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
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
• • 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
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/22—Carbohydrates or derivatives thereof
  • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
  • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
• • 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

• CMC carboxymethyl cellulose
• MC methyl cellulose
• EP 25 551-B1 teaches the use of copolymers of 90 to 40% by weight of acrylic acid or with methacrylic acid and 10 to 60% by weight of maleic acid as incrustation inhibitors in low-phosphate detergents.
• these copolymers are intended to prevent the formation of laundry encrustations which, owing to the reduced phosphate content, can form when washing with hard water.
• the phosphate content is 12.5 to 27% by weight, based on dry matter.
• Phosphate-free or zeolite-containing detergents were obviously not investigated and - like the problem of preventing graying - not included in the consideration.
• EP 66 915-A2 which is based on the known teaching of the aforementioned patent, is also the use of acrylic acid-maleic acid copolymers (molar ratio 4: 1 to 1: 4) as an additive to detergents with a reduced phosphate content and additional active ingredients, such as Foam inhibitors, photoactivators, polyamines and peracid activators.
• additional active ingredients such as Foam inhibitors, photoactivators, polyamines and peracid activators.
• the task was to develop a system which is suitable in phosphate-free detergents containing zeolites as phosphate substitutes to counteract the graying of the textiles to be washed from different types of fiber material. This object is achieved by the invention described below.
• the mixing ratio is preferably 1 part by weight of MC (component a) to 2 to 3 parts by weight of CMC (component b) to 4 to 8 parts by weight of copolymers (component c).
• the components (b) and (c) are expediently present as sodium salts.
• the cellulose ethers are known technical products.
• the copolymer acrylic acid or methacrylic acid and maleic acid (component c) or its preparation is characterized in more detail in EP 25 551-B1 and in the journal "Tenside” 16 (1979), pages 82-89. Copolymers of acrylic acid and maleic acid are preferably used.
• the graying inhibitor consisting of components a, b and c comes in the phosphate-free or low-phosphate detergents in amounts of 0.3 to 6% by weight, preferably in amounts of 0.6 to 4% by weight and in particular in amounts of 0.8 to 3% by weight is used.
• the MC content of the agents is then generally 0.05 to 1.0% by weight, CMC 0.1 to 2.0% by weight and copolymers 0.2 to 3% by weight.
• the agents preferably contain 0.1 to 0.5% by weight of MC, 0.3 to 1.0% by weight of CMC and 0.5 to 2.0% by weight of copolymer, taking into account the quantitative ratios mentioned above.
• Low-phosphate is understood to mean detergents whose calculated phosphorus content is at most 5% by weight and preferably less than 3% by weight in the form of phosphate or polyphosphate.
• the agents are phosphate-free.
• the sodium aluminosilicates of the NaA zeolite type can also contain a minor amount of those of the NaX zeolite and / or hydrosodalite type. These proportions are advantageously below 30%, preferably below 20%, based on sodium aluminosilicates.
• Optional components are so-called co-builders, such as polyphosphonic acids or their sodium, potassium or ammonium salts, the ammonium salts also being the salts derived from organic ammonium bases, such as mono-, di- or triethanolamine.
• Suitable polyphosphonic acids are 1-hydroxyethane-1,1-diphosphonic acid, aminotri- (methylenephosphonic acid), ethylenediaminetetra- (methylenephosphonic acid) and their higher homologs, such as, for example, diethylenetriamine-tetra- (methylenephosphonic acid).
• co-builders are complexing aminopolycarboxylic acids. These include in particular alkali salts of nitrilotriacetic acid and ethylenediaminotetraacetic acid.
• the agents may also contain phosphate-free skeletal salts and washing alkalis, which include the alkali silicates, alkali carbonates or bicarbonates, alkali borates and alkali sulfates, preferably in the form of the sodium salts.
• the sodium silicate can have a ratio of Si0 2 to Na 2 0 of 1: 1 to 1: 3.5.
• customary anionic and nonionic surfactants can be used as components of the detergents.
• Suitable anionic surfactants are those of the sulfonate or sulfate type, in particular alkylbenzenesulfonates, olefin sulfonates, alkyl sulfonates and ⁇ -sulfofatty acid esters, primary alkyl sulfates and the sulfates of ethoxylated, 2 to 3 glycol ether groups having higher molecular weight alcohols.
• alkali soaps of fatty acids of natural or synthetic origin for example the sodium soaps of coconut, palm or tallow fatty acids and, if foam control is desired, also those of hydrogenated rapeseed or fish oil fatty acids.
• Alkyl betaines and especially alkyl sulfobetaines are suitable as zwitterionic surfactants.
• the anionic surfactants are preferably in the form of the sodium salts. If the anionic and zwitterionic compounds mentioned have an aliphatic hydrocarbon radical, this should preferably be straight-chain and have 12 to 18 carbon atoms. In the compounds having an araliphatic hydrocarbon radical, the preferably unbranched alkyl chains contain 6 to 16, in particular 10 to 14, carbon atoms.
• Suitable nonionic surfactants are ethoxylated alcohols with 12 to 18 carbon atoms and an average of 3 to 20, preferably 5 to 15, glycol ether groups.
• Particularly suitable are mixtures of ethoxylated, primary C 14 -C 15 -alcohol, such as tallow fatty alcohol or oleyl alcohol, some of which have 10 to 16 glycol ether groups and a second part 3 to 7 glycol ether groups.
• the quantitative ratio of the two parts can be, for example, 4: 1 to 1: 4.
• nonionic surfactants are those which are derived from the abovementioned compounds and have both ethylene glycol and propylene glycol ether groups, for example alcohols with 10 to 30 ethylene glycol ether groups and 1 to 30 propylene glycol ether groups; also ethoxylation products of alkylphenols, fatty acid amides and fatty acids.
• the water-soluble polyethylene oxide adducts containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups on polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol with 1 to 10 carbon atoms in the alkyl chain can also be used.
• the compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
• Nonionic compounds of the amine oxide and sulfoxide type which can optionally also be ethoxylated, can also be used.
• Neutral salts in particular sodium sulfate, and magnesium silicate acting as a stabilizer for per compounds also come into consideration as further constituents.
• Further washing aids are optical brighteners and additives which improve the powder structure, for example alkali metal salts or toluene, cumene or xylene sulfonic acid.
• Suitable optical brighteners are alkali metal salts of 4,4-bis- (2 "-anilino-4" -morpholino-1,3,5-triazinyl-6 "-amino) -stilbene-2,2'-disulfonic acid or compounds of the same structure, which carry a diethanolamino group, a methylamino group or a ⁇ -methoxyethylamino group instead of the morpholino group.
• Brighteners of the substituted diphenylstyryl type are also suitable, for example the alkali metal salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4 ' -Bis (4-chloro-3-sulfostyryl) diphenyl and 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl.
• enzymes from the class of proteases, lipases and amylases or their mixtures are enzymes from the class of proteases, lipases and amylases or their mixtures. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. The enzymes can be embedded in coating substances or subsequently granulated onto the spray-dried second powder component. Fragrances and foam suppressants, such as silicones or paraffin hydrocarbons, are also generally added to the spray-dried second powder component to avoid loss of effectiveness.
• the perhydrates and per-compounds commonly used in washing and bleaching agents are suitable as bleaching components.
• the perhydrates preferably include sodium perborate, which can be present as a tetrahydrate or as a monohydrate, furthermore the perhydrates of sodium carbonate (sodium percarbonate), sodium pyrophosphate (perpyrophosphate), sodium silicate (persilicate) and of urea. These perhydrates are preferably used together with bleach activators.
• the bleach activators include in particular N-acyl compounds and 0-acyl compounds.
• suitable N-acyl compounds are polyacylated alkylenediamines, such as tetraacetylmethylene diamine, tetraacetylethylene diamine and their higher homologues, and acylated glycolurils, such as tetraacethylglycoluril.
• N-alkyl-N-sulfonyl-carbonamides N-acylhydantoins
• N-acylated cyclic hydrazides triazoles, urazoles, diketopiperazines, sulfurylamides, cyanurates and imidazolines.
• acylated sugars such as glucose pentaacetate are particularly suitable as 0-acyl compounds.
• Preferred bleach activators are tetraacetylethylene diamine and glucose pentaacetate.
• the bleach activators can be coated with coating substances in order to avoid interactions with the per-compounds, particularly during the storage of powdery mixtures, as is the case, for example, in DE-PS 11 62 967, DE-PS 21 38 584, DE-PS 22 20 296, DE -OS 23 38 412, DE-OS 26 50 429 and DE-OS 30 11 998 is described.
• Particularly suitable coating substances are water-soluble polymers, such as polyethylene glycol, cellulose ethers, cellulose esters, water-soluble starch ethers and starch esters, and nonionic surfactants of the alkoxylated alcohol, alkylphenol, fatty acid and fatty acid amide type.
• the polyphosphonic acids to be used according to the invention can be coated or coated before Bleach activators are mixed with these so that they are enclosed together with them by the wrapping material. This can have an additional stabilizing effect.
• the graying inhibitor mixture according to the invention can also be present in liquid to pasty preparations.
• the mixture of components a, b and c can also be in the form of a separate powdery to granular mixture which, as required, is added to a detergent or a detergent solution immediately before use, for example in order to increase its effectiveness or expand its range of use.
• the graying inhibitor mixture according to the invention is suitable for all types of textiles, for example those made from cellulose fiber, finished cellulose, from partially synthetic fibers, such as rayon and rayon, and from fully synthetic fabrics, for example those made from polyamide and polyester fibers, and also mixed fabrics made from the aforementioned fiber materials. They are characterized, in particular when used in low-phosphate or phosphate-free detergents or wash liquors containing zeolites, by surprisingly high graying-preventing properties which exceed the sum of the effects of the individual components.
• a phosphate-free detergent formulation I and a low-phosphate formulation II of the following composition were used in the following experiments:
• the graying inhibition was determined by the redeposition method.
• white test fabrics made of polyester-cotton blend (PB), cotton (BW) and polyester (PE) were repeatedly washed together with cotton yarn that had been soiled with a mixture of carbon black, iron oxide, kaolin and skin fat under defined conditions.
• the detergent concentration was 4.6 g / l, using tap water with 16 ° dH (160 mg CaO per liter of water), the washing temperature 60 ° C and the washing time 15 minutes. Then it was rinsed with tap water three times for 15 seconds each. After 2 or 10 washing cycles, the graying of the test fabrics was measured photometrically.
• the amounts used for the respective graying inhibitor components a, b and c and the results (mean values from 5 experiments each) can be found in the following tables.
• the sodium salt of a copolymer of acrylic acid and maleic acid in a weight ratio of 1: 1 was used as graying inhibitor component c.
• the methyl cellulose had a degree of substitution of 1.8 methyl groups
• the carboxymethyl cellulose (Na salt) had a degree of substitution of 0.7 carboxymethyl groups per anhydroglucose unit.
• Components a, b and c are given in% by weight, based on the detergent.
• the index V denotes the comparison tests.

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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)
• Health & Medical Sciences (AREA)
• Molecular Biology (AREA)
• Emergency Medicine (AREA)
• Detergent Compositions (AREA)
• Soil Conditioners And Soil-Stabilizing Materials (AREA)

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Citations (5)

• 1983
  • 1983-08-13 DE DE19833329400 patent/DE3329400A1/de not_active Withdrawn
• 1984
  • 1984-07-26 ZA ZA845798A patent/ZA845798B/xx unknown
  • 1984-08-06 EP EP84109302A patent/EP0133566A3/fr not_active Withdrawn
  • 1984-08-10 BR BR8404024A patent/BR8404024A/pt unknown
  • 1984-08-10 ES ES535088A patent/ES8504918A1/es not_active Expired

Patent Citations (5)

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