EP0944697A2 - Melanges tensioactifs exempts d'eau - Google Patents

Melanges tensioactifs exempts d'eau

Info

Publication number
EP0944697A2
EP0944697A2 EP97951883A EP97951883A EP0944697A2 EP 0944697 A2 EP0944697 A2 EP 0944697A2 EP 97951883 A EP97951883 A EP 97951883A EP 97951883 A EP97951883 A EP 97951883A EP 0944697 A2 EP0944697 A2 EP 0944697A2
Authority
EP
European Patent Office
Prior art keywords
acid
carbon atoms
weight
water
surfactant mixtures
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
EP97951883A
Other languages
German (de)
English (en)
Other versions
EP0944697B1 (fr
Inventor
Karl-Heinz Schmid
Ditmar Kischkel
Thomas Krohnen
Andreas Syldath
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.)
Cognis IP Management GmbH
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 EP0944697A2 publication Critical patent/EP0944697A2/fr
Application granted granted Critical
Publication of EP0944697B1 publication Critical patent/EP0944697B1/fr
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
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
    • 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
    • C11D1/146—Sulfuric 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
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds

Definitions

  • the invention relates to water-free surfactant mixtures with a reduced potential for irritation, containing selected fatty alcohol sulfates and alkylbenzenesulfonates in selected mixing ratios, and their use for the preparation of surface-active agents.
  • fatty alcohol sulfates are anionic surfactants, which are becoming increasingly important for the production of detergents, dishwashing detergents and cleaning agents.
  • DE-C2 2857292 discloses detergent preparations containing alkyl sulfates and alkyl benzenesulfonates, which contain selected polymers as soil repellants.
  • free-flowing surfactant granules are also obtained by 33 to 55% by weight of a liquid, acidic anionic surfactant mixture (for example alkylbenzenesulfonic acid or alkylsulfuric acid half-ester) with 20 to 50% by weight of zeolite and 2 up to 25% by weight of alkali metal carbonate.
  • the complex object of the invention was, however, to provide new water-free surfactant mixtures which at the same time are distinguished by a significantly reduced potential for irritation, improved flowability and solubility.
  • the invention relates to anhydrous surfactant mixtures containing
  • R 1 is a linear alkyl radical having 16 and / or 18 carbon atoms and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium, and
  • R 2 represents an alkyl radical having 10 to 14 carbon atoms
  • Ph represents a phenyl radical
  • X in turn represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium
  • the preparations according to the invention have a synergistic decrease in the potential for irritation with equally good application properties, in particular improved flowability and solubility in cold water.
  • Fatty alcohol sulfates which form component (a) are known anionic surfactants and are usually prepared by reacting fatty alcohols with sulfating agents such as sulfuric acid, oleum, chlorosulfonic acid and in particular gaseous sulfur trioxide. The resulting Sulfuric acid half-esters are then neutralized with suitable bases.
  • the fatty alcohol sulfates of the formula (I) are sulfation products of fatty alcohols having 16 to 18 carbon atoms. Typical examples are the sulfates of cetyl alcohol and stearyl alcohol.
  • Technical fatty alcohol cuts such as, for example, tallow alcohol are preferred, which may have shorter or longer-chain homologs in minor amounts.
  • Alkylbenzenesulfonates which form component (b) are also known anionic surfactants which are usually prepared by core sulfonation of linear alkylbenzenes and then neutralized in a suitable manner. Typical examples are sulfonation products of decylbenzene, dodecylbenzene and tetradecylbenzene and their technical mixtures, which are used in the form of their sodium or potassium salts.
  • the mixing of the components is not critical.
  • the aqueous pastes resulting after the neutralization of the crude sulfonation products are mixed, for example, in a Schugi mixer and simultaneously processed into an anhydrous, lumpy product.
  • dry-neutralized or spray-dried or steam-dried powders of the two components can also be mixed.
  • the acidic sulfonation products can also be neutralized together and then processed further.
  • the starting point is a tower powder which is produced by conventional processes and which, in addition to typical detergent components, may also already contain one of the two anionic surfactant components.
  • the powder is placed in a mixer and continuously mixed with at least one of the two anionic surfactant components, preferably in the form of an aqueous paste, dried and optionally further mechanically solidified.
  • the result is a dry detergent powder, granulate or extrudate with excellent detergent properties, high dissolution rate and reduced irritation potential.
  • the surfactant mixtures according to the invention are not only distinguished by very good detergent properties, but above all also by a potential for irritation which is reduced in a synergistic manner, i.e. improved skin and eye mucosa tolerance. They are therefore suitable for the production of detergents, dishwashing detergents and cleaning agents, in particular solid detergents, in which they can be present in amounts of 1 to 90, preferably 10 to 50% by weight, based on the detergent.
  • Typical examples of detergents, dishwashing detergents and cleaning agents which can contain the water-free surfactant mixtures according to the invention are liquid to pasty fabric softeners, hand dishwashing detergents, machine dishwashing detergents, rinse aids, and universal, household and sanitary cleaners, and powdered or granulated universal detergents.
  • the agents can have other typical ingredients such as builders, enzymes, enzyme stabilizers, bleaches, optical brighteners, thickeners, soil repellants, foam inhibitors, solubilizers, inorganic salts and fragrances and dyes.
  • Suitable builders are zeolites, phyllosilicates, phosphates and ethylenediaminetetraacetic acid, nitrilotriacetic acid, citric acid and inorganic phosphonic acids.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other bleaching agents are, for example, peroxy carbonate, citrate perhydrates and H ⁇ O ⁇ -delivering peracidic salts of peracids such as perbenzoates, peroxyphthalates or diperoxydodecanedioic acid. They are usually used in amounts of 8 to 25% by weight.
  • the use of sodium perborate monohydrate in amounts of 10 to 20% by weight and in particular 10 to 15% by weight is preferred. Due to its ability to bind free water with the formation of the tetrahydrate, it contributes to increasing the stability of the agent.
  • thickeners which can be used are hardened castor oil, salts of long-chain fatty acids, preferably in amounts of 0 to 5% by weight and in particular in amounts of 0.5 to 2% by weight, for example sodium, potassium, aluminum, magnesium - And titanium stearates or the sodium and / or potassium salts of behenic acid, and other polymeric compounds are used.
  • the latter preferably include polyvinylpyrrolidone, urethanes and the salts of polymeric polycarboxylates, for example homopolymeric or copolymeric polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those of 50 to 10% Maleic acid.
  • the relative molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200000, preferably between 50,000 to 120,000, based on the free acid.
  • water-soluble polyacrylates are suitable that the sucrose are crosslinked, for example with about 1% of a polyallyl ether and which have a relative molecular mass above 1,000,000 own Examples of these are under the name Carbopol ® 940 and 941 available polymers.
  • the crosslinked polyacrylates are preferably used in amounts not exceeding 1% by weight, particularly preferably in amounts of 0.2 to 0.7% by weight.
  • Suitable enzymes are those from the class of proteases, lipase, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus lichenformis and Strptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases obtained from Bacillus lentes are preferably used. Their proportion can be about 0.2 to 2% by weight. The enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition.
  • the agents can contain further enzyme stabilizers.
  • enzyme stabilizers For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • boron compounds for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H3BO3), metaboric acid (HBO2) and pyrobic acid (tetraboric acid H2B4O7), is particularly advantageous.
  • Suitable foam inhibitors contain, for example, known organopolysiloxanes, paraffins or waxes.
  • the free-flowing properties of the products were subjectively determined in the clump test; (+) means high flowability, (-) restricted flowability and (-) high tendency to clump.
  • (+) means high flowability, (-) restricted flowability and (-) high tendency to clump.
  • 10 g of the anhydrous formulations were dissolved or dispersed in 100 ml of water (30 ° C., 16 ° d). After 120 s, the solutions or dispersions were filtered and the residue was dried and weighed out. The information is given in% -rel based on the amount used.
  • the irritation potential was determined in accordance with OECD Method No.404 and the EEC Directive 84/449 EEC, Pt.B.4. The specified stimulus sum scores were formed from the stimulus scores obtained after 24, 48 and 72 hours.

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)
  • Cosmetics (AREA)

Abstract

L'invention concerne de nouveaux mélanges tensioactifs exempts d'eau, contenant (a) des sulfates d'alcool gras ayant 16 et/ou 18 atomes de carbone et (b) des sulfonates de benzène d'alkyle ayant entre 10 et 14 atomes de carbone dans le reste alkyle, dans un rapport en poids de 50:50 à 90:10. Ces mélanges se caractérisent par un potentiel d'effet irritant réduit de manière synergique, tout en conservant des propriétés détergentes exceptionnelles.
EP97951883A 1996-11-20 1997-11-11 Melanges tensioactifs exempts d'eau Expired - Lifetime EP0944697B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19648014 1996-11-20
DE19648014A DE19648014C2 (de) 1996-11-20 1996-11-20 Wasserfreie Tensidgemische
PCT/EP1997/006273 WO1998022561A2 (fr) 1996-11-20 1997-11-11 Melanges tensioactifs exempts d'eau

Publications (2)

Publication Number Publication Date
EP0944697A2 true EP0944697A2 (fr) 1999-09-29
EP0944697B1 EP0944697B1 (fr) 2001-10-17

Family

ID=7812238

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97951883A Expired - Lifetime EP0944697B1 (fr) 1996-11-20 1997-11-11 Melanges tensioactifs exempts d'eau

Country Status (5)

Country Link
US (1) US6165961A (fr)
EP (1) EP0944697B1 (fr)
DE (2) DE19648014C2 (fr)
ES (1) ES2166106T3 (fr)
WO (1) WO1998022561A2 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002525417A (ja) 1998-09-25 2002-08-13 ザ、プロクター、エンド、ギャンブル、カンパニー 洗剤顆粒
EP2043446A2 (fr) * 2006-02-08 2009-04-08 Phibro-Tech Inc. Concentres d'emulsion d'azole biocide ayant une teneur elevee en substance active
US8933131B2 (en) 2010-01-12 2015-01-13 The Procter & Gamble Company Intermediates and surfactants useful in household cleaning and personal care compositions, and methods of making the same
WO2016040248A2 (fr) 2014-09-08 2016-03-17 The Procter & Gamble Company Compositions détergentes contenant un tensioactif ramifié
JP6377840B2 (ja) 2014-09-08 2018-08-22 ザ プロクター アンド ギャンブル カンパニー 分岐界面活性剤を含有する洗剤組成物

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1317465A (en) * 1969-07-07 1973-05-16 Sterling Drug Inc Process for drying and grinding fluorescent whitening agents
US3703772A (en) * 1971-07-27 1972-11-28 Colgate Palmolive Co Drying of detergents
DE2226988A1 (de) * 1972-06-02 1973-12-20 Henkel & Cie Gmbh Geschirrspuel- und reinigungsmittel
US4116885A (en) * 1977-09-23 1978-09-26 The Procter & Gamble Company Anionic surfactant-containing detergent compositions having soil-release properties
US4715979A (en) * 1985-10-09 1987-12-29 The Procter & Gamble Company Granular detergent compositions having improved solubility
GB9012612D0 (en) * 1990-06-06 1990-07-25 Unilever Plc Detergents compositions
US5066425A (en) * 1990-07-16 1991-11-19 The Procter & Gamble Company Formation of high active detergent particles
DE4124701A1 (de) * 1991-07-25 1993-01-28 Henkel Kgaa Verfahren zur herstellung fester wasch- und reinigungsmittel mit hohem schuettgewicht und verbesserter loesegeschwindigkeit
DE69229218T2 (de) * 1992-03-10 1999-12-16 The Procter & Gamble Co., Cincinnati Hochaktive Tensidpasten
GB9313878D0 (en) * 1993-07-05 1993-08-18 Unilever Plc Detergent composition or component containing anionic surfactant and process for its preparation
DE4332373C2 (de) * 1993-09-23 2003-03-13 Cognis Deutschland Gmbh Wasserfreie Detergensgemische
DE4415369C1 (de) * 1994-05-02 1995-08-31 Henkel Kgaa Heterogene Tensidgranulate
DE4432365A1 (de) * 1994-09-12 1996-03-14 Henkel Kgaa Wasserfreie Tensidgemische
DE19510099C1 (de) * 1995-03-20 1996-08-22 Henkel Kgaa Wasserfreie Tensidgemische enthaltend lang- und kurzkettige sekundäre 2,3-Alkylsulfate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9822561A2 *

Also Published As

Publication number Publication date
EP0944697B1 (fr) 2001-10-17
DE19648014A1 (de) 1998-06-04
US6165961A (en) 2000-12-26
WO1998022561A3 (fr) 1998-10-15
DE59705005D1 (de) 2001-11-22
WO1998022561A2 (fr) 1998-05-28
ES2166106T3 (es) 2002-04-01
DE19648014C2 (de) 2002-09-19

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