EP1375633B1 - Compositions détergentes contenant des polymères - Google Patents

Compositions détergentes contenant des polymères Download PDF

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Publication number
EP1375633B1
EP1375633B1 EP02014121A EP02014121A EP1375633B1 EP 1375633 B1 EP1375633 B1 EP 1375633B1 EP 02014121 A EP02014121 A EP 02014121A EP 02014121 A EP02014121 A EP 02014121A EP 1375633 B1 EP1375633 B1 EP 1375633B1
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Prior art keywords
acid
und
bis
von
alcohol
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EP1375633A1 (fr
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Nuria Dr. Bonastre Gilabert
Agustin Sanchez
Dirk Dr. Mampe
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Cognis IP Management GmbH
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Cognis IP Management GmbH
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Priority to ES02014121T priority Critical patent/ES2273948T3/es
Priority to AT02014121T priority patent/ATE340845T1/de
Priority to DE50208257T priority patent/DE50208257D1/de
Priority to EP02014121A priority patent/EP1375633B1/fr
Priority to PCT/EP2003/006329 priority patent/WO2004000984A1/fr
Publication of EP1375633A1 publication Critical patent/EP1375633A1/fr
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
    • 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
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/20—Treatment influencing the crease behaviour, the wrinkle resistance, the crease recovery or the ironing ease

Definitions

  • the invention is in the field of detergents and relates to the use of special copolymers as viscosity regulators for liquid, surface-active preparations.
  • Modern liquid or solid detergents are complex mixtures of active ingredients which, in their entirety, are intended to cover the complex requirement profile of these products.
  • an equipment of the laundry for example, against the reabsorption of dirt, the avivierende and antistatic finish of the fibers by which the ironing is facilitated ("easy ironing") or - for liquid products - the setting of a sufficiently high and storage-stable viscosity, so that the funds can be easily applied.
  • the object of the present invention was thus to provide polymers for the production of liquid detergents which permanently and stably increase the viscosity of the preparations.
  • the polymers in detergents meet the desired profile of satisfaction.
  • the polymers are suitable for building up viscosity in liquid formulations and also stabilizing them against temperature and storage-time influences. They attract both natural and synthetic fibers and reduce the soil repellant effect on the one hand Film formation reduces the static charge and thus facilitates ironing ("easy ironing" effect).
  • the copolymers may contain as monomer component (a) methacrylic acid, but preferably acrylic acid.
  • monomer component (b) are esters of acrylic or methacrylic acid with lower linear or branched alcohols having 1 to 6 carbon atoms or fatty alcohols having 8 to 22 carbon atoms in question.
  • Homopolymers based on the cationic component (c) and their use for the preparation of agents for cleaning hard surfaces or as rinse aid are already known from the prior art (compare EP 0876460 B1, EP 0876459 B1, EP 0248185 B1 ).
  • Preferred monomer components (c) are those quaternary ammonium compounds of the formula (I) in which R 1 , R 2 , R 3 and R 4 are methyl, n is 3 and X is chloride.
  • the polymerization of the three components can be carried out in a conventional manner.
  • the monomer components (a), (b) and (c) may be in a weight ratio of 1: (0.5 to 10): (0.5 to 10), preferably 1: (2 to 7): (2 to 7) and preferably 1: (4 to 6): (4 to 6).
  • the polymers may have an average molecular weight of from 1,000 to 50,000, preferably from 5,000 to 30,000 and most preferably from 8,000 to 15,000 daltons.
  • the proportion of the copolymers in the end products can finally be 0.1 to 10, preferably 0.5 to 5 and in particular 1 to 3 wt .-% - based on the means - amount.
  • compositions may further contain typical auxiliaries and additives, such as, for example, anionic, nonionic, cationic, amphoteric or zwitterionic surfactants, builders, co-builders, oil and fat solvents, bleaches, bleach activators, grayness inhibitors, enzymes, enzyme stabilizers, optical brighteners, Other polymers, defoamers, disintegrants, fragrances, inorganic salts and the like, as they are explained in more detail below.
  • auxiliaries and additives such as, for example, anionic, nonionic, cationic, amphoteric or zwitterionic surfactants, builders, co-builders, oil and fat solvents, bleaches, bleach activators, grayness inhibitors, enzymes, enzyme stabilizers, optical brighteners, Other polymers, defoamers, disintegrants, fragrances, inorganic salts and the like, as they are explained in more detail below.
  • cationic surfactants are, in particular, tetraalkylammonium compounds, such as, for example, dimethyl distearyl ammonium chloride or hydroxyethyl hydroxycetyl dimmonium chloride (Dehyquart E) or esterquats.
  • R 15 and R 16 are each independently hydrogen or R 14 CO
  • R 15 is an alkyl radical having 1 to 4 carbon atoms or a (CH 2 CH 2 O) m4 H Group
  • m1, m2 and m3 are in total 0 or numbers from 1 to 12
  • m4 is numbers from 1 to 12
  • Y is halide, alkylsulfate or alkyl phosphate.
  • esterquats 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, arachidic acid, behenic acid and erucic acid and their technical mixtures, such as They occur, for example, in the pressure splitting of natural fats and oils.
  • the fatty acids and the triethanolamine in a molar ratio of 1.1: 1 to 3: 1 can be used.
  • an employment 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 oil fatty acid (iodine value 0 to 40).
  • quaternized fatty acid triethanolamine ester salts of the formula (VIII) have proven to be particularly advantageous in which R 14 CO is an acyl radical having 16 to 18 carbon atoms, R 15 is R 15 CO, R 16 is hydrogen, R 17 is a methyl group, m1 , m2 and m3 are 0 and Y is methylsulfate.
  • suitable esterquats are, in addition, quaternized ester salts of fatty acids with diethanolalkylamines of the formula (IX) , in the R 18 CO for an acyl radical having 6 to 22 carbon atoms, R 19 is hydrogen or R 18 CO, R 20 and R 21 are independently alkyl radicals having 1 to 4 carbon atoms, m5 and m6 in total for 0 or numbers from 1 to 12 and Y again represents halide, alkyl sulfate or alkyl phosphate.
  • R 22 CO for an acyl radical having 6 to 22 carbon atoms
  • R 23 is hydrogen or R 22 CO
  • R 24 , R 25 and R 26 are independently alkyl radicals having 1 to 4 carbon atoms, m7 and m8 in total for 0 or numbers from 1 to 12
  • X again represents halide, alkyl sulfate or alkyl phosphate.
  • suitable esterquats are substances in which the ester is replaced by an amide bond and which preferably follow the formula (XI) based on diethylenetriamine, in which R 27 is CO for an acyl radical having 6 to 22 carbon atoms, R 28 is hydrogen or R 27 CO, R 29 and R 30 are independently alkyl radicals having 1 to 4 carbon atoms and Y is again halide, alkyl sulfate or alkyl phosphate.
  • Such Amidesterquats are available for example under the brand Incroquat® (Croda) in the market.
  • alkylbetaines examples include alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines.
  • suitable alkylbetaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula ( XII ), R 31 is alkyl and / or alkenyl radicals having from 6 to 22 carbon atoms, R 32 is hydrogen or alkyl radicals having from 1 to 4 carbon atoms, R 33 is alkyl radicals having from 1 to 4 carbon atoms, q 1 is from 1 to 6, and Z is from 1 to 6 Alkali and / or alkaline earth metal or ammonium.
  • Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, dodecylethylmethylamine, C 12/14 cocoalkyldimethylamine, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, stearylethylmethylamine, oleyldimethylamine, C 16/18 tallowalkyldimethylamine, and technical mixtures thereof.
  • R 34 CO is an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds
  • R 35 is hydrogen or alkyl radicals having 1 to 4 carbon atoms
  • R 36 is alkyl radicals having 1 to 4 carbon atoms
  • q 2 is from 1 to 4 6
  • q3 represents numbers from 1 to 3 and Z again represents an alkali and / or alkaline earth metal or ammonium.
  • Typical examples are reaction products of fatty acids having 6 to 22 carbon atoms, namely caproic, caprylic, capric, lauric, myristic, palmitic, palmitic, stearic, isostearic, oleic, elaidic, petroselic, linoleic, linolenic, elaeostearic, arachidic, gadoleic, behenic and erucic acids and technical mixtures thereof, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylaminopropylamine, which are condensed with sodium chloroacetate.
  • condensation product of C 8/18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate is preferred.
  • imidazolinium betaines are also suitable. These substances are also known substances which can be obtained, for example, by cyclizing condensation of 1 or 2 moles of fatty acid with polyhydric amines, such as, for example, aminoethylethanolamine (AEEA) or diethylenetriamine.
  • AEEA aminoethylethanolamine
  • the corresponding carboxyalkylation products are mixtures of different open-chain betaines.
  • Typical examples are condensation products of the abovementioned fatty acids with AEEA, preferably imidazolines based on lauric acid or again C 12/14 coconut fatty acid, which are subsequently betainized with sodium chloroacetate.
  • the washing, rinsing, cleaning and softening compositions according to the invention may additionally contain additional inorganic and organic builders, for example in amounts of from 10 to 50 and preferably from 15 to 35% by weight, based on the compositions, of which the main inorganic builders are zeolites crystalline phyllosilicates, amorphous silicates and - as far as permissible - also phosphates, such as tripolyphosphate are used.
  • the amount of co-builder is to be counted towards the preferred amounts of phosphates.
  • zeolites The finely crystalline, synthetic and bound water-containing zeolite frequently used as detergent builder is preferably zeolite A and / or P.
  • zeolite P for example, zeolite MAP (R) (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P as well as Y are also suitable.
  • a cocrystallized sodium / potassium aluminosilicate of zeolite A and zeolite X which is known as VEGOBOND AX® (commercial product from Condea Augusta SpA) is commercially available.
  • VEGOBOND AX® commercial product from Condea Augusta SpA
  • the zeolite can be used as a spray-dried powder or else as undried, still moist, stabilized suspension of its preparation.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols having 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • suitable Zeolites have a mean particle size of less than 10 microns (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22 wt .-%, in particular 20 to 22 wt .-% of bound water.
  • Suitable substitutes or sub-substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi x O 2X + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 is up to 20 and preferred values for x are 2, 3 or 4.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred. Its usability is not limited to any particular composition or structural formula.
  • smectites in particular bentonites, are preferred here.
  • small amounts of iron may be incorporated in the crystal lattice of the layered silicates according to the above formulas.
  • the phyllosilicates may contain hydrogen, alkali, alkaline earth metal ions, in particular Na + and Ca 2+ , due to their ion-exchanging properties.
  • the amount of water of hydration is usually in the range of 8 to 20 wt .-% and is dependent on the swelling state or on the type of processing.
  • phyllosilicates are used, which are largely free of calcium ions and strong coloring iron ions due to an alkali treatment.
  • the preferred builder substances also include amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which are delay-delayed and have secondary washing properties.
  • the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • the term "amorphous” also understood as "X-ray amorphous”.
  • the silicates do not give sharp X-ray reflections typical of crystalline substances, but at most one or more maxima of the scattered X-rays which are several angstroms in width of the diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • densified / compacted amorphous silicates Especially preferred are densified / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • Phosphate Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons.
  • Their content is generally not more than 25 wt .-%, preferably not more than 20 wt .-%, each based on the finished agent. In some cases it has been shown that in particular tripolyphosphates even in small amounts up to a maximum of 10% by weight, based on the finished composition, in combination with other builder substances lead to a synergistic improvement in the secondary washing power.
  • compositions may also contain components that positively affect oil and grease washability from fabrics.
  • the preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic Cellulose ethers, as well as known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • the content of the bleaching agents is preferably from 5 to 35% by weight and in particular up to 30% by weight, it being advantageous to use perborate monohydrate or percarbonate.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran, enol ester
  • Such bleach activators are contained in the customary amount range, preferably in amounts of from 1% by weight to 10% by weight, in particular from 2% by weight to 8% by weight, based on the total agent.
  • sulfone imines and / or bleach-enhancing transition metal salts or transition metal complexes can also be present as so-called bleach catalysts.
  • Suitable transition metal compounds include in particular manganese, iron, cobalt, ruthenium or molybdenum-salene complexes and their N-analogues, manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, manganese, iron, , Cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, as well as cobalt, iron, copper and ruthenium amine complexes.
  • Bleach-enhancing transition metal complexes in particular having the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are used in customary amounts, preferably in an amount of up to 1% by weight, in particular 0.0025% by weight. % to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, based in each case on the total agent.
  • Suitable enzymes are, in particular, those from the class of the hydrolases, such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains, and graying. Cellulases and other glycosyl hydrolases can contribute to color retention and increase the softness of the fabric by removing pilling and microfibrils. It is also possible to use oxidoreductases for bleaching or inhibiting color transfer.
  • subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • lipolytic enzymes are the known cutinases. Peroxidases or O-xidases have proven to be suitable in some cases.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • As cellulases are preferably cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof used. Since the different cellulase types differ by their CMCase and avicelase activities, targeted mixtures of the cellulases can be used to set the desired activities.
  • the enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature degradation.
  • the proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-%.
  • the agents may contain other enzyme stabilizers.
  • enzyme stabilizers For example, 0.5 to 1 wt .-% sodium formate can be used. It is also possible to use proteases with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • calcium salts magnesium salts also serve as stabilizers.
  • boron compounds for example boric acid, boron oxide, borax and other alkali metal borates, such as the salts of orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ) and pyroboric acid (tetraboric acid H 2 B 4 O 7 ).
  • Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • soluble starch preparations and other than the above-mentioned starch products can be used, e.g. degraded starch, aldehyde levels, etc. Also polyvinylpyrrolidone is useful.
  • cellulose ethers such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, and polyvinylpyrrolidone, for example, in amounts of from 0.1 to 5% by weight, based on the compositions, used.
  • the agents may contain as optical brighteners derivatives of Diaminostilbendisulfonklare or their alkali metal salts.
  • Suitable salts are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar construction which are used in place of the morpholino Group a Diethanolaminooeuvre, a methylamino group, an anilino group or a 2-Methoxyethylaminoxx carry.
  • brighteners of the substituted diphenylstyrene type may be present, for example the alkali metal salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or (4-chlorostyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned brightener can be used.
  • Uniformly white granules are obtained when the means except the usual brighteners in conventional amounts, for example between 0.1 and 0.5 wt .-%, preferably between 0.1 and 0.3 wt .-%, even small amounts, for example From 10 -6 to 10 -3 % by weight, preferably by 10 -5 % by weight of a blue dye.
  • a particularly preferred dye is Tinolux® (commercial product of Ciba-Geigy).
  • Suitable soil repellents are those which preferably contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, the molar ratio of ethylene terephthalate to polyethylene glycol terephthalate being in the range from 50:50 to 90:10. More specifically, the molecular weight of the linking polyethylene glycol units is in the range of 750 to 5,000, that is, the degree of ethoxylation of the polymers containing polyethylene glycol groups may be about 15 to 100.
  • the polymers are characterized by an average molecular weight of about 5000 to 200,000 and may have a block, but preferably a random structure.
  • Preferred polymers are those having molar ratios of ethylene terephthalate / polyethylene glycol terephthalate of from about 65:35 to about 90:10, preferably from about 70:30 to 80:20. Further preferred are those polymers comprising linking polyethylene glycol units having a molecular weight of from 750 to 5,000, preferably from 1000 to about 3000 and a molecular weight of the polymer of about 10,000 to about 50,000. Examples of commercially available polymers are the products Milease® T (ICI) or Repelotex® SRP 3 (Rhöne-Poulenc).
  • the paraffin waxes described are particularly preferably used alone as waxy defoamers or in admixture with one of the other waxy defoamers, wherein the proportion of paraffin waxes in the mixture is preferably more than 50% by weight, based on waxy defoamer mixture.
  • the paraffin waxes can be applied to carriers as needed.
  • carrier material all known inorganic and / or organic carrier materials are suitable. Examples of typical inorganic carrier materials are alkali metal carbonates, aluminosilicates, water-soluble phyllosilicates, alkali metal silicates, alkali metal sulphates, for example sodium sulphate, and alkali metal phosphates.
  • the alkali metal silicates are preferably a compound having a molar ratio of alkali metal oxide to SiO 2 of from 1: 1.5 to 1: 3.5.
  • the use of such silicates results in particularly good grain properties, in particular high abrasion stability and yet high dissolution rate in water.
  • the aluminosilicates referred to as support material include, in particular, the zeolites, for example zeolite NaA and NaX.
  • the compounds referred to as water-soluble layered silicates include, for example, amorphous or crystalline water glass.
  • silicates can be used, which are under the name Aerosil® or Sipernat® commercially.
  • Suitable organic support materials are, for example, film-forming polymers, for example polyvinyl alcohols, polyvinylpyrrolidones, poly (meth) acrylates, polycarboxylates, cellulose derivatives and strength in question.
  • Useful cellulose ethers are, in particular, alkali metal carboxymethylcellulose, methylcellulose, ethylcellulose, hydroxyethylcellulose and so-called cellulose mixed ethers, such as, for example, methylhydroxyethylcellulose and methylhydroxypropylcellulose, and mixtures thereof.
  • Particularly suitable mixtures are composed of sodium carboxymethylcellulose and methylcellulose, wherein the carboxymethylcellulose usually has a degree of substitution of 0.5 to 0.8 carboxymethyl groups per anhydroglucose unit and the methylcellulose has a degree of substitution of 1.2 to 2 methyl groups per anhydroglucose unit.
  • the mixtures preferably contain alkali metal carboxymethylcellulose and nonionic cellulose ethers in weight ratios of from 80:20 to 40:60, in particular from 75:25 to 50:50.
  • Native starch composed of amylose and amylopectin is also suitable as the carrier. Native starch is starch, as it is available as an extract from natural sources, such as rice, potatoes, corn and wheat. Native starch is a commercial product and thus easily accessible.
  • one or more of the abovementioned compounds can be used, in particular selected from the group of alkali metal carbonates, alkali metal sulphates, alkali metal phosphates, zeolites, water-soluble phyllosilicates, alkali silicates, polycarboxylates, cellulose ethers, polyacrylate / polymethacrylate and starch.
  • Particularly suitable are mixtures of alkali metal carbonates, in particular sodium carbonate, alkali metal silicates, in particular sodium silicate, alkali metal sulphates, in particular sodium sulphate and zeolites.
  • perfume oils or fragrances individual perfume compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate.
  • the ethers include Benzyl ethyl ether, to the aldehydes, for example, the linear alkanals with 8-18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones such as the ionone, ⁇ -isomethylionone and methylatedryl ketone to the alcohols anethole, citronellol , Eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene.
  • fragrances are used, which together produce an attractive fragrance.
  • perfume oils may also contain natural fragrance mixtures as are available from vegetable sources, eg pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • the fragrances can be incorporated directly into the compositions of the invention, but it may also be advantageous to apply the fragrances on carriers, which enhance the adhesion of the perfume on the laundry and provide a slower fragrance release for long-lasting fragrance of the textiles.
  • carrier materials for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.
  • compositions are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates, normal water glasses which do not have outstanding builder properties, or mixtures of these;
  • alkali metal carbonate and / or amorphous alkali silicate especially sodium silicate with a molar ratio of Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5, are used.
  • the content of sodium carbonate in the final preparations is preferably up to 40 wt .-%, advantageously between 2 and 35 wt .-%.
  • the content of sodium silicate (without any special builder properties) is generally up to 10% by weight and preferably between 1 and 8% by weight.
  • Sodium sulfate in amounts of from 0 to 10, in particular from 1 to 5,% by weight, based on the composition, can furthermore be contained as fillers or leveling agents
  • Table 1 below shows a number of liquid example formulations. All amounts are by weight.
  • Examples 1 to 4 are liquid detergents, examples 5 and 6 are lubricants.

Claims (6)

  1. Utilisation de copolymères
    (a) d'acide (méth)acrylique
    (b) d'esters alkyliques de l'acide (méth)acrylique et
    (c) de monomères de formule (I)
    Figure imgb0030
    dans laquelle R1 représente un atome d'hydrogène ou un groupe méthyle, R2 représente un radical alkyle linéaire ou ramifié comportant 1 à 6 atomes de carbone, R3 et R4, représente indépendamment l'un de l'autre, un atome d'hydrogène ou un radical alkyle linéaire ou ramifié, le cas échéant substitué par un groupe hydroxy, comportant 1 à 12 atomes de carbone ou représentent seuls ou conjointement la partie d'un système cyclique aliphatique ou aromatique, n représente des nombres de 1 à 6 et X un halogénure, en tant que régulateurs de la viscosité de préparations liquides tensioactives.
  2. Utilisation selon la revendication 1,
    caractérisée en ce qu'
    on utilise des copolymères qui présentent de l'acide acrylique en tant que composant monomère (a).
  3. Utilisation selon les revendications 1 et/ou 2,
    caractérisée en ce qu'
    on utilise des copolymères qui, en tant que composant monomère (b) présentent des esters de l'acide acrylique ou méthacrylique et d'alcools linéaires ou ramifiés comportant 1 à 6, ou 8 à 22 atomes de carbone.
  4. Utilisation selon au moins l'une des revendications 1 à 3,
    caractérisée en ce qu'
    on utilise des copolymères qui, en tant que composant monomère (c) présentent des composés d'ammonium quaternaire de formule (I) dans laquelle R1, R2, R3 et R4 représentent un groupe méthyle, n est égal à 3 et X représente un chlorure.
  5. Utilisation selon au moins l'une des revendications 1 à 4,
    caractérisée en ce qu'
    on utilise des copolymères qui contiennent les composants monomères (a), (b) et (c) dans un rapport pondéral de 1:(0,5 à 10):(0,5 à 10).
  6. Utilisation selon au moins l'une des revendications 1 à 5,
    caractérisée en ce qu'
    on utilise les copolymères dans des quantités de 0,1 à 10% en poids - par rapport aux agents -.
EP02014121A 2002-06-25 2002-06-25 Compositions détergentes contenant des polymères Expired - Lifetime EP1375633B1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
ES02014121T ES2273948T3 (es) 2002-06-25 2002-06-25 Detergente con polimeros.
AT02014121T ATE340845T1 (de) 2002-06-25 2002-06-25 Waschmittel mit polymeren
DE50208257T DE50208257D1 (de) 2002-06-25 2002-06-25 Waschmittel mit Polymeren
EP02014121A EP1375633B1 (fr) 2002-06-25 2002-06-25 Compositions détergentes contenant des polymères
PCT/EP2003/006329 WO2004000984A1 (fr) 2002-06-25 2003-06-16 Detergents a base de polymeres

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP02014121A EP1375633B1 (fr) 2002-06-25 2002-06-25 Compositions détergentes contenant des polymères

Publications (2)

Publication Number Publication Date
EP1375633A1 EP1375633A1 (fr) 2004-01-02
EP1375633B1 true EP1375633B1 (fr) 2006-09-27

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AT (1) ATE340845T1 (fr)
DE (1) DE50208257D1 (fr)
ES (1) ES2273948T3 (fr)
WO (1) WO2004000984A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3541913A1 (fr) * 2016-11-18 2019-09-25 The Procter and Gamble Company Compositions de traitement de tissu et procédés apportant un bénéfice
US10870816B2 (en) 2016-11-18 2020-12-22 The Procter & Gamble Company Fabric treatment compositions having low calculated cationic charge density polymers and fabric softening actives and methods for providing a benefit

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE169331T1 (de) * 1992-03-10 1998-08-15 Rohm & Haas Verwendung von wasserlöslichen polymeren in reinigungsmittelzusammensetzungen und für solche anwendungen geeignete wasserlösliche polymere
DE19545630A1 (de) * 1995-12-07 1997-06-12 Henkel Kgaa Reinigungsmittel für harte Oberflächen
DE19649288A1 (de) * 1996-11-28 1998-06-04 Henkel Kgaa Baumwollaktive schmutzablösevermögende Polymere
US5879670A (en) * 1997-03-31 1999-03-09 Calgon Corporation Ampholyte polymers for use in personal care products
DE59908424D1 (de) * 1999-07-02 2004-03-04 Cognis Iberia Sl Mikrokapseln - I
DE19934704A1 (de) * 1999-07-23 2001-01-25 Henkel Kgaa Wasch- und Reinigungsmittelformkörper mit Dispersionsmitteln
DE10062355A1 (de) * 1999-12-27 2001-06-28 Lion Corp Verwendung eines ampholytischen, amphiphilen Copolymers als Oberflächenbehandlungsmittel und Oberflächenbehandlungszusammensetzung, die das Copolymer enthält
CA2398156A1 (fr) * 2000-02-02 2001-08-09 Kenneth Wong Polymeres pour applications de nettoyage

Also Published As

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ES2273948T3 (es) 2007-05-16
ATE340845T1 (de) 2006-10-15
DE50208257D1 (de) 2006-11-09
WO2004000984A1 (fr) 2003-12-31
EP1375633A1 (fr) 2004-01-02

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