EP0527824B1 - Utilisation d'une combinaison de tensio-actifs ioniques et non ioniques - Google Patents

Utilisation d'une combinaison de tensio-actifs ioniques et non ioniques Download PDF

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Publication number
EP0527824B1
EP0527824B1 EP91908642A EP91908642A EP0527824B1 EP 0527824 B1 EP0527824 B1 EP 0527824B1 EP 91908642 A EP91908642 A EP 91908642A EP 91908642 A EP91908642 A EP 91908642A EP 0527824 B1 EP0527824 B1 EP 0527824B1
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carbon atoms
component
general formula
alkyl group
parts
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EP0527824A1 (fr
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Jürgen Geke
Bernd Stedry
Raina Hirthe
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/835—Mixtures of non-ionic with cationic 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
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium 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
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups

Definitions

  • the present invention relates to the use of a combination of ionic and nonionic surfactants - optionally with customary additives - for cleaning hard surfaces. So-called “industrial cleaners” are usually used for such tasks.
  • Industrial cleaners of this type are mainly used in the automotive industry and their supplier industries for cleaning and passivation, primarily in spray cleaning systems. They are suitable for intermediate and final cleaning without cutting as well as machined parts in unit and assembly plants. Practically all relevant materials, such as iron and steel, aluminum, silumin, copper, brass, zinc and plastics, can be treated and the majority of all contaminations on an organic or inorganic basis, such as cooling lubricants, rust protection oils, processing oils, drawing aids, pigments and light metal abrasion, can be removed. Such cleaning agents can also be used in customary immersion processes, but their use in the spraying process is usually preferred.
  • anti-foaming agents may also be necessary due to the fact that the cleaning agents themselves contain constituents which, under the given working conditions - i.e. especially in spraying processes - give rise to undesirable foaming, for example anionic surfactants or nonionic surfactants foaming at the respective working temperature.
  • DE-A-36 20 011 describes cationic surfactants based on quaternary ammonium compounds and their use in cleaning agents.
  • the cationic surfactants are used in the alkaline pH range in addition to other detergent components.
  • EP-A-0 116 151 describes a process for the regeneration or recycling of aqueous degreasing and cleaning solutions by adding cationic surfactants or cationically modified polymers or mixtures thereof.
  • EP-A-0 054 894 describes a surfactant-containing mixture for the mechanical cleaning of hard surfaces in the alkaline liquor range, which contains nonionic surfactants of the alkyl ethoxylate or propoxylate type (component A), quaternary ammonium compounds (component B) and fluorinated alcohols ( Component C) contains.
  • the nonionic surfactants of this type mentioned in the examples contain only tertiary butyl groups as C1 ⁇ 4-alkyl radical.
  • the quaternary ammonium compounds only have short to medium carbon chains - up to a maximum of 12 carbon atoms. It is also necessary to add fluorinated alcohols as an anti-foaming agent.
  • EP-A-0 054 895 also describes a surfactant mixture for cleaning hard surfaces in the alkaline liquor range, which contains nonionic surfactants (component A) and selected quaternary ammonium compounds as cationic surfactants (component B).
  • Suitable nonionic surfactants here are alkyl-polyethylene glycol mixed ethers of the type C6 ⁇ 18-alkyl - 6 to 12 EO - C1 ⁇ 4-alkyl, in turn the compounds of this type mentioned in the examples as C1 ⁇ 4-alkyl radical being exclusively tertiary butyl groups contain.
  • the quaternary ammonium compounds only have short to medium carbon chains - up to a maximum of 8 carbon atoms.
  • DE-A-25 56 499 relates to low-foaming disinfectant cleaners which, as nonionic surfactants, include alkyl-polyethylene glycol mixed ethers of the type C6 ⁇ 2 2-alkyl - 5 to 50 EO - tert. Contain butyl.
  • formulations of this type can contain, among other things, quaternary ammonium compounds, which also have long-chain alkyl radicals with 8 to 18 carbon atoms, as a disinfectant component.
  • EP-A-0 254 208 relates to low-foam and / or foam-suppressing surfactant mixtures which are also suitable for use in the field of machine spray or high-pressure cleaning at temperatures below 50 ° C.
  • the object of the present invention was to provide surfactant combinations for cleaning hard surfaces which have low-foaming properties in the entire temperature range relevant to the application, namely in the range from 15 to 80 ° C., and are therefore suitable for use in spraying processes.
  • these surfactant combinations should have a high cleaning ability and excellent wetting properties compared to the substrates treated with them;
  • these surfactant combinations should be easy to assemble with additives customary in industrial cleaners, allow the cleaning agent solutions to run off the treated substrate surfaces without stains and have demulsifying properties with regard to non-self-emulsifying oils and fats.
  • advantageous electrostatic effects are to be achieved.
  • R8 is a linear or branched alkyl radical or alkenyl radical having 6 to 18 carbon atoms.
  • R8 the following radicals in question: n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl and n-octadecyl and the branched chain isomers of the alkyl radicals mentioned.
  • R8 can also mean the unsaturated alkyl radicals (alkenyl radicals) with a number of carbon atoms in the above range, which can also be linear or branched. Furthermore, R8 can also be a cyclic alkyl radical having 5 to 6 carbon atoms, i.e. Cyclopentyl or cyclohexyl. The number of ethoxy residues in the molecule - index m - is in the range from 2 to 12.
  • component (c) those compounds of the general formula (III) are preferably used as component (c) in which R8 is a linear alkyl radical or alkenyl radical having 6 to 18 carbon atoms and m is a number in the range from 2 to 10.
  • R linear represents a linear or branched alkyl radical or alkenyl radical with 6 to 18 carbon atoms or a cyclic alkyl radical with 5 to 6 carbon atoms.
  • Suitable substituents R9 are all those radicals which have already been explained above in connection with the substituent R8 of the general formula (III).
  • the number of ethoxy radicals in the molecule - index p - is in the range from 2 to 10.
  • the substituent A in the general formula (IV) stands for propoxy radicals, the number of propoxy radicals - index (q + r) - in the range from 2 to 8 lies.
  • those compounds of the general formula (IV) are preferably used as component (d) in which R9 is a linear alkyl radical having 8 to 18 carbon atoms, p is a number in the range from 2 to 5 and A is propoxy radicals, and the sum (q + r) is a number in the range 4 to 6.
  • the reaction product of technical lauryl alcohol - which has alkyl radicals with 12 to 18 carbon atoms (thereof approx.
  • 80% with 12 to 14 carbon atoms) - is used as the surfactant component (d) with 2 up to 4 moles of ethylene oxide and 4 to 6 moles of propylene oxide or the reaction product of n-octanol with 2 to 6 moles of ethylene oxide and 2 to 5 moles of propylene oxide.
  • surfactant combinations of cationic surfactant (a) and nonionic surfactant (b) to be used according to the invention are further characterized by a specific weight ratio of components (a): (b), which is preferably in the range from 20: 1 to 1:20 is in the range from 2: 1 to 1:10.
  • the mixture also contains the nonionic surfactants (c) and / or (d)
  • these ratios also apply to (a): [(b) + (c)], (a): [ (b) + (d)] and (a): [(b) + (c) + (d)].
  • the total of the mixed ethers in (b) and any ethoxylated and / or propoxylated fatty alcohols [(c) and / or (d)] are to be understood as nonionic surfactants.
  • the ratio of mixed ether (b) to ethoxylated and / or propoxylated fatty alcohols [(c) and / or (d)] is between 10: 1 and 1:10.
  • the surfactant combinations to be used according to the invention are notable for high cleaning and demulsifying properties at temperatures in the range from 15 to 80.degree. In the temperature range mentioned, they can also be used without any problems in the spraying process, since they do not cause any undesirable foaming. Further advantages are: very good wetting properties, enabling the cleaning liquids to drain off the items to be cleaned without stains, very good demulsifying properties with regard to Non-self-emulsifying oils and greases, achieving antistatic effects, easy to assemble with additives commonly used in industrial cleaners and a low foam height in the Götte foam whipping apparatus (DIN 53902).
  • additives which are preferably used in addition to the surfactant combinations to be used according to the invention are: builder substances and / or complexing agents, corrosion inhibitors and bases or acids.
  • stabilizers, solubilizers or antimicrobial agents can also be used as additives.
  • alkali metal orthophosphates for example, alkali metal orthophosphates, polyphosphates, silicates, borates, carbonates, polyacrylates and gluconates can be used, as well as phosphonic acids or phosphonoalkane carboxylic acids or their water-soluble alkali metal salts, for example 1-hydroxyethane-1,1-diphosphate or 2-phosphonobutane-1,2,4-tricarboxylic acid.
  • Straight-chain or branched aliphatic carboxylic acids or their salts are suitable as effective corrosion inhibitors.
  • alkanolamine salts of straight-chain or branched monocarboxylic acids with 8 to 11 carbon atoms are used as corrosion inhibitors.
  • the aqueous solutions of the surfactant combinations to be used according to the invention can be acidic or also alkaline; accordingly, they contain excess acid or bases, for example sodium hydroxide and / or potassium hydroxide.
  • the surfactant combinations to be used according to the invention are produced by simply mixing the individual components.
  • Corresponding powdery or liquid cleaning agents are also produced in the same way by mixing the Surfactant combinations to be used according to the invention with the other additives and optionally water.
  • cleaning agents of this type contain 1 to 70% by weight, preferably 2 to 20% by weight, of the surfactant combinations to be used according to the invention.
  • the surfactant combinations to be used according to the invention are preferably used in the form of application solutions diluted with water.
  • Such application solutions preferably contain the surfactant combinations to be used according to the invention in concentrations of 0.0001 to 1.5% by weight, in particular 0.0005 to 0.5% by weight.
  • Ready-to-use application solutions of this type which are used in the sense of the invention for cleaning hard surfaces in the spray process have a pH of ⁇ 7. The preparation of such application solutions is carried out by simply mixing the surfactant combinations with water.
  • Demineralized water was used in all experiments.
  • Mixtures 1 to 4 are designed so that the mixed ethers (b) have gradations in both the fatty alcohol and the EO content.
  • the mixed ether in mixtures 1 and 2 is outside the invention.
  • the quaternary ammonium compounds (a), however, are all within the scope of the present invention.
  • Foam test in the foam whipping apparatus according to DIN 53902 (foam height in ml) 100 blows / 25 ° C t / s mixture 1* 2 * 3rd 4th 0 800 260 20th 350 30th 700 30th 10th 40 60 680 30th 5 10th 100 blows / 30 ° C t / s mixture 1* 2 * 3rd 4th 0 800 50 10th 350 30th 780 15 5 20th 60 750 ⁇ 10 ⁇ 5 ⁇ 5 100 blows / 45 ° C t / s mixture 1* 2 * 3rd 4th 0 750 40 10th 200 30th 700 10th ⁇ 5 ⁇ 5 60 600 10th ⁇ 5 0

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
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  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
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  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
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Claims (11)

  1. Utilisation d'une combinaison d'agents tensioactifs ioniques et non ioniques contenant :
    a) au moins un dérivé d'ammonium quaternaire de formule générale I
    Figure imgb0002
     dans laquelle :
    R¹   peut être un radical alcoyle linéaire ou ramifié, ayant de 1 à 22 atomes de carbone,
    R²   peut être de l'hydrogène, ou un radical alcoyle linéaire ou ramifié ayant de 1 à 21 atomes,
    dans lequel le nombre global des atomes de carbone, des substituants R¹ et R² se situe dans la zone de 10 à 22,
    n   est 0 ou 1
    R³ et R⁴   représentent un méthyle, un éthyle, un 2-hydroxyéthyle ou un hydroxypropyle,
    R⁵   représente un radical alcoyle ayant de 4 à 6 atomes de carbone ouu un radical phénylalcoyle ayant de 1 à 3 atomes de carbone dans le radical alcoyle, et X⁻ représente un halogénure ou l'anion d'un acide organique ayant de 4 à 15 atomes de carbone et
    b) au moins un éther mixte d'alc(en)yle et depolyéthylène glycol de formule générale II



            R⁶-O-(CH₂CH₂O)sR⁷   (II)



    dans laquelle R⁶ signifie un radical alcoyle linéaire ayant de 8 à 10 atomes de carbone,
    s   est un nombre dans la zone allant de 3,5 à 4,5 et
    R⁷   représente un radical alcoyle linéaire ayant 4 atomes de carbone,
    le rapport pondéral des composants a), b) se situant dans la zone allant de 20:1 à 1:20, en vue du nettoyage des surfaces dures.
  2. Utilisation selon la revendication 1, caractérisée en ce que le rapport pondéral des composants a) : b) se situe dans la zone allant de 2:1 à 1:10.
  3. Utilisation selon les revendications 1 ou 2, caractérisée en ce que l'anion du composant a)à est un chlorure, un bromure, un benzoate, ou un benzoate monosubstitué par CH₃, NH₂, NO₂, COOH, OH ou SO₃H ou un isononanoate.
  4. Utilisation selon les revendications 1 ou 2, caractérisée en ce que l'on met en oeuvre come dérivé d'ammonium quaternaire, le chlorure de lauryldiméthylbenzyl ammonium, l'isononanoate de N-benzyl-N-2hydroxydodecyl N,N-diméthylammonium, ou le benzoate de N-benzyl-N-2-hydroxydodécyl NN-diméthylammonium.
  5. Utilisation selon l'une ou plusieurs des revendications 1 à 4, caractérisée en ce que la combinaison d'agents tensioactifs contient en supplément au moins un alc(en)oylethoxylate de formule générale (III) :



            R⁸-O-(CH₂CH₂-O)m-H   (III)



    dans laquelle, R⁸ signifie un radical alcoyle linéaire ou ramifié ou un radical alcényle ayant de 6 à 18 atomes de carbone ou un radical alcoyle cyclique ayant 5 ou 6 atomes de carbone et, m est un nombre dans la zone allant de 2 à 12.
  6. Utilisation selon une ou plusieurs des revendications 1 à 4, caractérisée en ce que la combinaison d'agents tensio-actifs contient en supplément au moins un alc(en)oyléthoxylate/proxylate de formule générale IV,



            R⁹-O-(CH₂CH₂O)p-A-H   (IV)



    dans laquelle,
    R⁹   signifie un radical alcoyle linéaire ou ramifié ou un radical alcényle ayant de 6 à 18 atomes de carbone ou un radical alcoyle cyclique ayant de 5 à 6 atomes de carbone.
    P   est un nombre dans la zone allant de 2 à 10 et,
    A   est un reste du type -(CH₂₋CH(CH₃)-O)q et un reste du type --(CH(CH₃)-CH₂₋O)r pour lesquels la somme (q+r ) est un nombre dans la zone allant de 2 à 8.
  7. Utilisation selon l'une ou plusieurs des revendications 1 à 4, caractérisée en ce que la combinaison d'agents tensioactifs contient en supplément un alc(en)oyléthoxylate de formule générale (III) selon la revendication 5 et un alc(en)oyléthoxylate/propoxylate de formule générale (IV) selon la revendication 6.
  8. Utilisation selon l'une ou plusieurs des revendications 1 à 7, caractérisée en ce que le rapport pondéral des composants (a) : [(b) + c)], (a): [(b) + (d)] ou (a) : [b) c) + d)] se situe à entre 20:1 et 1:20, de préférence entre 2:1 et 1:10.
  9. Utilisation selon l'une ou plusieurs des revendications 1 à 8, caractérisée en ce que le rapport pondéral des composants (b) : [(c) et/ou (d)] se situe entre 10:1 et 1:10.
  10. Utilisation selon l'une ou plusieurs des revendications 1 à 9, caractérisée en ce que la combinaison d'agents tensioactifs contient en supplément des substances de structuration et ou des agents formateurs de complexe, des inhibiteurs de corrosion ainsi que des bases ou des acides.
  11. Utilisation selon l'une ou plusieurs des revendications 1 à 10, caractérisée en ce que la combinaison d'agents tensioactifs est mise en oeuvre dans des solutions d'utilisation diluées avec de l'eau à des concentrations en poids allant de 0,0001 à 1,5 % en poids, de préférence de 0,0005 à 0,5 % en poids.
EP91908642A 1990-05-09 1991-04-30 Utilisation d'une combinaison de tensio-actifs ioniques et non ioniques Expired - Lifetime EP0527824B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4014859 1990-05-09
DE4014859A DE4014859A1 (de) 1990-05-09 1990-05-09 Verwendung einer kombination ionischer und nichtionischer tenside
PCT/EP1991/000823 WO1991017233A1 (fr) 1990-05-09 1991-04-30 Utilisation d'une combinaison de tensio-actifs ioniques et non ioniques

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EP0527824A1 EP0527824A1 (fr) 1993-02-24
EP0527824B1 true EP0527824B1 (fr) 1995-01-04

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US (1) US5308401A (fr)
EP (1) EP0527824B1 (fr)
JP (1) JPH05506689A (fr)
AT (1) ATE116681T1 (fr)
AU (1) AU7769091A (fr)
CA (1) CA2082517A1 (fr)
DE (2) DE4014859A1 (fr)
DK (1) DK0527824T3 (fr)
ES (1) ES2066441T3 (fr)
PT (1) PT97594B (fr)
WO (1) WO1991017233A1 (fr)

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US5308401A (en) 1994-05-03
ATE116681T1 (de) 1995-01-15
DE59104163D1 (de) 1995-02-16
EP0527824A1 (fr) 1993-02-24
PT97594B (pt) 1998-08-31
PT97594A (pt) 1992-02-28
JPH05506689A (ja) 1993-09-30
WO1991017233A1 (fr) 1991-11-14
DE4014859A1 (de) 1991-11-14
AU7769091A (en) 1991-11-27
ES2066441T3 (es) 1995-03-01
CA2082517A1 (fr) 1991-11-10
DK0527824T3 (da) 1995-06-19

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