EP0744459A1 - Matière première détergente multifonctionelle - Google Patents

Matière première détergente multifonctionelle Download PDF

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Publication number
EP0744459A1
EP0744459A1 EP96810283A EP96810283A EP0744459A1 EP 0744459 A1 EP0744459 A1 EP 0744459A1 EP 96810283 A EP96810283 A EP 96810283A EP 96810283 A EP96810283 A EP 96810283A EP 0744459 A1 EP0744459 A1 EP 0744459A1
Authority
EP
European Patent Office
Prior art keywords
weight
raw material
material according
alkyl
washing raw
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
EP96810283A
Other languages
German (de)
English (en)
Other versions
EP0744459B1 (fr
Inventor
Rolf Kuratli
Claude Dr. Eckhardt
Frank Dr. Bachmann
Werner Schreiber
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 Schweiz AG
Original Assignee
Ciba Geigy AG
Ciba Spezialitaetenchemie Holding AG
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 Ciba Geigy AG, Ciba Spezialitaetenchemie Holding AG filed Critical Ciba Geigy AG
Priority to MX9601857A priority Critical patent/MX201083B/es
Publication of EP0744459A1 publication Critical patent/EP0744459A1/fr
Application granted granted Critical
Publication of EP0744459B1 publication Critical patent/EP0744459B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C11D9/00—Compositions of detergents based essentially on soap
    • 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
    • C11D3/3788—Graft polymers

Definitions

  • the present invention relates to a multifunctional detergent, the production of this raw material, its use in household detergents, and household detergents containing the detergent.
  • reaction products of an ethylenically unsaturated sulfonic acid or carboxylic acid or its anhydride and certain nonionic surfactants and, if appropriate, sugar derivatives are washing raw materials which are capable of carrying out the components (a 1 ) - (a 6 ) specified in the above washing powder composition ) completely and to replace components (b), (e), (l) and (n) partially or completely.
  • low-ethoxylated fatty alcohol ethoxylates such as C 13 oxo alcohols with 4 to 6 ethylene oxide units, can be added to foam inhibitors (component ( I)) to be dispensed with.
  • the washing raw material according to the invention also has excellent anti-redeposition properties, so that in detergents containing this washing raw material, the The addition of anti-redeposition agents, such as carboxymethyl cellulose and / or polyacrylic acid, can be dispensed with (cf. Examples 21 to 23).
  • anti-redeposition agents such as carboxymethyl cellulose and / or polyacrylic acid
  • the substituents R 1 and R 2 in the formula (1) advantageously represent the hydrocarbon radical of an unsaturated or preferably saturated aliphatic monoalcohol having 8 to 22 carbon atoms.
  • the hydrocarbon radical can be straight-chain or branched.
  • R 1 and R 2 are preferably an alkyl radical having 9 to 14 carbon atoms.
  • aliphatic saturated monoalcohols natural alcohols, such as, for example, lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol, and synthetic alcohols, such as, for example, 2-ethylhexanol, 1,1,3,3-tetramethylbutanol, octan-2-ol, isononyl alcohol, trimethylhexanol, trimethylnonyl alcohol
  • Decanol, C 9 -C 11 oxo alcohol, tridecyl alcohol, isotridecyl alcohol or linear primary alcohols (alfoles) with 8 to 22 carbon atoms can be used. Some representatives of these alfoles are Alfol (8-10), Alfol (9-11), Alfol (10-14), Alfol (12-13) or Alfol (16-18).
  • Alfol is a registered trademark).
  • Unsaturated aliphatic monoalcohols are, for example, dodecenyl alcohol, hexadecenyl alcohol or oleyl alcohol.
  • the alcohol residues can be present individually or in the form of mixtures of two or more components, e.g. Mixtures of alkyl and / or alkenyl groups which are derived from soy fatty acids, palm kernel fatty acids or tallow oils.
  • Alkylene-O chains are preferably divalent radicals of the formulas - (CH 2 -CH 2 -O) -,
  • cycloaliphatic radical examples include cycloheptyl, cyclooctyl or preferably cyclohexyl.
  • nonionic surfactants of the formulas (1), (2) or (3) are reaction products of a C 10 -C 13 fatty alcohol, for example a C 13 oxo alcohol with 3 to 10 moles of ethylene oxide, propylene oxide and / or butylene oxide or that To name reaction product of one mole of a C 13 fatty alcohol with 6 moles of ethylene oxide and 1 mole of butylene oxide, it being possible for the addition products in each case to be end-capped with C 1 -C 4 -alkyl, preferably methyl or butyl.
  • the nonionic surfactants of the formula (1) are prepared in a manner known per se, for example by reacting a fatty alcohol with alkylene oxides.
  • the corresponding end-capped nonionic surfactants are prepared by subsequent reaction of the adduct formed with an alkyl halide R 2 -Hal, R 4 -Hal or R 6 -Hal, preferably with C 1 -C 4 -alkyl chloride.
  • monocarboxylic acids having 3 to 5 carbon atoms e.g. acrylic acid, methacrylic acid, ⁇ -haloacrylic acid, 2-hydroxyethylacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid and vinyl acetic acid.
  • Ethylenically unsaturated dicarboxylic acids are preferably fumaric acid, maleic acid or itaconic acid, furthermore mesaconic acid, citraconic acid, glutaconic acid and methylmalonic acid.
  • Maleic anhydride should be mentioned in particular as the anhydride of these acids.
  • Suitable monomeric sulfonic acids which are used for the reaction are vinylsulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid.
  • Monosaccharides, disaccharides, trisaccharides or oligosaccharides are suitable as sugar derivatives.
  • monosaccharide is understood to mean an aldopentose, aldohexose, aldotreose, ketopentose or ketohexose.
  • the compounds mentioned can also be present as lactones, e.g. D (+) - gluconic acid ⁇ -lactone.
  • aldopentose examples include D-ribose, D-arabinose, D-xylose or D-lyose; for an aldohexose D-Allose, D-Altrose, D-Glucose, D-Mannose, D-Gulose, D-Idose, D-Galactose, D-Talose, L-Fucose or L-Rhamnose; for a ketopentose D-ribulose or D-xylulose; for a tetrose D erythrosis or threosis; for a ketohexose D-psicose, D-fructose, D-sorbose or D-tagatose.
  • Examples of a disaccharide are trehalose, maltose, isomaltose, cellobiose, gentiobiose, sucrose, lactose. Chitobiose, N, N-diacetylchitobiose, palatinose or sucrose.
  • Raffinose, panose or maltotriose may be mentioned as examples of trisaccharide.
  • Maltotetraose, maltohexaose and chitoheptaose may be mentioned as examples of oligosaccharide.
  • sugar derivatives are enolizable saccharides, e.g. Fructose or palatinose.
  • sugar acids e.g. Gluconic acids (D-gluconic acid and its salts), glucaric acids (mucic acid), glucuronic acids (D-glucuronic acid, D-galacturonic acid) can be used according to the invention.
  • the individual components are preferably used in the following amounts for the reaction: 50 to 90% by weight of one or more nonionic surfactants, 5 to 13% by weight of an ethylenically unsaturated sulfonic acid or carboxylic acid or its anhydride, 0 to 30 wt .-% sugar derivatives, and 1 to 60, especially 1 to 20% water.
  • the raw material for washing according to the invention preferably corresponds to the reaction product of 5 to 13% by weight of acrylic acid or methacrylic acid and 50 to 90% by weight of the nonionic surfactant of the formula (2) and 0 to 30% by weight of gluconic acid.
  • the raw material for washing according to the invention is prepared by reacting the nonionic surfactant of the formula (1) with an ethylenically unsaturated sulfonic acid or carboxylic acid or its anhydride at temperatures from 30 to 100 ° C., preferably 80 to 95 ° C., using a catalyst.
  • the ratio of nonionic surfactant or several nonionic tenides to ethylenically unsaturated sulfonic acid or carboxylic acid or its anhydride is 8: 1 to 1: 1, in particular 6: 1 to 3: 1.
  • the reaction is advantageously carried out in an inert atmosphere, for example in the presence of nitrogen.
  • Free radical-forming organic initiators are preferably used as catalysts.
  • Suitable initiators for carrying out the radical polymerization are e.g. symmetrical aliphatic azo compounds such as azo-bis-isobutyronitrile, azo-bis-2-methylvaleronitrile, 1,1-azo-bis-1-cyclo-hexanitrile and 2,2-azo-bis-isobutyric acid alkyl ester; symmetrical diacyl peroxides, e.g.
  • Suitable peroxides are: tert-butyl hydroperoxide, di-tert-butyl peroxide, cumene hydroperoxide, di-cumene peroxide and tert-butyl perpivalate.
  • Another suitable compound is potassium persulfate, which is preferably used for the production of the washing raw material according to the invention.
  • the catalysts are generally used in amounts of 0.01 to 1% by weight, based on the starting products.
  • the ethylenically unsaturated sulfonic acid or carboxylic acid is introduced in a high concentration in a first stage and then the fatty alcohol ethoxylate and optionally the sugar derivative are formulated.
  • the reaction product obtained is treated with an inorganic and / or organic base, such as e.g. Sodium hydroxide solution, potassium hydroxide solution, magnesium hydroxide, ethanolamine or triethanolamine to a pH of 3 to 10, preferably 4 to 5, partially neutralized.
  • an inorganic and / or organic base such as e.g. Sodium hydroxide solution, potassium hydroxide solution, magnesium hydroxide, ethanolamine or triethanolamine to a pH of 3 to 10, preferably 4 to 5, partially neutralized.
  • bases one uses e.g. 1 to 8% by weight inorganic or organic bases, e.g. Sodium hydroxide, magnesium hydroxide, ethanolamine, triethanolamine, N, N, N, N-tetrakis (2-hydroxypropyl) ethylene amine or 1-amino-1-deoxysorbitol or mixtures thereof. Water is added to 100% by weight.
  • auxiliaries such as hydrotroping agents, higher fatty alcohols, etc.
  • hydrotroping agents such as hydrotroping agents, higher fatty alcohols, etc.
  • the washing raw material according to the invention has a good Ca dispersing capacity, i.e. additional amounts of polycarboxylates in the later detergent are no longer necessary. In addition, it is very stable to electrolytes and temperature. It has an excellent washing effect. The formation of macromicelles at elevated temperatures is eliminated by the polymerization.
  • the raw material for washing is therefore ideal for the production of household detergents, e.g. Powder or liquid detergents according to the usual methods.
  • the use of the washing raw material according to the invention for the production of household detergents represents a further subject of the invention.
  • Sodium perborate compounds include e.g. Sodium perborate tetrahydrate or in particular sodium perborate monohydrate or sodium perborate percarbonate.
  • Peroxide activators include e.g. TAED, NOBS or TAGU.
  • additives come e.g. Perfume oil, optical brighteners or dyes.
  • the detergent raw material according to the invention simultaneously replaces the components LAS, nonionic surfactant, defoamer, complexing agent and fatty alcohol sulfate, the use of only one component facilitates the metering in the detergent composition and leads to a simplification of the detergent powder production process.
  • nonionic surfactants of the formula (1), (2) or (3) in the production of the detergent raw material according to the invention, a further variability of the properties of the detergent can be achieved.
  • the wetting capacity, the washing effect or the foaming behavior can be adjusted by using appropriate non-ionic surfactants.
  • the complexing action and the washing action can be controlled via the amount of the ethylenically unsaturated sulfonic acids or carboxylic acids used.
  • the sugar-acrylic acid polymers are known, highly biodegradable complexing agents and therefore also allow the calcium dispersing capacity to be adjusted.
  • the mixture is stirred for a further 30 minutes at 90 ° C. and then cooled to room temperature. At an internal temperature of approx. 70 ° C 15.0 g sodium hydroxide solution (30%) added and cooled further.
  • the reaction products prepared in Examples 1 to 11 can with sodium hydroxide solution, potassium hydroxide solution, org. Amines (ethanolamine, triethanolamine), magnesium hydroxide etc. can be neutralized.
  • the pH value can be set between 3.0 and 10.0.
  • the water contained in the reaction product is preferably removed in a falling film evaporator.
  • EXAMPLE 13 The procedure is as described in Example 12, but a subset of the wash raw material obtainable from Examples 1 to 11 is mixed into the spray slurry. The final formulation contains 5 to 35% by weight of the active wash raw material.
  • Example 14 The procedure is as described in Example 12, but the entire amount of the wash raw material obtainable from Examples 1 to 11 is mixed into the spray slurry.
  • the powder detergent contains 5 to 35% by weight of the active detergent.
  • Example 15 The ingredients mentioned in Example 12 are granulated or mixed directly in the fluidized bed or ploughshare mixer and low-water or water-free washing raw materials from Examples 1 to 11 are sprayed on.
  • the active wash raw material content is 5 to 35% by weight.
  • Example 16 All solid components of the spray slurry mentioned in Example 12 are subjected to a mixing and grinding process, for example in a ploughshare mixer and / or a fluidized bed unit. The resulting powder material is sprayed with the wash raw material and with perfume oil, so that compact granules with a high bulk density are obtained. Finally, perborate / tetra or preferably monohydrate or percarbonate, and an activator such as TAED, NOBS and optionally a protective silicate are mixed in the fluidized bed or ploughshare mixer. A stable, non-sticky, compact detergent is obtained.
  • Example 17 The wash raw material obtainable from Examples 1 to 11 is diluted with water, so that the final formulation contains 50 to 58% by weight of active wash raw material and has a viscosity which is favorable for the end user.
  • Silicate is added to the solution to adjust a pH between 7.5 and 11, and perfume oil, optical brighteners and, if appropriate, dyes.
  • An "opazifier” can also be added. Very effective, liquid heavy-duty detergents are obtained.
  • the brightness Y of the samples is measured spectrophotometrically before and after washing.
  • the difference ⁇ Y before and after washing is a measure of the removal of dirt.
  • detergents contain so-called “anti-redeposition agents”, mostly carboxymethyl cellulose (CMC) and / or polyacrylic acid, Na triphosphates also having such a dirt-carrying effect.
  • CMC carboxymethyl cellulose
  • polyacrylic acid Na triphosphates also having such a dirt-carrying effect.
  • the anti-redeposition properties are tested as follows: 5 g of bleached cotton test fabric are washed in 100 ml of deionized water with a pH of 10.5 (adjusted with NaOH) for 20 minutes at 60 ° C., whereby 40 mg of defined soot types are added to the wash bath. Then it is rinsed briefly with tap water and dried at 60 ° C.
  • Example 21 Washing raw material from example 5 73.2 1.8 64.2 1.6
  • Example 22 Washing raw material from example 6 70.8 2.4 68.7 2.2
  • Example 23 Washing raw material from example 7 70.6 1.0 63.8 2.0
  • Examples 24 to 26 Surfactant solutions a) to c) are prepared, each containing 2.0 g / l of the wash raw material obtainable from Examples 5, 6 and 7. In total, 9 solutions are produced.

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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)
EP96810283A 1995-05-19 1996-05-03 Matière première détergente multifonctionelle Expired - Lifetime EP0744459B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
MX9601857A MX201083B (en) 1995-05-19 1996-05-17 Multifunctional detergent base

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH149495 1995-05-19
CH1494/95 1995-05-19
CH149495 1995-05-19

Publications (2)

Publication Number Publication Date
EP0744459A1 true EP0744459A1 (fr) 1996-11-27
EP0744459B1 EP0744459B1 (fr) 2001-10-10

Family

ID=4211774

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96810283A Expired - Lifetime EP0744459B1 (fr) 1995-05-19 1996-05-03 Matière première détergente multifonctionelle

Country Status (11)

Country Link
US (1) US5885952A (fr)
EP (1) EP0744459B1 (fr)
JP (1) JPH08325598A (fr)
KR (1) KR100406065B1 (fr)
CN (1) CN1079426C (fr)
BR (1) BR9602332A (fr)
CA (1) CA2176894A1 (fr)
DE (1) DE59607860D1 (fr)
ES (1) ES2163606T3 (fr)
MX (1) MX201083B (fr)
ZA (1) ZA963936B (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6458756B1 (en) * 1999-07-14 2002-10-01 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Powder detergent process
TWI480258B (zh) 2008-03-28 2015-04-11 Asahi Kasei Finechem Co Ltd Vinyl sulfonic acid, a polymer thereof and a process for producing the same
GB2529138A (en) * 2014-07-02 2016-02-17 Basf Se Detergent
CN116574567A (zh) * 2023-04-23 2023-08-11 山东福洋生物科技股份有限公司 一种环境友好型加酶洗涤剂及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0441197A2 (fr) * 1990-02-03 1991-08-14 BASF Aktiengesellschaft Copolymère greffé à base de monosaccharides, oligosaccharides, polysaccharides et de polysaccharides modifiées, procédé de fabrication de celle-ci et son utilisation
EP0462059A2 (fr) * 1990-06-11 1991-12-18 Ciba-Geigy Ag Adjuvants textiles aqueux, peu moussants et exempts de silicones, leur préparation et leur application
WO1994001476A1 (fr) * 1992-07-02 1994-01-20 Chemische Fabrik Stockhausen Gmbh Copolymeres greffes de monomeres insatures et de sucres, leur procede de fabrication et leur utilisation
DE4316740A1 (de) * 1993-05-19 1994-11-24 Huels Chemische Werke Ag Polymerhaltige Universalreinigungsmittel
EP0696661A1 (fr) * 1994-08-11 1996-02-14 Ciba-Geigy Ag Compositions d'agents de finition multi-fonctionnels

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE605230A (fr) * 1960-06-27
US3149078A (en) * 1960-06-27 1964-09-15 Colgate Palmolive Co Liquid abrasive cleanser
BE636822A (fr) * 1962-09-04
US3623990A (en) * 1967-06-26 1971-11-30 Procter & Gamble Liquid detergent composition
US3677954A (en) * 1969-07-28 1972-07-18 Kao Corp Liquid abrasive cleanser composition
US3813349A (en) * 1969-12-29 1974-05-28 Procter & Gamble Liquid detergent composition
US4129527A (en) * 1974-11-07 1978-12-12 The Clorox Company Liquid abrasive detergent composition and method for preparing same
US4124523A (en) * 1977-03-07 1978-11-07 Dow Corning Corporation Silicone-containing acidic cleaner and conditioner
US4457856A (en) * 1980-01-07 1984-07-03 The Procter & Gamble Company Liquid detergent composition contains abrasive particles, anionic and nonionic surfactants
EP0098803B1 (fr) * 1982-07-06 1986-07-30 Ciba-Geigy Ag Polymères greffés solubles ou dispersables dans l'eau, leur fabrication et utilisation
DE3714732C3 (de) * 1987-05-02 1994-07-14 Grillo Werke Ag Copolymerisate auf der Basis von ungesättigten Carbonsäuren und zur Enolatbildung befähigten Monosacchariden, Verfahren zur Herstellung derselben und ihre Verwendung
DE3801633A1 (de) * 1988-01-21 1989-07-27 Starchem Gmbh Verfahren zur herstellung von wasserabsorbierenden und wasserquellbaren polysaccharid-pfropfpolymeren

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0441197A2 (fr) * 1990-02-03 1991-08-14 BASF Aktiengesellschaft Copolymère greffé à base de monosaccharides, oligosaccharides, polysaccharides et de polysaccharides modifiées, procédé de fabrication de celle-ci et son utilisation
EP0462059A2 (fr) * 1990-06-11 1991-12-18 Ciba-Geigy Ag Adjuvants textiles aqueux, peu moussants et exempts de silicones, leur préparation et leur application
WO1994001476A1 (fr) * 1992-07-02 1994-01-20 Chemische Fabrik Stockhausen Gmbh Copolymeres greffes de monomeres insatures et de sucres, leur procede de fabrication et leur utilisation
DE4316740A1 (de) * 1993-05-19 1994-11-24 Huels Chemische Werke Ag Polymerhaltige Universalreinigungsmittel
EP0696661A1 (fr) * 1994-08-11 1996-02-14 Ciba-Geigy Ag Compositions d'agents de finition multi-fonctionnels

Also Published As

Publication number Publication date
ZA963936B (en) 1996-11-19
US5885952A (en) 1999-03-23
KR960041338A (ko) 1996-12-19
KR100406065B1 (ko) 2004-03-26
CN1138090A (zh) 1996-12-18
CN1079426C (zh) 2002-02-20
ES2163606T3 (es) 2002-02-01
DE59607860D1 (de) 2001-11-15
JPH08325598A (ja) 1996-12-10
CA2176894A1 (fr) 1996-11-20
BR9602332A (pt) 1998-04-22
MX201083B (en) 2001-03-19
EP0744459B1 (fr) 2001-10-10

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