EP0632824B1 - Produits liquides de nettoyage - Google Patents

Produits liquides de nettoyage Download PDF

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Publication number
EP0632824B1
EP0632824B1 EP93906556A EP93906556A EP0632824B1 EP 0632824 B1 EP0632824 B1 EP 0632824B1 EP 93906556 A EP93906556 A EP 93906556A EP 93906556 A EP93906556 A EP 93906556A EP 0632824 B1 EP0632824 B1 EP 0632824B1
Authority
EP
European Patent Office
Prior art keywords
weight
carbon atoms
detergent
copolymer
acrylic
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.)
Expired - Lifetime
Application number
EP93906556A
Other languages
German (de)
English (en)
Other versions
EP0632824A1 (fr
Inventor
Dimitrios Ouzounis
Ulrich Eicken
Ortburg Guirr
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
Publication of EP0632824A1 publication Critical patent/EP0632824A1/fr
Application granted granted Critical
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Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions 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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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

Definitions

  • Liquid detergents, dishwashing detergents and cleaning agents are usually aqueous solutions of anionic and / or nonionic surfactants and customary additives.
  • a preferred area of application for such agents is the manual washing of dining utensils and other related equipment.
  • Such cleaning agents are all the more effective the better their fat emulsifying capacity is, because with them e.g. the number of plates that can be cleaned with a given amount of detergent increases.
  • the present invention therefore relates to liquid cleaning agents with improved emulsifying power and increased cleaning power.
  • alkyl ether sulfates that is to say sulfated adducts of about 2 to 5 moles of ethylene oxide with fatty alcohols with about 10 to 16 carbon atoms in the alkyl radical, have a good cleansing power with a mild effect on the skin at the same time.
  • the commercially available dishwashing detergents customary in the market therefore generally represent aqueous solutions of such alkyl ether sulfates in combination with other anionic surfactants such as n-alkylbenzenesulfonates and / or alkanesulfonates, optionally also olefin sulfonates, alkyl sulfates or alkyl sulfosuccinates as well as nonionic surfactants, solubilizers, colorants and fragrances.
  • anionic surfactants such as n-alkylbenzenesulfonates and / or alkanesulfonates
  • olefin sulfonates alkyl sulfates or alkyl sulfosuccinates
  • nonionic surfactants solubilizers, colorants and fragrances.
  • alkyl ether sulfate mixture consisting of 50% by weight of a C 12 alkyl ether sulfate and 50% by weight of a C 14 alkyl ether sulfate with 1 to 5, preferably 2 to 4, ethylene oxide groups as an ether component compared to the commonly used alkyl ether sulfate mixture, which contains the same components in a weight ratio of 70:30, leads to an unexpected further reduction in skin irritation without changing the known good cleaning power of such agents.
  • European patent application 89 213 describes a thickened surfactant preparation which consists of water and 5 to 40% by weight of anionic, nonionic or amphoteric surfactants and contains a copolymer which is soluble in alkaline and is prepared by emulsion polymerization. However, this copolymer is used as a thickener.
  • the European patent application gives no information about a cleaning-enhancing effect.
  • French patent application 2294231 relates to a floor cleaning agent which contains 5 to 20% by weight of a copolymer which, on the other hand, is insoluble in acid in alkali and which has a molecular weight between 100,000 and 2.5 million. Surfactants and other ingredients are also present. Although quite high molecular weights are mentioned here, it is not clear to the person skilled in the art that in the extreme molecular weight range such as that due to intrinsic viscosities of more than 400 ml. g -1 is to be defined, a drastic increase in the cleaning performance and the emulsifying capacity can be determined.
  • amphoteric surfactants of the betaine type usually have a mild effect on the skin or that their use can achieve a significant increase in cleansing effectiveness. Liquid, manual dishwashing detergents containing the above-mentioned components are therefore often used.
  • the present invention now relates to a liquid cleaning agent, in particular for manual dishwashing, based on an aqueous solution of anionic surfactants, optionally together with nonionic and / or amphoteric surfactants, solvents, solubilizers, corrosion inhibitors, preservatives, thickeners and colorants and fragrances, which is characterized in that it additionally contains 0.001 to 1% by weight of a cleaning-enhancing, water-soluble, anionic, practically uncrosslinked copolymer of a) esters of acrylic and / or methacrylic acid with 1 to 8 carbon atoms in the alcohol radical and b) contains unsaturated, aliphatic carboxylic acids with 3 to 5 carbon atoms in the acyl residue with an intrinsic viscosity [n] ⁇ 400ml ⁇ g -1 , measured in tetrohydrofuran (THF) at 20 ° C.
  • anionic surfactants optionally together with nonionic and / or amphoteric surfactants, solvents,
  • a preferred copolymer consists of approximately 80-20, in particular approximately 60-40% by weight of a) and approximately 20-80, in particular 40-60% by weight b).
  • the alcohol residue of the esters a) preferably contains 1 to 4, in particular 1 to 2, carbon atoms.
  • the copolymers can also be used in minor amounts of up to about 5% by weight of other radically polymerizable vinyl monomers such as e.g. Contain ayrolamides or (meth) acrylates.
  • the copolymer is an acidic dispersion and can advantageously be used in this form.
  • the cleaning agents which generally have a neutral to slightly alkaline pH, the copolymers are partially or completely neutralized and dissolved so that they are no longer in dispersion form.
  • the water-soluble anionic copolymers used according to the invention are prepared in a known manner by emulsion polymerization, as described, for example, in US Pat. No. 4,795,772 or EP 184,785.
  • the unsaturated carboxylic acids used for this purpose are preferably acrylic or methacrylic acid.
  • the intrinsic viscosity is determined according to the method described in B. Vollmert: "Floor plan of macromolecular chemistry", Volume III, page 55 ff, E. Vollmert Verlag, Düsseldorf, 1988.
  • the specific viscosity increases proportionally with the concentration at high concentrations, while at low concentrations the viscosity can decrease with increasing concentration.
  • the intrinsic viscosities of these copolymers are determined with the aid of diagrams in which the concentration is plotted on the abscissa and the specific viscosity is plotted on the ordinate by extrapolation of the part which rises linearly at high concentrations to the concentration 0.
  • alkyl ether sulfates can also be used as further anionic surfactants, just like n-alkylbenzenesulfonates with 9 to 16, preferably 12 carbon atoms in the alkyl radical, alkanesulfonates with 10 to 20, preferably 12 to 18 carbon atoms in the alkyl radical, olefin sulfonates with 12 to 16, preferably 12 up to 14 carbon atoms in the n-alkyl radical and alkyl sulfates with 8 to 18, preferably 8 to 14 carbon atoms in the alkyl radical, individually or as mixtures with one another or with one another.
  • Betaine compounds of the formula can be used as amphoteric surfactants are used in which R 1 is an alkyl radical with 8 to 20, preferably 10 to 18 carbon atoms, which is optionally interrupted by heteroatoms or heteroatom groups, and R 2 and R 3 are identical or different alkyl radicals with 1 to 3 carbon atoms.
  • R 1 is an alkyl radical with 8 to 20, preferably 10 to 18 carbon atoms, which is optionally interrupted by heteroatoms or heteroatom groups
  • R 2 and R 3 are identical or different alkyl radicals with 1 to 3 carbon atoms.
  • C 10 -C 18 -Alkyldimethylcarboxymethylbetaine and C 11 -C 17 -Alkylamidopropyldimethylcarboxymethylbetaine are preferred.
  • adducts are from 4 to 20, preferably from 4 to 10, mol of alkylene oxide, preferably ethylene oxide to C 8 -C 12 alkylbenzenes, C 10 -C 20 -, preferably C 12 -C 18 -alkanols, C 10 -C 18 -, carboxylic acid alkanolamides, but also the addition products of ethylene oxide and polypropylene glycols, which have become known under the name Pluronics (R) , and addition products of 1 to 7 mol of ethylene oxide with C 12 -C 18 reacted with 1 to 5 mol of propylene oxide -Alcanole suitable.
  • C 8 -C 18 preferably C 8 -C 12 alkyl polyglucosides with 1 to 10, preferably 1 to 2 and in particular 1.1 to 1.4 glucose units in the molecule are particularly suitable.
  • the solvents to be added if necessary are low molecular weight alkanols with 1 to 4 carbon atoms in the molecule, preferably ethanol and isopropanol.
  • Solubilizers for example for dyes and perfume oils, can be used, for example, as alkanolamines, polyols such as ethylene glycol, 1,2-propylene glycol, glycerol and alkylbenzenesulfonates having 1 to 3 carbon atoms in the alkyl radical.
  • the preferred thickeners include urea, sodium chloride, ammonium chloride and magnesium chloride, which can also be used in combination.
  • Corrosion inhibitors and preservatives include, for example, sodium benzoate, formaldehyde and sodium sulfite.
  • the cleaning agents can also contain conventional disinfectants.
  • liquid cleaning agents according to the invention of the following examples were obtained by stirring the individual constituents in any order and leaving the mixture to stand until there were no bubbles.
  • the sodium salts were used as anionic surfactants.
  • a polymer emulsion was made 55 g Ethyl acrylate, 25 g Methacrylic acid, 20 g Acrylic acid and the same amounts of other ingredients as in Example A. It also had a polymer content of 20% by weight.
  • the emulsion was then poured into a 250 ml measuring cylinder with a diameter of 3.6 cm (2 ml graduation, industrial standard) and the aqueous phase which separated out was determined after 1 hour and after 4 hours.
  • the data relate to% by weight of the pure active ingredient (AS).

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)
  • Detergent Compositions (AREA)
  • Fluid-Pressure Circuits (AREA)
  • Lubricants (AREA)
  • Cleaning By Liquid Or Steam (AREA)

Claims (5)

  1. Produit de nettoyage liquide à base d'une solution aqueuse de tensioactifs anioniques, le cas échéant en présence de tensioactifs non ioniques et/ou de tensioactifs amphotères, de solvants, de dissolvants, d'inhibiteurs de corrosion, de conservateurs, d'épaississants ainsi que de colorants et de parfums,
    caractérisé en ce qu'
    il contient en plus 0,001 à 1 % en poids d'un copolymère renforçant le pouvoir nettoyant pratiquement non réticulé constitué de a) esters d'acide acrylique et/ou méthacrylique avec 1 à 4 atomes de C dans le radical alcool et b) des acides carboxyliques insaturés aliphatiques de 3 à 5 atomes de C avec une viscosité limite : [n] ≥ 400 ml . g-1 mesurée dans le tétrahydrofurane à 20°C;
  2. Produit selon la revendication 1,
    caractérisé en ce qu'
    il contient un copolymère de 80-20, de préférence 60-40 % en poids de a) et 20-80, de préférence 40-60 % en poids de b).
  3. Produit selon les revendications 1 et 2,
    caractérisé en ce que
    le radical alcool de l'ester a) contient 1 à 2 atomes de C;
  4. Produit selon les revendications 1 à 3,
    caractérisé en ce que
    les fractions d'acides carboxyliques aliphatiques insaturées des copolymères proviennent de l'acide acrylique ou de l'acide méthacrylique.
  5. Produit selon les revendications 1 à 4,
    caractérisé en ce qu'
    il est constitué d'une solution aqueuse de
    5 à 65,   de préférence 10 à 40 % en poids d'un mélange, constitué d'au moins deux des tensioactifs suivants,
    0 à 40,   de préférence 5 à 20 % en poids d'un mélange de chacun, 50 parties d'un produit d'addition sulfaté de 1 à 5, de préférence 2 à 4 mol d'oxyde d'éthylène sur un n-alcanol C12 et un n-alcanol C14,
    0 à 40,   de préférence 5 à 20 % en poids d'un ou plusieurs autres tensioactifs anioniques,
    0 à 20,   de préférence 1 à 5 % en poids d'un tensioactif amphotère,
    0 à 20,   de préférence 1 à 5 % en poids d'un tensioactif non ionique,
    0,005 à 0,5 %   en poids d'un copolymère renforçant le pouvoir nettoyant, hydrosoluble, anionique à partir de a) environ 80-20, de préférence environ 60-40 % en poids d'esters d'acide acrylique et/ou d'acide méthacrylique avec 1 à 8, de préférence 1 à 4 et notamment 1 à 2 atomes de C dans le radical alcool et environ 20-80, de préférence environ 40-60 % en poids d'acides aliphatiques carboxyliques insaturés avec 3 à 5 atomes de C dans le radical acyle, avec une viscosité limite : [n] ≥ 400 me . g-1, mesurée dans le tétrahydrofurane à 20°C,
    0 à 20,   notamment 2 à 10 % en poids d'un solvant,
    0 à 10,   notamment 0,2 à 5 % en poids d'un dissolvant,
    0 à 10,   notamment 0,5 à 8 % en poids d'un épaississant,
    0 à 5,   notamment 0,1 à 2 % en poids d'inhibiteurs de corrosion et de conservateurs,
    0 à 0,1 %   en poids de colorant,
    0 à 1,0 %   d'huile essentielle et,
    le radical représente jusqu'à 100 % d'eau.
EP93906556A 1992-03-27 1993-03-18 Produits liquides de nettoyage Expired - Lifetime EP0632824B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4209922 1992-03-27
DE4209922A DE4209922A1 (de) 1992-03-27 1992-03-27 Flüssige Reinigungsmittel
PCT/EP1993/000660 WO1993020174A1 (fr) 1992-03-27 1993-03-18 Produits liquides de nettoyage

Publications (2)

Publication Number Publication Date
EP0632824A1 EP0632824A1 (fr) 1995-01-11
EP0632824B1 true EP0632824B1 (fr) 1997-05-14

Family

ID=6455117

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93906556A Expired - Lifetime EP0632824B1 (fr) 1992-03-27 1993-03-18 Produits liquides de nettoyage

Country Status (6)

Country Link
EP (1) EP0632824B1 (fr)
JP (1) JPH07505181A (fr)
AT (1) ATE153058T1 (fr)
DE (2) DE4209922A1 (fr)
ES (1) ES2102025T3 (fr)
WO (1) WO1993020174A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999000470A1 (fr) * 1997-06-30 1999-01-07 The Procter & Gamble Company COMPOSITIONS DE DETERGENTS DELICATS POUR LAVER LA VAISSELLE SOUS FORME DE LIQUIDES OU DE GELS, AYANT UN pH REGULE ET LES CARACTERISTIQUES SOUHAITABLES DE MOUSSAGE, DE PROPRIETES RHEOLOGIQUES ET D'ELIMINATION DES TACHES D'ALIMENTS
DE19817833A1 (de) * 1997-11-26 1999-10-28 Henkel Kgaa Geschirrspülmittel mit spezifischem Viskositätsprofil
DE19814768A1 (de) 1998-04-02 1999-10-07 Viessmann Werke Kg Blaubrenner
US7063895B2 (en) * 2001-08-01 2006-06-20 National Starch And Chemical Investment Holding Corporation Hydrophobically modified solution polymers and their use in surface protecting formulations
FR2865401B1 (fr) * 2004-01-27 2006-04-28 Oreal Composition de nettoyage de la peau
US8802616B2 (en) * 2010-07-19 2014-08-12 Rohm And Haas Company Polymers for laundry detergents

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1528592A (en) * 1974-12-10 1978-10-11 Procter & Gamble Floor care and cleaning composition
US4230605A (en) * 1978-12-13 1980-10-28 Armstrong Cork Company Cleaning composition for no-wax vinyl composition floor covering
US4529773A (en) * 1982-03-17 1985-07-16 David Witiak Alkali-soluble emulsion polymers in acidic surfactant compositions
DE3445549A1 (de) * 1984-12-14 1986-06-19 Henkel KGaA, 4000 Düsseldorf Acrylatdispersion und deren verwendung zur verdickung von wasserstoffperoxid-zubereitungen
DE3533531A1 (de) * 1985-09-20 1987-04-02 Henkel Kgaa Reinigungsmittel fuer harte oberflaechen
US4678596A (en) * 1986-05-01 1987-07-07 Rohm And Haas Company Rinse aid formulation
DE3813651A1 (de) * 1988-04-22 1989-11-02 Henkel Kgaa Verdickungsmittel auf basis waessriger emulsions-copolymerlatices und ihre verwendung zur eindickung waessriger fluessigphasen

Also Published As

Publication number Publication date
JPH07505181A (ja) 1995-06-08
WO1993020174A1 (fr) 1993-10-14
ATE153058T1 (de) 1997-05-15
ES2102025T3 (es) 1997-07-16
EP0632824A1 (fr) 1995-01-11
DE4209922A1 (de) 1993-09-30
DE59306460D1 (de) 1997-06-19

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