutral to alkaline hard-surface cleaning composition
EP1667536A2 (en) * 2003-10-03 2006-06-14 Eco Holdings, LLC Process for producing natural surfactants and compositions based on natural surfactants
DE102004063765A1 (en) * 2004-12-29 2006-07-13 Henkel Kgaa Foam-reinforced cleaner
WO2008059453A1 (en) * 2006-11-14 2008-05-22 The Procter & Gamble Company Liquid hard surfaces cleaning compositions
WO2014012868A1 (en) * 2012-07-19 2014-01-23 Henkel Ag & Co. Kgaa Stable, liquid detergent with anti-redeposition action
EP2875108B1 (en) * 2012-07-19 2018-11-14 Henkel AG & Co. KGaA Liquid detergent composition having dye transfer inhibition

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1164469B (en) * 1982-11-09 1987-04-08 Mira Lanza Spa CONCENTRATED DETERGENT COMPOSITION IN THE FORM OF QUICKLY SOLUBLE VISCOUS LIQUID IN WATER SUITABLE FOR PREPARATION BY DILUTION OF LIQUID DETERGENTS READY FOR USE
DE3320727A1 (en) * 1983-06-09 1984-12-13 Henkel KGaA, 4000 Düsseldorf USE OF FATTY ACID CYANAMIDES AS A SURFACTANT FOR CLEANING HARD SURFACES
US4690779A (en) * 1983-06-16 1987-09-01 The Clorox Company Hard surface cleaning composition
DE3726912A1 (en) * 1987-08-13 1989-02-23 Henkel Kgaa LIQUID MEDIUM TO CLEAN HARD SURFACES
DE4209923A1 (en) * 1992-03-27 1993-09-30 Henkel Kgaa Liquid detergent for hard surfaces
US6762162B1 (en) 2003-06-18 2004-07-13 S. C. Johnson & Son, Inc. Disinfecting cationic polymer cleaner comprising an acrylate cationic polymer
DE102005020799A1 (en) * 2005-04-28 2006-11-02 Karl Spiegl cleaning device

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE773574Q (en) * 1965-02-16 1972-01-31 Unilever Nv COPOLYMERS IN NON-IONIC DETERGENT COMPOSITIONS DRIED BY SPRAY
DE2327861A1 (en) * 1973-06-01 1975-01-02 Henkel & Cie Gmbh LAUNDRY DETERGENT
DE2610995A1 (en) * 1975-03-18 1976-10-07 Procter & Gamble CLEANING AGENTS FOR HARD SURFACES
FR2339672A1 (en) * 1976-02-02 1977-08-26 Procter & Gamble DETERGENT COMPOSITIONS CONTAINING A NON-IONIC SURFACTANT AND A CELLULOSIC ETHER
DE2745275A1 (en) * 1976-10-11 1978-04-13 Unilever Nv LIQUID DETERGENT COMPOSITION
DE2850256A1 (en) * 1977-11-28 1979-05-31 Kao Corp LIQUID DETERGENT MIXTURE

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU458526B2 (en) * 1972-04-12 1975-02-27 The Dow Chemical Company Cleaning composition for glass and reflective surfaces
DE2648304A1 (en) * 1975-10-31 1977-05-05 Procter & Gamble Europ LIQUID DETERGENT
GB1562793A (en) * 1975-11-07 1980-03-19 Unilever Ltd Cleaning composition
DE2709690B1 (en) * 1977-03-05 1978-05-11 Henkel Kgaa Liquid detergent
DE2840464C3 (en) * 1978-09-16 1981-04-09 Henkel KGaA, 4000 Düsseldorf Cleaning agents for windows, mirrors and reflective surfaces
DE2840463C2 (en) * 1978-09-16 1983-12-22 Henkel KGaA, 4000 Düsseldorf Using a liquid agent to clean hard surfaces

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE773574Q (en) * 1965-02-16 1972-01-31 Unilever Nv COPOLYMERS IN NON-IONIC DETERGENT COMPOSITIONS DRIED BY SPRAY
DE2327861A1 (en) * 1973-06-01 1975-01-02 Henkel & Cie Gmbh LAUNDRY DETERGENT
DE2610995A1 (en) * 1975-03-18 1976-10-07 Procter & Gamble CLEANING AGENTS FOR HARD SURFACES
FR2339672A1 (en) * 1976-02-02 1977-08-26 Procter & Gamble DETERGENT COMPOSITIONS CONTAINING A NON-IONIC SURFACTANT AND A CELLULOSIC ETHER
DE2745275A1 (en) * 1976-10-11 1978-04-13 Unilever Nv LIQUID DETERGENT COMPOSITION
DE2850256A1 (en) * 1977-11-28 1979-05-31 Kao Corp LIQUID DETERGENT MIXTURE

Cited By (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4657690A (en) * 1983-04-15 1987-04-14 L'oreal Washing and foaming composition based on non-ionic surface-active agents and anionic polymers
FR2544329A1 (en) * 1983-04-15 1984-10-19 Oreal WASHING AND FOAMING COMPOSITION BASED ON NON-IONIC SURFACTANTS AND ANIONIC POLYMERS
GB2172009A (en) * 1985-03-05 1986-09-10 Drew Chem Corp Rinse water additive
EP0244006A1 (en) * 1986-04-22 1987-11-04 Unilever N.V. General-purpose cleaning composition
US4759868A (en) * 1986-04-22 1988-07-26 Lever Brothers Company General-purpose cleaning composition
EP0262358A1 (en) * 1986-08-21 1988-04-06 Henkel Kommanditgesellschaft auf Aktien Glass cleaning agent in tablet form
EP0268064A2 (en) * 1986-10-18 1988-05-25 Henkel Kommanditgesellschaft auf Aktien Aqueous composition for the pretreatment of dishes
EP0268064A3 (en) * 1986-10-18 1990-12-27 Henkel Kommanditgesellschaft Auf Aktien Aqueous composition for the pretreatment of dishes
EP0295590A3 (en) * 1987-06-19 1990-09-12 Henkel Kommanditgesellschaft auf Aktien Liquid cleaning composition for hard surfaces
EP0295590A2 (en) * 1987-06-19 1988-12-21 Henkel Kommanditgesellschaft auf Aktien Liquid cleaning composition for hard surfaces
EP0353408A2 (en) * 1988-08-01 1990-02-07 Ecolab Inc. Non-filming high performance solid floor cleaner
EP0353408A3 (en) * 1988-08-01 1991-04-03 Ecolab Inc. Non-filming high performance solid floor cleaner
EP0359491A3 (en) * 1988-09-12 1990-09-05 Unilever Plc Liquid cleaning products
EP0359492A3 (en) * 1988-09-12 1990-09-05 Unilever Plc Thickened liquids
EP0359491A2 (en) * 1988-09-12 1990-03-21 Unilever Plc Liquid cleaning products
EP0359492A2 (en) * 1988-09-12 1990-03-21 Unilever Plc Thickened liquids
AU625804B2 (en) * 1988-09-12 1992-07-16 Unilever Plc Thickened non-aqueous-liquid composition comprising polyalkoxylated material
EP0408279A2 (en) * 1989-07-11 1991-01-16 Unilever Plc Fabric softening composition
EP0408279A3 (en) * 1989-07-11 1991-10-23 Unilever Plc Fabric softening composition
EP0420802A2 (en) * 1989-09-26 1991-04-03 Ciba-Geigy Ag Aqueous, storage stable, low foaming wetting agent
EP0420802A3 (en) * 1989-09-26 1991-05-15 Ciba-Geigy Ag Aqueous, storage stable, low foaming wetting agent
US5286405A (en) * 1989-11-28 1994-02-15 Lever Brothers Company, Division Of Conopco, Inc. Polymer-thickened liquid abrasive cleaning compositions
WO1991008283A2 (en) * 1989-11-28 1991-06-13 Unilever N.V. Thickened composition
WO1991008283A3 (en) * 1989-11-28 1991-08-22 Unilever Plc Thickened composition
EP0467472A2 (en) * 1990-07-16 1992-01-22 Colgate-Palmolive Company Hard surface liquid cleaning composition with anti-soiling polymer
EP0467472A3 (en) * 1990-07-16 1993-06-02 Colgate-Palmolive Company Hard surface liquid cleaning composition with anti-soiling polymer
GR910100312A (en) * 1990-07-16 1992-08-26 Colgate Palmolive Co Liquid cleaning composition for rough surfaces
EP0607529A2 (en) * 1993-01-20 1994-07-27 Hüls Aktiengesellschaft Aqeous softeners for the treatment of textiles
EP0607529A3 (en) * 1993-01-20 1995-03-22 Huels Chemische Werke Ag Aqeous softeners for the treatment of textiles.
US5447643A (en) * 1993-01-20 1995-09-05 Huels Aktiengesellschaft Aqueous fabric softener for the treatment of textile
US6537957B1 (en) 1998-05-15 2003-03-25 The Procter & Gamble Company Liquid acidic hard surface cleaning composition
WO1999060086A1 (en) * 1998-05-15 1999-11-25 The Procter & Gamble Company Liquid acidic hard surface cleaning composition
EP0957156A1 (en) * 1998-05-15 1999-11-17 The Procter & Gamble Company Liquid acidic hard surface cleaning composition
EP0982394A1 (en) * 1998-08-27 2000-03-01 The Procter & Gamble Company Liquid neutral or alkaline hard-surface cleaning composition
WO2000012661A1 (en) * 1998-08-27 2000-03-09 The Procter & Gamble Company Liquid neutral to alkaline hard-surface cleaning composition
US6718992B1 (en) 1998-08-27 2004-04-13 Sergio Cardola Liquid neutral to alkaline hard-surface cleaning composition
WO2001085889A1 (en) * 2000-05-12 2001-11-15 Unilever N.V. Process and composition for providing shine to a hard surface
EP1667536A2 (en) * 2003-10-03 2006-06-14 Eco Holdings, LLC Process for producing natural surfactants and compositions based on natural surfactants
EP1667536A4 (en) * 2003-10-03 2007-12-05 Eco Holdings Llc Process for producing natural surfactants and compositions based on natural surfactants
DE102004063765A1 (en) * 2004-12-29 2006-07-13 Henkel Kgaa Foam-reinforced cleaner
WO2008059453A1 (en) * 2006-11-14 2008-05-22 The Procter & Gamble Company Liquid hard surfaces cleaning compositions
EP1927651A1 (en) * 2006-11-14 2008-06-04 The Procter and Gamble Company Liquid hard surface cleaning compositions
US8163687B2 (en) 2006-11-14 2012-04-24 The Procter & Gamble Company Liquid hard surfaces cleaning compositions
WO2014012868A1 (en) * 2012-07-19 2014-01-23 Henkel Ag & Co. Kgaa Stable, liquid detergent with anti-redeposition action
EP2875108B1 (en) * 2012-07-19 2018-11-14 Henkel AG & Co. KGaA Liquid detergent composition having dye transfer inhibition

Also Published As

Publication number Publication date
ATE6268T1 (en) 1984-03-15
DE3066542D1 (en) 1984-03-22
DE2913049A1 (en) 1980-10-16
EP0017149B1 (en) 1984-02-15

Similar Documents

Publication Publication Date Title
EP0017149B1 (en) Use of a liquid composition for cleaning hard surfaces
EP0009193B1 (en) Liquid cleanser for hard surfaces
DE2709690C2 (en)
EP0303188A2 (en) Liquid products for cleaning hard surfaces
EP0248185B1 (en) Liquid aqueous detergents for hard surfaces
EP0295590A2 (en) Liquid cleaning composition for hard surfaces
DE1801411A1 (en) Buildings for detergents and cleaning agents
DE3431003A1 (en) LIQUID DETERGENT
EP0131138B1 (en) Use of fatty acid cyanamides as surface-active agents in the cleaning of hard surfaces
DE2552353B2 (en) LIQUID AQUATIC DETERGENT COMPOSITION
DE4209923A1 (en) Liquid detergent for hard surfaces
DE1617172B2 (en) Soap compositions
WO1991009926A1 (en) Liquid cleaning material for hard surfaces
EP0197480A2 (en) Manual cleaning process of objects with hard surfaces
DE2532802C2 (en) Wool detergent
DE2544242A1 (en) METHOD OF WASHING TEXTILES, AND MEANS OF CARRYING OUT THE METHOD
DE2125249A1 (en) Builder substances for detergents and cleaning agents
DE1957456A1 (en) Building agent for a cleaning agent
DE3838533A1 (en) LIQUID CLEANER FOR HARD SURFACES
DE3530506A1 (en) DETERGENT COMPOSITION SUITABLE FOR WASHING AND SOFTENING TEXTILES IN WASHING WATER AT AN INCREASED TEMPERATURE OF AT LEAST 60 (DEGREE) C.
DE1954080C3 (en) Polyglycol ether urethanes and their use as wetting agents, detergents and cleaning agents
AT281242B (en) Liquid detergent
DE3001937C2 (en) Dishwashing liquid
DE3830536A1 (en) WATER-LIQUID DETERGENT PREPARATIONS FOR TEXTILE MATERIALS
DE2934484C2 (en)

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): AT BE CH DE FR IT NL

17P Request for examination filed

Effective date: 19810219

ITF It: translation for a ep patent filed

Owner name: STUDIO JAUMANN

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): AT BE CH DE FR IT NL

REF Corresponds to:

Ref document number: 6268

Country of ref document: AT

Date of ref document: 19840315

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3066542

Country of ref document: DE

Date of ref document: 19840322

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19900216

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19900222

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19900301

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19900319

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19900330

Year of fee payment: 11

ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19900331

Year of fee payment: 11

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Effective date: 19910326

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Effective date: 19910331

Ref country code: BE

Effective date: 19910331

BERE Be: lapsed

Owner name: HENKEL K.G.A.A.

Effective date: 19910331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19911001

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19911129

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19920101

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST