EP1047766A1 - Agent de blanchiment aqueux sous forme de microemulsion - Google Patents

Agent de blanchiment aqueux sous forme de microemulsion

Info

Publication number
EP1047766A1
EP1047766A1 EP99906103A EP99906103A EP1047766A1 EP 1047766 A1 EP1047766 A1 EP 1047766A1 EP 99906103 A EP99906103 A EP 99906103A EP 99906103 A EP99906103 A EP 99906103A EP 1047766 A1 EP1047766 A1 EP 1047766A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
carbon atoms
weight
radical
hydrogen peroxide
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.)
Withdrawn
Application number
EP99906103A
Other languages
German (de)
English (en)
Inventor
Rafael Pi Subirana
Joaquin Bigorra
Nuria Bonastre Gilabert
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.)
BASF Personal Care and Nutrition GmbH
Original Assignee
Cognis Deutschland GmbH and Co KG
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 Cognis Deutschland GmbH and Co KG filed Critical Cognis Deutschland GmbH and Co KG
Publication of EP1047766A1 publication Critical patent/EP1047766A1/fr
Withdrawn legal-status Critical Current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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
    • C07H15/02—Acyclic radicals, not substituted by cyclic structures
    • C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
    • 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
    • C11D1/86—Mixtures of anionic, cationic, and 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
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
    • C11D1/38—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
    • C11D1/662—Carbohydrates or derivatives

Definitions

  • Aqueous bleach in microemulsion form Aqueous bleach in microemulsion form
  • the invention relates to aqueous bleaching agents in microemulsion form, containing hydrogen peroxide and a ternary emulsifier mixture.
  • Preparations are used to clean hard surfaces, particularly in the sanitary area, which simultaneously have a bleaching and disinfecting effect.
  • aqueous hydrogen peroxide solutions are also used, to which tensides are added as cleaning and emulsifying components.
  • EP-A 0415652 EP-B 0431747, EP-A 0463801, EP-A 0463802, EP-A 0694607, EP-B 0530949 (Clorox), EP-A 0745664 (Eka ), EP-B 0332259, EP-B 0468103, EP-A 0751214, EP-A 0776966, EP-A 0790297, EP-A 0794245 (Procter & Gamble) and EP-B 0687293 (Unilever).
  • the object of the invention was therefore to provide aqueous bleaching agents with a high hydrogen peroxide content which have a sufficiently high and largely stable viscosity and at the same time have excellent cleaning properties.
  • the invention relates to aqueous bleaching agents in microemulsion form containing
  • preparations of the type mentioned which contain a ternary mixture of special cationic, nonionic and anionic emulsifiers as emulsifiers and are in the form of microemulsions, even when large amounts are used, for example 5 to 15% by weight, based on the preparations (or 20 to 40% by weight of hydrogen peroxide - based on the non-aqueous portion) - in addition to the desired bleaching and disinfecting action, also have a sufficiently high and constant viscosity.
  • esters (component b1) is generally understood to mean quaternized fatty acid triethanolamine ester salts. These are known substances which can be obtained by the relevant methods of preparative organic chemistry. In this connection, reference is made to the international patent application WO 91 / 01295 (Henkel), according to which triethanolamine is partially esterified with fatty acids in the presence of hypophosphorous acid, air is passed through and then quaternized with dimethyl sulfate or ethylene oxide.
  • German Patent DE-C1 4308794 also describes a process for the preparation solid ester quats, in which the quaternization of triethanolamine esters is carried out in the presence of suitable dispersants, preferably fatty alcohols, and reviews on this topic are given, for example, by R. Puchta et al. in Tens. Surf. De, 30, 186 (1993), M .Brock in Tens.Surf.Det. 30, 394 (1993), R. Lagerman et al. In J.Am.Oil Chem.Soc, 71, 97 (1994) and I. Shapiro in Cosm.Toil. 109, 77 (1994) appeared.
  • R 1 CO for an acyl radical with 6 to 22 carbon atoms
  • R 2 and R 3 independently of one another for hydrogen or R 1 CO
  • R 4 for an alkyl radical with 1 to 4 carbon atoms or a (CH2CH2 ⁇ ) q H group
  • m, n and p in total stand for 0 or numbers from 1 to 12
  • q stands for numbers from 1 to 12
  • X stands for halide, alkyl sulfate or alkyl phosphate.
  • ester quats which can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachic acid, behenic acid and erucic acid and their technical mixtures , as they occur, for example, in the pressure splitting of natural fats and oils.
  • Technical C12 / 18 coconut fatty acids and in particular partially hardened Ci6 / ß ⁇ -tallow or palm fatty acids as well as elaidic acid-rich Ci6 / ⁇ fatty acid cuts are preferably used.
  • the fatty acids and the triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1 to produce the quaternized esters.
  • an application ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1 has proven to be particularly advantageous.
  • the preferred esterquats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C16 / 18-tallow or palm fatty acid (iodine number 0 to 40).
  • quaternized fatty acid triethanolamine ester salts of the formula (I) have proven to be particularly advantageous in which R 1 CO for an acyl radical having 16 to 18 carbon atoms, R 2 for R 1 CO, R 3 for hydrogen, R 4 for a methyl group , m, n and p is 0 and X is methyl sulfate.
  • quaternized ester salts of fatty acids with diethanolalkylamines of the formula (II) are also suitable as esterquats,
  • R 1 is C0 for an acyl radical with 6 to 22 carbon atoms
  • R 2 for hydrogen or R 1 CO
  • R 4 and R 5 independently of one another for alkyl radicals with 1 to 4 carbon atoms
  • m and n in total for 0 or numbers from 1 to 12
  • X represents halide, alkyl sulfate or alkyl phosphate.
  • ester quats are the quaternized ester salts of fatty acids with 1,2-dihydroxypropyl dialkylamines of the formula (III)
  • R7 in which R 1 CO for an acyl radical with 6 to 22 carbon atoms, R 2 for hydrogen or R 1 CO, R 4 , R 6 and R 7 independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate.
  • esterquats of the formulas (II) and (III).
  • the esterquats usually come on the market in the form of 50 to 90% strength by weight alcoholic solutions, which can be diluted with water if required.
  • Alkyl and alkenyl oligoglycosides are known nonionic surfactants which follow the formula (IV)
  • R 8 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms
  • G is a sugar radical having 5 or 6 carbon atoms
  • p is a number from 1 to 10.
  • the alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose.
  • the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.
  • the index number p in the general formula (IV) indicates the degree of oligomerization (DP), i.e. H. the distribution of mono- and oligoglycosides is present and stands for a number between 1 and 10.
  • Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.4 and 1.6.
  • the alkyl or alkenyl radical R 8 can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capro alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are used, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roeien's oxosynthesis can be obtained.
  • the alkyl or alkenyl radical R 8 can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms.
  • Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, Paim oleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol as well as their technical mixtures can be obtained as well as their technical mixtures.
  • Alkyl oligoglucosides based on hydrogenated Ci2 / i4 coconut alcohol with a DP of 1 to 3 are preferred.
  • Alkylbenzenesulfonates which form component (b3) are anionic surfactants which follow the formula (V)
  • R 9 is a linear or branched alkyl radical having 12 to 18 carbon atoms
  • Ph is a phenyl radical
  • X is an alkali and / or alkaline earth metal or ammonium.
  • Typical examples are dodecylbenzenesulfonate, tetradecylbenzenesulfonate, hexadecylbenzenesulfonate and octadecylbenzenesulfonate and their technical mixtures in the form of the sodium, potassium, calcium or ammonium salts.
  • the bleaching agents contain 20 to 60, preferably 30 to 50% by weight hydrogen peroxide and 40 to 80, preferably 50 to 70% by weight surfactants, based on the nonaqueous fraction. Preparations containing - again based on the non-aqueous portion - are particularly preferred.
  • the preparations have an aqueous fraction of 50 to 90 and preferably 60 to 80% by weight.
  • the mixtures can be prepared, for example, by introducing the aqueous emulsifiers, for example in the form of 30 to 60% by weight solutions or pastes, heating them to 70 to 80 ° C., homogenizing them and cooling them into the microemulsion obtained aqueous, for example 35 wt .-% hydrogen peroxide solution.
  • Microemulsions are obtained which have a droplet size below 100 ⁇ m.
  • a typical microemulsion of the invention has the following composition:
  • the aqueous bleaching agents according to the invention have a viscosity which is high enough on the one hand to ensure simple metering, and on the other hand so low that the preparations can be pumped. Compared to other products of the prior art, which have a comparatively high hydrogen peroxide concentration, they are distinguished by a particularly high storage stability.
  • Another object of the invention therefore relates to the use of ternary mixtures consisting of esterquats, alkyl and / or alkenyl oligoglycosides and alkylbenzenesulfonates as emulsifiers for the production of bleaching agents with a minimum content of - based on the non-aqueous portion - 20 wt .-% hydrogen peroxide.
  • Auxiliaries and additives which the preparations may further contain include, for example, other peroxide-stable surfactants or hydrotropes, such as, for example, alkyl sulfates, alkyl sulfonates, xylene sulfonates, sarcosinates, taurides, isethionates, sulfosuccinates, betaines, sugar esters, fatty alcohol polyglycol ethers, Fatty acids, soaps and (alkanol) amines.
  • the sum of these additional lent tensides at most 10% by weight of the total amount of surfactants in the formulation.
  • C8-C22 preferably Ci2-Ci8 fatty alcohol polyglycol ethers with degrees of ethoxylation in the range from 1 to 10 in amounts of 0.5 to 3% by weight is particularly preferred.
  • the agents can contain peroxide-stable fragrances, optical brighteners, dyes and pigments in a total amount of 0.01 to 0.5% by weight, based on the agents.
  • the fragrances known as peroxide-resistant include, for example, monoeyclic and bicyclic monoterpene alcohols and their esters with acetic or propionic acid (for example isoborneal, dihydroterpene oil, isobornylacetate, dihydroterpenylacetate).
  • the optical brighteners can be, for example, the potassium salt of 4,4'-bis (1, 2,3-triazolyl) - (2 -) - stilbin-2,2-sulfonic acid, which is sold under the Phorwite® BHC brand 766 is distributed.
  • Possible color pigments include green chlorophthalocyanines (Pigmosol® Green, Hostaphine® Green) or yellow Solar Yellow® BG 300 (Sandoz).
  • the sequestering agent may furthermore contain electrolyte salts in amounts of 0.1 to 2 and preferably 0.5 to 1% by weight, which are polyacrylates, carbonates, silicates, phosphates, amine oxide phosphonates and lignin sulfonates and mixtures thereof can.
  • Aqueous bleaching agents (quantities as% by weight)

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Biochemistry (AREA)
  • Biotechnology (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Molecular Biology (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne de nouveaux agents de blanchiment aqueux sous forme de microémulsion, contenant (a) du peroxyde d'hydrogène et (b) un mélange ternaire d'émulsifiants comprenant (b1) des composés quaternaires d'ester, (b2) des oligoglucosides d'alkyle et/ou d'alkylène et (b3) des sulfonates d'alkylbenzène. Les préparations possèdent non seulement un effet de blanchiment et un effet désinfectant excellents, mais sont également stables au stockage même avec des teneurs en peroxyde d'hydrogène supérieures à 20 % en poids, par rapport à la proportion non aqueuse.
EP99906103A 1998-01-14 1999-01-07 Agent de blanchiment aqueux sous forme de microemulsion Withdrawn EP1047766A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19801086A DE19801086C1 (de) 1998-01-14 1998-01-14 Wäßrige Bleichmittel in Mikroemulsionsform
DE19801086 1998-01-14
PCT/EP1999/000037 WO1999036502A1 (fr) 1998-01-14 1999-01-07 Agent de blanchiment aqueux sous forme de microemulsion

Publications (1)

Publication Number Publication Date
EP1047766A1 true EP1047766A1 (fr) 2000-11-02

Family

ID=7854551

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99906103A Withdrawn EP1047766A1 (fr) 1998-01-14 1999-01-07 Agent de blanchiment aqueux sous forme de microemulsion

Country Status (3)

Country Link
EP (1) EP1047766A1 (fr)
DE (1) DE19801086C1 (fr)
WO (1) WO1999036502A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19803803C1 (de) * 1998-01-31 1999-09-09 Henkel Kgaa Verfahren zur dauerhaften Verformung von Keratinfasern
DE19810885A1 (de) * 1998-03-13 1999-10-07 Henkel Kgaa Verfahren zur schonenden Bleiche von textilen Flächengebilden
DE19918183A1 (de) * 1999-04-22 2000-10-26 Cognis Deutschland Gmbh Reinigungsmittel für harte Oberflächen
US20100009888A1 (en) * 2008-07-14 2010-01-14 Freddy Arthur Barnabas Microemulsion or protomicroemulsion cleaning composition with disrupting surfactants
KR20130140702A (ko) * 2010-11-01 2013-12-24 코그니스 아이피 매니지먼트 게엠베하 마이크로에멀젼용 유화제로서의 생분해성 4차 화합물

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE145424T1 (de) * 1989-11-30 1996-12-15 Clorox Co Stabiles wässeriges oxidationswaschmittel
DE4023893A1 (de) * 1990-07-27 1992-01-30 Henkel Kgaa Bleichendes fluessigwaschmittel
CA2183749C (fr) * 1994-02-25 2000-10-17 Hans Lagnemo Agent de blanchiment
ES2152974T3 (es) * 1994-06-17 2001-02-16 Procter & Gamble Composiciones blanqueantes basadas en mezclas de tensioactivos cationicos y no ionicos.
EP0751214A1 (fr) * 1995-06-30 1997-01-02 The Procter & Gamble Company Compositions de blanchiment stables contenant des agents de blanchiment péroxydés
EP0776966B1 (fr) * 1995-12-02 2002-09-11 The Procter & Gamble Company Compositions de blanchiment liquides, emballées dans un atomiseur, et procédé pour la prétraitement des tissus avec celles-ci
US5602090A (en) * 1995-12-27 1997-02-11 Alphen, Inc. Surfactants based aqueous compositions with D-limonene and hydrogen peroxide and methods using the same
EP0790297A1 (fr) * 1996-02-16 1997-08-20 The Procter & Gamble Company Compositions de blanchiment
DE19715836C1 (de) * 1997-04-16 1998-07-23 Henkel Kgaa Flüssige Feinwaschmittel in Mikroemulsionsform

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9936502A1 *

Also Published As

Publication number Publication date
WO1999036502A1 (fr) 1999-07-22
DE19801086C1 (de) 1998-12-17

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