EP1563046B1 - Produit d'entretien doux pour textiles - Google Patents
Produit d'entretien doux pour textiles Download PDFInfo
- Publication number
- EP1563046B1 EP1563046B1 EP03767523A EP03767523A EP1563046B1 EP 1563046 B1 EP1563046 B1 EP 1563046B1 EP 03767523 A EP03767523 A EP 03767523A EP 03767523 A EP03767523 A EP 03767523A EP 1563046 B1 EP1563046 B1 EP 1563046B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- use according
- textile care
- textile
- agents
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000004753 textile Substances 0.000 title claims abstract description 98
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 94
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 48
- 229920001577 copolymer Polymers 0.000 claims abstract description 48
- 235000014633 carbohydrates Nutrition 0.000 claims abstract description 32
- 150000003839 salts Chemical class 0.000 claims abstract description 32
- 230000003750 conditioning effect Effects 0.000 claims abstract description 23
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 239000007800 oxidant agent Substances 0.000 claims abstract description 14
- 239000008139 complexing agent Substances 0.000 claims abstract description 11
- -1 alkali metal salts Chemical class 0.000 claims description 120
- 239000000203 mixture Substances 0.000 claims description 101
- 239000004744 fabric Substances 0.000 claims description 54
- 239000000047 product Substances 0.000 claims description 41
- 239000002253 acid Substances 0.000 claims description 33
- 239000003599 detergent Substances 0.000 claims description 33
- 239000011734 sodium Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 30
- 229910052708 sodium Inorganic materials 0.000 claims description 30
- 229920002472 Starch Polymers 0.000 claims description 29
- 235000019698 starch Nutrition 0.000 claims description 29
- 239000000178 monomer Substances 0.000 claims description 28
- 229920006395 saturated elastomer Polymers 0.000 claims description 28
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- 239000005017 polysaccharide Substances 0.000 claims description 27
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- 229910052783 alkali metal Inorganic materials 0.000 claims description 18
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 108091005804 Peptidases Proteins 0.000 claims description 13
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- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 229920001221 xylan Polymers 0.000 claims description 4
- 150000004823 xylans Chemical class 0.000 claims description 4
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 claims description 4
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- 235000010489 acacia gum Nutrition 0.000 claims description 3
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- 235000010417 guar gum Nutrition 0.000 claims description 3
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- 229960002154 guar gum Drugs 0.000 claims description 3
- 235000019314 gum ghatti Nutrition 0.000 claims description 3
- 150000004965 peroxy acids Chemical class 0.000 claims description 3
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- 229920000856 Amylose Polymers 0.000 claims description 2
- 229920002307 Dextran Polymers 0.000 claims description 2
- 229920000569 Gum karaya Polymers 0.000 claims description 2
- HTTJABKRGRZYRN-UHFFFAOYSA-N Heparin Chemical compound OC1C(NC(=O)C)C(O)OC(COS(O)(=O)=O)C1OC1C(OS(O)(=O)=O)C(O)C(OC2C(C(OS(O)(=O)=O)C(OC3C(C(O)C(O)C(O3)C(O)=O)OS(O)(=O)=O)C(CO)O2)NS(O)(=O)=O)C(C(O)=O)O1 HTTJABKRGRZYRN-UHFFFAOYSA-N 0.000 claims description 2
- 229920001202 Inulin Polymers 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 239000008272 agar Substances 0.000 claims description 2
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- 229920000669 heparin Polymers 0.000 claims description 2
- 229960002897 heparin Drugs 0.000 claims description 2
- JYJIGFIDKWBXDU-MNNPPOADSA-N inulin Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@]1(OC[C@]2(OC[C@]3(OC[C@]4(OC[C@]5(OC[C@]6(OC[C@]7(OC[C@]8(OC[C@]9(OC[C@]%10(OC[C@]%11(OC[C@]%12(OC[C@]%13(OC[C@]%14(OC[C@]%15(OC[C@]%16(OC[C@]%17(OC[C@]%18(OC[C@]%19(OC[C@]%20(OC[C@]%21(OC[C@]%22(OC[C@]%23(OC[C@]%24(OC[C@]%25(OC[C@]%26(OC[C@]%27(OC[C@]%28(OC[C@]%29(OC[C@]%30(OC[C@]%31(OC[C@]%32(OC[C@]%33(OC[C@]%34(OC[C@]%35(OC[C@]%36(O[C@@H]%37[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O%37)O)[C@H]([C@H](O)[C@@H](CO)O%36)O)[C@H]([C@H](O)[C@@H](CO)O%35)O)[C@H]([C@H](O)[C@@H](CO)O%34)O)[C@H]([C@H](O)[C@@H](CO)O%33)O)[C@H]([C@H](O)[C@@H](CO)O%32)O)[C@H]([C@H](O)[C@@H](CO)O%31)O)[C@H]([C@H](O)[C@@H](CO)O%30)O)[C@H]([C@H](O)[C@@H](CO)O%29)O)[C@H]([C@H](O)[C@@H](CO)O%28)O)[C@H]([C@H](O)[C@@H](CO)O%27)O)[C@H]([C@H](O)[C@@H](CO)O%26)O)[C@H]([C@H](O)[C@@H](CO)O%25)O)[C@H]([C@H](O)[C@@H](CO)O%24)O)[C@H]([C@H](O)[C@@H](CO)O%23)O)[C@H]([C@H](O)[C@@H](CO)O%22)O)[C@H]([C@H](O)[C@@H](CO)O%21)O)[C@H]([C@H](O)[C@@H](CO)O%20)O)[C@H]([C@H](O)[C@@H](CO)O%19)O)[C@H]([C@H](O)[C@@H](CO)O%18)O)[C@H]([C@H](O)[C@@H](CO)O%17)O)[C@H]([C@H](O)[C@@H](CO)O%16)O)[C@H]([C@H](O)[C@@H](CO)O%15)O)[C@H]([C@H](O)[C@@H](CO)O%14)O)[C@H]([C@H](O)[C@@H](CO)O%13)O)[C@H]([C@H](O)[C@@H](CO)O%12)O)[C@H]([C@H](O)[C@@H](CO)O%11)O)[C@H]([C@H](O)[C@@H](CO)O%10)O)[C@H]([C@H](O)[C@@H](CO)O9)O)[C@H]([C@H](O)[C@@H](CO)O8)O)[C@H]([C@H](O)[C@@H](CO)O7)O)[C@H]([C@H](O)[C@@H](CO)O6)O)[C@H]([C@H](O)[C@@H](CO)O5)O)[C@H]([C@H](O)[C@@H](CO)O4)O)[C@H]([C@H](O)[C@@H](CO)O3)O)[C@H]([C@H](O)[C@@H](CO)O2)O)[C@@H](O)[C@H](O)[C@@H](CO)O1 JYJIGFIDKWBXDU-MNNPPOADSA-N 0.000 claims description 2
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- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical class OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 1
- FAGMGMRSURYROS-UHFFFAOYSA-M trihexadecyl(methyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(CCCCCCCCCCCCCCCC)CCCCCCCCCCCCCCCC FAGMGMRSURYROS-UHFFFAOYSA-M 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 1
- 229940036248 turpentine Drugs 0.000 description 1
- HFTAFOQKODTIJY-UHFFFAOYSA-N umbelliferone Natural products Cc1cc2C=CC(=O)Oc2cc1OCC=CC(C)(C)O HFTAFOQKODTIJY-UHFFFAOYSA-N 0.000 description 1
- ORHBXUUXSCNDEV-UHFFFAOYSA-N umbelliferone Chemical compound C1=CC(=O)OC2=CC(O)=CC=C21 ORHBXUUXSCNDEV-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- ZFNVDHOSLNRHNN-UHFFFAOYSA-N xi-3-(4-Isopropylphenyl)-2-methylpropanal Chemical compound O=CC(C)CC1=CC=C(C(C)C)C=C1 ZFNVDHOSLNRHNN-UHFFFAOYSA-N 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- MXODCLTZTIFYDV-JHZYRPMRSA-L zinc;(1r,4ar,4br,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylate Chemical compound [Zn+2].C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C([O-])=O.C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C([O-])=O MXODCLTZTIFYDV-JHZYRPMRSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
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
- C11D3/3788—Graft polymers
-
- 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
Definitions
- the invention relates to the use of a textile care composition containing a copolymer of unsaturated carboxylic acids and / or their salts with carbohydrates to reduce linting or to reduce pilling.
- the modern textile cleaning makes high demands on the laundry to be cleaned. For example, the frequent washing of garments in a washing machine and the subsequent drying in a tumble dryer is associated with a high mechanical stress on the fabric. The frictional forces often lead to damage to the textile fabric, recognizable by a fluff and pilling. With each washing or drying cycle, but also by wearing the garments, a further abrasion and / or breakage of tiny fibers takes place on the surface of the textile surface fabrics. The conventional textile cleaners are unable to reduce this damage to the fabric or try to eliminate only resulting textile damage.
- the WO 99/16956 A1 describes the elimination of lint or pills through the use of cellulases.
- the cellulases thereby digest microfibers protruding from the textile fabrics and thus ensure a smooth and therefore pill-free textile surface.
- the WO 97/00272 A1 describes a polymer having at least one carbohydrate moiety and at least one 2-hydroxy-2-carboxaethylene moiety. These polymers are prepared by polymerization of at least one vinyl monomer A, which is predominantly an ⁇ -haloacrylic acid, and at least one other vinyl monomer B, in the presence of at least one optionally modified carbohydrate. The polymers are used in bleach-containing agents for textile pretreatment and paper bleaching.
- WO 96/37530 A1 describes water-soluble graft copolymers of monosaccharides, oligosaccharides and polysaccharides and their derivatives obtainable by free-radically initiated copolymerization of A) monomer mixtures of a) more than 40-100% by weight of at least one ⁇ - ⁇ -unsaturated aldehyde, b) 0-60 % By weight of a) various unsaturated monomers which are copolymerizable with a) and c) 0-5% by weight of at least two monomers having ethylenic, non-conjugated double bonds in the molecule, in the presence of B) mono-, oligo-, or polysaccharides and C) one or more oxidizing agents.
- the polymers are used, inter alia, in detergents as builders and co-builders with good incrustation-inhibiting effects.
- the graft copolymers are used inter alia as an additive in detergents and cleaners.
- EP 0 465 287 A1 discloses graft polymers based on polysaccharides which are at least partially biodegradable and have a polydextrose having an average molecular weight below 10000 g / mol, which is characterized by a water-soluble unsaturated Monomer is grafted.
- the graft polymers are used in detergents because of their builder properties.
- Object of the present invention is to provide a fabric care agent that significantly reduces the fluffing and pilling of textile fabrics in the textile care.
- the present invention therefore relates in a first embodiment to the use of a copolymer obtainable by copolymerization of a component (a) comprising one or more ethylenically unsaturated carboxylic acid (s) and / or salts thereof with a component (b) comprising carbohydrates
- a component (a) comprising one or more ethylenically unsaturated carboxylic acid (s) and / or salts thereof
- a component (b) comprising carbohydrates
- optionally component (c) comprising one or more oxidizing agents in a fabric care composition to reduce linting.
- the invention also relates to the use of a copolymer obtainable by copolymerization of a component (a) comprising one or more ethylenically unsaturated carboxylic acid (s) and / or salts thereof with a component (b) comprising carbohydrates in the presence of optionally component (c ) comprising one or more oxidizing agents in a fabric care composition for reducing pilling of fabrics.
- textile care products are understood as meaning both washing and cleaning agents and pretreatment agents and agents for conditioning textile fabrics, such as mild detergents and post-treatment agents, such as fabric softeners.
- conditioning is understood to mean the scavenging treatment of textile fabrics, fabrics, yarns and fabrics.
- the conditioning gives the textiles positive properties, such as improved softness, increased gloss and color brilliance, a fragrance refreshment and the reduction of creasing and static charge.
- the textile care agents contain a copolymer.
- the copolymer is obtainable by copolymerization of a component (a) comprising one or more ethylenically unsaturated carboxylic acid (s) and / or salts thereof Component (b) comprising carbohydrates in the presence of optionally component (c) comprising one or more oxidizing agents.
- ethylenically unsaturated carboxylic acids and / or their salts for example ethylenically unsaturated C 3 -C 10 -carboxylic acids, preferably C 3 -C 6 -carboxylic acid, more preferably ⁇ - ⁇ -unsaturated Carboxylic acids, in particular ⁇ - ⁇ -unsaturated C 3 -C 6 carboxylic acids and / or their alkali metal and / or ammonium salts and any mixtures thereof, exposed.
- component (a) usable ethylenically unsaturated carboxylic acids which are fed as a monomer of the copolymerization acrylic acid, methacrylic acid, ethylacrylic acid, allylacetic acid and vinylacetic acid.
- Acrylic acid, methacrylic acid, mixtures thereof and the sodium, potassium or ammonium salts or mixtures thereof are preferably used from this group of monomers.
- the monomers of group a), which may optionally be used in the copolymerization include, for example, C 1 - to C 6 alkyl and / or hydroxyalkyl esters of said compounds, for example methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate, monomethyl maleate, Diethyl maleate, hydroxyethyl acrylate, hydroxypropyl acrylates, hydroxybutyl acrylates, hydroxyethyl methacrylate and hydroxypropyl methacrylate and esters of acrylic acid and methacrylic acid with polyhydric alcohols, for example Glycol diacrylate, glycerol triacrylate, glycol dimethacrylate, glycerol trimethacrylate, as well as at least two polyols esterified with acrylic acid or methacrylic acid, such as pentaerythritol and glucose
- the amides and N-substituted al for example
- alkylaminoalkyl (meth) acrylates for example dimethylaminoethyl, dimethylaminoethyl, diethylaminoethyl, diethylaminoethyl, dimethylaminopropyl and / or dimethylaminopropyl.
- carbohydrates which contain at least three carbon atoms and have polyol character, ie contain at least three hydroxyl groups per carbon chain or ring, and are soluble, suspendable or swellable in water.
- carbohydrates it is meant natural saccharides or modification products thereof, that is, saccharides derived from animal or vegetable products (eg from the processing of milk, honey or plant parts), or simple ones Modification products thereof, for example enzymatically or chemically modified (for example by hydrolysis, hydrogenation, oxidation, partial etherification or esterification and / or derivatization), as far as the essential polyol character of the saccharide is retained.
- saccharides can be used, primarily polymerization of mono- and / or disaccharides, as they can be prepared by polymerization in aqueous solution, but preferably the carbohydrates are natural saccharides or simple modification products thereof: Suitable carbohydrates are oligo- or polysaccharides whose monomer units contain 4 to 7, preferably 5 or 6, carbon atoms.
- modified carbohydrates are primarily those carbohydrates into consideration, in which one or two functional groups have been chemically modified, for example by alkylation, for example with unsubstituted or substituted low molecular weight alkyl, especially alkylation with unsubstituted C 1-4 alkyl, especially methyl or butyl, Carboxyalkylation, especially carboxymethylation (eg by reaction with chloroacetic acid), addition of epoxides (eg ethylene oxide or propylene oxide) to alkoxylation, or reaction with optionally substituted chlorohydrins, or by acylation, for example with acyl radicals of low molecular weight carboxylic acids, especially of C 2-4 carboxylic acids, in particular acetyl, or derivatization, as far as at least three hydroxy groups of carbon hydride character are present per carbon chain or ring.
- alkylation for example with unsubstituted or substituted low molecular weight alkyl, especially alkylation with unsubstituted C 1-4 al
- Modification products are also cationically modified polysaccharides to understand, for example, with 2,3-Epoxipropyltrimethylammoniumchlorid reacted starches such as those in the U.S. Patent 3,649,616 are described.
- Chemically modified polysaccharides include, for example, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylhydroxyethylcellulose, sulfoethylcellulose, carboxymethylsulfoethylcellulose, hydroxypropylsulfoethylcellulose, hydroxyethylsulfoethylcellulose, methylsulfoethylcellulose, and ethylsulfoethylcellulose.
- Suitable carbohydrates are any oligo- or polysaccharides or simple modification products thereof or mixtures thereof.
- Carbohydrates are, for example, starch, pectin, algin, chitin, chitosan, heparin, carrageenan, agar, gum arabic, tragacanth, karaya gum, ghatti gum, locust bean gum, guar gum, tare gum, inulin, xanthan, dextran, sucrose, nigeran and pentosans such as xylan and araban, the main components of which are D-glucuronic acid, D-galacturonic acid, D-galacturonic acid methyl ester, D-mannuronic acid, L-guluronic acid, D- and L-galactose, 3,6-anhydro-D-galactose, L-arabinose, L-rhamnose, D-glucuronic acid, D-xylose, L-fucose,
- oligosaccharides are open-chain or cyclic oligosaccharides, such as, for example, lactose, maltose, cellobiose, raffinose, gentiobiose, trehalose, melezitose, dextrins and cyclodextrins .alpha., .Beta. And / or .gamma.) And mixtures thereof.
- carbohydrates which are present as polysaccharides are, in particular, those which are soluble, suspendable or swellable in water, chiefly starch polysaccharides, and / or substantially linear polysaccharides which occur in starches, in particular amylose, and degradation products (preferably hydrolysis products) thereof; for example, syrup or dextrins, and mixtures of such polysaccharides, and / or substantially linear other polysaccharides and branched polysaccharides, for example, cellulose, xylans, arabans and galactans. From an economical point of view, particularly preferred carbohydrates are polysaccharides, which are particularly suitable for graft copolymerization.
- starches In a preferred embodiment of the present invention are used as carbohydrates starch, thermally and / or mechanically treated starch, oxidatively, hydrolytically or oxidized enzymatically degraded starches, oxidized hydrolytically or oxidized enzymatically degraded starches and chemically modified starches.
- all strengths are suitable.
- starches from maize, wheat, rice, tapioca and in particular potato starch are preferred.
- the starches are practically not soluble in water and can be converted in a known manner by thermal and / or mechanical treatment or by an enzymatic or an acid-catalyzed degradation in a water-soluble form.
- starch-degrading products obtainable by oxidative, hydrolytic or enzymatic degradation of starch include: dextrins such as white and yellow dextrins, maltodextrins, glucose syrups, maltose syrups, high D-glucose hydrolysates, starch saccharification products, and maltose and D. Glucose and its isomerization fructose.
- starch components for the polymers to be used according to the invention are used as carbohydrates technical, optionally purified or / and enzymatically modified starches, for example in the form of starch flours.
- the process for the preparation of the copolymer or a mixture to be used according to the invention is preferably carried out in a suitable solvent, preferably in a polar solvent, in particular in an aqueous medium.
- the polymerization takes place at pH values which are preferably in the acidic range, particularly preferably below a pH of 6, in particular below a pH of 5 and in particular within a pH of 0.1 to 4 , lie.
- Aqueous media with the aforementioned pH ranges have been found in the context of the present invention to be advantageous. .
- the pH is advantageously adjusted with a strong mineral acid, for example phosphoric acid or preferably sulfuric acid, or a strong carboxylic acid, for example citric acid.
- component (b) is at least partially soluble in the reaction medium.
- component (b) may therefore already be a modification product of the natural carbohydrates, for example products of the metabolism of microorganisms, which ensure that the carbohydrates are already soluble and / or dispersible in water.
- an enzymatic pretreatment for example of oligosaccharides or polysaccharides or pectins, even in one operation, in a same reaction vessel, the above polymerization preceded.
- the enzymatic reaction can then be terminated expediently by addition of acids.
- the molar ratio of component (a) to component (b) may vary within a wide range, advantageously so that on average at least one basic unit of component (a) per basic carbohydrate molecule is present in the final product.
- Carbohydrate moiety in the optionally modified starting carbohydrate is understood as meaning an open-chain or preferably cyclic, optionally modified carbohydrate group which carries at least three hydroxyl groups as substituents per group of contiguous carbon atoms and, if it is cyclic, contains an (preferably furanosides or pyranosides) oxygen atom as ring member and wherein the carbohydrate moieties may optionally be bridged with one another via oxygen (eg a glucoside ring, as occurs in oligo- or polyglucosides).
- the copolymer to be used according to the invention is present as a graft copolymer.
- Graft copolymers are formed, for example, when monomers are preferably free-radically polymerized in the presence of prefabricated polymers which serve as macroinitiators and thus simultaneously as graft substrates.
- the carbohydrates as component (b) form the grafting substrate to which the monomers of component (a) can be grafted.
- graft copolymers which have a high graft density and short grafts have proven to be suitable, in particular for the effect of lint reduction and reduction of crease formation.
- the average degree of substitution is preferably above 1.5, preferably above 2 and in particular above 2.5. Also particularly suitable are those graft copolymers in which, on average, each grafting point has more than one monomer, preferably more than 2 monomers, particularly preferably 2.5 to 5 monomer units of component (a). Degree of substitution and length of the Pfropfine can be determined for example by NMR measurements in comparison to corresponding standards.
- the reaction temperature for the polymerization is predominantly values in the range from 20 to 150.degree. C., advantageously from 40 to 100.degree. C., preferably from 60 to 98.degree. C., in particular from 70 to 90.degree.
- component (c) comprising one or more oxidizing agents.
- a component (c) is preferably in the weight ratio of component (c) to the components (a) + (b) of (1: 100) to (1: 1), particularly preferably of (1: 70 ) to (1: 2), in particular from (1:50) to (1:10), component (c) preferably having sufficient oxidizing power to promote oxidation of carbonyl groups and oxidation and degradation of the component (b ), preferably a polysaccharide, and thus to initiate polymerization of the reaction mixture starting from component (b).
- Suitable components (c) are all oxidizing agents known to the person skilled in the art.
- Hydrogen peroxide is preferably used as oxidizing agent.
- the hydrogen peroxide can be used as such or as an H 2 O 2 - donating compound, for example as potassium peroxide or in the form of an organic peracid, but it is preferably used directly as H 2 O 2 . It is also possible to mix several oxidizing agents. In a preferred embodiment, the oxidizing agent is free of transition metal ions.
- component (c) may be added all at once or in stages; a good reaction control can be achieved, for example, by stepwise addition of component (c).
- the degree of polymerization of the components (a) and (b) used can be controlled, for example, by means known to the person skilled in the art, by means of the amount of component (c).
- copolymers to be used according to the invention are advantageously obtainable by a free-radical polymerization, it may be expedient to carry out the copolymerization in the presence of free-radical initiators or under the action of suitable high-energy radiation.
- the following initiators or catalysts are suitable: water-soluble azo compounds, for example 4,4'-azobis (4-cyanopentanoic acid), 2,2'-azobis (2-aminodipropane) dihydrochloride or azobisisobutyric acid dinitrile, redox systems or peroxy compounds (especially diacetyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, tert-butyl perpivalate, cumene hydroperoxide, benzoyl hydroperoxide, dibenzoyl peroxide, diisopropyl peroxydicarbonate, sodium perborate , Hydrogen peroxide or ammonium or alkali metal peroxydisulfate.
- water-soluble azo compounds for example 4,4'-azobis (4-cyanopentanoic acid), 2,2'-azobis (2-aminodipropane) dihydrochloride or azobisisobutyric acid dinitrile
- the copolymerization which preferably takes place in an acidic medium, can be mixed with suitable bases in a preferred embodiment for neutralization and / or hydrolysis and / or salt formation.
- suitable basic components are, for example, ammonia, alkali metal hydroxides and / or low molecular weight mono-, di- or trialkylamines or -alkanolamines, in particular triethanolamine or triisopropanolamine, and / or puffing alkali metal salts, of which alkali metal hydroxides (lithium, sodium or potassium hydroxide) especially preferred are sodium hydroxide and potassium hydroxide.
- the copolymers may contain or incorporated component (a) to form copolymers or / and graft copolymers.
- component (b) In the case of an acidic (partial) hydrolysis of component (b), it is also possible to add or incorporate carbohydrate units at the corresponding site.
- the average molecular weight M w of the copolymers to be used according to the invention is, for example, in the range of above 1000, preferably above 5000, more preferably above 10 000, in particular above 15 000, advantageously between 18000 and 70000, most preferably between 20 000 and 65 000 g / mol.
- the molecular weight can be determined by gel permeation chromatography against normalized polyacrylic acid standards.
- graft copolymers are already known in the art, for example from US 3,558,499 and the DE 40 03 172 A1 known.
- the preparation of graft copolymers preferably used according to the invention is illustrated by way of example.
- Preparation of Graft Copolymer A A mixture of 20 to 45 parts by weight of an acidic complexing agent and about the same amount of starch are dissolved in warm water and then the same amount by weight of acrylic acid and simultaneously 1 to 10 parts by weight of hydrogen peroxide in combination with a free radical initiator, diluted as an aqueous solution, slowly added with cooling and constant temperature, the polymerization proceeds. After completion of the reaction, the product may optionally be diluted with water to the desired concentration and / or adjusted to a desired pH with suitable bases.
- the textile care agent contains the copolymers in an effective amount, preferably above 0.05 wt .-%, particularly preferably from 0.1 to 10 wt .-%, in particular from 1 to 5 wt .-%, each based on the total agent ,
- the fabric care agents may additionally contain complexing agents . It has surprisingly been found that in particular organic, advantageously water-soluble, complexing agents can be incorporated particularly well into the textile care products and, in particular, together with the copolymers to be used according to the invention gives the textile care agent, in particular the liquid textile care agent, increased stability.
- the complexing agents improve the stability of the agents and protect, for example, against the heavy metals catalyzed decomposition of certain ingredients of washing active formulations. Together with the copolymers, they contribute to the inhibition of incrustations.
- the polymerization reaction for the preparation of the copolymers is carried out already in the presence of the complexing agent. Particular preference is given in particular to acid-group-containing coplexing agents which can additionally assume a pH-controlling function.
- the group of complexing agents includes, for example, the alkali metal salts of nitrilotriacetic acid (NTA) and derivatives thereof, as well as alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulfonates.
- NTA nitrilotriacetic acid
- anionic polyelectrolytes such as polymaleates and polysulfonates.
- citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids and their derivatives as well as mixtures of these are suitable.
- Particularly preferred compounds include organophosphonates such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine-penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1,2, 4-tricarboxylic acid (PBS-AM), which are mostly used in the form of their ammonium or alkali metal salts.
- organophosphonates such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine-penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1,2, 4-tricarboxylic acid (PBS-AM), which are mostly used in the form of their ammonium or alkali metal salts.
- citric acid and / or its alkali metal salts for example sodium citrate and / or potassium citrate.
- the fabric care agents contain complexing agents in an amount of up to 20 wt .-%, preferably from 0.01 to 15 wt .-%, particularly preferably from 0.1 to 10 and in particular from 0.3 to 5.0 wt. %, preferably from 1.5 to 3 wt.%, in each case based on the total agent.
- the textile care agents may be present both in solid form, for example as a powder, granules, extrudate, pressed and / or molten molded articles, for example as tablets or preferably in liquid form, for example as dispersion, suspension, emulsion, solution, microemulsion, gel or paste.
- the fabric care agents additionally contain nonionic surfactants.
- nonionic surfactants not only increases the washing performance of the compositions according to the invention, but additionally supports the dispersion and homogeneous distribution of the copolymer to be used according to the invention.
- nonionic surfactants are preferably alkoxylated, advantageously ethoxylated and / or propoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) and / or 1 to 10 moles of propylene oxide (PO) per mole of alcohol, used.
- C 8 -C 16 -alcohol alkoxylates advantageously ethoxylated and / or propoxylated C 10 -C 15 -alcohol alkoxylates, in particular C 12 -C 14 -alcohol alkoxylates, having a degree of ethoxylation of between 2 and 10, preferably between 3 and 8, and / or a degree of propoxylation between 1 and 6, preferably between 1.5 and 5.
- the alcohol radical may preferably be linear or more preferably methyl-branched in the 2-position or contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
- alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
- the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
- ethoxylation and propoxylation represent statistical averages which, for a particular product, are whole or fractional Number can be.
- Preferred alcohol ethoxylates and propoxylates have a narrow homolog distribution (narrow range ethoxylates / propoxylates, NRE / NRP).
- fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
- alkoxylated amines advantageously ethoxylated and / or propoxylated, in particular primary and secondary amines having preferably 1 to 18 carbon atoms per alkyl chain and an average of 1 to 12 moles of ethylene oxide (EO) and / or 1 to 10 moles of propylene oxide (PO) per Mole of amine.
- EO ethylene oxide
- PO propylene oxide
- end-capped alkoxylated fatty amines and fatty alcohols have proved to be particularly advantageous, in particular for use in the non-aqueous formulations according to the invention.
- the terminal hydroxy groups of the fatty alcohol alkoxylates and fatty amine alkoxylates are etherified by C 1 -C 20 -alkyl groups, preferably methyl or ethyl groups, in the end-capped fatty alcohol alkoxylates and fatty amine alkoxylates.
- nonionic surfactants and alkyl glycosides of the general formula RO (G) x for example as compounds, especially with anionic surfactants, are used in which R is a primary straight-chain or methyl-branched, especially methyl-branched in the 2-position aliphatic radical having 8 to 22 , preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
- the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
- nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters as they are
- alkoxylated preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters as they are
- JP 58/217598 are described or preferably according to the in the international patent application WO 90/13533 be prepared described methods.
- gemini surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups and two possess hydrophobic groups per molecule These groups are usually separated by a so-called “spacer”. This spacer is usually a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, however, the term gemini surfactants is understood to mean not only dimeric but also trimeric surfactants.
- Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to the German patent application DE-A-43 21 022 or dimer alcohol bis- and trimeralcohol tris-sulfates and ether sulfates according to the international patent application WO-A96 / 23768 , End-capped dimeric and trimeric mixed ethers according to the German patent application DE-A-195 13 391 are characterized in particular by their Biund multifunctionality.
- the end-capped surfactants mentioned have good wetting properties and are low foaming, so that they are particularly suitable for use in machine washing or cleaning processes.
- gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides as described in international patent applications WO-A95 / 19953 .
- WO 95/19954 and WO 95/19955 to be discribed.
- polyhydroxy fatty acid amides of the following formula wherein RCO is an aliphatic acyl radical having 6 to 22 carbon atoms, R 5 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
- the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
- the group of polyhydroxy fatty acid amides also includes compounds of the following formula R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 6 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 7 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
- [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- the N-alkoxy- or N-aryloxy-substituted compounds can then be used, for example, according to the teaching of the international application WO-A-95/07331 be converted by conversion with fatty acid methyl esters in the presence of an alkoxide as catalyst into the desired Polyhydroxyfettklaamide.
- nonionic surfactants selected from the group of the alkoxylated fatty alcohols and / or alkyl glycosides, in particular mixtures of alkoxylated fatty alcohols and alkyl glycosides, are used.
- nonionic surfactants in amounts of up to 35 wt .-%, preferably from 5 to 25 wt .-%, particularly preferably from 10 to 20 wt .-%, each based on the total agent.
- the fabric care agents may additionally contain anionic surfactants.
- anionic surfactants Through the use of anionic surfactants, the soil release behavior of the agent during the washing process is significantly increased without significantly impairing the effect of the copolymers to be used according to the invention as a lint reduction component and anti-crease component.
- anionic surfactants for example, those of the sulfonate type and sulfates are used.
- the surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and, subsequently, alkaline or acidic hydrolysis of the sulfonation products, into consideration.
- alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
- esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.
- anionic surfactants are sulfated fatty acid glycerol esters.
- Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
- Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
- Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
- C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
- 2,3-alkyl sulfates which, for example, according to the U.S. Patents 3,234,258 or 5,075,041 are manufactured and can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
- EO ethylene oxide
- Fatty alcohols with 1 to 4 EO, referred to as Fatty alcohol ether sulfates are suitable, and in the context of this invention are particularly preferred anionic surfactants.
- Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
- alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
- Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures of these.
- Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which by themselves are nonionic surfactants.
- alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
- anionic surfactants are particularly soaps into consideration. Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
- the anionic surfactants may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
- the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
- the ammonium salts in particular the salts of organic bases, such as, for example, isopropylamine, are preferred.
- Ether carboxylic acids are water hardness insensitive and have excellent surfactant properties. Production and application are, for example, in soaps, oils, fats, waxes 101, 37 (1975 ); 115, 235 (1989 ) and Surfactants Deterg. 25, 308 (1988 ).
- the textile cleaners contain in a preferred embodiment, anionic surfactants, preferably selected from the group of fatty alcohol holsulfates and / or fatty alcohol ether sulfates and / or alkylbenzenesulfonates and / or soaps.
- the content of anionic surfactants can vary considerably. If the textile care agents are present as mild detergents or after-treatment agents, for example as fabric softeners, the amounts are below 10% by weight, preferably below 5% by weight and in particular below 1% by weight, in each case based on the total composition.
- anionic surfactants may be used in amounts of up to 65% by weight, preferably in amounts of up to 50% by weight, more preferably in amounts of from 5 to 35% by weight. -%, in each case based on the total mean, be included.
- the fabric care agents may additionally contain enzymes.
- Enzymes support the washing processes in a variety of ways, especially in the removal of poorly bleachable contaminants, such as protein stains.
- the incorporation of enzymes in detergent formulations, especially in liquid fabric care products often causes problems, since it can lead to incompatibilities with other detergent ingredients, which in turn can cause a loss of activity of the enzymes.
- the stability of the enzymes in wash liquor or textile care formulation, in particular in liquid fabric care formulations can be improved by the use of the copolymers to be used according to the invention.
- Particularly suitable enzymes are those from the classes of 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. In addition, cellulases and other glycosyl hydrolases may contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils. Oxireductases can also be used for bleaching or inhibiting color transfer.
- 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.
- 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 oxidases have also proved 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 different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
- the enzymes may be adsorbed as a shaped body to carriers or embedded coated to protect against premature decomposition.
- the textile care agents in a preferred embodiment contain enzymes, preferably selected from the group of proteases and / or amylases and / or cellulases.
- the textile care products are present as mild detergents or post-treatment agents, for example as fabric softeners, they can, in a preferred embodiment, comprise cellulase, preferably in an amount of 0.005 to 2% by weight, particularly preferably 0.01 to 1% by weight, in particular 0 , 02 to 0.5 wt .-%, each based on the total agent included.
- the textile care agents are in liquid form and advantageously have a viscosity of from 50 to 5000 mPas, more preferably from 50 to 3000 mPas and in particular from 500 to 1500 mPas (measured at 20 ° C. with a rotational viscometer (Brookfield RV, spindle 2 ) at 20 rpm (rpm: revolutions per minute)).
- Preferred liquid fabric care agents in one preferred embodiment contain one or more solvents.
- Solvents that can be used in the compositions according to the invention originate, for example, from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the concentration range indicated.
- the solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl- or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether Propylene glycol methyl, ethyl or propyl ether, butoxy-propoxy-propanol (BPP), dipropylene glycol monomethyl, or ethyl ether, di-
- glycol ethers are available under the trade name Arcosolv ® (Arco Chemical Co.) or Cellosolve ®, carbitol ® or Propasol ® (Union Carbide Corp.); this includes for example ButylCarbitol® ®, hexyl carbitol ®, MethylCarbitol® ®, and carbitol ® itself, (2- (2-ethoxy) ethoxy) ethanol.
- Arcosolv ® Arco Chemical Co.
- Cellosolve ® Cellosolve ®
- Carbitol ® or Propasol ® Union Carbide Corp.
- ButylCarbitol® ® hexyl carbitol ®
- MethylCarbitol® ® MethylCarbitol®
- carbitol ® itself, (2- (2-ethoxy) ethoxy) ethanol.
- the choice of glycol ether can be readily made by one skilled in the art on the
- Pyrrolidone solvents such as N-alkylpyrrolidones, for example N-methyl-2-pyrrolidone or NC 8 -C 12 -alkylpyrrolidone, or 2-pyrrolidone, may also be used.
- alcohols can be used. These include low molecular weight liquid polyethylene glycols, for example polyethylene glycols having a molecular weight of 200, 300, 400 or 600.
- suitable other alcohols are, for example, lower alcohols such as ethanol, propanol, isopropanol and n-butanol, C 2 -C 4 - Polyols, such as diols or triols, for example ethylene glycol, propylene glycol, glycerol or mixtures thereof.
- lower alcohols such as ethanol, propanol, isopropanol and n-butanol
- C 2 -C 4 - Polyols such as diols or triols, for example ethylene glycol, propylene glycol, glycerol or mixtures thereof.
- the fabric care products if they are in liquid form, in a preferred embodiment, up to 95 wt .-%, particularly preferably 20 to 90 wt .-% and in particular 50 to 80 wt .-% of one or more solvents, preferably water-soluble solvents and especially water.
- the fabric care agents additionally contain plasticizer components, preferably cationic surfactants.
- plasticizer components preferably cationic surfactants.
- the textile care agents according to the invention are present as mild detergents or textile aftertreatment agents, for example as fabric softeners, the use of additional plasticizer components has proven to be extremely advantageous.
- the plasticizer components additionally facilitate the ironing of the textiles and reduce the static charge of the textile materials.
- fabric softening components are quaternary ammonium compounds, cationic polymers and emulsifiers, such as those used in hair care products and also in textile saliva.
- Suitable examples are quaternary ammonium compounds of the formulas (I) and (II), wherein in (I) R and R 1 is an acyclic alkyl radical having 12 to 24 carbon atoms, R 2 is a saturated C 1 -C 4 alkyl or hydroxyalkyl radical, R 3 is either R, R 1 or R 2 or is a aromatic residue stands.
- X- represents either a halide, methosulfate, methophosphate or phosphate ion, as well as mixtures of these.
- Examples of cationic compounds of the formula (I) are didecyldimethylammonium chloride, ditallowdimethylammonium chloride or dihexadecylammonium chloride.
- Ester quats are so-called ester quats. Esterquats are characterized by excellent biodegradability and are particularly preferred in the context of the present invention.
- R 4 is an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds
- R 5 is H, OH or O (CO)
- R 7 is independently of R 5 is H, OH or O (CO) R 8
- R 7 and R 8 are each independently an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds.
- m, n and p can each independently be 1, 2 or 3.
- X - can be either a halide, methosulfate, methophosphate or phosphate ion and mixtures thereof: 'Preference is given to compounds which for R 5 is the group O (CO) R 7 and for R 4 and R 7 are alkyl radicals having 16 to 18 Contain carbon atoms. Particularly preferred are compounds in which R 6 is also OH.
- Examples of compounds of the formula (II) are methyl N- (2-hydroxyethyl) -N, N-di (tallowacyl-oxyethyl) ammonium methosulfate, bis (palmitoyl) -ethyl-hydroxyethyl-methyl-ammonium methosulfate or methyl -N, N-bis (acyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulfate.
- acyl groups whose corresponding fatty acids have an iodine number between 5 and 80, preferably between 10 and 60 and in particular between 15 and 45 and which have a cis / trans isomer ratio are preferred (in wt .-%) of greater than 30: 70, preferably greater than 50: 50 and in particular greater than 70: 30 have.
- Commercial examples are sold by Stepan under the tradename Stepantex ® methylhydroxyalkyldialkoyloxyalkylammonium or those known under Dehyquart ® Cognis products known under or Rewoquat ® manufactured by Goldschmidt-Witco.
- Further preferred compounds are the diesterquats corresponding to formula (III) which are obtainable under the name Rewoquat ® 3099 W 222 LM or CR and provide in addition to the softness also for stability and color protection.
- R 21 and R 22 are each independently an aliphatic radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds.
- quaternary imidazolinium compounds of the formula (IV) wherein R 9 is H or a saturated alkyl radical having 1 to 4 carbon atoms, R 10 and R 11 are each independently an aliphatic, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms, R 10 alternatively also O (CO) R 20 wherein R 20 is an aliphatic, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms, and Z is an NH group or oxygen and X - is an anion.
- q can take integer values between 1 and 4.
- R 12 , R 13 and R 14 independently represent a C 1-4 alkyl, alkenyl or hydroxyalkyl group, each of R 15 and R 16 independently represents a C 8-28 alkyl group and r is a number between 0 and 5 is.
- short-chain, water-soluble, quaternary ammonium compounds may also be used, such as trihydroxyethylmethylammonium methosulfate or the alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. Cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride and tricetylmethyl ammonium chloride.
- trihydroxyethylmethylammonium methosulfate or the alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides e.g. Cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dimethyl ammonium chlor
- protonated alkylamine compounds which have plasticizing effect, as well as the non-quaternized, protonated precursors of cationic emulsifiers are suitable.
- cationic compounds which can be used according to the invention are the quaternized protein hydrolysates.
- Suitable cationic polymers include the polyquaternium polymers as described in U.S. Pat CTFA Cosmetic Ingredient Dictionary (The Cosmetic, Toiletry and Fragrance, Inc., 1997 ), in particular the polyquaternium-6, polyquaternium-7, polyquaterium-10 polymers (Ucare Polymer IR 400, Amerchol), also referred to as merquats, polyquaternium-4-copolymers, such as graft copolymers with a cellulose backbone and quaternary ammonium groups, which react via allyldimethylammonium chloride cationic cellulose derivatives such as cationic guar, such as guar hydroxypropyltriammonium chloride, and similar quaternized guar derivatives (eg Cosmedia guar, manufacturer: Cognis GmbH) are attached, cationic quaternary sugar derivatives (cationic alkyl polyglucosides), for example the commercial product Glucquat ® 100, according to CTFA Nomenclature a "Lau
- Polyquaternized polymers for example Luviquat Care from BASF
- cationic biopolymers based on chitin and derivatives thereof for example, under the trade designation chitosan ® (manufacturer: Cognis) polymer obtainable.
- cationic silicone oils such as the commercially available products Q2-7224 (manufacturer: Dow Corning, a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicon, which is also referred to as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) Abil ® quat 3270 and 3272 (manufacturer: Goldschmidt-Rewo; diquaternary polydimethylsiloxanes, quaternium-80), and Silicone quat Rewoquat ® SQ 1 (Tegopren® ® 6922 , Manufacturer: Goldschmidt-Rewo).
- the alkylamidoamines may be in their quaternized or, as shown, their quaternized form.
- R 17 may be an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds. s can take values between 0 and 5.
- R 18 and R 19 are each independently H, C 1-4 alkyl or hydroxyalkyl.
- fatty acid amidoamines such as the Stearylamidopropyldimethylamin available under the name Tego Amid ® S 18 or 3-Talgamidopropyl trimethylammonium methosulfate available under the name Stepantex ® X 9124, which in addition to a good conditioning effect also by color transfer inhibiting effect and especially by their good biological Distinguish degradability.
- alkylated quaternary ammonium compounds of which at least one alkyl chain is interrupted by an ester group and / or amido group, in particular N-methyl-N (2-hydroxyethyl) -N, N- (ditalgacyloxyethyl) -ammonium methosulfate and / or N- methyl-N (2-hydroxyethyl) -N, N- (palmitoyloxyethyl) ammonium methosulfate.
- nonionic plasticizers are especially Polyoxyalkylenglycerolalkanoate, as described in British Patent GB 2,202,244 , Polybutylenes, as described in the British patent specification GB 2,199,855 , long-chain fatty acids, as in the EP 13 780 , ethoxylated fatty acid ethanolamides as described in the EP 43 547 , Alkylpolyglycoside, in particular sorbitan mono-, di- and triester, as described in the EP 698,140 and fatty acid esters of polycarboxylic acids, as described in the German patent DE 2,822,891 to be discribed.
- the mild detergents contain cationic surfactants, preferably alkylated quaternary ammonium compounds, of which at least one alkyl chain is interrupted by an ester group and / or amido group, in particular N-methyl-N (2-hydroxyethyl) -N, N- (ditalgacyloxyethyl) ammonium methosulfate or N-methyl-N (2-hydroxyethyl) -N, N- (dipalmitoylethyl) ammonium methosulfate.
- cationic surfactants preferably alkylated quaternary ammonium compounds, of which at least one alkyl chain is interrupted by an ester group and / or amido group, in particular N-methyl-N (2-hydroxyethyl) -N, N- (ditalgacyloxyethyl) ammonium methosulfate or N-methyl-N (2-hydroxyethyl) -N, N- (dipalmitoylethyl)
- the fabric care compositions contain plasticizer components in an amount of up to 35 wt .-%, preferably from 0.1 to 25 wt .-%, particularly preferably from 0.5 to 15 wt .-% and in particular from 1 to 10 Wt .-%, each based on the total agent.
- the textile care products are present as light-duty detergents or fabric softeners, containing plasticizers, preferably cationic plasticizers, particularly preferably esterquats.
- the fabric care agents may contain pearlescing agents. Pearlescent agents give the textiles one too additional shine and are therefore preferably used in the mild detergents.
- suitable pearlescing agents are: alkylene glycol esters; fatty acid; partial glycerides; Esters of polybasic, optionally hydroxy-substituted carboxylic acids with fatty alcohols having 6 to 22 carbon atoms; Fatty substances, such as, for example, fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which in total have at least 24 carbon atoms; Ring opening products of olefin epoxides having 12 to 22 carbon atoms with fatty alcohols having 12 to 22 carbon atoms, fatty acids and / or polyols having 2 to 15 carbon atoms and 2 to 10 hydroxyl groups and mixtures thereof.
- the textile care agents may additionally contain thickeners.
- thickeners in the textile care agents has proven that are present as a liquid detergent.
- the use of thickening agents has proven particularly useful in gel-type liquid detergents. The thickened consistency of the agent simplifies the application of the agent directly to the spots to be treated. A run, as usual with thin liquids, is thereby prevented.
- Naturally derived polymers which are used as thickening agents are, for example, agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin and casein.
- Modified natural substances are derived primarily from the group of modified starches and celluloses, examples being carboxymethylcellulose and cellulose ethers, hydroxyethyl and - propylcellulose and core flour ethers mentioned.
- a large group of thickeners which find wide use in a variety of applications, are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes.
- Thickeners from said substance classes are widely available commercially and are -820 (methacrylic acid, for example, under the trade names Acusol ® (ste aryl alcohol-EO-20) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Dapral ®-GT-282-S (alkyl polyglycol ethers, Akzo), DEUTEROL ® polymer-11 (dicarboxylic acid copolymer, Halloween GmbH), deuteron ® -xg (anionic heteropolysaccharide based on ⁇ -D-glucose, D-mannose, D-glucuronic acid, Schoner GmbH) deuteron ® -XN (nichtionoge-nes polysaccharide Schoner GmbH), DICRYLAN ® -Verdicker- O (ethylene oxide adduct, 50% solution in water / isopropanol, Pfersse Chemie), EMA ® -81 and EMA ® -91 (ethylene-
- a preferred polymeric polysaccharide thickener is xanthan gum, a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions and having a molecular weight of from 2 to 15 million g / mole.
- Xanthan is formed from a chain of ⁇ -1,4-linked glucose (cellulose) with side chains.
- the structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan gum.
- Xanthan can be described by the following formula:
- the textile care agents additionally comprise thickeners, preferably in amounts of up to 10% by weight, more preferably up to 5% by weight, in particular from 0.1 to 1% by weight, in each case based on the total composition.
- the textile care agents may additionally contain odor absorbers and / or color transfer inhibitors.
- odor absorbers In particular for the textile care products used as fine. Aftertreatment and liquid detergents are present, the use of Farbübertragungsinhibtoren has proven. The use of odor absorbers has proven to be very useful for deodorizing foul-smelling constituents of formulations, for example amine-containing components, but also for the sustainable deodorizing of the washed textiles.
- the fabric care agents optionally contain from 0.1% to 2% by weight, preferably from 0.2% to 1% by weight dye transfer inhibitor; which in a preferred embodiment of the invention is a polymer of vinylpyrrolidone, vinylimidazole, vinylpyridine-N-oxide or a copolymer thereof.
- a mediator compound for the peroxidase for example one from the international patent application WO 96/10079 known acetosyringone, one from the international patent application WO 96/12845 known phenol derivative or one from the international patent application WO 96/12846 known phenotiazine or phenoxazine, is preferred in this case, whereby also above-mentioned polymeric Farbübertragungsinhibitorwirkstoffe can be used.
- Polyvinylpyrrolidone preferably has an average molecular weight in the range from 10 000 to 60 000, in particular in the range from 25 000 to 50 000, for use in compositions according to the invention.
- those of vinylpyrrolidone and vinylimidazole in a molar ratio of 5: 1 to 1: 1 having an average molecular weight in the range of 5,000 to 50,000, especially 10,000 to 20,000 are preferred.
- Preferred deodorizing substances in the context of the invention are one or more metal salts of an unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acid having at least 16 carbon atoms and / or a rosin acid with the exception of the alkali metal salts and any desired mixtures thereof.
- a particularly preferred unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acid having at least 16 carbon atoms is ricinoleic acid.
- a particularly preferred rosin acid is abietic acid.
- Preferred metals are the transition metals and the lanthanides, in particular the transition metals of Groups VIIIa, Ib and IIb of the Periodic Table, and lanthanum, cerium and neodymium, more preferably cobalt, nickel, copper and zinc, most preferably zinc.
- the cobalt, nickel and copper salts and the zinc salts are similarly effective, but for toxicological reasons, the zinc salts are to be preferred.
- one or more metal salts of ricinoleic acid and / or abietic acid preferably zinc ricinoleate and / or zinc abietate, in particular zinc ricinoleate.
- Cyclodextrins as well as any desired mixtures of the abovementioned metal salts with cyclodextrins, preferably in a weight ratio of from 1:10 to 10: 1, particularly preferably from 1: 5 to 5: 1 and in particular from 1, also prove to be suitable further deodorizing substances : 3 to 3: 1.
- cyclocodextrin includes all known cyclodextrins, i. both unsubstituted cyclodextrins with 6 to 12 glucose units, in particular alphabet and gamma-cyclodextrins and their mixtures and / or derivatives thereof and / or mixtures thereof.
- the textile care agents may additionally contain other surfactants, for example amphoteric surfactants.
- amphoteric surfactants which can be used according to the invention include betaines, amine oxides, alkylamidoalkylamines, alkyl-substituted amino acids, acylated amino acids or biosurfactants, of which the betaines are particularly preferred within the scope of the teaching according to the invention.
- Preferred amphoteric surfactants are the alkylbetaines of the formula (Ia), the alkylamidobetaines of the formula (Ib), the sulfobetaines of the formula (Ic) and the amidosulfobetaines of the formula (Id), R 1 -N + (CH 3 ) 2 -CH 2 COO - (la) R 1 -CO-NH- (CH 2 ) 3 -N + (CH 3 ) 2 -CH 2 COO - (Ib) R 1 is -N + (CH 3 ) 2 -CH 2 CH (OH) CH 2 SO 3 - (Ic) R 1 -CO-NH- (CH 2 ) 3 -N + (CH 3 ) 2 -CH 2 CH (OH) CH 2 SO 3 - (Id) in which R 1 has the same meaning as in formula I.
- amphoteric surfactants are the carbo-betaines, in particular the carbo-betaines of the formula (Ia) and (Ib), most preferably the alkylamido-betaines of the formula (Ib).
- betaines and sulfobetaines are the following compounds designated as INCI : almondamidopropyl betaines, apricotamidopropyl betaines, avocadamidopropyl betaines, babassuamidopropyl betaines, behenamidopropyl betaines, behenyl betaines, betaines, canolamidopropyl betaines, caprylic / capramidopropyl betaines, carnitines, cetyl betaines, cocamidoethyl betaines, cocamidopropyl Betaines, cocamidopropyl hydroxysultaines, coco-betaines, coco-hydroxysultaines, coco / oleamidopropyl) betaines, coco-sultaines, decyl betaines, dihydroxyethyl oleyl glycinates, dihydroxyethyl soy glycinates, dihydroxy,
- Suitable amine oxides are the following compounds designated as INCI : Almondamidopropylamine oxides, Babassuamidopropylamine oxides, Behenamine oxides, Cocamidopropyl Amine oxides, Cocamidopropylamine oxides, Cocamine oxides, Coco-Morpholine oxides, Decylamine oxides, Decyltetradecylamine oxides, Diaminopyrimidine oxides, Dihydroxyethyl C8-10 alkoxypropylamines oxides , Dihydroxyethyl C9-11 alkoxypropylamines oxides, dihydroxyethyl C12-15 alkoxypropylamines oxides, dihydroxyethyl cocamine oxides, dihydroxyethyl lauramine oxides, dihydroxyethyl stearamines oxides, dihydroxyethyl tallowamine oxides, hydrogenated palm kernel amine oxides, hydrogenated tallowamine oxides, hydroxyethyl hydroxypropyl
- R 9 is -CO-NH- (CH 2 ) 2 -N (R 11 ) -CH 2 CH 2 OCH 2 -COOM (IIIa).
- IIIc R 9 -CO-NH- (CH 2 ) 2 -N (R 11 ) -CH 2 CH 2 O-CH 2 CH (OH) CH 2 -OPO 3 HM (IIId) in which R 11 and M have the same meaning as in formula (III).
- alkylamidoalkylamines are the following named according to INCI compounds: Cocoamphodipropionic Acid, Cocobetainamido amphopropionates, DEA-Cocoamphodipropionate, Disodium Caproamphodiacetate, Disodium Caproamphodipropionate, Disodium Capryloamphodiacetate, Disodium Capryloamphodipropionate, Disodium Cocoamphocarboxyethylhydroxypropylsulfonate, Disodium Cocoamphodiacetate, Disodium Cocoamphodipropionate, Disodium Isostearoamphodiacetate, Disodium Isostearoamphodipropionate, Disodium laureth 5 carboxyamphodiacetates, disodium lauroamphodiacetate, disodium lauroamphodipropionate, disodium oleoamphodipropionate, disodium PPG-2-Isodeceth-7 Carboxyamph
- alkyl-substituted amino acids are the aminopropionates according to formula (IVa), R 13 -NH-CH 2 CH 2 COOM '(IVa) in which R 13 and M 'have the same meaning as in formula (IV).
- alkyl substituted amino acids are the following INCI compounds: Aminopropyl Laurylglutamine, Cocaminobutyric Acid, Cocaminopropionic Acid, DEA Lauraminopropionate, Disodium Cocaminopropyl Iminodiacetate, Disodium Dicarboxyethyl Cocopropylenediamine, Disodium Lauriminodipropionate, Disodium Steariminodipropionate, Disodium Tallowiminodipropionate, Lauraminopropionic Acid, Lauryl Aminopropylglycine, Lauryl Diethylenediaminoglycine, Myristaminopropionic Acid, Sodium C12-15 Alkoxypropyl Iminodipropionate, Sodium Cocaminopropionate, Sodium Lauraminopropionate, Sodium Liminiminodipropionate, Sodium Lauroyl Methylaminopropionate, TEA Lauraminopropionate and TEA Myristaminoprop
- Acylated amino acids are amino acids, in particular the 20 natural ⁇ -amino acids which carry on the amino nitrogen atom the acyl radical R 19 CO of a saturated or unsaturated fatty acid R 19 COOH, where R 19 is a saturated or unsaturated C 6-22 alkyl radical, preferably C 8-18 alkyl group, preferably a saturated C 10-16 alkyl group, for example a saturated C 12-14 alkyl group.
- the acylated amino acids can also be used as the alkali metal salt, alkaline earth metal salt or alkanolammonium salt, for example mono-, di- or triethanolammonium salt.
- acylated amino acids are the acyl derivatives summarized in accordance with INCI under Amino Acids, for example sodium cocoyl glutamate, lauroyl glutamic acid, capryloyl glycine or myristoyl methylalanine.
- the total surfactant content of the fabric care compositions, without the amount of fatty acid soap is below 55% by weight, preferably below 50% by weight, more preferably between 38 and 48% by weight, based in each case on the entire composition.
- the textile care agents may additionally comprise further detergent additives, for example from the group of builders, bleaches, bleach activators, electrolytes, pH adjusters, fragrances.
- the funds may contain builders. All the builders conventionally used in detergents and cleaners can be incorporated into the compositions according to the invention, in particular zeolites, silicates, carbonates, organic cobuilders and-where there are no ecological prejudices against their use-the phosphates also exist.
- Suitable crystalline layered sodium silicates have the general formula NaMSi x O 2x + 1 • H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are.
- Such crystalline sheet silicates are described, for example, in the European patent application EP-A-0 164 514 described.
- 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, with ⁇ -Na-triumdisilikat
- ⁇ -Na-triumdisilikat For example, according to the method can be obtained in the international patent application WO-A-91/08171 is described.
- 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 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” is also understood to mean "X-ray amorphous”.
- the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of 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, values of up to max. 50 nm and in particular up to max. 20 nm are preferred.
- Such so-called X-ray amorphous silicates which likewise have a dissolution delay compared to the conventional water glasses, are described, for example, in the German patent application DE-A-44 00 024 described.
- Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
- the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
- zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
- zeolite X and mixtures of A, X and / or P are particularly preferred.
- zeolite X and zeolite A are cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company CONDEA Augusta SpA under the brand name VEGOBOND AX ® and by the formula nNa 2 O • (1-n) K 2 O • Al 2 O 3 • (2-2.5) SiO 2 • (3.5-5.5) H 2 O can be described.
- Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
- the zeolites can also be used as overdried zeolites with lower water contents and then, due to their hygroscopicity, are suitable for removing unwanted residual traces of free water.
- phosphates as builders are possible, unless such use should not be avoided for environmental reasons.
- polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular weight of 500 to 70,000 g / mol.
- the molecular weights given for polymeric polycarboxylates are weight-average molar masses M W of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard.
- Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 2,000 to 10,000 g / mol, and particularly preferably from 3,000 to 5,000 g / mol, may again be preferred from this group. Suitable polymers may also include substances consisting partly or wholly of units of vinyl alcohol or its derivatives.
- copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
- Particularly suitable copolymers of acrylic acid with maleic acid have proven to be the 50th to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid.
- Their molecular weight relative to free acids is generally from 2,000 to 70,000 g / mol: preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
- the (co) polymeric polycarboxylates can be used either as an aqueous solution or, preferably, as a powder.
- the polymers may also allylsulfonic acids, such as in the EP-B-0 727 448 Allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.
- copolymers are those described in the German patent applications DE-A-43 03 320 and DE-A-44 17 734 and monomers preferably having acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
- polymeric aminodicarboxylic acids their salts or their precursors.
- Particularly preferred are polyaspartic acids or their salts and derivatives, of which in the German patent application DE-A-195 40 086 is disclosed that they also have a bleach-stabilizing effect in addition to Cobuilder properties.
- polyvinylpyrrolidones polyamine derivatives such as quaternized and / or ethoxylated hexamethylenediamines.
- polyacetals which are prepared by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups, for example as in the European patent application EP-A0 280 223 described, can be obtained.
- Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
- dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
- the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500 000 g / mol.
- a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is.
- DE dextrose equivalent
- oxidized dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
- oxidized dextrins and methods of their preparation are, for example, from the European patent applications EP-A-0 232 202 . EP-A-0 427 349 .
- EP-A-0 472 042 and EP-A-0 542 496 as well as the international patent applications WO-A92 / 18542 . WO-A-93108251 . WO-A-93/16110 . WO 94/28030 . WO-A-95/07303 . WO 95/12619 and WO 95/20608 known. Also suitable is an oxidized oligosaccharide according to the German patent application DE-A-196 00 018 , A product oxidized to C 6 of the saccharide ring may be particularly advantageous. Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable co-builders.
- ethylenediamine-N, N'-disuccinate EDDS
- EDDS ethylenediamine-N, N'-disuccinate
- glycerol disuccinates and glycerol trisuccinates as described, for example, in US Pat US 4,524,009 .
- US 4,639,325 In the European patent application EP-A-0 150 930 and Japanese Patent Application JP-A-93 / 339,896 to be discribed. Suitable amounts are in zeolith lotteryn and / or silicate-containing formulations at 3 to 15 wt .-%.
- organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
- Such co-builders are described, for example, in the international patent application WO 95/20029 described.
- the agents may optionally be builders in amounts of 1 to 30 wt .-%, preferably 10 to 25 wt .-% ..
- the agents may contain bleach.
- bleach Among the compounds serving as bleaches in water H 2 O 2 , sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
- Other useful bleaching agents are, for example, peroxopyro phosphate, citrate perhydrates and H 2 O 2 supplying persaure salts or peracids, such as persulfates or persulfuric acid.
- the urea peroxohydrate percarbamide which can be described by the formula H 2 N-CO-NH 2 -H 2 O 2 .
- the means for cleaning hard surfaces for example in automatic dishwashing, they may, if desired, also contain bleaching agents from the group of organic bleaches, although their use is also possible in principle for laundry detergents.
- Typical organic bleaches are the diacyl peroxides, such as dibenzoyl peroxide.
- Other typical organic bleaching agents are the peroxyacids, examples of which include the alkylperoxy acids and the aryl peroxyacids.
- Preferred representatives are the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid (phthalimidoperoxyhexanoic acid, PAP), o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-di
- the agents according to the invention can particularly preferably contain phthalimidoperoxyhexanoic acid (PAP).
- PAP phthalimidoperoxyhexanoic acid
- the bleaching agents may be coated to protect against premature degradation.
- the agents may contain bleach activators.
- 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, triethylacetylcitrate (TEAC), ethylene glycol diacetate, 2 , 5-diacetoxy-2
- TAED
- the agents may contain electrolytes.
- electrolytes from the group of inorganic salts, a wide number of different salts can be used. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a production point of view, the use of NaCl or MgCl 2 in the agents according to the invention is preferred.
- the proportion of electrolytes in the inventive compositions is usually 0.5 to 5 wt .-%.
- the agents may contain pH adjusters. In order to bring the pH of the agent in the desired range, the use of pH adjusters may be indicated. Can be used here are all known acids or alkalis, unless their use is not for technical application or environmental reasons or for reasons of consumer protection prohibited. Usually, the amount of these adjusting agents does not exceed 2% by weight of the total formulation.
- the agents may contain dyes and perfumes.
- Dyes and fragrances are added to the compositions in order to improve the aesthetic impression of the products and to provide the consumer, in addition to the washing or cleaning performance, a visually and sensory "typical and unmistakable" product.
- perfume oils or fragrances individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Fragrance compounds of the ester type are known e.g.
- the ethers include, for example, benzyl ethyl ether, to the aldehydes e.g.
- the linear alkanals having 8-18 C atoms citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the ionones, ⁇ -isomethylionone and methyl cedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene.
- fragrance oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood.
- the agents may contain UV absorbers.
- the agents may contain UV absorbers which are applied to the treated fabrics and improve the light fastness of the fibers and / or the lightfastness of the other ingredients of the formulation.
- Under UV absorber are organic substances (sunscreen) to understand, which are able to absorb ultraviolet rays and the absorbed energy in the form of longer-wave radiation, eg heat to give back.
- Compounds having these desired properties include, for example, the non-radiative deactivation compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position.
- substituted benzotriazoles such as the water-soluble benzenesulfonic acid-3- (2H-benzotriazol-2-yl) -4-hydroxy-5- (methylpropyl) monosodium salt (Ciba ® Fast H), in the 3-position Phe nylsubstituiert acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural products such as umbelliferone and the body's own urocanic acid suitable.
- UV-B absorber are 3-benzylidene camphor or 3-Benzylidennorcampher and its derivatives, for example 3- (4-methylbenzylidene) camphor, as in EP 0693471 B1 described; 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and 4- (dimethylamino) benzoic acid ester; Esters of cinnamic acid, preferably 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isoamyl ester, 2-cyano-3
- EP 0694521 B1 described. Also suitable are 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts; Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophe-non-5-sulfonic acid and its salts; Sulfonic acid derivatives of 3-Benzylidencamphers, such as 4- (2-oxo-3-bomylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and salts thereof.
- UV-A filter in particular derivatives of benzoylmethane are suitable, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl 4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) -propane-1,3-dione, and enamine compounds as described in U.S.P. DE 19712033 A1 (BASF).
- the UV-A and UV-B filters can also be used in mixtures.
- insoluble photoprotective pigments namely finely dispersed, preferably nano-metal oxides or salts
- suitable metal oxides are in particular zinc oxide and titanium dioxide and in addition oxides of iron, zirconium, silicon, manganese, aluminum and cerium, and mixtures thereof.
- salts silicates (talc), barium sulfate or zinc stearate can be used.
- the oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics.
- the particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm.
- the pigments may have a spherical shape, but it is also possible to use those particles which have an ellipsoidal or otherwise deviating shape from the spherical shape.
- the pigments can also be surface-treated, ie hydrophilized or hydrophobized. Typical examples are coated titanium dioxides, for example Titandioxid T 805 (Degussa) or Eusolex ® T2000 (Merck). Suitable hydrophobic coating agents are in particular silicones and in particular trialkoxyoctylsilanes or simethicones. Preferably, micronized zinc oxide is used. Further suitable UV sunscreen filters are the overview of P. Finkel in S ⁇ FW Journal 122, 543 (1996 ) refer to.
- the UV absorbers are usually used in amounts of from 0.01% by weight to 5% by weight, preferably from 0.03% by weight to 1% by weight.
- the agents may contain anti-crease agents. Since fabrics, in particular of rayon, wool, cotton and their blends, may tend to wrinkle because the individual fibers are susceptible to flexing, buckling, squeezing and squeezing across the grain, the compositions may contain synthetic crease inhibitors. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, -alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.
- the agents may contain grayness inhibitors. Grayness inhibitors have the task to keep suspended from the fiber debris suspended in the fleet and so prevent the re-raising of the dirt.
- Water-soluble colloids of mostly organic nature are suitable for this purpose, for example glue, gelatine, salts of ether sulfonic acids or 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 such as degraded starch, aldehyde starches, etc.
- polyvinylpyrrolidone is useful.
- cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose.
- the textile care agents preferably liquid detergents
- the textile care agents are present as a portion in a completely or partially water-soluble coating. Portioning makes it easier for the consumer to dose.
- the textile care products are packed in foil bags, for example. Film bags made of water-soluble film make it unnecessary for the consumer to tear open the packaging. In this way, a convenient dosing of a single, sized for a wash portion by inserting the bag directly into the washing machine or by inserting the bag into a certain amount of water, for example in a bucket, a bowl or in Handwasch- or - Hughesbecken, possible.
- the film bag surrounding the washing portion dissolves without residue when it reaches a certain temperature.
- Laundry detergents also packaged in bags of water-soluble film are described in large numbers in the prior art.
- the older patent application discloses DE 198 31 703 a portioned detergent or cleaner preparation in a bag of water-soluble film, in particular in a bag of (optionally acetalized) polyvinyl alcohol (PVAL), wherein at least 70 wt .-% of the particles of the detergent or cleaning preparation particle sizes> 800 microns .
- PVAL polyvinyl alcohol
- Thermoformverrfahren thermoforming method
- Thermoformverrfahren thermoforming method
- the prior art discloses processes for preparing water-soluble capsules of polyvinyl alcohol or gelatin, which in principle offer the possibility of providing capsules with a high degree of filling.
- the methods are based on introducing the water-soluble polymer into a shaping cavity.
- the filling and sealing of the capsules takes place either synchronously or in successive steps, in which case the filling takes place through a small opening in the latter case. Processes in which the filling and sealing is parallel, for example, in WO 97/35537 described.
- the filling of the capsules takes place by means of a filling wedge which is arranged above two mutually rotating drums which have ball half shells on their surface.
- the drums carry polymer bands that cover the ball half-shell cavities.
- a seal takes place at the positions where the polymer band of one drum coincides with the polymer tape of the opposite drum.
- the filling material is injected into the forming capsule, wherein the injection pressure of the filling liquid presses the polymer bands in the Kugelschschalenkavticianen.
- a process for producing water-soluble capsules in which first the filling and then the sealing is carried out in the WO 01/64421 disclosed.
- the manufacturing process is based on the so-called Bottle-Pack ® method, as described for example in German Offenlegungsschrift DE 14114 69 is described.
- Bottle-Pack ® method as described for example in German Offenlegungsschrift DE 14114 69 is described.
- a tubular preform is guided into a two-part cavity.
- the cavity is closed, the lower tube portion is sealed, then the tube is inflated to form the capsule shape in the cavity, filled and finally sealed.
- the shell material used for the preparation of the water-soluble portion is preferably a water-soluble polymeric thermoplastic, more preferably selected from the group (optionally partially acetalized) polyvinyl alcohol, polyvinyl alcohol copolymers, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and derivatives thereof, starch and derivatives thereof, blends and composites, inorganic salts and mixtures of said materials, preferably hydroxypropylmethylcellulose and / or polyvinyl alcohol blends.
- a water-soluble polymeric thermoplastic more preferably selected from the group (optionally partially acetalized) polyvinyl alcohol, polyvinyl alcohol copolymers, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and derivatives thereof, starch and derivatives thereof, blends and composites, inorganic salts and mixtures of said materials, preferably hydroxypropylmethylcellulose and / or polyvinyl alcohol blends.
- the shell material consists entirely or partially of the copolymers to be used according to the invention in the textile care compositions.
- the polyvinyl alcohols described above are commercially available, for example under the trade name Mowiol ® (Clariant).
- particularly suitable polyvinyl alcohols are, for example, Mowiol ® 3-83, Mowiol ® 4-88, Mowiol ® 5-88, Mowiol ® 8-88 and Clariant L648.
- polyvinyl alcohols ® ELVANOL 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont)
- ALCOTEX ® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.)
- Gohsenol ® NK-05, A-300, AH-22, C -500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (Trademark of Nippon Gohsei KK ).
- the water-soluble thermoplastic used to prepare the portion may additionally comprise polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers and / or mixtures of the above polymers.
- the water-soluble thermoplastic used comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
- the water-soluble thermoplastic used comprises a polyvinyl alcohol whose molecular weight is in the range of 10,000 to 100,000 gmol -1 , preferably 11,000 to 90,000 gmol -1 , more preferably 12,000 to 80,000 gmol -1 and especially 13,000 to 70,000 gmol -1 lies.
- thermoplastics are used in amounts of at least 50% by weight, preferably of at least 70% by weight, more preferably of at least 80% by weight and in particular of at least 90% by weight, based in each case on the weight of the water-soluble polymeric thermoplastic, is present.
- the polymeric thermoplastics may contain plasticizing aids to improve their machinability. This may be advantageous in particular if polyvinyl alcohol or partially hydrolyzed polyvinyl acetate has been chosen as the polymer material for the portion. Glycerol, triethanolamine, ethylene glycol, propylene glycol, diethylene or dipropylene glycol, diethanolamine and methyldiethylamine have proved particularly suitable as plasticizing auxiliaries.
- the polymeric thermoplastics plasticizing in amounts of at least> 0 wt .-%, preferably of ⁇ 10 wt .-%, particularly preferably of ⁇ 20 wt .-% and in particular of ⁇ 30 wt .-%, each based on the weight of the wrapping material.
- the fabric care agent is used in a conditioning substrate comprising a substrate impregnated and / or impregnated with the fabric care agent.
- the substrate material is made of porous materials capable of reversibly adding and dispensing an impregnating liquid.
- porous materials capable of reversibly adding and dispensing an impregnating liquid.
- the substrate material may consist of a fibrous or cellular flexible material which has sufficient thermal stability for use in the dryer and which can retain sufficient quantities of impregnating or coating agent to effectively condition fabrics without significant bleeding or bleeding during storage By means of done.
- wipes include cloths of woven and non-woven synthetic and natural fibers, felt, paper or foam, such as hydrophilic polyurethane foam.
- Nonwovens are generally defined as adhesively bonded fibrous products having a mat or layered fibrous structure, or those comprising fibrous mats in which the fibers are randomly or randomly distributed.
- the fibers may be natural such as wool, silk, jute, hemp, cotton, flax, sisal or ramie; or synthetic, such as rayon, cellulose esters, polyvinyl derivatives, polyolefins, polyamides, viscose or polyesters.
- any fiber diameter or titer is suitable for the present invention.
- Preferred conditioning substrates according to the invention consist of a nonwoven material which contains cellulose.
- nonwoven fabrics employed herein tend not to rupture or disintegrate due to the random or random arrangement of fibers in the nonwoven material which impart excellent strength in all directions when used, for example, in a household tumble dryer.
- nonwoven fabrics suitable as substrates in the present invention include, for example WO 93/23603 known.
- Preferred porous and flat conditioning cloths consist of one or different fiber materials, in particular of cotton, refined cotton, polyamide, polyester or mixtures of these.
- the conditioning substrates in fabric form preferably have an area of from 0.2 to 0.005 m 2 , preferably from 0.15 to 0.01 m 2 , in particular from 0.1 to 0.03 cm 2 and particularly preferably from 0.09 to 0, 06 m 2 up.
- the grammage of the material is usually between 20 and 500 g / m 2 , preferably from 25 to 200 g / m 2 , in particular from 30 to 100 g / m 2 and particularly preferably from 40 to 80 g / m 2 .
- the conditioning process is carried out by using the conditioning substrate in a textile drying process together with wet textiles, for example obtained from a previous washing process.
- the textile drying process usually takes place in a device for drying textiles, preferably in a household tumble dryer.
- the conditioning substrates may be added directly to the wet laundry in a household dryer and / or a washing machine.
- the textile care products are prepared by simple, familiar to the expert, mixing together and stirring of the individual components.
- the copolymers to be used according to the invention can be admixed as a solution, preferably as an aqueous solution, the agent and / or can be compounded or granulated, mixed, tableted or pelletized as a dried powder, preferably as a carrier on a detergent component.
- the esterquats are first melted and incorporated the melt with a highly dispersive stirring in a preferably aqueous, preferably preheated formulation.
- Table 1 shows the formulation according to the invention E1 and the comparative formulation V1. All information is given in weight percent, in each case based on the total mean.
- Table 1 ⁇ / b> raw material E1 E2 V1 Sodium alkylbenzenesulfonate 11.43 11.43 11.43 Enzyme (protease, amylase, cellulase) 0.7 0.7 0.7 0.7 Perfume 0.32 0.32 0.32 C 12 -C 18 fatty alcohol + 7 EO 2.7 2.7 2.7 Hydroxyethane-1,1-diphosphonic 0.74 0.74 0.74 Hydroxypropane-1,2,3-tricarboxylic acid * 1H 2 O 1.0 1.0 1.0 paraffin 0.44 0.44 0.44 sodium 20.5 20.5 20.5 sodium carbonate peroxyhydrate 13.0 13.0 13.0 sodium 5.0 5.0 5.0 sodium hydroxide 0.5 0.5 0.5 0.5 Sodium silicate 2.0 [a] 4.7 4.7 4.7 sodium sulphate 26.8 26.8 26.8 polyacrylates 3.0 3.
- a commercially available Rowenta P2 Professional iron was pulled across the fabric by a Zwick universal testing machine (type 2.5 / TN1 P) over a pulley longitudinally at a speed of 800 mm per minute.
- the temperature of the iron has been set to level III.
- the weight of the 1680 g heavy iron was increased by additional weights to 2940 g.
- the force required to move the iron was measured in [N].
- test fabrics (fabric: bleached nettle, 100% cotton, 1.2 * 0.2 m) were treated with the formulations E1, E2 and the comparative formulation without fabric care component V1 as follows: 6 fabric strips were washed with 109 g of the respective formulation [water hardness: 16 ° dH] (Miele Novotronik W918, washing program: standard cotton / color 60 ° C./spinning: 900 rpm) and then dried (2 days hanging on a line in the climate chamber at 20 ° C and 65% humidity). The washing and drying cycles were repeated 3 times each.
- Table 2 shows the measured sliding friction forces as a function of the test fabric treated with the formulations: ⁇ b> Table 2 ⁇ / b> Test tissue treated with E1 E2 V1 Measured force in [N] 9.5 8.0 13
- the determination of the creasing takes place in accordance with the AATCC Test 124 (American Association of Textile and Color Chemistry). Creases are evaluated after the washing and subsequent drying process, with a panel of five assessing the creasing of the test fabrics against crumpled standard tissues (AATCC124). The grade 5 is awarded for wrinkle-free fabrics and the grade 1 for heavily wrinkled fabric. The overall grade represents the arithmetic mean of the ratings.
- the test fabrics (textile: whitehead, 100% cotton, 1.0 m * 0.9 m) were mixed with the formulations E1 and the comparative formulation without a textile care component.
- V1 treated as follows: 3 tissue pieces were washed with 109 g of the respective formulation [water hardness: 16 ° dH] (Miele Novotronik W918, washing program: Standard Cotton / Color 60 ° C / Spinning: 900 rpm) and then dried (2 days hanging on a line in the climatic chamber at 20 ° C and 65% humidity). The washing and drying cycles were repeated 3 times each.
- Table 3 shows the evaluation of the wrinkles of the test fabrics depending on the recipes: ⁇ b> Table 3 ⁇ / b> Test tissue treated with E1 V1 Wrinkle Rating [Note] 2.1 1.4
- Textile care agents formulated according to the invention which are present as liquid detergents are, for example, E3 to E5 , the compositions of which are reproduced in Table 4.
- Table 4 ⁇ / b> raw material
- E3 E4 E5 APG 600 [a] 1.5 --- --- Defoamer [b] 0.03 0.03 0.03 glycerin 5.0 --- diethylene glycol 0.5 --- Propylene-1,2-glycol --- 5 5 ethanol --- 2.5 2.3 Texapon N70 [c] 5 5 5 5 Dehydrol LT7 [d] 12 13 12 boric acid 0.25 1 1 sodium 1.5 --- --- Sodium Citrate x 2H 2 O --- 2 4 sodium hydroxide 0.85 0.85 1.5 lauric acid 3 3 6 oleic acid 1.5 1.5 2.4 ricinoleate 0.5 0.5 --- Acusol 820 [e] 0.2 --- --- Dequest 2066 [f] 0.5 0.5 0.03 polyvinylpyrrolidone 0.1 0.1 0.1
- Table 5 shows the formulation of a formulated according to the invention textile care product, which is present as a mild detergent E6.
- E6 ⁇ b> Table 5
- Table 5 ⁇ / b> raw material
- E6 APG 600 2.5 ethylene glycol 0.3 ethanol 0.37 Cetylstearylalkoholsulfat Na salt 0.47 Dehydrol LT7 14.0
- Stepantex VA90 [n] 2.5 citric acid 0.05 cellulase 0.04 Perfume 0.7 Polymer A 0.5 water ad 100 [n] N-methyl-N (2-hydroxyethyl) -N, N- (ditallowacyloxyethyl) -ammonium methosulfate ex Stepan
- Table 6 shows a textile care agent formulated according to the invention which is formulated as a nonaqueous liquid detergent E7.
- Table 6 ⁇ / b> raw material E7 glycerin 1 ethanol 3.3 C12-14 fatty alcohol + EO + PO 22.5 Dodecylbenzenesulfonic-isopropylamine salt 24.5 C 12-18 fatty acid 17.5 Dequest 2066 0.6 Monoethanolamine 4.9 protease 1 amylase 0.2 cellulase 0.06 water 6 Perfume 0.25 dye + Polymer A 5.0 propylene glycol ad 100
- the agents formulated according to the invention E3 to E7 showed a reduced formation of fluff and pilling in comparison to non-inventively formulated agents which did not contain copolymers to be used according to the invention.
- a textile care agent formulated according to the invention which is formulated as a fabric conditioning agent is, for example, E8
- a comparison formulation is V1 whose compositions are given in Table 7.
- Formulation E8 was prepared by melting the esterquat in water. The molten esterquat is then stirred with a high dispersing device and the remaining active substances added. The perfume addition was carried out after cooling the mixture to below 30 ° C.
- nonwovens made of cellulose were impregnated with 20 g of the fabric softener E8 according to the invention.
- a comparison substrate with formulation V2 was produced.
- the weight of the fluff was determined after each drying cycle and added over the 10 cycles. It showed for a) 7.58 g, for b) 8.39 g and for c) 5.51 g.
- the scouring discs with a diameter of 14.0 mm are clamped over the scrubbing tables, underlaid by standard felt discs.
- the test specimens (diameter 140 mm) are fixed in special specimen holders and placed with the right side to the counter-textile.
- the guide plate of the device is placed above and spindles loaded with weights are inserted through the guide plate into the underlying sample holders.
- the drive mechanism consists of two outer and one inner drive, which forces the sample holder guide plate to describe a Lissajous figure.
- the Lissajous movement changes into a circular motion to gradually narrowing ellipses until it becomes a straight line from which progressively expanding ellipses develop in a diagonally opposite direction before repeating the pattern. Pill grade is determined by comparing the sample to prepared photographs of standard items. The measurement has shown that the pilling of the textiles, which is significantly reduced with the conditioning substrate c) compared to the samples from a) and b).
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Claims (20)
- Utilisation d'un copolymère, pouvant être obtenu par copolymérisation d'un composant (a), comprenant un ou plusieurs acides carboxyliques éthyléniquement insaturés et/ou leurs sels, avec un composant (b) comprenant des hydrates de carbone, en présence le cas échéant d'un composant (c), comprenant un ou plusieurs oxydants, dans un agent d'entretien des textiles pour la réduction de la formation de peluches.
- Utilisation d'un copolymère, pouvant être obtenu par copolymérisation d'un composant (a), comprenant un ou plusieurs acides carboxyliques éthyléniquement insaturés et/ou leurs sels, avec un composant (b) comprenant des hydrates de carbone, en présence le cas échéant du composant (c), comprenant un ou plusieurs oxydants, dans un agent d'entretien des textiles pour la réduction de la formation de bouloches de structures planes textiles.
- Utilisation selon la revendication 1 ou la revendication 2, caractérisée en ce que le composant (a) représente un ou plusieurs acides carboxyliques éthyléniquement insaturés en C3-C10, de préférence un ou plusieurs acides carboxyliques en C3-C6, de manière particulièrement préférée un ou plusieurs acides carboxyliques α,β-insaturés, en particulier un ou plusieurs acides carboxyliques α,β-insaturés en C3-C6 et/ou leurs sels de métal alcalin et/ou d'ammonium ainsi que des mélanges quelconques.
- Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que le composant (a) est choisi dans le groupe formé par l'acide acrylique, l'acide méthacrylique, leurs mélanges ainsi que les sels de sodium, de potassium ou d'ammonium ou leurs mélanges.
- Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que l'hydrate de carbone est choisi dans le groupe des oligosaccharides et des polysaccharides, de préférence l'amidon, la pectine, l'algine, la chitine, le chitosane, l'héparine, le carraghénane, l'agar, la gomme arabique, la gomme adragante, la gomme de karaya, la gomme ghatti, la farine de graines de caroube, la gomme guar, la gomme de tara, l'inuline, le xanthane, le dextran, le saccharose, le nigérane et les pentosanes tels que le xylane et l'arabane, de manière particulièrement préférée les hydrates de carbonate solubles dans l'eau, pouvant être mis en suspension ou gonflables dans l'eau, principalement les polysaccharides d'amidon et/ou les polysaccharides essentiellement linéaires qui existent dans les amidons, en particulier l'amylose, et leurs produits de dégradation, par exemple le sirop ou les dextrines, ainsi que les mélanges de ces polysaccharides, et/ou d'autres polysaccharides essentiellement linéaires, ainsi que des polysaccharides ramifiés, tels que la cellulose, le xylane, l'arabane et le galactane.
- Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que le copolymère peut être obtenu en présence d'un oxydant, de préférence d'un peracide, en particulier le peroxyde d'hydrogène.
- Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que le copolymère se trouve sous forme de copolymère greffé.
- Utilisation selon la revendication 7, caractérisée en ce que le copolymère greffé présente une densité de greffage élevée et des branches greffées courtes, de préférence avec un degré de substitution moyen, c'est-à-dire le nombre de positions dans une unité d'hydrate de carbone qui ont été substituées par des composants (a), supérieur à 1,5, de préférence supérieur à 2 et en particulier supérieur à 2,5.
- Utilisation selon l'une quelconque des revendications 7 ou 8, caractérisée en ce qu'en moyenne chaque site de greffage sur le copolymère greffé présente plus d'un monomère, de préférence plus de 2 monomères, de manière particulièrement préférée 2,5 à 5 unités monomères de composant (a).
- Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que le copolymère présente une masse molaire moyenne dans la plage supérieure à 1000, de préférence supérieure à 5000, de manière particulièrement préférée supérieure à 10000, en particulier supérieure à 15 000, avantageusement entre 18 000 et 70 000, de manière extrêmement préférée entre 20 000 et 65 000 g/mole.
- Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle contient le copolymère en une quantité activé, de préférence supérieure à 0,05% en poids, de manière particulièrement préférée de 0,1 à 10% en poids, en particulier de 1 à 5% en poids, à chaque fois par rapport à la totalité de l'agent.
- Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que l'agent d'entretien des textiles contient des complexants, en particulier des complexants organiques, avantageusement solubles dans l'eau, de manière particulièrement préférée des complexants présentant des groupes acides, de manière extrêmement préférée l'acide citrique et/ou ses sels de métal alcalin.
- Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que l'agent d'entretien des textiles est utilisé sous forme solide, de préférence sous forme de poudre, de granulat, d'extrudat, de corps façonné comprimé et/ou fondu ou sous forme de comprimé, de manière particulièrement préférée sous forme liquide, en particulier sous forme de dispersion, suspension, émulsion, solution, microémulsion, gel ou pâte.
- Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que l'agent d'entretien des textiles contient des agents tensioactifs non ioniques en des quantités jusqu'à 35% en poids, de préférence de 5 à 25% en poids, de manière particulièrement préférée de 10 à 20% en poids, à chaque fois par rapport à la totalité de l'agent.
- Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que l'agent d'entretien des textiles contient des enzymes, de préférence choisies dans le groupe des protéases et/ou des amylases et/ou des cellulases.
- Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que l'agent d'entretien des textiles contient en outre des composants assouplissants, de préférence des agents tensioactifs cationiques, de manière particulièrement préférée des esters quaternaires.
- Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que l'agent d'entretien des textiles se trouve sous forme d'agent de lavage doux ou d'agent assouplissant, contenant des assouplissants, de préférence des assouplissants cationiques, de manière particulièrement préférée des esters quaternaires.
- Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que l'agent d'entretien des textiles se trouve sous forme d'agent de lavage liquide.
- Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que l'agent d'entretien des textiles se trouve sous forme de portion dans une enveloppe totalement ou partiellement soluble dans l'eau.
- Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que l'agent d'entretien des textiles est utilisé dans un substrat de conditionnement, qui présente un substrat qui est imprégné et/ou imbibé par l'agent d'entretien des textiles.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10253975 | 2002-11-20 | ||
DE10253975 | 2002-11-20 | ||
PCT/EP2003/012484 WO2004046288A2 (fr) | 2002-11-20 | 2003-11-08 | Produit d'entretien doux pour textiles |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1563046A2 EP1563046A2 (fr) | 2005-08-17 |
EP1563046B1 true EP1563046B1 (fr) | 2008-08-20 |
Family
ID=32318547
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP03767523A Expired - Lifetime EP1563046B1 (fr) | 2002-11-20 | 2003-11-08 | Produit d'entretien doux pour textiles |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP1563046B1 (fr) |
AT (1) | ATE405626T1 (fr) |
AU (1) | AU2003292000A1 (fr) |
DE (1) | DE50310385D1 (fr) |
ES (1) | ES2309356T3 (fr) |
WO (1) | WO2004046288A2 (fr) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060281664A1 (en) * | 2005-04-26 | 2006-12-14 | Stickney Janese C O | Dryer added article for lint or hair repulsion on fabric |
DE102005044514A1 (de) * | 2005-09-16 | 2007-03-22 | Henkel Kgaa | Wasch- und Reinigungsmittel mit hautpflegenden Inhaltsstoffen |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4003172A1 (de) * | 1990-02-03 | 1991-08-08 | Basf Ag | Pfropfcopolymerisate von monosacchariden, oligosacchariden, polysacchariden und modifizierten polysacchariden, verfahren zu ihrer herstellung und ihre verwendung |
FR2663948B1 (fr) * | 1990-07-02 | 1994-06-03 | Rhone Poulenc Chimie | Composition detergente contenant un polysaccharide greffe biodegradable. |
DE4233497A1 (de) * | 1992-10-06 | 1994-04-07 | Basf Ag | Verwendung von wäßrigen Polymerisatdispersionen als Textilhilfsmittel zur pflegeleichten Veredlung von Textilien |
EP1280879B1 (fr) * | 2000-05-09 | 2005-07-27 | Unilever Plc | Polymeres eliminant les salissures et compositions de detergents de blanchisserie les contenant |
DE10112318A1 (de) * | 2001-02-05 | 2002-08-14 | Henkel Kgaa | Konditioniermittel |
AU2002246051A1 (en) * | 2001-03-02 | 2002-09-19 | Unilever Plc | Soil release polymers and laundry detergent compositions containing them |
-
2003
- 2003-11-08 AT AT03767523T patent/ATE405626T1/de not_active IP Right Cessation
- 2003-11-08 EP EP03767523A patent/EP1563046B1/fr not_active Expired - Lifetime
- 2003-11-08 ES ES03767523T patent/ES2309356T3/es not_active Expired - Lifetime
- 2003-11-08 WO PCT/EP2003/012484 patent/WO2004046288A2/fr active IP Right Grant
- 2003-11-08 DE DE50310385T patent/DE50310385D1/de not_active Expired - Lifetime
- 2003-11-08 AU AU2003292000A patent/AU2003292000A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
ATE405626T1 (de) | 2008-09-15 |
WO2004046288A2 (fr) | 2004-06-03 |
DE50310385D1 (de) | 2008-10-02 |
ES2309356T3 (es) | 2008-12-16 |
WO2004046288A3 (fr) | 2004-08-12 |
AU2003292000A8 (en) | 2004-06-15 |
AU2003292000A1 (en) | 2004-06-15 |
EP1563046A2 (fr) | 2005-08-17 |
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