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
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
  • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Definitions

• the invention relates to detergent formulations which are free of phosphates, zeolites and crystalline phyllosilicates and which contain polymers with biodegradability as builder substances.
• the function of the detergent builder is mainly to eliminate the calcium and magnesium ions from the water or the dirt by complexing, dispersing and sequestering from the washing process and to support the washing action of the surfactants.
• the builders prevent tissue deposits, reduce the incrustation of the textiles and improve the primary washing effect.
• the zeolites or crystalline layered silicates contained in the abovementioned agents are not environmentally hazardous, but they do Disadvantage that they contribute to a significant increase in the amount of sewage sludge. For this reason, attempts have been made in the past to also dispense with the use of water-softening silicates in phosphate-free detergent powders.
• formulations which contain surfactants, biodegradable copolymers, washing alkalis, adjusting agents and other functional auxiliaries.
• the detergents according to the invention can contain anionic, nonionic or cationic surfactants a.
• anionic, nonionic or cationic surfactants a In Central Europe, mixtures of anionic and nonionic products are typically used, which show synergistic washing effects and are often combined with soaps. However, only anionic or nonionic surfactants can also be used.
• the amount of surfactant a is preferably 5 to 40% by weight, with contents of 7 to 25% by weight being very particularly preferred.
• Sulfonate type surfactants are e.g. B. C11-C13 alkylbenzenesulfonates, C13-C17 alkanesulfonates and ester sulfonates with chain lengths of 12 to 20 carbon atoms.
• Suitable surfactants of the sulfate type are, for example, the sulfuric acid monoesters from fatty alcohols of synthetic and native origin, such as. B. coconut oil alcohol, tallow fatty alcohol, oleyl alcohol or C10-C20 oxo alcohols.
• fatty alcohol ether sulfates such as. B. lauryl ether sulfate can be used.
• anionic surfactants are also soaps, for. B. saturated fatty acid soaps, such as the alkali or alkanolamine soaps of lauric acid, myristic acid, palmitic acid and stearic acid.
• Natural fatty acids e.g. B. from coconut, palm kernel or tallow fatty acids, derived soap mixtures.
• Suitable nonionic surfactants are, for example, adducts of ethylene oxide and / or propylene oxide with alkylphenols, oxo alcohols or native fatty alcohols, fatty acids, fatty amines and fatty acid amides.
• alkylphenols oxo alcohols or native fatty alcohols
• fatty acids fatty acids
• fatty amines and fatty acid amides fatty acid amide
• the addition products of 3 to 15 mol of ethylene oxide with coconut oil and tallow fatty alcohols, with oleyl alcohol or with synthetic alcohols with 8 to 18 carbon atoms are particularly important.
• surfactants of the type of C8-C18 alkyl polyglucosides such as. B. C10-C12 and C12-C16 alkyl polyglucosides, and amine oxides can be used.
• cationic surfactants and amphoteric products such as ampholytes and betaines can also be used.
• the detergents according to the invention also contain the copolymers b.
• the amount of b is preferably 5 to 40% by weight, proportions of 5 to 20% by weight being very preferably set.
• Monomers of group A are monoethylenically unsaturated C4-C8 dicarboxylic acids, their anhydrides or their alkali and / or ammonium salts and / or amine salts.
• Suitable dicarboxylic acids are, for example, maleic acid, fumaric acid, itaconic acid and methylene malonic acid.
• Maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and the corresponding sodium, potassium or ammonium salts of maleic or itaconic acid are preferably used.
• the group A monomers are preferably present in the monomer mixture in an amount of 10 to 70% by weight, more preferably 20 to 60% by weight and very particularly preferably 25 to 55% by weight.
• Monomers of group B are monoethylenically unsaturated C3-C10 monocarboxylic acids and their alkali and / or ammonium salts and / or amine salts. These monomers include, for example, acrylic acid, methacrylic acid, dimethylacrylic acid, ethyl acrylic acid, vinyl acetic acid and allylacetic acid. From this group of monomers, preference is given to using acrylic acid, methacrylic acid, their mixtures and the sodium, potassium or ammonium salts or mixtures thereof.
• the group B monomers are preferably 20 to 85% by weight, particularly preferably 25 up to 60% by weight and very particularly preferably 30 to 60% by weight, are present in the monomer mixture.
• the group C monomers include those which, after copolymerization and subsequent hydrolysis or saponification of the polymer, release one or more hydroxyl groups which are covalently bonded directly to the C-C polymer carbon chain. Examples include: vinyl acetate, vinyl propionate, methyl vinyl acetate, methyl vinyl ether, ethylene glycol monovinyl ether and vinylidene carbonate.
• the group C monomers are preferably present in the monomer mixture in an amount of 1 to 50% by weight, particularly preferably 4 to 40% by weight and very particularly preferably 8 to 30% by weight.
• group D monomers that can be used to modify the copolymers are, for. B. sulfone groups and sulfate group-containing monomers, such as meth (allylsulfonic acid), vinylsulfonic acid, styrene sulfonic acid, acrylamidomethylpropanesulfonic acid and monomers containing phosphonic acid groups, such as vinylphosphonic acid, allylphosphonic acid and acrylamidomethylpropanephosphonic acid and their salts, and hydroxyethyl (meth) acrylate sulfates, allyl sulfates.
• sulfone groups and sulfate group-containing monomers such as meth (allylsulfonic acid), vinylsulfonic acid, styrene sulfonic acid, acrylamidomethylpropanesulfonic acid and monomers containing phosphonic acid groups, such as vinylphosphonic acid, allylphosphonic acid and acrylamidomethylpropan
• group D monomers it is also possible - because of the required solubility, but only in a limited amount - to use double-ethylenically unsaturated non-conjugated compounds and polyalkylene glycol esters of (meth) acrylic acid and polyalkylene glycol ether with (meth) allyl alcohol, which may or may not be end-capped.
• the group D monomers are optionally present in the monomer mixture up to 15% by weight, preferably up to 10% by weight.
• the copolymers can be prepared by radical polymerization in an aqueous medium. Such a polymerization is described in German patent application 43 00 772.
• the polymers obtained in aqueous solution can, if necessary, be converted into pulverulent products by drying methods, in particular spray drying processes.
• the copolymers act as dispersants and complexing agents. With them polyvalent metal ions, e.g. B. Ca, Mg and Fe ions, bound in water-soluble complexes. The copolymers disperse unusual water hardness and dirt particles. The products are characterized by their biodegradability. On the use of previously used complexing and dispersing agents, such as. B. of phosphates, phosphonates, poorly degradable polyacrylates, nitrilotriacetic acid and its salts, ethylenediaminetetraacetic acid and its salts, which have ecological disadvantages, can generally be dispensed with or the amounts of the abovementioned agents can be reduced.
• complexing and dispersing agents such as. B. of phosphates, phosphonates, poorly degradable polyacrylates, nitrilotriacetic acid and its salts, ethylenediaminetetraacetic acid and its salts, which have ecological disadvantages, can generally be dispensed with or the
• copolymers with water-softening silicates such as. B. zeolites and crystalline layered sodium silicates can be combined. This increases the performance as a cobuilder.
• water softening silicates are accepted. - The combinations mentioned are not the subject of this invention.
• the copolymers are biodegradable if they are used in the modified OECD Sturm test (EC Directive 84/449 / EEC C 5 and OECD Guideline 301 B) (see, for example, soap-oil-fat waxes 117 (1991), 740 to 744), have a degree of degradation of ⁇ 60%.
• Usable washing alkalis c are water-soluble, alkaline salts, such as alkali carbonates, alkali bicarbonates and alkali hydroxides.
• the group of washing alkalis also includes the water-soluble alkali metal silicates, which also have corrosion-inhibiting properties, such as. B. sodium metasilicates and sodium disilicates.
• the proportion of washing alkalis in the compositions is preferably 5 to 50% by weight.
• inorganic neutral salts such as e.g. As sodium sulfate or sodium chloride can be used. If such products are used, they are preferably dosed in amounts of 5 to 60% by weight.
• the detergent formulations can contain further functional auxiliaries described below.
• peroxo compounds such as sodium perborate mono- and tetrahydrate and percarbonates are used.
• the bleaching agents are dosed in amounts of 0 to 30% by weight, with amounts of 5 to 20% by weight being preferred.
• oxygen bleaching can be carried out by activators such.
• B. Tetraacetylethylenediamine (TAED) can be improved.
• the bleach activator TAED is usually used in amounts of 0 to 10% by weight, portions of 2 to 7% by weight being preferred.
• the formulations can also contain further dispersing and complexing agents.
• Suitable products are, for example, citrates, phosphonates, biodegradable homopolymers and copolymers of acrylic acid, isoserine diacetic acid, polyaspartic acid, ethylenediaminetetraacetic acid and nitrilotriacetic acid and the alkali metal salts of the aforementioned substances.
• Such substances are contained in the detergents in concentrations of 0 to 50% by weight, preferably in amounts of 0.5 to 20% by weight.
• Graying inhibitors such as carboxymethyl cellulose and carboxymethyl starches, can also be used.
• the products increase the dirt-carrying capacity of the washing liquors and are typically contained in amounts of 0 to 2% by weight.
• the formulations can optionally also contain enzymes, in particular proteases, amylases and lipases. These enzymes are typically dosed in amounts of 0 to 5% by weight.
• the detergent formulations according to the invention can furthermore contain defoamers, trickling aids, optical brighteners, color transfer inhibitors and fragrances and dyes.
• the detergents according to the invention can be powdery types or granules.
• the powder detergents can be prepared by mixing the solid ingredients and, if appropriate, by spraying on the liquid constituents or by spray-drying an aqueous, liquid to pasty batch of the starting components.
• Granulated products can e.g. B. by extrusion of pasty premixes.
• the formulations according to the invention can be used as textile detergents in the household sector and in commercial cleaning processes.
• the copolymers b contained in the formulations have an excellent binding capacity for alkaline earth metal ions and a high dispersibility, so that the use of water-softening silicates, such as zeolites or crystalline sodium layered silicates, can be dispensed with.
• the detergents according to the invention bring about good soil detachment and soil dispersion and lead only to a slight incrustation when washing the textiles with hard water.
• the agents can be highly foaming formulations, such as those used in hand washing, or else foam-regulating surfactant systems used in machine washing.
• the formulations according to the invention are better or at least equally good in their effectiveness.
• the formulations now claimed also have improved biodegradability.
• a copolymer with an average molar mass of approximately 15,000 g / mol is obtained by radical polymerization of the sodium maleinate from 35% by weight of maleic anhydride, 45% by weight of acrylic acid and 20% by weight of vinyl acetate in aqueous solution and saponification.
• the copolymer obtained in aqueous solution is converted into a powdery product by spray drying.
• the biodegradability of the copolymers is tested in accordance with the modified OECD Sturm test in accordance with EC Directive 84/449 / EEC C 5 and OECD Guideline 301 B.
• a degree of degradation of over 60% is determined for the substance mentioned in Example 1.
• polycarboxylates such as. B. homopolyacrylates and copolymers of acrylic acid and maleic acid, on the other hand, have lower biodegradability.
• detergents of the following composition are produced (data in% by weight): Detergent powder 1 % 2% n-alkylbenzenesulfonate, Na salt 5.0 4.5 C12-C14 fatty alcohol ethoxylate-7-EO 7.0 5.0 Soap 5.0 7.0 Copolymer, powdery 15.0 10.0 sodium 30.0 25.0 Sodium bicarbonate - 25.0 Sodium perborate tetrahydrate 15.0 15.0 Sodium sulfate, light 23.0 8.5 Detergent powder 3% 4% 5% C12-C18 fatty alcohol sulfate, Na salt - 2.0 15.0 C12-C14 fatty alcohol oxyethylate-7-EO - 5.0 4.0 C13-oxo alcohol ethoxylate mixture (9 EO, 3 EO) 9.0 - - Soap - 5.0 2.0 Copolymer, powdery 15.0 20.0 8.0 sodium 15.0 25.0 8.0 Sodium bicarbonate 26.0 25.0
• a comparative formulation V1 is prepared using the commercially available polycarboxylate Sokalan CP 5 (BASF, acrylic acid-maleic acid copolymer, Na salt, average molar mass 70,000 g / mol): Comparative formulation V1% n-alkylbenzenesulfonate, Na salt 5.0 C12-C14 fatty alcohol ethoxylate-7-EO 7.0 Soap 5.0 Polycarboxylate, powdery 15.0 sodium 30.0 Sodium perborate tetrahydrate 15.0 Sodium sulfate, light 23.0
• Table 1 shows the ash content as a measure of the deposits.
• Table 1 formulation 1 2nd 3rd V1 Ash content (%) 0.47 0.46 0.43 0.51

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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)

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• 1993
  • 1993-08-04 DE DE4326129A patent/DE4326129A1/de not_active Withdrawn
• 1994
  • 1994-06-15 AT AT94109139T patent/ATE197468T1/de not_active IP Right Cessation
  • 1994-06-15 DE DE59409578T patent/DE59409578D1/de not_active Expired - Fee Related
  • 1994-06-15 EP EP94109139A patent/EP0637627B1/fr not_active Expired - Lifetime
  • 1994-08-03 US US08/285,279 patent/US5496495A/en not_active Expired - Fee Related

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