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WO1993013192A1 - Polycondensats d'acide butantetracarboxylique et de composes polyhydroxy et leur utilisation dans des produits de lavage et des produits detergents - Google Patents

Polycondensats d'acide butantetracarboxylique et de composes polyhydroxy et leur utilisation dans des produits de lavage et des produits detergents Download PDF

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Publication number
WO1993013192A1
WO1993013192A1 PCT/EP1992/002848 EP9202848W WO9313192A1 WO 1993013192 A1 WO1993013192 A1 WO 1993013192A1 EP 9202848 W EP9202848 W EP 9202848W WO 9313192 A1 WO9313192 A1 WO 9313192A1
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Prior art keywords
acid
mono
condensation
washing
water
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PCT/EP1992/002848
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German (de)
English (en)
Inventor
Dieter Boeckh
Heinrich Hartmann
Elisabeth Kappes
Alfred Oftring
Richard Baur
Alexander Kud
Volker Schwendemann
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Basf Aktiengesellschaft
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Publication of WO1993013192A1 publication Critical patent/WO1993013192A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/14—Esterification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • 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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates

Definitions

  • the invention relates to polycondensates of butane tetracarboxylic acid, which can optionally be partially replaced by other carboxylic acids, with polyhydroxy compounds from the group of mono-, oligo- and polysaccharides, reduced mono- or oligosaccharides and their amino derivatives, sugar carboxylic acids, polyvinyl alcohols, oligoglycerols or mixtures thereof and optionally Glycols, polyalkylene glycols or alkoxylated alcohols and the use of the polycondensates as an additive to low-phosphate or phosphate-free washing and cleaning agents.
  • detergents and cleaning agents which have water-soluble salts of acidic carboxylic acid esters from at least trihydric aliphatic or olefinically unsaturated carboxylic acids or hydroxycarboxylic acids and at least trihydric aliphatic alcohols as builders, with each hydroxyl group containing Alcohol is a molecule of carboxylic acid bound.
  • Typical examples of such esters are glycerol tricitrate, sorbitol hexacitrate and pentaerythritol tetracitrate.
  • These citric acid esters are readily biodegradable, act as builders in detergents and cleaners and form stable dispersions in the wash liquor with hydrophilic pigment particles.
  • washing and cleaning agents which contain 0.1 to 20% by weight, based on the total weight of the agent, of water-soluble salts of free carboxyl groups containing polyesters are characterized, the acid esters of tricarboxylic acids and / or tetracarboxylic acids and their alcohol residues derived from dihydric alcohols.
  • Suitable polyesters of this type are, for example, polyesters from citric acid and ethylene glycol. The polyesters described have a graying-inhibiting effect in washing liquors and prevent the re-accumulation of dirt particles from the washing liquor on the textile goods to be washed.
  • aqueous paints which contain reaction products from polycarboxylic acids, such as citric acid, isocitric acid, tricarballylic acid or butanetetracarboxylic acid, and polyols, such as, for example, glycerol, diglycerin, pentaerythritol, ethylene glycol or polyethylene glycol, as binders ⁇ th.
  • polycarboxylic acids such as citric acid, isocitric acid, tricarballylic acid or butanetetracarboxylic acid
  • polyols such as, for example, glycerol, diglycerin, pentaerythritol, ethylene glycol or polyethylene glycol, as binders ⁇ th.
  • EP-A-0 433 010 discloses polycarboxylates which can be obtained by esterification of citric acid, isocitric acid or propane tricarboxylic acid with glycol, glycerol, erythritol, pentaerythritol, mono-, oligo- and polysaccharides as well as polyvinyl alcohol or polyallyl alcohol.
  • Polyvinyl citrate and polyallyl citrate are emphasized as preferred compounds.
  • the polycarboxylates are used as builders in detergent formulations.
  • the object of the present invention is to produce new substances which are suitable as detergent additives.
  • butane-l, 2,3,4-tetracarboxylic acid which can be replaced by up to 70 mol% with mono- or dibasic hydroxycarboxylic acids or up to 49 mol% with other two- to four-basic aliphatic carboxylic acids,
  • polyhydroxy compounds from the group of mono-, oligo- and polysaccharides, reduced mono- or oligosaccharides and their amino derivatives, oxidized mono-, oligo- or polysaccharides, alkyl (poly) glycosides, polyvinyl alcohols, oligoglycerols with more than 2 glycerol units or their mixtures
  • component a) up to 20 mol%, based on component a), of C 2 - to C 1 -alkylene glycols, polyalkylene glycols with a molar mass of up to 2000 or monovalent C - to C o-alcohols optionally alkoxylated with up to 50 mol of alkylene oxide.
  • the polycondensates are used as additives to low-phosphate or phosphate-free washing and cleaning agents in amounts of 0.1 to 30% by weight, based on the agent.
  • Component a) is preferably butane-1,2,3,4-racarboxylic acid.
  • butanetetracarboxylic acid can be used in a mixture with 1- or 2-basic hydroxycarboxylic acids and / or other 1- to 4-basic aliphatic carboxylic acids in the polycondensation.
  • Suitable 1- or 2-basic hydroxycarboxylic acid Ren are for example glycolic acid, lactic acid, malic acid and tartaric acid. This group of acids can replace up to 70 mol% of butane tetracarboxylic acid as component a).
  • Suitable other di- to 4-basic aliphatic carboxylic acids are, for example, succinic acid, adipic acid, citric acid, oxalic acid, alkenyl succinic acids, alkyl succinic acids, aconitic acid, tricarballyl acid.
  • This group of carboxylic acids can replace up to 49 mol- '* of butane tetracarboxylic acid as component a) in the polycondensation.
  • the mono- or dianhydride or the mono- or diesters with C - to C 4 -alcohols of this carboxylic acid can also be used in the condensation.
  • component b) comprises polyhydroxy compounds from the group of the mono-, oligo- and polysaccharides, the reduced mono- or oligosaccharides and their amino derivatives, oxidized mono-, oligo- or polysaccharides, alkyl (poly ) glycosides, polyvinyl alcohols, oligoglycerols with more than 2 glycerol units or mixtures thereof.
  • Individual compounds from the group of the monosaccharides are, for example, glucose, manose and fructose, from the group of the oligosaccharides, sucrose, lactose, leucrose, isomaltulose, cellulose, maltose, glucose syrups and dextrins are mentioned as examples.
  • polysaccharides are starch, degraded starches, acidic, enzymatically or thermally degraded starches, oxidized starches, etherified starches such as carboxymethyl starch, hydroxypropyl starch, cellulose, methyl cellulose, hydroxymethyl cellulose, carboxymethyl cellulose, inulin, chitin, chitosan, pectins and Alginate.
  • Individual compounds from the group of reduced sugars and their aminated derivatives are, for example, sorbitol, mannitol, xylitol, inositol and aminosorbitol.
  • suitable sugar carboxylic acids are gluconic acid, glucaric acid, glucoheptonic acid, alginic acid, sucrose mono-, di- and tricarboxylic acids.
  • Suitable compounds b) are also alkyl glycosides and alkyl polyglycosides.
  • the alkyl group can contain 1-20, preferably 1-4 and 8-16, particularly preferably 12-14, carbon atoms.
  • Examples include methyl glucoside, butyl glucoside or the substance class of alkyl polyglycosides, as described in EP-A-0 357 696.
  • the alkyl group can be saturated or unsaturated, branched or unbranched.
  • the alkyl group can also be substituted, for example carry a hydroxyl group.
  • Suitable compounds of this type are, for example, hydroxyethyl glucoside and hydroxypropyl glucoside and the corresponding polyglucosides.
  • the polyglucosides contain an average of 1.1 to 10, preferably 1.3 to 3, glucoside units.
  • Suitable oligoglycerols contain 3 to 10 glycerol units.
  • Suitable oligoglycerols are, for example, triglycerol, tetraglycerol, pentaglycerol and hexaglycerol as well as polymers which have up to 10 glycerol units in the molecule.
  • Polyvinyl alcohols are also suitable as component b), all water-soluble polyvinyl alcohols being suitable. They generally have viscosities of 3 to 10,000, preferably 10 to 5,000, mPas (determined in a 10% strength aqueous solution at 20 ° C. using a Höppler ball falling viscometer in accordance with DIN 53 015).
  • the polyvinyl alcohols are usually produced by hydrolysis of polyvinyl acetate. They can be used in partially or completely hydrolyzed form in the preparation of the polycondensates according to the invention.
  • the molar masses of the polyvinyl alcohols are up to 100,000 and preferably up to 25,000. It is also possible to use oxidatively degraded polyvinyl alcohols as component (b).
  • Such degraded polyvinyl alcohols have molecular weights in the range from approximately 500 to 50,000.
  • the molecular weights of the polyvinyl alcohols are preferably 1,000 to 10,000.
  • the degree of hydrolysis of the polyvinyl alcohols produced from polyvinyl acetate is generally 50 to 100, preferably 85 up to 99%.
  • Component b) is preferably sorbitol, mannitol, methyl glucoside, gluconic acid, polyvinyl alcohols with molecular weights up to 15,000 and oligoglycerols with 3 to 10 glycerol units.
  • Component c) can optionally contain up to 20 mol%, based on component a), of C 2 -C 4 -alkylene glycols, polyalkylene glycols with a molar mass of up to 2,000 or monovalent, if appropriate with up to 50 mols Alkylene oxide alkylated C 4 - to C *; o-alcohols are used.
  • Examples of individual compounds of component c) are ethylene glycol, propylene glycol, 1,4-butanediol, polyethylene glycols and polypropylene glycols with molar masses of up to 2,000, block copolymers of ethylene oxide and propylene oxide with molar masses of up to 2,000, butanol, lauryl alcohol or Stearyl alcohol.
  • the polycondensates are produced by condensing components a) and b). This creates polyester.
  • the condensation is carried out to such an extent that condensation products with a K value of 8 to 100, preferably 10 to 60, (determined according to H. Fikentscher in 2% strength by weight aqueous solution at 25 ° C. and pH 7 on sodium hydroxide) salting of the condensation products).
  • the condensation can be carried out in inert organic solvents or in a melt the reactants are carried out. Which method is the most suitable depends on the nature of component b). Insoluble polysaccharides b) are preferably used in the finest possible form.
  • an aqueous solution of components a) and b) can be partially neutralized by adding sodium hydroxide solution or another base such as potassium hydroxide solution or ammonia, ethanolamine, triethanolamine, diethanolamine, morpholine or alkylamines.
  • sodium hydroxide solution or another base such as potassium hydroxide solution or ammonia, ethanolamine, triethanolamine, diethanolamine, morpholine or alkylamines.
  • the water is then largely distilled off at temperatures from 50 to 120 ° C., and the temperature of the reaction mixture is then increased to 100 to 220, preferably 120 to 170 ° C.
  • the process variant in which one assumes a water-containing melt of the reaction participants and the water is distilled off at temperatures of 120 to 220 ° C. is preferred.
  • the butanetetracarboxylic acid is used in a stoichiometric amount compared to the polyhydroxy compounds, in particular if they have higher molar masses, in order to avoid crosslinking of the
  • Suitable diluents are, for example, monobasic aliphatic carboxylic acids, such as formic acid, acetic acid, propionic acid, lauric acid, palmitic acid, stearic acid, coconut fatty acid, tallow fatty acid, oleic acid and mixtures thereof.
  • the condensation is carried out under increased pressure. This is especially the case when using formic acid, acetic acid and propionic acid.
  • the readily volatile monobasic aliphatic carboxylic acids serve both as diluents and as entraining agents for the water formed during condensation.
  • the difficultly volatile carboxylic acids, which are used to lower the viscosity, can remain in the condensation product.
  • the condensation In the condensation, viscous melts are obtained, some of which become solid as conversion progresses or when they cool to room temperature.
  • the condensation is preferably carried out in an inert gas stream or under reduced pressure. If the condensation of components a), b) and optionally c) is carried out in an inert organic solvent, it is preferably carried out in suspension.
  • the compounds which are suitable as component a) can be introduced into the reactor together with the inert solvent and, if appropriate, a protective colloid, and components b) can be added batchwise or continuously and by boiling under reflux and distilling off the water formed in the reaction the reaction mixture are condensed.
  • Suitable organic solvents are, for example, toluene, o-, m- and p-xylene, mesitylene, Cu ol, higher-boiling aliphatic hydrocarbon (boiling range from 120 to 160 ° C.) and mixtures of these solvents.
  • the abovementioned solvents can also be used with polar aprotic solvents. agents such as ethylene glycol dimethyl ether, diethylene glycol diethyl ether, dioxane and / or cyclohexanone are used. In some cases it can be advantageous to carry out the condensation in the presence of protective colloids which then disperse the condensate formed and prevent the formation of a viscous mass which solidifies after cooling.
  • Suitable protective colloids are, for example, alkylated polyhydric C 2 to Ca alcohols, such as the reaction products of 3 to 35 mol of ethylene oxide and / or propylene oxide with glycerol, oligoglycerol or pentaerythritol.
  • the protective colloids can additionally contain Cg to C 22 alkyl groups bonded via ether, ester or amide bonds.
  • the amount of protective colloid in the condensation is 0.05 to 5% by weight, based on the polyester. If an inert organic solvent is used in the condensation, the concentration of the solids, ie the polyester formed, in the inert diluent is 10 to 70, preferably 20 to 65% by weight.
  • Control of the progress of the reaction in the esterification can be determined in all process variants by determining the amount of water distilled off from the reaction mixture. Since the acid number and the viscosity of the reaction mixture also change during the esterification, the course of the esterification can be checked by determining these measurands on samples taken from the reaction mixture.
  • the esterification of components a), b) and optionally c) is preferably carried out in the melt in the absence of catalysts. However, the use of customary acidic catalysts, which are usually used in esterification reactions, is possible.
  • the condensation in the melt can be carried out in the usual flasks or kettles, each of which is equipped with a stirrer.
  • a reactor which has a more powerful mechanical mixing device than a vessel provided with a conventional stirrer.
  • an evacuable kneading reactor with a vertical or horizontal shaft, inert gas supply and distillation device is particularly suitable.
  • Other suitable reactors are, for example, condensation extrusion reactors which allow melt condensation in a first reaction zone by distilling off the water of reaction and in which the melt is then extruded in a shaping zone. The extruded strands are distributed or pulverized into a lumpy reaction product.
  • Components a) and b) are used in the condensation in a weight ratio of 50: 1 to 0.5: 1, preferably 10: 1 to 1: 1.
  • the weight ratio of components (a): (b) in the condensation is preferably 40: 1 to 4: 1.
  • polycondensates by condensation of a) butane-1,2,3,4-tetracarboxylic acid as the sole component a) with b) sorbitol, mannitol, gluconic acid, methylglucoside, oligoglycerol with 3-10 is particularly preferred Glycerol units, polyvinyl alcohol or mixtures thereof with a): b) weight ratio of 10: 1 to 1: 1.
  • Portions of component a) used with stoichiometry favor the process of condensation in the melt. They can remain in the product as monomers or oligomers or can be partially or completely separated from the polycondensate by ultrafiltration, extraction or precipitation.
  • the degree of esterification of the hydroxyl groups of the polyhydroxy compounds of component b) is at least 10, preferably 15 to 100%.
  • the polyester carboxylates obtainable in this way are biodegradable. For example, over 85% of the reaction product of sorbitol with 6 mol of butane tetracarboxylic acid is degraded within 28 days (determined according to the Zahn-Wellens test, static test according to DIN 38 412, part 24.
  • the polycarboxylates can be used in the acid form or in partially neutralized form, if component a) has been partially neutralized during the manufacture of the products, directly after use. But you can also completely neutralize.
  • the salts of the polycondensates are obtained by customary neutralization with bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, sodium, potassium, lithium, calcium, ammonium carbonate or hydrogen carbonate, ammonium hydroxide, ethanolamine, diethanolamine or trietha - nolamine.
  • bases are preferably used as aqueous solutions for neutralization. Neutralization with sodium hydroxide solution is preferred. Soda or sodium bicarbonate carried out, the pH being monitored continuously so that the polyester hydrolysis is as low as possible.
  • polyesters obtained in the condensation without modification by hydrolysis they can be isolated from the neutralized aqueous solution, preferably in the form of the neutral sodium salt. Freeze drying, spray drying or spray fluidized bed drying of the aqueous solutions is suitable for this.
  • the aqueous solution can be dried without further additives or with a mixture with washing-active substances.
  • the polycondensates described above are used as additives in low-phosphate or phosphate-free detergents and cleaning agents. gene from 0.1 to 30 wt .-%, based on the washing and cleaning agents used.
  • Low-phosphate detergents are understood to mean those formulations which contain no more than 25% by weight of phosphate, calculated as sodium triphosphate.
  • the polyesters are preferably used in amounts of 0.5 to 15% by weight, based on the detergent or cleaning agent formulation.
  • the polycondensates in the detergent fleet have good dispersibility for particle dirt, especially for clay minerals (clay). This property is important because loamy dirt from textile goods is widespread.
  • the polyesters are builders for detergents and reduce the incrustation and graying on the washed fabric during the washing process. They are therefore also suitable as incrustation and graying inhibitors.
  • composition of the washing and cleaning formulations can be very different.
  • Detergents and cleaning agents usually contain 2 to 50% by weight of surfactants and optionally builders. This information applies to both liquid and powder detergents. Examples of the composition of detergent formulations which are common in Europe, the USA and Japan can be found, for example, in Chemical and Engn. News, Vol. 67, 35 (1989) tabulated. Further information on the composition of detergents and cleaners can be found in WO-A-90 13581 and Ulimann's Encyclopedia of Industrial Chemistry, Verlag Chemie, Weinhein 1983, 4th edition, Pages 63-160 are taken. Also of interest are detergent formulations which contain up to 60% by weight of an alkali silicate and up to 10% by weight of a polycondensation product according to the invention.
  • alkali silicates examples include the 5 amorphous sodium disilicates which are described in EP-A-0 444 41, and crystalline sheet silicates which, according to EP-A-0 337 219, are contained in detergent formulations as builders and according to EP -B-0 164 514 are used for softening water, and sodium silicates, which are obtainable by dewatering 10 sodium silicate solutions and drying to water contents of 15 to 23, preferably 18 to 20% by weight.
  • detergents can also contain a bleaching agent, e.g. Sodium perborate, which in case of its use in quantity
  • the detergents and cleaning agents can optionally contain further conventional additives, e.g. Complexing agents, citrates, opacifiers, optical brighteners, enzymes, perfume oils, color transfer inhibitors, graying inhibitors and / or lead actives
  • the K values of the polyesters were determined according to H. Fikentscher, Cellulose Chemie, Vol. 13, 58 to 64 and 71 to 74 (1932) in an aqueous solution at a temperature of 25 ° C. and a concentration of 25 2% by weight. determined at pH 7 on the sodium salt of the polyester.
  • the percentages in the examples mean% by weight.
  • the polyaddition product has a K value of 15.3.
  • the removal of particle dirt from tissue surfaces is supported by the addition of polyelectrolytes.
  • the stabilization of the dispersion resulting from the detachment of the particles from the tissue surface is an important task of these polyelectrolytes.
  • the stabilizing influence of the anionic dispersants results from the fact that, owing to the adsorption of dispersant molecules on the solid surface, their surface charge is increased and the repulsive energy is increased.
  • Other factors influencing the stability of a dispersion include steric effects, temperature, pH value and the electrolyte concentration.
  • Finely ground china clay SPS 151 is used as a model for particulate dirt.
  • 1 g of clay is intensively dispersed in a standing cylinder (100 ml) for 10 minutes with the addition of 1 ml of a 0.1% sodium salt solution of the polyelectrolyte in 98 ml of water.
  • a 2.5 ml sample is taken from the center of the standing cylinder and, after dilution to 25 ml, the turbidity of the dispersion is determined using a turbidimeter. After the dispersion has stood for 30 or 60 minutes, samples are taken again and the turbidity determined as above.
  • the turbidity of the dispersion is specified in NTU (nephelometric turbidity units). The less the dispersion settles during storage, the higher the measured turbidity values and the more stable the dispersion.
  • the measured values show that the polycondensates according to the invention are good dispersants for clay.
  • Clay minerals are colored and, when deposited on the fabric, give it a color veil.
  • a fabric soiled with clay was produced by mixing cotton / polyester fabric with a clay mixture consisting of 33.3% each of the types 178 / R (ocher), 262 (brown) and 84 / rf (red-brown) from Carl Jäger, Hilgert, evenly coated.
  • the types of clay are different "bold”; ie they differ in the content of aluminum, iron and manganese oxide.
  • the clay mixture was homogeneously applied to the tissue in the form of a 20% suspension in deionized water with vigorous pumping around the suspension.
  • Washing machine Launder-o-meter
  • the fabric After rinsing, the fabric is spun and the fabrics are hung up to dry individually.
  • the fabric is measured with an Elrepho 2000 from Data Color, Heidenheim, namely 6 measuring points per piece of fabric.
  • the wavelength range used for the evaluation is 420-700 nm.
  • the reflectance is measured as a function of the wavelength.
  • Barium sulfate serves as a reference. According to W. Baumann, R. Broßmann, BT Groebel, N. Kleinemeier, M. Krayer, AT Leaver and H.-P. Oesch; Melliand Textilberichte 67 (1986), 562 ff. Calculated the color strength without weighting the eye irritation function.
  • the primary wash efficiency in% is calculated using the following equation: (fs.b - fs, a) /(fs.b - ⁇ , O '' 100
  • fs, b color strength of the soiled fabric (clay fabric) before washing.
  • the table shows that by adding the claimed compounds, the primary washing action is higher than without addition. These compounds thus positively support the washing effect.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
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Abstract

Polycondensats obtenus par condensation (a) d'acide butan-1,2,3,4- tétracarboxylique mélangé éventuellement à des acides hydroxycarboxyliques ou à d'autres acides carboxyliques, avec (b) des composés polyhydroxy appartenant au groupe des mono, oligo et polysaccharides, des mono ou oligosaccharides réduits et de leurs dérivés amino, des mono, oligo ou polysaccharides oxydés, des alkyl(poly)glucosides, alcools polyvinyliques, oligoglycérines ayant plus de deux motifs glycériniques ou des mélanges de ces produits et, éventuellement, (c) jusqu'à 20 % en moles par rapport aux composants (a), en alkylèneglycols, polyalkylèneglycols ou alcools monovalents en C4 à C20, dans un rapport pondéral (a):(b) de 50:1 à 0.5:1, les produits de condensation ayant une valeur K de 8 à 100 (déterminée selon H. Fikentscher, dans une solution aqueuse à 2 % en poids, à 25 °C et à pH 7, sur des sels de sodium des produits de condensation). L'invention concerne également l'utilisation de ces polycondensats comme additifs pour des produits de lavage et des produits détergents exempts de phosphates ou à faible teneur en phosphates, à raison de 0,1 à 30 % en poids par rapport aux produits.
PCT/EP1992/002848 1991-12-20 1992-12-10 Polycondensats d'acide butantetracarboxylique et de composes polyhydroxy et leur utilisation dans des produits de lavage et des produits detergents WO1993013192A1 (fr)

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DEP4142131.0 1991-12-20
DE19914142131 DE4142131A1 (de) 1991-12-20 1991-12-20 Polykondensate aus butantetracarbonsaeure und polyhydroxyverbindungen und ihre verwendung in wasch- und reinigungsmitteln

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EP0752468B1 (fr) * 1995-07-06 2003-08-27 Unilever Plc Polyétheresters antisalissure et compositions détergentes les contenant
DE19916208B4 (de) 1999-04-10 2006-05-04 Cognis Ip Management Gmbh Sonnenschutzmittel

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CH476780A (fr) * 1966-06-13 1969-08-15 Pechiney Saint Gobain Procédé de préparation de résines alkydes
DE2147778A1 (de) * 1971-09-24 1973-03-29 Knapsack Ag Gerueststoffe fuer wasch- und reinigungsmittel
JPS5092306A (fr) * 1973-12-21 1975-07-23
US3941771A (en) * 1973-08-22 1976-03-02 Fmc Corporation Dextrin carboxylates and their use as detergent builders
JPH03287888A (ja) * 1990-03-29 1991-12-18 Kao Corp 古紙再生用脱墨剤

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Publication number Priority date Publication date Assignee Title
BE654653A (fr) * 1963-10-26 1965-04-21
CH476780A (fr) * 1966-06-13 1969-08-15 Pechiney Saint Gobain Procédé de préparation de résines alkydes
DE2147778A1 (de) * 1971-09-24 1973-03-29 Knapsack Ag Gerueststoffe fuer wasch- und reinigungsmittel
US3941771A (en) * 1973-08-22 1976-03-02 Fmc Corporation Dextrin carboxylates and their use as detergent builders
JPS5092306A (fr) * 1973-12-21 1975-07-23
JPH03287888A (ja) * 1990-03-29 1991-12-18 Kao Corp 古紙再生用脱墨剤

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Title
WPI, AN=76-06222X (04), Derwent Publications Ltd, (London, GB), & JP,A,50092306 (MITSUI TOATSU CHEM. INC.) 23. Juli 1975, siehe Zusammenfassung *
WPIL, AN=92-044622 (06), Derwent Publications Ltd, (London, GB), & JP,A,3287888 (KAO CORP.) 18. Dezember 1991, siehe Zusammenfassung *

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