EP0808357A1 - Hochalkalisches waschmittel mit schmutzablösevermögendem polymer - Google Patents
Hochalkalisches waschmittel mit schmutzablösevermögendem polymerInfo
- Publication number
- EP0808357A1 EP0808357A1 EP96902941A EP96902941A EP0808357A1 EP 0808357 A1 EP0808357 A1 EP 0808357A1 EP 96902941 A EP96902941 A EP 96902941A EP 96902941 A EP96902941 A EP 96902941A EP 0808357 A1 EP0808357 A1 EP 0808357A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- acid
- composition according
- mpa
- dirt
- 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.)
- Granted
Links
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- 239000003599 detergent Substances 0.000 title claims abstract description 27
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- 239000000203 mixture Substances 0.000 claims description 49
- -1 hydroxypropyl Chemical group 0.000 claims description 48
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 239000002736 nonionic surfactant Substances 0.000 claims description 18
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 239000000344 soap Substances 0.000 claims description 15
- 239000002689 soil Substances 0.000 claims description 15
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- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 14
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- 239000004094 surface-active agent Substances 0.000 claims description 12
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 claims description 11
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- 150000002191 fatty alcohols Chemical class 0.000 claims description 10
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- 230000003287 optical effect Effects 0.000 claims description 8
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- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 3
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
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- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
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- 229920003086 cellulose ether Polymers 0.000 abstract description 5
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- 238000005406 washing Methods 0.000 description 16
- 239000000178 monomer Substances 0.000 description 12
- 150000007513 acids Chemical class 0.000 description 11
- 150000002170 ethers Chemical class 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical group OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 102000004882 Lipase Human genes 0.000 description 7
- 108090001060 Lipase Proteins 0.000 description 7
- 239000004367 Lipase Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- 235000019421 lipase Nutrition 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 229940040461 lipase Drugs 0.000 description 6
- 239000004115 Sodium Silicate Substances 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229940088598 enzyme Drugs 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 229930182470 glycoside Natural products 0.000 description 5
- 150000003839 salts Chemical group 0.000 description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 4
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- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 239000007844 bleaching agent Substances 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 150000002338 glycosides Chemical class 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000010705 motor oil Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- 239000004435 Oxo alcohol Substances 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 229920013820 alkyl cellulose Polymers 0.000 description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000012459 cleaning agent Substances 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
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- 239000000835 fiber Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
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- 238000006384 oligomerization reaction Methods 0.000 description 3
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- 239000005871 repellent Substances 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- YWWVWXASSLXJHU-AATRIKPKSA-N (9E)-tetradecenoic acid Chemical compound CCCC\C=C\CCCCCCCC(O)=O YWWVWXASSLXJHU-AATRIKPKSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 102000013142 Amylases Human genes 0.000 description 2
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- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 2
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- 108010075550 termamyl Proteins 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000009988 textile finishing Methods 0.000 description 1
- DPUOLQHDNGRHBS-MDZDMXLPSA-N trans-Brassidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-MDZDMXLPSA-N 0.000 description 1
- AQWHMKSIVLSRNY-UHFFFAOYSA-N trans-Octadec-5-ensaeure Natural products CCCCCCCCCCCCC=CCCCC(O)=O AQWHMKSIVLSRNY-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000009736 wetting Methods 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent compositions
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
- C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3715—Polyesters or polycarbonates
Definitions
- the invention relates to detergents for the industrial sector which contain dirt-releasing polymer.
- detergents In addition to the ingredients that are indispensable for the washing process, such as surfactants and builder materials, detergents generally contain further constituents which can be summarized under the term washing auxiliaries and which comprise such different active ingredient groups as foam regulators, graying inhibitors, bleaching agents, bleach activators and color transfer inhibitors.
- auxiliary substances also include substances which impart dirt-repellent properties to the laundry fiber and which, if present during the washing process, support the dirt-removing ability of the other detergent components.
- soil release agents are often referred to as "soil release” actives or because of their ability to make the treated surface, for example the fiber, dirt repellent, "soil repellents".
- copolyesters which contain dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. Soil-removing copolyesters of the type mentioned and their use in detergents have been known for a long time.
- German Offenlegungsschrift DT 16 17 141 describes a washing process using polyethylene terephthalate-polyoxyethylene glycol copolymers.
- German laid-open specification DT 2200911 relates to detergents which contain nonionic surfactant and a copolymer of polyoxyethylene glycol and polyethylene terephthalate.
- German laid-open specification DT 22 53 063 lists acidic textile finishing agents which contain a copolymer of a dibasic carboxylic acid and an alkylene or cycloalkylene polyglycol and, if appropriate, an alkylene or cycloalkylene glycol.
- European or European patent EP 185 427 discloses methyl or ethyl end-capped polyesters with ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units and detergents which contain such a soil release polymer.
- European patent EP 241 984 relates to polyesters which, in addition to oxyethylene groups and terephthalic acid units, also contain substituted ethylene units and glycerol units. Polyesters are known from European patent EP 241 985, which contain, in addition to oxyethylene groups and terephthalic acid units, 1,2-propylene, 1,2-butylene and / or 3-methoxy-1,2-propylene groups and glycerol units and with d- to C 4 -alkyl groups are end group-capped.
- the European patent EP 253 567 relates to soil release polymers with a molecular weight of 900 to 9000 made of ethylene terephthalate and polyethylene oxide terephthalate, the polyethylene glycol units having molecular weights of 300 to 3000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate Is 0.6 to 0.95.
- the European patent application EP 272 033 discloses polyesters with poly-propylene terephthalate and polyoxyethylene terephthalate units which are at least partially capped by C 4 alkyl or acyl radicals.
- European patent EP 274 907 describes sulfoethyl end group capped terephthalate-containing soil release polyesters.
- German patent DE 28 46 984 discloses certain hydrophilic polyurethanes and copolyesters with recurring alkoyl terephthalate and polyalkoyl terephthalate units as well as their mixtures as anti-soiling detergent ingredients.
- the German patent DE 26 13 791 describes detergents which contain 0J to 3% by weight of dirt-releasing alkyl cellulose ethers, hydroxyalkyl cellulose ethers or hydroxyalkyl alkyl cellulose ethers.
- detergents for the commercial sector generally contain neither bleach nor bleach activator, since bleaching or disinfection as part of the commercial washing process is a separate treatment step, normally in one of the last zones before leaving the car wash.
- the invention accordingly relates to a highly alkaline detergent which contains nonionic surfactant and has a pH in the range from 10 to 13, in particular from 10 to 12, at a concentration of 1% by weight, which is characterized in that contains a soil release polymer.
- Suitable dirt-releasing polymers for the purposes of the invention are in particular copolyesters from dicarboxylic acids, for example adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or polypropylene glycol, and nonionic hydroxyalkyleliulose ethers, for example hydroxypropyl cellulose.
- dicarboxylic acids for example adipic acid, phthalic acid or terephthalic acid
- diols for example ethylene glycol or propylene glycol
- polydiols for example polyethylene glycol or polypropylene glycol
- nonionic hydroxyalkyleliulose ethers for example hydroxypropyl cellulose.
- Suitable dirt-releasing polyesters are known from the documents cited above and from the unpublished German patent applications DE 44 17 686 and 1 95 02 181.9 and are commercially available, for example, under the names Sokalan® from BASF or Velvetol® 251 C from Rh ⁇ ne-Poulenc.
- the preferred dirt-releasing polyesters include those compounds which are formally accessible by esterification of two monomer parts, the first monomer being a dicarboxylic acid HOOC-Ph-COOH and the second monomer being a diol HO- (CHR 3 -) a OH, which is also used as a polymeric diol H- (O- (CHR 3 -) a ) b OH can be present.
- Ph represents an o-, m- or p-phenylene radical, which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 carbon atoms, sulfonic acid groups, carboxyl groups and mixtures thereof
- R 3 is hydrogen, an alkyl radical 1 to 22 carbon atoms and their mixtures
- a is a number from 2 to 6
- b is a number from 1 to 300.
- the polyesters which can be prepared from these preferably contain both monomer diol units -O- (CHR 3 -). O - as well as polymer diol units - (O- (CHR 3 -).) b O-.
- the molar ratio of monomer diol units to polymer diol units is preferably 100.J to 1: 100, in particular 10: 1 to 1:10.
- the degree of polymerization b in the polymer diol units is preferably in the range from 4 to 200, in particular from 12 to 140.
- the molecular weight or the average molecular weight or the maximum of the molecular weight distribution of preferred dirt-releasing polyesters is in the range from 250 to 100,000, in particular from 500 to 50,000.
- the acid on which the residue Ph is based is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as an alkali or ammonium salt. Among these, the sodium and potassium salts are particularly preferred.
- HOOC-Ph-COOH monomer small proportions, in particular not more than 10 mol%, based on the proportion of Ph with the meaning given above, of other acids which have at least two carboxyl groups can be present in the dirt-releasing polyester.
- these include, for example, alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
- the preferred diols HO- (CHR 3 -) 8 OH include those in which R 3 is hydrogen and a is a number from 2 to 6, and those in which a is 2 and R 3 is hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 carbon atoms is selected.
- R 3 is hydrogen and a is a number from 2 to 6
- R 3 is hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 carbon atoms is selected.
- those of the formula HO-CH 2 -CHR 3 -OH, in which R 3 has the meaning given above are particularly preferred.
- diol components are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2- Decanediol, 1, 2-dodecanediol and neopentyl glycol.
- Particularly preferred among the polymeric diols is polyethylene glycol with an average molecular weight in the range from 1000 to 6000.
- the polyesters composed as described above can also be end-capped, with end groups being alkyl groups having 1 to 22 carbon atoms and esters of monocarboxylic acids come into question.
- the end groups bonded via ester bonds can be based on alkyl, alkenyl and aryl monocarboxylic acids having 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms.
- valeric acid caproic acid, oenanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, oleic acid, oleic acid, laidrose acid , Linolaidic acid, linolenic acid, eläostearic acid, arachic acid, gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotinic acid, melissic acid, benzoic acid, the 1 to 5 substituents with a total of up to 25 carbon atoms, in particular 1 to Can carry 12 carbon atoms, for example tert-butylbenzo
- the end groups can also be based on hydroxymonocarboxylic acids having 5 to 22 carbon atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, their hydrogenation product hydroxystearic acid and o-, m- and p-hydroxybenzoic acid.
- the hydroxymonocarboxylic acids can in turn be connected to one another via their hydroxyl group and their carboxyl group and can therefore be present several times in an end group.
- the number of hydroxymonocarboxylic acid units per end group is preferably in the range from 1 to 50, in particular from 1 to 10.
- the washing or cleaning agent contains polymers of ethylene terephthalate and polyethylene oxide terephthalate, in which the polyethylene glycol units have molecular weights of 750 to 5000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate 50:50 to 90 : 10 is.
- the nonionic hydroxyalkyl cellulose ethers which can be used as soil release agents in the context of the invention include, in particular, hydroxyethyl, hydroxypropyl and / or hydroxybutyl celluloses which can additionally carry alkyl ether groups, in particular methyl, ethyl and / or propyl groups.
- Their content of hydroxyalkoxy groups is preferably in the range from 1% by weight to 20% by weight, in particular from 2% by weight to 15% by weight and particularly preferably from 5% by weight to 10% by weight, each based on nonionic hydroxyalkyl cellulose ethers.
- nonionic hydroxyalkyl cellulose ethers such as, for example, carboxymethyl cellulose, have a noticeably lower activity than the nonionic cellulose ethers.
- the preferred nonionic cellulose ethers include alkyl hydroxylal alkyl celluloses, for example methyl-hydroxyethyl cellulose, methyl-hydroxypropyl cellulose, methyl-hydroxybutyl cellulose, ethyl-hydroxyethyl cellulose, ethyl-hydroxypropyl cellulose and / or ethyl-hydroxybutyl cellulose.
- a soil release polymer is preferably incorporated into detergent in amounts of 0.5% by weight to 5% by weight, in particular 1% by weight to 3% by weight.
- nonionic cellulose ether is used as the dirt-releasing polymer, it can be present in the form of, for example, a solid mixture of the cellulose ether with up to about 10% by weight of sodium chloride and about 6% by weight to 8% by weight of water without this has negative effects on the improvement of fat washability.
- the agent according to the invention contains larger amounts of alkalizing agents, which include, in particular, alkali metal silicates and alkali metal carbonates, but also the alkali metal hydroxides.
- alkalizing agents are contained in the agents according to the invention preferably in amounts from 30% by weight to 85% by weight, in particular from 35% by weight to 80% by weight, mixtures of anhydrous alkali metasilicate, in particular sodium metasilicate, and Alkali carbonate, especially sodium carbonate, of 8: 1 to 1: 2 are preferred.
- An agent according to the invention also contains nonionic surfactant, in particular in an amount in the range from 1% by weight to 25% by weight, preferably from 1.5% by weight to 15% by weight.
- the nonionic surfactants in question include the alkoxylates, in particular the ethoxylates and / or propoxylates of saturated or mono- to polyunsaturated linear or branched chain alcohols having 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms.
- the degree of alkoxylation of the alcohols is generally in the range from 1 to 20, preferably from 3 and 14. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides.
- the derivatives of fatty alcohols are particularly suitable, although their branched-chain isomers, in particular so-called oxo alcohols, can also be used to prepare usable alkoxylates.
- the alkoxylates in particular the ethoxylates, of primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals, and mixtures thereof, can be used.
- 1 to 20 times, in particular 3 to 10 times, alkoxylation products of alkylamines, vicinal diols and carboxamides, which with regard to the Alkyl -enen mentioned alcohols can be used.
- ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters such as can be prepared in accordance with the process specified in international patent application WO 90/13533, and fatty acid polyhydroxyamides, as are used, for example, in accordance with the processes of US Pat. No. 1 985 424, US 2 016 962 and US 2 703 798 and international patent application WO 92/06984 can be considered.
- alkyl polyglycosides suitable for incorporation into the compositions according to the invention are compounds of the general formula (G) p -OR 4 , in which R 4 is an alkyl or alkenyl radical having 8 to 22 C atoms, G is a glycose unit and p is a number between 1 and 10 mean.
- R 4 is an alkyl or alkenyl radical having 8 to 22 C atoms
- G is a glycose unit
- p is a number between 1 and 10 mean.
- the glycoside component (G) p is oligomers or polymers from naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, taiose, gulose, altrose, allose, idose, ribose, arabinose, Xylose and Lyxose belong to.
- the oligomers consisting of such glycosidically linked monomers are characterized not only by the type of sugar they contain, but also by their number, the so-called degree of oligomerization.
- the degree of oligomerization p generally takes fractional numerical values as the quantity to be determined analytically; it is between 1 and 10, for the glycosides preferably used below 1.5, in particular between 1.2 and 1.4.
- the preferred monomer building block is glucose because of its good availability.
- the alkyl or alkenyl part R 4 of the glycosides preferably also originates from easily accessible derivatives of renewable raw materials, in particular from fatty alcohols, although their branched chain isomers, in particular so-called oxo alcohols, can also be used to produce usable glycosides. Accordingly, the primary alcohols with linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful.
- Detergents according to the invention can contain all the usual other constituents of such compositions which do not interact undesirably with the soil-release polymer or the nonionic surfactant.
- Agents according to the invention can additionally contain further surfactants, in particular synthetic anionic surfactants of the sulfate or sulfonate type, in amounts of preferably not more than 10% by weight, in particular OJ% by weight to 5% by weight, in each case based on the total agent, contain.
- Synthetic anionic surfactants which are particularly suitable for use in agents of this type are the alkyl and / or alkenyl sulfates having 8 to 22 carbon atoms and carrying an alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as countercation, to call.
- Soaps are suitable as further optional surfactant ingredients, saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids, being suitable.
- those soap mixtures are preferred which are composed of 50% by weight to 100% by weight of saturated C 2 -C 18 fatty acid soaps and up to 50% by weight of oleic acid soap.
- Soap is preferably contained in amounts of up to 15% by weight, in particular from 2% by weight to 8% by weight.
- higher amounts of beef generally up to 20% by weight, can also be present.
- An agent according to the invention can be water-soluble and / or water-insoluble builders, in particular selected from alkali metal tripolyphosphate, alkali alumosilicate, crystalline alkali silicate with a modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and their mixtures, in particular in amounts in the range from 2% by weight to Contain 30 wt .-% ent.
- the water-soluble organic builder substances include, in particular, those from the class of the polycarboxylic acids, in particular citric acid and sugar.
- the relative molecular mass of the homopolymers of unsaturated carboxylic acids is generally between 5000 and 200000, that of the copolymers between 2000 and 200000, preferably 50,000 to 120,000, based on free acid.
- a particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000.
- Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ether, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight.
- vinyl ethers such as vinyl methyl ether, vinyl esters, ethylene, propylene and styrene
- the proportion of acid is at least 50% by weight.
- Terpolymers which contain two unsaturated acids and / or salts thereof as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer can also be used as water-soluble organic builder substances. The use of the third monomer presumably creates predetermined breaking points in the polymer, which are responsible for the good biodegradability of the polymer.
- terpolymers can be prepared in particular by processes which are described in German patent specification DE 42 21 381 and German patent application DE 43 00 772 and generally have a relative molecular weight between 1000 and 200000, preferably between 200 and 50,000 and in particular between 3000 and 10000. They can be used, in particular for the production of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the polycarboxylic acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
- crystalline or amorphous alkali alumosilicates are used as water-insoluble, water-dispersible inorganic builder materials, in amounts of up to 50% by weight, preferably not more than 40% by weight and in liquid compositions in particular from 1% by weight to 5% by weight. %, used.
- the crystalline aluminosilicates in detergent quality in particular zeolite A, zeolite P and optionally zeolite X, are preferred. Quantities close to the upper limit mentioned are preferably used in solid, particulate compositions.
- Suitable aluminosilicates in particular have no particles with a grain size above 30 ⁇ m and preferably consist of at least 80% by weight of particles with a size below 10 ⁇ m.
- Your calcium binding capacity which can be determined according to the information in German patent DE 24 12 837, is usually in Range from 100 to 200 mg CaO per gram.
- Suitable substitutes or partial substitutes for the aluminosilicate mentioned are certain crystalline or amorphous alkali silicates, which can be present alone or in a mixture with one another.
- the alkali silicates which can be used as builders in the agents according to the invention have a molar ratio of alkali oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12.
- Alkali silicates preferred as builder substances are the sodium silicates, in particular the amorphous sodium silicates, with a Na 2 O: SiO 2 molar ratio of 1: 2 to 1: 2.8, as obtained, for example, according to the method of European patent application EP 0 425 427 can be manufactured.
- Silicates which can be used as builders are also described, for example, in European patent application EP 0 164 514.
- inorganic builder mentioned and the alkalizing agent further water-soluble or water-insoluble inorganic substances can be used in the agents according to the invention.
- the alkali metal chloride, alkali metal bicarbonates and alkali metal sulfates and mixtures thereof are suitable in this connection.
- Such additional inorganic filler material can be present in quantities of up to 40% by weight, but is preferably absent entirely.
- the agents can contain further constituents customary in washing and cleaning agents.
- These optional ingredients include, in particular enzymes, Enzym ⁇ stabilizers, complexing agents for heavy metals, for example aminopolycarboxylic acids, aminohydroxypolycarboxylic, polyphosphonic acids, hydroxypolyphosphonic and / or aminopolyphosphonic acids, redeposition inhibitors, Farbübertragungsinhibito- reindeer, for example, polyvinyl pyrrolidone or polyvinyl pyridine-N-oxide, foam inhibitors, for example organopolysiloxanes or paraffins , Solvents and optical brighteners, for example stilbene disulfonic acid derivatives.
- enzymes Enzym ⁇ stabilizers
- complexing agents for heavy metals for example aminopolycarboxylic acids, aminohydroxypolycarboxylic, polyphosphonic acids, hydroxypolyphosphonic and / or aminopolyphosphonic acids
- redeposition inhibitors for example, Farbübertragungsinhibito- rein
- optical brighteners in particular compounds from the class of the substituted 4,4'-bis
- the agents according to the invention - (2,4,6-tri- amino-s-triaziny -stilbene ⁇ '- disulfonic acids, up to 5% by weight, in particular 0J% by weight to 2% by weight, of complexing agents for heavy metals, in particular hydroxyalkylenephosphone acids and their salts, and up to 2% by weight, in particular 0.05% by weight to 1% by weight, of foam inhibitors, the proportions by weight in each case referring to a total agent.
- solvents which are used in particular in the case of liquid agents according to the invention are preferably those which are water-miscible. These include the lower alcohols, for example ethanol, propanol, isopropanol, and the isomeric butanols, glycerol, lower glycols, for example ethylene and propylene glycol, and the ethers which can be derived from the compound classes mentioned.
- the dirt-releasing polyemers are usually dissolved or in suspended form.
- Any enzyme present is preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase or mixtures thereof.
- Protease obtained from microorganisms, such as bacteria or fungi is primarily suitable. It can be obtained in a known manner by fermentation processes from suitable microorganisms, which are described, for example, in German patent applications DE 19 40488, DE 2044 161, DE 22 01 803 and DE 21 21 397, US Pat. Nos. 3,632,957 and US 4,264,738, European patent application EP 006 638 and international patent application WO 91/02792 are described.
- the lipase which can be used can be obtained from Humicola lanuginosa, as described, for example, in European patent applications EP 258 068, EP 305 216 and EP 341 947, from Bacillus species, as described, for example, in international patent application WO 91/16422 or European patent application EP 384 717 , from Pseudomonas species, as for example in the European patent applications EP 468 102, EP 385 401, EP 375 102, EP 334 462, EP 331 376, EP 330 641, EP 214 761, EP 218 272 or EP 204 284 or the international patent application WO 90/10695 described, from Fusarium species, as described for example in the European patent application EP 130 064, from Rhizopus species, as described for example in the European patent application EP 117 553, or from Aspergillus species, as for example in described in European patent application EP 167 309.
- Suitable lipases are commercially available, for example, under the names Lipolase®, Lipozym®, Lipomax®, Amano® lipase, Toyo-Jozo® lipase, Meito® lipase and Diosynth® lipase.
- Suitable amylases are commercially available, for example, under the names Maxamyl® and Termamyl®.
- the cellulase which can be used can be an enzyme which can be obtained from bacteria or fungi and which has a pH optimum, preferably in the weakly acidic to weakly alkaline range from 6 to 9.5.
- the customary enzyme stabilizers which are optionally present, in particular in liquid compositions according to the invention, include amino alcohols, for example mono-, di-, triethanol- and propanolamine and mixtures thereof, lower carboxylic acids, as for example from European patent applications EP 376 705 and EP 378 261 known, boric acid or alkali borates, boric acid-carboxylic acid combinations, such as known from European patent application EP 451 921, boric acid esters, such as known from international patent application WO 93/11215 or European patent application EP 511 456, boronic acid derivatives , as is known, for example, from European patent application EP 583 536, calcium salts, for example the Ca-formic acid combination known from European patent EP 28 865, magnesium salts, as known for example from European patent application EP 378 262, and / or sulfur-containing reduct Ionizing agents, as known for example from European patent applications EP 080 748 or EP 080 223.
- amino alcohols for example mono-, di-, triethanol-
- Suitable foam inhibitors include long-chain soaps, in particular behe ⁇ soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which may also contain microfine, optionally silanized or otherwise hydrophobized silica.
- foam inhibitors are preferably bound to granular, water-soluble carrier substances, such as, for example, in German Offenlegungsschrift DE 34 36 194, European Patent Applications EP 262 588, EP 301 414, EP 309 931 or European Patent EP 150 386 described.
- an agent according to the invention is particulate, has a bulk density in particular in the range from 650 g / l to 800 g / l and contains up to 6% by weight, in particular 2% by weight to 5% by weight, of synthetic material
- Anionic surfactant from the group comprising alkylbenzenesulfonate and alkyl sulfate, up to 10% by weight, in particular 3% by weight to 8% by weight of soap, 2% by weight to 15% by weight, in particular 5% by weight % to 12% by weight of nonionic surfactant in the form of alkoxylated fatty alcohols, in particular an approximately 1: 1 mixture of low ethoxylated fatty alcohol, for example 5-fold ethoxylated with higher ethoxylated fatty alcohol, for example 14-fold ethoxylated C-15/13 fatty alcohol, 20% by weight to 50% by weight of alkali metal silicate, 4% by weight to 10% by weight of alkali metal silicate with
- a further preferred embodiment comprises a powdery agent with a bulk density of preferably 700 g / l to 900 g / l, which is free of builder, synthetic anionic surfactant and soap and 8% by weight to 15% by weight of nonionic surfactant, 7, 5% by weight to 30% by weight of alkali metal silicate, 2% by weight to 6% by weight of alkali metal silicate with a ratio of alkali metal oxide to silicon dioxide of approximately 1.20% by weight to 40% by weight of alkali metal carbonate, 0.3 wt.% to 1.5 wt.% complexing agent, up to 0.5 wt.% optical brightener, up to 0.5 wt.% foam regulator, up to 1 wt. % Enzyme, in particular protease, and 0.2 wt .-% to 1 wt .-% soil release polymer.
- a powdery composition according to the invention in particular for use as so-called washing alkali, is free from synthetic anionic surfactant and soap and contains up to 3% by weight of nonionic surfactant, 30% by weight to 70% by weight of alkali metal silicate, 2% by weight to 15% by weight of alkali carbonate, 0.2% by weight to 1% by weight of complexing agent from the class of the phosphonic acids, 10% by weight to 40% by weight of water-soluble inorganic builder, in particular sodium tripoly - Phosphate, up to 0.5% by weight of optical brightener and 0.5% by weight to 3% by weight of dirt-releasing polymer.
- a composition composed in this way preferably has a bulk density in the range from 800 g / l to 1200 g / l and can be produced by a mixing process.
- a further preferred embodiment comprises a paste-like, essentially anhydrous agent containing 20% by weight to 80% by weight of a surfactant mixture, based on the surfactant mixture, 40% by weight to 70% by weight of nonionic liquid at room temperature
- Surfactant of the general formula R 1 - (OC 2 H) n -OH in which R 1 is an alkyl or alkenyl radical having 10 to 20 carbon atoms and the average degree of ethoxylation n can assume values from 1 to 8, 20% by weight % to 50% by weight, based on the surfactant mixture, of a nonionic surfactant of the general formula R 2 - (OC 2 H 4 ) (OC 3 H 6 ) p -OH which is liquid at room temperature and in which R 2 is an alkyl or alkenyl radical with 10 to 20 carbon atoms means that the average degree of ethoxylation r can take on values from 2 to 8 and the average degree of propoxylation p can take on values from 1 to 6, and 1% by weight to
- Powder detergents of the composition given in Table 1 below were tested for their washing performance against greasy soiling.
- the standardized test stains listed in Tables 2 and 3 (fabric pre-washed and dried once with the respective detergent to be tested) were washed in an E-Lux FL 120-MP washing machine with steam heating using the 1-bath method ( Detergent dosage 5 g / l; a pH in the wash liquor of 11.5 was established).
- the test fabrics were then dried and their cleanliness or freedom from stains was assessed by a test panel of 5 people.
- the following rating system was used:
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19504006A DE19504006A1 (de) | 1995-02-08 | 1995-02-08 | Hochalkalisches Waschmittel mit schmutzablösevermögendem Polymer |
DE19504006 | 1995-02-08 | ||
PCT/EP1996/000359 WO1996024657A1 (de) | 1995-02-08 | 1996-01-30 | Hochalkalisches waschmittel mit schmutzablösevermögendem polymer |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0808357A1 true EP0808357A1 (de) | 1997-11-26 |
EP0808357B1 EP0808357B1 (de) | 2002-10-09 |
Family
ID=7753376
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96902941A Expired - Lifetime EP0808357B1 (de) | 1995-02-08 | 1996-01-30 | Hochalkalisches waschmittel mit schmutzablösevermögendem polymer |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0808357B1 (de) |
DE (2) | DE19504006A1 (de) |
WO (1) | WO1996024657A1 (de) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19646866A1 (de) | 1996-11-13 | 1998-05-14 | Henkel Ecolab Gmbh & Co Ohg | Gewerbliches Waschverfahren unter Einsatz von schmutzablösevermögendem Polymer |
DE502004003835D1 (de) | 2003-02-10 | 2007-06-28 | Henkel Kgaa | Bleichmittelhaltige wasch- oder reinigungsmittel mit wasserlöslichem buildersystem und schmutzablösevermögendem cellulosederivat |
DE10351325A1 (de) | 2003-02-10 | 2004-08-26 | Henkel Kgaa | Wasch- oder Reinigungsmittel mit wasserlöslichem Buildersystem und schmutzablösevermögendem Cellulosederivat |
US8900328B2 (en) | 2009-03-16 | 2014-12-02 | The Procter & Gamble Company | Cleaning method |
US20100229312A1 (en) * | 2009-03-16 | 2010-09-16 | De Buzzaccarini Francesco | Cleaning method |
US9890350B2 (en) * | 2015-10-28 | 2018-02-13 | Ecolab Usa Inc. | Methods of using a soil release polymer in a neutral or low alkaline prewash |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
USRE30472E (en) * | 1979-08-20 | 1981-01-06 | The Dow Chemical Company | Detergent composition with antisoil and antiredeposition properties |
DE3324258A1 (de) * | 1982-07-09 | 1984-01-12 | Colgate-Palmolive Co., 10022 New York, N.Y. | Nichtionogene waschmittelzusammensetzung mit verbesserter schmutzauswaschbarkeit |
US4441881A (en) * | 1982-09-07 | 1984-04-10 | Lever Brothers Company | Detergent compositions containing ethoxylated fatty alcohols with narrow ethylene oxide distributions |
US5104584A (en) * | 1990-06-22 | 1992-04-14 | The Clorox Company | Composition and method for fabric encrustation prevention comprising a lignin derivative |
DE69328173T2 (de) * | 1993-07-14 | 2000-11-09 | The Procter & Gamble Company, Cincinnati | Reinigungsmittelzusammensetzungen |
-
1995
- 1995-02-08 DE DE19504006A patent/DE19504006A1/de not_active Withdrawn
-
1996
- 1996-01-30 EP EP96902941A patent/EP0808357B1/de not_active Expired - Lifetime
- 1996-01-30 DE DE59609781T patent/DE59609781D1/de not_active Expired - Fee Related
- 1996-01-30 WO PCT/EP1996/000359 patent/WO1996024657A1/de active IP Right Grant
Non-Patent Citations (1)
Title |
---|
See references of WO9624657A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE59609781D1 (de) | 2002-11-14 |
EP0808357B1 (de) | 2002-10-09 |
WO1996024657A1 (de) | 1996-08-15 |
DE19504006A1 (de) | 1996-08-14 |
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