WO1990008813A1 - Detergents liquides - Google Patents

Detergents liquides Download PDF

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Publication number
WO1990008813A1
WO1990008813A1 PCT/EP1990/000115 EP9000115W WO9008813A1 WO 1990008813 A1 WO1990008813 A1 WO 1990008813A1 EP 9000115 W EP9000115 W EP 9000115W WO 9008813 A1 WO9008813 A1 WO 9008813A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
contain
cleaning agent
agent according
anionic
Prior art date
Application number
PCT/EP1990/000115
Other languages
German (de)
English (en)
Inventor
Brigitte Giesen
Bernd Fabry
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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 Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO1990008813A1 publication Critical patent/WO1990008813A1/fr

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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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • 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
    • C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
    • 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
    • C11D1/37—Mixtures of compounds all of which are anionic
    • 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
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • 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
    • C11D1/16—Sulfonic acids or sulfuric acid esters; Salts thereof derived from divalent or polyvalent alcohols
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/523—Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group

Definitions

  • Liquid washing, rinsing and cleaning agents are usually aqueous solutions of anionic and / or nonionic surfactants and conventional additives. They are used for washing textiles, for cleaning hard surfaces, for example glasses or ceramic materials, plastics, lacquered and polished Surfaces, which can also be metallic in nature, are used. A preferred area of application for such agents is the manual washing of dining utensils and other related equipment. The respective cleaning processes are usually carried out at slightly elevated temperatures. There is always an increased impact on human skin.
  • the present invention therefore relates to cleaning agents with strong cleaning performance and improved skin protection.
  • the commercially available dishwashing agents which are to be used manually are aqueous solutions of alkyl ether sulfates, that is to say sulfated adducts of ethylene oxide with fatty alcohols, preferably n-alkylbenzenesulfonates and / or alkanesulfonates, optionally also olefin sulfonates or alkyl sulfates, and also nonionic surfactants, solubilizers, colorants and fragrances.
  • alkyl ether sulfates that is to say sulfated adducts of ethylene oxide with fatty alcohols, preferably n-alkylbenzenesulfonates and / or alkanesulfonates, optionally also olefin sulfonates or alkyl sulfates, and also nonionic surfactants, solubilizers, colorants and fragrances.
  • liquid dishwashing detergents which, in addition to alkyl sulfates or alkyl ether sulfates, contain alkyl sulfosuccinates in the form of dialkyl (C 7 -C 9 ) esters of sulfosuccinic acid.
  • the agents can additionally contain other detergents, hydrotropes, solvents, opaque agents, phosphates, silicates, dyes, fragrances and skin-friendly additives.
  • EP 71 411 discloses a detergent composition comprising a mixture of di (C 8 alkyl) and di (C 6 alkyl) sulfosuccinate in combination with other anionic and / or nonionic surfactants.
  • European patent specification 112 044 describes dishwashing detergents which contain water-soluble salts of a dialkyl ester of sulfosuccinic acid with identical or different, straight-chain or branched-chain C 3 -C 12 -alkyl radicals and special alkyl ether sulfates. According to European patent 112 045, similar agents should also be added to electrolytes containing magnesium ions.
  • foaming liquid detergent compositions composed of C 3 to C 12 dialkyl esters of sulfosuccinic acid, alkyl ether sulfates and / or polyethoxylated nonionic detergents and also carboxylic acid di (C 2 -C 3 ) alkanolamides.
  • aqueous mixture of alkyl sulfosuccinates and alkyl ether sulfates is also known from European patent 124367. It also describes aqueous solutions of alkyl sulfosuccinates alone and of alkyl sulfosuccinates in a mixture with alkyl benzene sulfonates.
  • Many of the commercially available dishwashing detergents contain, as an anionic surfactant component, salts of alkylbenzenesulfonic acid, which have excellent cleaning effects, but because of their petrochemical origin are to be gradually replaced by other, but at least equally effective, surfactants.
  • the present invention therefore relates to liquid detergents for the manual washing of dishes based on an aqueous solution of dialkyl sulfosuccinates, optionally together with other anionic and / or nonionic surfactants and other usual constituents such as solvents, solubilizers, corrosion inhibitors, foam stabilizers, preservatives, electrolytes, thickeners , Dyes and fragrances, which is characterized in that they contain surface-active hydroxysulfonates from unsaturated fatty alcohols having 16 to 22 carbon atoms in the alkyl radical.
  • hydroxysulfonates used according to the invention correspond to formulas I or II
  • hydroxysulfonates are described in detail in the older German patent application P 37 25 030.2. They are obtained, for example, by using an unsaturated fatty alkyl or fatty alkyl polyoxyalkyl ester of the general formula III
  • R 2 CO represents an acyl group with 1 to 4 carbon atoms, reacted with sulfur trioxide, the reaction product in an aqueous solution of 1 to 2.5 moles of alkali, alkaline earth or ammonium hydroxide per mole of SO 3 added and the solution hydrolyzed at 90 to 100 ° C for 0.5 to 240 minutes, cyclic Sulfonation products change into open-chain compounds and at the same time the ester protecting group is saponified quantitatively to recover a terminal OH function.
  • the end products may also contain compounds as by-products which are formally derived from formulas (I) and (II) in each case by the loss of a molecule of water.
  • the alkaline hydrolysis product can, if desired, be bleached in a manner known per se, for example with hydrogen peroxide or sodium hypochlorite and is in any case with the aid of aqueous mineral acids, e.g. B. hydrochloric acid, adjusted to a pH around 7.
  • aqueous mineral acids e.g. B. hydrochloric acid
  • an unsaturated fatty alcohol is used.
  • the group R 2 -CO can be a formyl, acetyl, propionyl or butyryl group; the acetyl group is preferred.
  • the group R 1 is preferably an oleyl group or a fatty alkyl radical consisting predominantly of oleyl groups.
  • dialkyl sulfosuccinates used are preferably those with the same straight-chain or branched-chain C ⁇ -alkyl radicals, that is to say di-n-octyl or di-iso-octylsulfosuccinates, in the form of their alkali metal salts, in particular their sodium salts.
  • the di-n-octyl sulfosuccinates are particularly preferred.
  • the cleaning agents according to the invention show a significantly better skin tolerance in the epidermal swelling test compared to those which contain alkyl ether sulfates, as will be shown below.
  • Suitable other common constituents of such agents for the purposes of this invention are solvents, solubilizers, electrolytes, thickeners, corrosion inhibitors, preservatives, foam stabilizers, dyes, fragrances, complexing agents, etc.
  • anionic and / or nonionic and / or amphoteric surfactants can also be added to the mixture, provided that they do not interfere with the synergistic effect of the detergent mixture according to the invention.
  • composition of the aqueous cleaning agent solution according to the invention is as follows:
  • a surfactant mixture consisting of 1 to 50, preferably 2 to 25 parts by weight of a hydroxysulfonate and 50 to 99, preferably 75 to 98 parts by weight of a dialkyl sulfosuccinate,
  • anionic surfactant 0 to 10, preferably 0 to 5% by weight of a nonionic surfactant
  • anionic surfactants that can be used are, in particular, C 10 to C 18 , in particular C 12 to C 16, alkyl ether sulfates with 1 to 5, preferably 2 to 4, moles of ethylene oxide in the molecule, but also 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 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 and other sulfates or Sulfonates.
  • formulations free of alkylbenzenesulfonate are of particular interest.
  • Surface-active betaines of the formula I can be used as amphoteric surfactants
  • 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.
  • nonionic surfactants include alkyl glycosides, preferably alkyl glucosides, with 8 to 18, preferably 12 to 16 carbon atoms in the alkyl radical and 1 to 10, preferably 1.2 to 4, glycose units in the molecule and addition products from 4 to 20, preferably from 6 to 15 mol of alkylene oxide, preferably ethylene oxide over 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 with polypropylene glycols have become known under the name Pluronics (R) , and addition products of 1 to 7 moles of ethylene oxide with C 12 -C 18 -alkanols reacted with 1 to 5 moles of propylene oxide are suitable.
  • Pluronics (R) Pluronics
  • 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.
  • Alkanolamines, polyols such as ethylene glycol, 1,2-propylene glycol, glycerol and alkylbenzenesulfonates with 1 to 3 carbon atoms in the alkyl radical can be used as solubilizers, for example for small amounts of colorants and fragrances.
  • Higher molecular weight ethylene glycols with MG 200 to 600 are also suitable as solubilizers.
  • C 8 -C 12 preferably C 8 -C 10 fatty alcohol sulfates and unsaturated C 16 -C 22 , preferably C 16 -C 18 fatty acid sulfonates.
  • the preferred thickeners include urea or electrolytes such as sodium chloride, ammonium chloride and magnesium chloride, which can also be used in combination.
  • the totality of solvents, solubilizers, thickeners and electrolytes, which can be used individually or in any mixtures with one another, is also referred to as a viscosity regulator.
  • corrosion inhibitors and preservatives examples include sodium benzoate and sodium sulfite.
  • Known fatty acid alkanolamides can be used as foam stabilizers.
  • the liquid cleaning agents according to the invention can also contain conventional disinfectants such as bactericides or fungicides, provided that they have no effect on the skin-protecting effect of the surfactant mixture according to the invention.
  • liquid cleaning agents according to the invention of the following examples were obtained by stirring the individual components together obtained in any order and allowing the mixture to stand until there are no bubbles.
  • Sodium salts were used as anionic surfactants.
  • the application concentration of liquid, manually usable dishwashing detergents is generally 0.1 to 0.5, preferably 0.15 to 0.45 g of active substance (AS) per liter of water.
  • i-OAS i-oleyl alcohol sulfonate Na salt based on ocenol
  • ABS dodecylbenzenesulfonate Na salt
  • FAS C 12 -C 14 fatty alcohol sulfate Na salt
  • Di-iO di-iso-octylsulfosuccinate Na salt
  • Conserlan KD coconut diethanolamide
  • Texapon 842 C 8 fatty alcohol sulfate Na salt
  • Texapon NSO C 12/14 -2EO sulfate Na salt (FAES)
  • the swelling of swine epidermis served as a measure of the skin tolerance of the surfactant mixtures.
  • the required epidermis was obtained immediately after young pigs were slaughtered and stored frozen.
  • the Q value of the water-treated skin is therefore by definition 0%, negative values indicate swelling-inhibiting properties.
  • the swelling factors for anionic surfactants and systems containing anionic surfactants found using this method correlate very well with measurements of skin tolerance in vivo (cf. J. Soc. Cosmet. Chem. Jap. 20 (1986) 17).
  • a number of ready-made dishwashing detergents according to the invention are shown in the table below. They are ideal for use in both hard and soft water.
  • the ternary blends with FAES are particularly suitable for obtaining clear, cold-stable formulations.

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  • 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)

Abstract

Dans des détergents de lavage manuel de la vaisselle caractérisés par un fort pouvoir de lavage et par une protection améliorée de la peau, composés de dialkylsulfosuccinates, d'agents tensio-actifs anioniques et non ioniques ainsi que d'hydroxysulfonates d'alcools gras insaturés, les hydroxysulfonates utilisés correspondent à des alcools gras insaturés ayant les formules (I) ou (II), ou à leurs sels alcalins, alcalinoterreux et ammonicaux. Dans les formules (I) et (II), y et z sont compris entre 0 et 18; p est égal à 0, 1 ou 2; (y + z + p) est compris entre 4 et 18; x est compris entre 1 et 20 et n est compris entre 2 et 4. Les dialkysulfosuccinates (sels Na) comprennent des résidus identiques de C8-alkyl à chaîne ramifiée ou de préférence linéaire, tels que le di-n-octylsulfosuccinate. Ces compositions contiennent en tant qu'agents tensio-actifs anioniques supplémentaires des C10 à C18 alkyléthersulfates, de préference des C12 à C16 alkyléthersulfates ayant entre 1 et 5 moles d'éthylènoxyde.
PCT/EP1990/000115 1989-01-30 1990-01-22 Detergents liquides WO1990008813A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19893902619 DE3902619A1 (de) 1989-01-30 1989-01-30 Fluessige reinigungsmittel
DEP3902619.1 1989-01-30

Publications (1)

Publication Number Publication Date
WO1990008813A1 true WO1990008813A1 (fr) 1990-08-09

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PCT/EP1990/000115 WO1990008813A1 (fr) 1989-01-30 1990-01-22 Detergents liquides

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EP (1) EP0383053A1 (fr)
DE (1) DE3902619A1 (fr)
WO (1) WO1990008813A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3926345A1 (de) * 1989-08-09 1991-02-14 Henkel Kgaa Waessrige aniontensidkonzentrate mit einem gehalt an oelsaeuresulfonaten sowie die verwendung von oelsaeuresulfonaten als viskositaetsregler fuer waessrige aniontensidkonzentrate

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0112044A1 (fr) * 1982-11-16 1984-06-27 Unilever N.V. Compositions détergentes
FR2564103A1 (fr) * 1984-05-11 1985-11-15 Unilever Nv Compositions detergentes

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0112044A1 (fr) * 1982-11-16 1984-06-27 Unilever N.V. Compositions détergentes
FR2564103A1 (fr) * 1984-05-11 1985-11-15 Unilever Nv Compositions detergentes

Also Published As

Publication number Publication date
EP0383053A1 (fr) 1990-08-22
DE3902619A1 (de) 1990-08-02

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