EP0200953A2 - Granular detergent - Google Patents
Granular detergent Download PDFInfo
- Publication number
- EP0200953A2 EP0200953A2 EP86105031A EP86105031A EP0200953A2 EP 0200953 A2 EP0200953 A2 EP 0200953A2 EP 86105031 A EP86105031 A EP 86105031A EP 86105031 A EP86105031 A EP 86105031A EP 0200953 A2 EP0200953 A2 EP 0200953A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- component
- weight
- water
- composition according
- salts
- 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.)
- Withdrawn
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- 239000003599 detergent Substances 0.000 title claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 60
- 239000000843 powder Substances 0.000 claims abstract description 36
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 25
- 150000003839 salts Chemical class 0.000 claims abstract description 23
- 239000004094 surface-active agent Substances 0.000 claims abstract description 21
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010457 zeolite Substances 0.000 claims abstract description 18
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 16
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 15
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000001298 alcohols Chemical class 0.000 claims abstract description 9
- 239000004615 ingredient Substances 0.000 claims abstract description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 6
- 239000008187 granular material Substances 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 18
- 238000001694 spray drying Methods 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical group OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 11
- 229920006395 saturated elastomer Polymers 0.000 claims description 10
- 239000003381 stabilizer Substances 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 7
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 7
- 239000011976 maleic acid Substances 0.000 claims description 7
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 159000000000 sodium salts Chemical class 0.000 claims description 5
- 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 4
- 238000000034 method Methods 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- 229920000151 polyglycol Polymers 0.000 claims description 4
- 239000010695 polyglycol Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000012876 carrier material Substances 0.000 claims description 3
- 125000001033 ether group Chemical group 0.000 claims description 3
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 229920003145 methacrylic acid copolymer Polymers 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 15
- 229920001577 copolymer Polymers 0.000 abstract description 14
- 239000000470 constituent Substances 0.000 abstract description 6
- 150000003973 alkyl amines Chemical class 0.000 abstract description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 3
- 239000011363 dried mixture Substances 0.000 abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 33
- 229910052938 sodium sulfate Inorganic materials 0.000 description 33
- 235000011152 sodium sulphate Nutrition 0.000 description 33
- 229920003086 cellulose ether Polymers 0.000 description 25
- 125000004432 carbon atom Chemical group C* 0.000 description 14
- 238000005406 washing Methods 0.000 description 13
- 239000003945 anionic surfactant Substances 0.000 description 12
- -1 fatty alcohol sulfates Chemical class 0.000 description 12
- 239000003112 inhibitor Substances 0.000 description 11
- 239000007844 bleaching agent Substances 0.000 description 10
- 239000012190 activator Substances 0.000 description 9
- 102000004190 Enzymes Human genes 0.000 description 8
- 108090000790 Enzymes Proteins 0.000 description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229940088598 enzyme Drugs 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 7
- 150000002191 fatty alcohols Chemical class 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 239000006260 foam Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000007046 ethoxylation reaction Methods 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- FRPJTGXMTIIFIT-UHFFFAOYSA-N tetraacetylethylenediamine Chemical compound CC(=O)C(N)(C(C)=O)C(N)(C(C)=O)C(C)=O FRPJTGXMTIIFIT-UHFFFAOYSA-N 0.000 description 5
- 239000004753 textile Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000003760 tallow Substances 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 244000060011 Cocos nucifera Species 0.000 description 3
- 235000013162 Cocos nucifera Nutrition 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 239000000443 aerosol Substances 0.000 description 3
- 239000003139 biocide Substances 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229940043348 myristyl alcohol Drugs 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 150000004671 saturated fatty acids Chemical class 0.000 description 3
- 235000003441 saturated fatty acids Nutrition 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000001083 [(2R,3R,4S,5R)-1,2,4,5-tetraacetyloxy-6-oxohexan-3-yl] acetate Substances 0.000 description 2
- UAOKXEHOENRFMP-ZJIFWQFVSA-N [(2r,3r,4s,5r)-2,3,4,5-tetraacetyloxy-6-oxohexyl] acetate Chemical compound CC(=O)OC[C@@H](OC(C)=O)[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](OC(C)=O)C=O UAOKXEHOENRFMP-ZJIFWQFVSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 229960000541 cetyl alcohol Drugs 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
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- 238000002156 mixing Methods 0.000 description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229960001922 sodium perborate Drugs 0.000 description 2
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 description 1
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- DYBIGIADVHIODH-UHFFFAOYSA-N 2-nonylphenol;oxirane Chemical compound C1CO1.CCCCCCCCCC1=CC=CC=C1O DYBIGIADVHIODH-UHFFFAOYSA-N 0.000 description 1
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- 239000004482 other powder Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 238000005029 sieve analysis Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 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
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 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
- 239000001993 wax Substances 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
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- 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
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/02—Preparation in the form of powder by spray drying
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/42—Amino alcohols or amino ethers
- C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
Definitions
- the invention relates to a granular detergent which, owing to a particularly selected combination of water-soluble anionic surfactants with water-insoluble nonionic surfactants, has improved cleaning properties compared to oil and fat-containing soiling.
- a gel-like agent is known with which the greasy textiles are pretreated.
- This agent contains a mixture of "oil-friendly" nonionic surfactants and anionic surfactants from the sulfate or. Sulfonate type.
- a nonionic component such. B. with 3 moles of ethylene oxide reacted lauryl alcohol-myristyl alcohol mixtures or used with 5 moles of ethylene oxide nonylphenol.
- the preferred anionic surfactant is linear alkyl benzene sulfonate.
- the application is cumbersome and time-consuming, since it requires the gel-like cleaning composition to be applied beforehand and the textiles to be left for up to 30 minutes before being placed in the washing machine. Due to their gel-like character, the detergents are usually difficult to incorporate into a conventional, all-purpose detergent.
- Solid additives can consist of 0.1 to 60% by weight of water-insoluble surfactants or mixtures of water-insoluble and water-soluble surfactants as well as 99.9 to 40% by weight of builder salts, fillers, bleaches or other detergent ingredients.
- the surfactants can be dry mixed into these materials to avoid aerosol formation (pluming) during spray drying. This way of working is said to pose no problems since the amounts of water-insoluble surfactant required are small.
- Another object was to develop a dosage form in which the detergent-enhancing additives are incorporated into the detergent without the powder properties suffering or the undesired exhaust air problems during spray drying during the preparation of the detergents.
- Component (a) consists of a mixture of selected nonionic surfactants which, owing to their comparatively low degree of ethoxylation, are insoluble or only partially soluble in water, but are nevertheless dispersible. Their HLB values are below 12, mostly between 6 and 11.5.
- the nonionic surfactant listed under (a1) is derived from primary fatty alcohols of natural or synthetic origin, which can be saturated, monounsaturated, linear or methyl-branched in the 2-position (oxo radical).
- Linear fatty alcohols are preferably assumed, i. H. Cetyl alcohol, stearyl alcohol, oleyl alcohol and mixtures thereof, e.g. B. tallow fatty alcohol.
- the average number of glycol ether groups is 4 to 6, in particular 5.
- these are mixtures which can also contain fractions with a lower and higher degree of ethoxylation. However, as stated, the statistical maximum or the average degree of ethoxylation should be 4 to 6, preferably 5.
- the HLB value of the (a1) fraction is between 7.5 and 10, preferably 8.2 to 9.3.
- the nonionic surfactant listed under (a2) is also derived from fatty alcohols or oxoalcohols with 10 to 14 carbon atoms.
- Linear alcohols with 12 to 14 carbon atoms are preferably used as starting materials, ie lauryl alcohol and myristyl alcohol and mixtures thereof.
- CI 2 -C ' 4 alcohol mixtures obtained from coconut fatty alcohols are particularly useful, the proportion of shorter-chain alcohols advantageously being less than 5% by weight.
- the average number of ethylene polyglycol ether groups is 4 to 6, in particular 5. With regard to the statistical distribution of the glycol ether groups, what has been said in section (a1) applies analogously.
- the HLB value of the (a2) fraction is between 8, 5 and 12, preferably between 9 and 11.5.
- the nonionic surfactant listed under (a3) is derived from saturated primary alkylamines having 10 to 18, preferably 12 to 18, carbon atoms, with particular preference being given to those alkylamines whose alkyl groups are more than 50%, in particular more than 65% exist with 12 to 14 carbon atoms.
- mixtures obtained from coconut alcohols are suitable, from which the fraction with 10 and fewer carbon atoms has been largely separated.
- the average number of glycol ether groups is 1 to 3, in particular 2.
- the ethoxylate mixture can contain parts with a lower and a higher degree of ethoxylation, corresponding to an inevitably established statistical distribution.
- the HLB value of the (a3) fraction is in the range from 4 to 8, preferably from 5.5 to 7.5.
- the weight ratio (a1): (a2): (a3) is 1: (2 -6): (0.8 -2.5), preferably 1: (3 -5): (1 - 2), in which preferred range there is a particularly balanced ratio with regard to the cleaning ability, in particular with respect to greasy and oily soiling.
- Component (b) consists of anionic surfactants of the suifonate type or sulfate type.
- Alkylbenzenesulfonates with linear alkyl radicals which have 10 to 13, in particular 12, C atoms are particularly useful.
- Further preferred anionic surfactants are primary alkyl sulfates, which are derived from linear alcohols with 12 to 18 carbon atoms, and alpha-sulfofatty acid alkyl esters, which are derived from saturated fatty acids with 12 to 18, in particular 14 to 18, carbon atoms and alkanols with 1 to 3 carbon atoms. Derive atoms, especially methanol.
- anionic surfactants are also suitable, in particular mixtures of alkylbenzenesulfonates and fatty alcohol sulfates in a weight ratio of 3: 1 to 1: 3 and alkylbenzenesulfonates and alpha-sulfofatty acid esters in a ratio of 3: 1 to 1: 3.
- the anionic surfactants mentioned are generally in the form of their sodium salts Commitment.
- Suitable anionic surfactants are aikansuifonate, as can be obtained by sulfochlorination or sulfoxidation from paraffin hydrocarbons having 12 to 18 or 14 to 16 carbon atoms.
- the olefin sulfonates obtainable from terminal olefins by sulfonation with sulfur trioxide and subsequent hydrolysis can also be used.
- Other known surfactants from sulfonate or. Sulphate types may be present, but their importance is less than that of the aforementioned types. Soaps of saturated or unsaturated fatty acids with 12 to 18 carbon atoms can also be used, but such additives do not significantly improve the properties of the detergent, which is why the detergents are preferably soap-free.
- the content of the anionic surfactants is lower than their nonionic surfactant content.
- the weight ratio of nonionic component (a) to anionic component (b) is preferably 4: 1 to 4: 3, in particular 3: 1 to 3: 2. In this range, the detergency is both greasy and mineral Soiling is particularly pronounced.
- the content of the agent in the aforementioned surfactants is a total of 10 to 25% by weight, preferably 12 to 20% by weight.
- Suitable framework salts which are present in proportions of 35 to 50% by weight, are synthetic sodium aluminosilicates containing bound water, preferably of the zeolite A type. It is also possible to use zeolite NaX and mixtures thereof with zeolite NaA, the proportion of zeolite NaX in such mixtures advantageously being less than 30%, in particular less than 20%, based on the proportion of zeolite.
- Suitable zeolites have no particles larger than 30 microns and consist of at least 80% particles smaller than 10 microns.
- Their calcium binding capacity which is determined according to the information in DE 24 12 837, is in the range from 100 to 200 mg CaO / g.
- a further mandatory component of component (c) consists of a homopolymeric and / or copolymeric carboxylic acid or its sodium or potassium salt, the sodium salts being preferred.
- Suitable homopolymers are polyacrylic acid, polymethacrylic acid and polymic acid.
- Suitable copolymers are those of acrylic acid or methacrylic acid with maleic acid or copolymers of acrylic acid, methacrylic acid or maleic acid with vinyl ethers, such as vinyl methyl ether or
- Vinyl ethyl ether also with vinyl esters, such as vinyl acetate or vinyl propionate, acrylamide, methacrylamide and with ethylene, propylene or styrene.
- the proportion thereof in the interest of sufficient water solubility is not more than 70 mole percent, preferably less than 60 mole percent.
- Copolymers of acrylic acid with maleic acid have proven to be particularly suitable, as are described in more detail, for example, in EP 25 551-B1 and in the journal "Tenside", 16 (1979), pages 82-89. These are copolymers which contain 40 to 90% by weight of acrylic acid or methacrylic acid and 60 to 10% by weight of maleic acid. Copolymers in which 45 to 85% by weight of acrylic acid and 55 to 15% by weight of maleic acid are present are particularly preferred.
- the molecular weight of the homo- or copolymers is generally 1,000 to 150,000, preferably 1,500 to 100,000.
- the zeolite content of the compositions is 10 to 40% by weight, preferably 12 to 20% by weight, of polymeric or copolymeric carboxylic acids or their salts 0.5 to 5, preferably 0.8 to 4% by weight and on Sodium silicate 1 to 7% by weight, preferably 2 to 6% by weight.
- Suitable skeletal salts are sodium carbonate and, in so far as there are no concerns about the use of minor amounts of phosphates, polyphosphates, in particular pentasodium tripolyphosphate. Under the conditions mentioned, its proportion can be up to 25% by weight, preferably 5 to 22% by weight. In cases where phosphates cannot be used, replacement by sodium nitrilotriacetate in proportions of, for example, 2 to 10% by weight is also possible.
- Other known water-soluble phosphate substitutes can optionally also be used, for example polyacetals of glyoxylic acid in the form of the sodium salts.
- the framework salts (c) also include the sequestering agents from the class of aminopolycarboxylic acids and polyphosphonic acids, which are usually present in comparatively small amounts and act as so-called co-builders, stabilizers, precipitation inhibitors (threshold substances).
- the aminopolycarboxylic acids include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and their higher homologues.
- Suitable polyphosphonic acids are 1-hydroxyethane-1,1-diphosphonic acid, aminotri- (methylenephosphonic acid), ethylenediaminteira- (methylenephosphonic acid) and their higher homologs, such as.
- the aforementioned polycarboxylic acids or polyphosphonic acids usually come in the form of the sodium or. Potassium salts for use.
- the amount used is generally 0.1 to 5% by weight, preferably 0.2 to 1% by weight.
- the other usual detergent ingredients include anti-graying substances, optical brighteners, enzymes, bleaching agents and bleach activators, foam inhibitors, colorants and fragrances, biocides, neutral salts and substances which improve the quality of the powder.
- Suitable graying inhibitors are cellulose ethers, such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl celluloses and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose and methyl carboxymethyl cellulose. Mixtures of various cellulose ethers, in particular mixtures of carboxymethyl cellulose and methyl cellulose, are also suitable.
- Suitable optical brighteners are alkali metal salts of 4,4-bis- (2 "-anilino-4" -morpholino-1,3,5-triazinyl-6 "-amino) -stilbene-2,2'-disulfonic acid or compounds of the same structure, which carry a diethanolamino group instead of the morpholino group.
- Brighteners of the substituted diphenylstyryl type for example the alkali metal salts of 4,4'-bis - (2-sulfostyryl) -diphenyl, 4,4'-bis- ( 4-chloro-3-sulfostyryl) diphenyls and 4- (4-chlorostyryl-4 '- (2-su! Fostyry! - diphenyis.
- Enzymes from the class of proteases, lipases and amylases or mixtures thereof are possible. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. The enzymes can be embedded in coating substances to protect them against premature decomposition.
- the perhydrates and per-compounds commonly used in washing and bleaching agents are suitable as bleaching components.
- the perhydrates preferably include sodium perborate, which can be present as a tetrahydrate or as a monohydrate, furthermore the perhydrates of sodium carbonate (sodium percarbonate), sodium pyrophosphate (perpyrophosphate), sodium silicate (persilicate) and urea. These perhydrates are preferably used together with bleach activators.
- the bleach activators include in particular N-acyl compounds and O-acyl compounds.
- suitable N-acyl compounds are multiply acylated alkylenediamines, such as tetraacetylmethylene diamine, tetraacetylethylenediamine and their higher homologues, and acylated glycolurils, such as tetraacetylglycoluril.
- carboxylic acid anhydrides such as phthalic anhydride and esters, such as Na (iso) nonanoylphenol sulfonate
- acylated sugars such as glucose pentaacetate are suitable as 0-acyl compounds.
- Preferred bleach activators are tetraacetylethylene diamine and glucose pentaacetate.
- the bleach activators can also be coated with coating substances in order to avoid interactions with the per compounds, especially during the storage of powdery mixtures.
- Suitable foam inhibitors are organopolysiloxanes and their mixtures with microfine, optionally silanized silica, paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica and saturated fatty acids with 18 to 24 carbon atoms or their alkali soaps. Mixtures of various foam inhibitors, e.g. B. from silicones and paraffins are useful.
- Neutral salts in particular sodium sulfate, and magnesium silicate acting as a stabilizer for per compounds also come into consideration as further constituents.
- Other washing aids are additives that improve the powder structure, e.g. B. alkali salts or toluene, cumene or xylene sulfonic acid.
- the components belonging to component (d) can be present in amounts which are generally customary in known detergent compositions.
- the proportion of graying inhibitors is generally 0.2 to 2% by weight, the proportion of optical brighteners 0.05 to 0.5% by weight.
- the proportion of enzymes depends primarily on their activity.
- Technical enzyme preparations which are usually mixed with stabilizers, calcium salts and blending agents and adjusted to a specific activity, are usually used in proportions of 0.1 to 2% by weight.
- the proportion of perborate is usually 5 to 25% by weight.
- the amounts of bleach activators used are also based on their effectiveness. Highly effective activators, such as tetraacetylethylenediamine, are usually used in amounts of 0.5 to 5% by weight.
- foam inhibitors the proportion of which can generally be from 0.01 to 0.5% by weight in the case of highly effective silicone defoamers, and up to 2% by weight in the case of waxy or paraffinic substances or higher molecular weight fatty acids.
- the proportion of sodium sulfate can be up to 25% by weight, in special cases even more.
- the agents according to the invention are in the form of granular powders or powder mixtures which can be suitably granulated, spray-dried, spray-mixed, homogenized or. can be obtained through a combination of these working methods. Since component (a) consists of liquid compounds which tend to stick and which, owing to their tendency to "pluming", are only suitable for spray drying to a limited extent, it is necessary for them to be adsorbed on a carrier substance.
- skeleton salts (c) in particular zeolite, phosphates, silicates, nitrilotriacetate and their mixtures, are also spray-dried mixtures of skeleton salts (c), anionic surfactants (b) and other constituents (d), provided that these are stable under the conditions of spray drying .
- Carrier substances consisting of skeletal salts can also contain neutral salts, such as sodium sulfate, graying inhibitors, Mg silicate and additional adsorbents, such as finely divided silica, finely divided aluminum oxide, smectite clays, layered silicates and bentonites.
- framework salt mixtures prepared by build-up granulation as the carrier substance for component (a).
- the granules can also be provided with adsorbing coatings which prevent them from sticking, which can be done, for example, by means of the aforementioned fine-particle adsorbents.
- Dispersion stabilizers are to be understood as meaning compounds which are used to stabilize aqueous or pasty zeolite slurries. They are generally added to these slurries during their manufacture or moist filter cake and remain in the zeolites even during further processing. For this purpose, reference is made to DE 25 27 388.
- stabilizers are neutral salts, such as sodium sulfate, nonionic surfactants from the class of ethoxylated fatty alcohols with 12 to 18 carbon atoms and 3 to 10 glycol ether groups, and polymeric and copolymeric carboxylic acids.
- the dispersion stabilizer preferably consists of the nonionic surfactant listed under (a1) or a part thereof.
- the granulate which is preferably produced by spray drying and is described in more detail in patent application P 34 44 960 (D 7180), has an average grain size of 0.2 to 1.2 mm and contains less than 2% by weight of dust-like Proportions (grain size less than 0.05 mm) and no more than 5% by weight of coarse parts (grain size more than 2 mm). Its bulk density is 400 to 700 g / l. It is characterized by a very high adsorption capacity for liquid or paste-like substances and is therefore particularly suitable as a carrier for the nonionic surfactants (component a).
- the agents according to the invention are characterized by a high washing capacity, in particular by an excellent cleaning power against stubborn greasy soiling, for example those from food and sauce residues, skin fat, lipstick and mascara.
- a high washing capacity in particular by an excellent cleaning power against stubborn greasy soiling, for example those from food and sauce residues, skin fat, lipstick and mascara.
- liquid non-ionic surfactants Despite their comparatively high content of liquid non-ionic surfactants, they are extremely pourable and free-flowing and do not tend to grease cardboard packaging. If they are made according to the preferred procedure, i. H. Adsorbing the non-ionic surfactant on the previously prepared granules of zeolite, polymeric acid and sodium silicate completely avoids the formation of aerosols in the exhaust air from the spray towers.
- the zeolite used had a particle size of 1 to 8 microns, the proportion over 8 microns being 6% by weight. There were no portions above 20 microns.
- a copolymer of acrylic acid and maleic acid (molar ratio 7: 3) with an average molecular weight of 70,000 in the form of the sodium salt was used as the polycarboxylic acid.
- EO ethylene oxide
- the surfactant mixture consisted of 4.1 parts by weight of tallow alcohol with 5 EO (remaining part of component at), 20 parts by weight of a lauryl alcohol-myristyl alcohol mixture (2: 1) with 5 EO - (component a2) and 8.3 parts by weight of cocoalkylamine + 2 EO (C 12 -C 18 mixture, average chain length C, 3 , 5 ). After cooling, a non-sticky, granular product was obtained, the flowability of which was excellent despite a total content of 34% by weight of liquid nonionic surfactant.
- the bulk density was 740 g / l.
- Granulated enzymes of granulated silicone defoamers, sodium perborate and granulated tetraacetylethylenediamine (TAED) were added to further powder components. These powdery or granular constituents are summarized under the term "partial powder III", the proportion of which is a total of 15.3 parts by weight.
- composition of the agent was (in% by weight)
- detergents were used that contained the following surfactants with an otherwise unchanged composition (see Table I):
- the qualitative and quantitative composition of coconut alkyl residues was identical to that used in the example.
- the compositions of experiments 1 and 2 correspond to the surfactant compositions of commercially available high-performance detergents.
- Trials 3 and 4 correspond to agents according to US 3 925 224.
- the results are shown in Table II.
- the grade 1 means the highest, 6 the - worst rating.
- the improved washing power of the agents according to the invention is particularly evident in the 60 ° C. washing area.
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
Ein Waschmittel mit verbesserter Waschkraft gegenüber fetthaltigen Verschmutzungen enthält (a) ein Gemisch in Wasser nur teilweise löslicher nichtionischer Tenside, (b) wasserlösliche Tenside vom Sulfonat- bzw. Sulfat-Typ, (c) Gerüstsalze und (d) sonstige übliche Waschmittelbestandteile. Die Komponente (a) besteht aus (a1) C16-C18-Alkoholen mit 4 bis 6 EO (Ethylenglykolethergruppen), (a2) C10-C14-Alkoholen mit 4 bis 6 EO und (a3) C10-C18-Alkylaminen mit 1 bis 3 EO und ist an einer in Wasser löslichen bzw. dispergierbaren, körnigen Trägersubstanz adsorbiert. Die Gewichtsverhältnisse betragen (a1) : (a2) : (a3) = 1 : (2 - 6) : (0,8 - 2,5) und (a) : (b) = 4 : 1 bis 4 : 3. Die Trägersubstanz besteht bevorzugt aus einem sprühgetrockneten Gemisch von 60 bis 80 % Zeolith, 3 - 20 % einer (co)-polymeren Carbonsäure, 0,1 bis 3 % Natriumsilikat sowie Wasser und kann bis zu 40 Gew.-% an nichtionischem Tensid aufnehmen. Die mit dem nichtionischen Tensid imprägnierte Trägersubstanz wird mit weiteren, gegebenenfalls sprühgetrockneten Pulverbestandteilen, welche die übrigen Komponenten enthalten, zu einem homogenen Pulvergemisch vereinigt.A detergent with improved detergency against greasy soiling contains (a) a mixture of nonionic surfactants which are only partially soluble in water, (b) water-soluble surfactants of the sulfonate or sulfate type, (c) skeletal salts and (d) other common detergent ingredients. Component (a) consists of (a1) C16-C18 alcohols with 4 to 6 EO (ethylene glycol ether groups), (a2) C10-C14 alcohols with 4 to 6 EO and (a3) C10-C18 alkylamines with 1 to 3 EO and is adsorbed on a water-soluble or dispersible, granular carrier substance. The weight ratios are (a1): (a2): (a3) = 1: (2 - 6): (0.8 - 2.5) and (a): (b) = 4: 1 to 4: 3 The carrier substance preferably consists of a spray-dried mixture of 60 to 80% zeolite, 3 to 20% of a (co) polymeric carboxylic acid, 0.1 to 3% sodium silicate and water and can absorb up to 40% by weight of nonionic surfactant. The carrier substance impregnated with the nonionic surfactant is combined with further, optionally spray-dried powder constituents which contain the other components to form a homogeneous powder mixture.
Description
Die Erfindung betrifft ein kömiges Waschmittel, das aufgrund einer besonders ausgewählten Kombination wasserlöslicher anionischer Tenside mit wasserunlöslichen nichtionischen Tensiden ein verbessertes Reinigungsvermögen gegenüber öl-und fetthaltigen Anschmutzungen besitzt.The invention relates to a granular detergent which, owing to a particularly selected combination of water-soluble anionic surfactants with water-insoluble nonionic surfactants, has improved cleaning properties compared to oil and fat-containing soiling.
Aus der DE 22 26 925 -A1 (US 3 849 347) ist ein gelartiges Mittel bekannt, mit dem die fettverschmutzten Textilien vorbehandelt werden. Dieses Mittel enthält eine Mischung aus "ölfreundlichen" nichtionischen Tensiden und anionischen Tensiden vom Sulfat-bzw. Sulfonat-Typ. Als nichtionische Komponente werden z. B. mit 3 Mol Ethylenoxid umgesetzte Laurylalkohol-Myristylalkohol-Gemische oder mit 5 Mol Ethylenoxid umgesetztes Nonylphenol verwendet. Bevorzugtes Aniontensid ist lineares Alkylbenzolsulfonat. Die Anwendung ist jedoch umständlich und zeitraubend, da sie ein vorheriges Auftragen der gelartigen Reinigungsmasse und ein bis zu 30 Minuten dauerndes Liegenlassen des Textilgutes vor dem Einlegen in die Waschmaschine erfordert. In ein übliches, kömiges Allzweckwaschmittel lassen sich die Mittel aufgrund ihres gelartigen Charakters meist nur schwierig inkorporieren.From DE 22 26 925 -A1 (US 3 849 347) a gel-like agent is known with which the greasy textiles are pretreated. This agent contains a mixture of "oil-friendly" nonionic surfactants and anionic surfactants from the sulfate or. Sulfonate type. As a nonionic component such. B. with 3 moles of ethylene oxide reacted lauryl alcohol-myristyl alcohol mixtures or used with 5 moles of ethylene oxide nonylphenol. The preferred anionic surfactant is linear alkyl benzene sulfonate. However, the application is cumbersome and time-consuming, since it requires the gel-like cleaning composition to be applied beforehand and the textiles to be left for up to 30 minutes before being placed in the washing machine. Due to their gel-like character, the detergents are usually difficult to incorporate into a conventional, all-purpose detergent.
Aus der US 3 925 224 ist bekannt, daß der Zusatz eines wasserunlöslichen Tensids zu Waschmitteln mit einem Gehalt an üblichen wasserlöslichen anionischen, nichtionischen oder zwitterionischen Tensiden zu einer Steigerung der Waschkraft führt. Als Beispiele für das wasserunlösliche Tensid werden ethoxylierte Alkohole mit 12 bis 15 C-Atomen bzw. Octylphenol mit jeweils 3 Glykolethergruppen (EO) sowie ethoxyliertes Cocosamin mit 2 EO-Gruppen genannt. Die wasserunlöslichen Tenside werden den Waschmitteln bzw. den Waschlaugen als sogenannte "Additive" zugesetzt, die fest oder flüssig sein können. Feste Additive können aus 0,1 bis 60 Gew.-% wasserunlöslichen Tensiden bzw. Gemischen wasserunlöslicher und wasserlöslicher Tenside sowie 99,9 bis 40 Gew.-% Buildersalzen, Füllstoffen, Bleichmitteln oder anderen Waschmittelinhaltsstoffen bestehen. Die Tenside können diesen Materialien trocken zugemischt werden, um eine Aerosolbildung (Pluming) bei der Sprühtrocknung zu vermeiden. Diese Arbeitsweise soll angeblich keine Probleme aufwerfen, da die benötigten Mengen an wasserunlöslichem Tensid gering seien.From US 3 925 224 it is known that the addition of a water-insoluble surfactant to detergents containing conventional water-soluble anionic, nonionic or zwitterionic surfactants leads to an increase in washing power. Examples of the water-insoluble surfactant are ethoxylated alcohols with 12 to 15 carbon atoms or octylphenol with 3 glycol ether groups (EO) and ethoxylated cocosamine with 2 EO groups. The water-insoluble surfactants are added to the detergents or the wash liquors as so-called "additives", which can be solid or liquid. Solid additives can consist of 0.1 to 60% by weight of water-insoluble surfactants or mixtures of water-insoluble and water-soluble surfactants as well as 99.9 to 40% by weight of builder salts, fillers, bleaches or other detergent ingredients. The surfactants can be dry mixed into these materials to avoid aerosol formation (pluming) during spray drying. This way of working is said to pose no problems since the amounts of water-insoluble surfactant required are small.
Bekanntlich sind nichtionische Tenside mit niedrigem Ethoxylierungsgrad ölartige Stoffe, die sich nur schwierig in größerer, d. h. 5 - 8 % übersteigender Menge in herkömmliche Waschpulver einarbeiten lassen, da sie deren Rieselfähigkeit verschlechtem. Ein Lösungsvorschlag, wie größere Mengen,. insbesondere bis 60 % dieser Tenside bekannten pulverförmigen "Buildem" und Füllstoffen zugemischt werden können, ohne daß sie ihre Rieselfähigkeit einbüßen, ist der US 3 925 224 nicht zu entnehmen. Eine Sprühtrocknung kommt wegen ihrer erhöhten Neigung zur Aerosolbildung in der Abluft der Sprühtürme im allgemeinen nicht in Frage.It is known that nonionic surfactants with a low degree of ethoxylation are oily substances which are difficult to find in larger, i.e. H. Allow 5 - 8% excess amount to be incorporated into conventional washing powder, as they impair their free-flowing properties. A proposed solution, such as larger quantities. US Pat. No. 3,925,224 cannot be deduced in particular up to 60% of known powdery "builders" and fillers without reducing their free-flowing properties. Spray drying is generally out of the question because of its increased tendency to form aerosols in the exhaust air from the spray towers.
Es bestand daher die Aufgabe, ein kömiges Waschmittel zu entwickeln, das die Nachteile der vorbekannten Mittel vermeidet und sich durch ein hohes Waschvermögen, insbesondere auch gegenüber fett-und ölhaltigen Verschmutzungen auszeichnet. Eine weitere Aufgabe bestand darin, eine Darreichungsform zu entwickeln, bei der die waschkraftverstärkenden Zusätze in das Waschmittel inkorporiert sind, ohne daß darunter die Pulverbeschaffenheit leidet bzw. es bei der Herstellung der Mittel zu unerwünschten Abluftproblemen bei der Sprühtrocknung kommt.It was therefore the task of developing a granular detergent which avoids the disadvantages of the known agents and is distinguished by a high detergent capacity, in particular also against greasy and oily soiling. Another object was to develop a dosage form in which the detergent-enhancing additives are incorporated into the detergent without the powder properties suffering or the undesired exhaust air problems during spray drying during the preparation of the detergents.
Gegenstand der Erfindung, mit der die Probleme gelöst werden, ist ein kömiges Waschmittel mit verbessertem Reinigungsvermögen gegenüber öl-und fetthaltigen Verschmutzungen enthaltend eine Tensidkombination aus (a) in Wasser unlöslichen bis teilweise löslichen, nichtionischen Polyglykolethergruppen enthaltenden Tensiden, die an einem kömigen Trägermaterial adsorbiert sind und (b) wasserlöslichen Tensiden vom Sulfonat-Typ und/ oder Sulfat-Typ, enthaltend ferner (c) Gerüstsalze sowie (d) sonstige übliche Waschmittelbestandteile, dadurch gekennzeichnet, daß die Komponente (a) aus folgenden Bestandteilen besteht:
- (a1) ethoxylierten, linearen oder in 2-Stellung methylverzweigten, gesättigten oder einfach ungesättigten primären C16-C18-Alkoholen mit durchschnittlich 4 bis 6 Glykolethergruppen,
- (a2) ethoxylierten, linearen oder in 2-Stellung methylverzweigten, gesättigten primären CIO-C,4-Alkoholen mit durchschnittlich 4 bis 6 Glykolethergruppen,
- (a3) ethoxylierten N-Monoalkylaminen mit linearen, gesättigten C10-C18-Alkylketten und durchschnittlich 1 bis 3 Glykolethergruppen,
wobei das Gewichtsverhältnis von (a1) : (a2) : - (a3) = 1 : (2 -6) : (0,8 -2,5) beträgt und der Anteil der Komponente (a) en Anteil der Komponente (b) übertrifft.The object of the invention, with which the problems are solved, is a granular detergent with improved cleaning ability against oil and fat-containing soiling, comprising a surfactant combination of (a) water-insoluble to partially soluble, nonionic polyglycol ether groups, which are adsorbed on a granular carrier material and (b) water-soluble surfactants of the sulfonate type and / or sulfate type, further comprising (c) skeleton salts and (d) other customary detergent ingredients, characterized in that component (a) consists of the following ingredients:
- (a1) ethoxylated, linear or methyl-branched, saturated or monounsaturated primary C 16 -C 18 alcohols with an average of 4 to 6 glycol ether groups,
- (a2) ethoxylated, linear or saturated primary CIO-C, 4-alcohols with methyl branching in the 2-position, with an average of 4 to 6 glycol ether groups,
- (a3) ethoxylated N-monoalkylamines with linear, saturated C 10 -C 18 alkyl chains and an average of 1 to 3 glycol ether groups,
the weight ratio of (a1): (a2): - (a3) = 1: (2 -6): (0.8 -2.5) and the proportion of component (a) and proportion of component (b) surpasses.
Die Komponente (a) besteht aus einem Gemisch ausgewählter nichtionischer Tenside, die aufgrund ihres vergleichsweise niedrigen Ethoxylierungsgrades in Wasser nicht oder nur teilweise löslich, wohl aber dispergierbar sind. Ihre HLB-Werte liegen unter 12, meist zwischen 6 und 11,5.Component (a) consists of a mixture of selected nonionic surfactants which, owing to their comparatively low degree of ethoxylation, are insoluble or only partially soluble in water, but are nevertheless dispersible. Their HLB values are below 12, mostly between 6 and 11.5.
Das unter (a1) aufgeführte nichtionische Tensid leitet sich von primären Fettalkoholen natürlichen oder synthetischen Ursprungs ab, die gesättigt, einfach ungesättigt, linear oder in 2-Stellung methylverzweigt (Oxo-Rest) sein können. Vorzugsweise wird von linearen Fettalkoholen ausgegangen, d. h. Cetylalkohol, Stearylalkohol, Oleylalkohol und deren Gemischen, z. B. Talgfettalkohol. Die durchschnittliche Anzahl an Glykolethergruppen beträgt 4 bis 6, insbesondere 5. Entsprechend der bei Polyglykolethern üblichen statistischen Verteilung handelt es sich um Gemische, die auch Anteile mit geringerem und höherem Ethoxylierungsgrad enthalten können. Das statistische Maximum bzw. der durchschnittliche Ethoxylierungsgrad soll jedoch, wie angegeben, bei 4 bis 6, vorzugsweise bei 5 liegen. Der HLB-Wert der (a1)-Fraktion liegt zwischen 7,5 und 10, vorzugsweise bei 8,2 bis 9,3.The nonionic surfactant listed under (a1) is derived from primary fatty alcohols of natural or synthetic origin, which can be saturated, monounsaturated, linear or methyl-branched in the 2-position (oxo radical). Linear fatty alcohols are preferably assumed, i. H. Cetyl alcohol, stearyl alcohol, oleyl alcohol and mixtures thereof, e.g. B. tallow fatty alcohol. The average number of glycol ether groups is 4 to 6, in particular 5. Corresponding to the statistical distribution customary for polyglycol ethers, these are mixtures which can also contain fractions with a lower and higher degree of ethoxylation. However, as stated, the statistical maximum or the average degree of ethoxylation should be 4 to 6, preferably 5. The HLB value of the (a1) fraction is between 7.5 and 10, preferably 8.2 to 9.3.
Das unter (a2) aufgeführte nichtionische Tensid leitet sich ebenfalls von Fettalkoholen oder Oxoalkoholen mit 10 bis 14 C-Atomen ab. Vorzugsweise werden lineare Alkohole mit 12 bis 14 C-Atomen als Ausgangsstoffe verwendet, d. h. Laurylalkohol und Myristylalkohol sowie deren Gemische. Brauchbar sind insbesondere aus Cocosfettalkoholen gewonnene CI2-C'4-Alkoholgemische, wobei der Anteil an kürzerkettigen Alkoholen zweckmäßigerweise unter 5 Gew.-% liegt. Die durchschnittliche Anzahl der Ethylenpolyglykolethergruppen beträgt 4 bis 6, insbesondere 5. Hinsichtlich der statistischen Verteilung der Glykolethergruppen gilt analog das unter Abschnitt (a1) Gesagte. Der HLB-Wert der (a2)-Fraktion liegt zwischen 8, 5 und 12, vorzugsweise zwischen 9 und 11,5.The nonionic surfactant listed under (a2) is also derived from fatty alcohols or oxoalcohols with 10 to 14 carbon atoms. Linear alcohols with 12 to 14 carbon atoms are preferably used as starting materials, ie lauryl alcohol and myristyl alcohol and mixtures thereof. CI 2 -C ' 4 alcohol mixtures obtained from coconut fatty alcohols are particularly useful, the proportion of shorter-chain alcohols advantageously being less than 5% by weight. The average number of ethylene polyglycol ether groups is 4 to 6, in particular 5. With regard to the statistical distribution of the glycol ether groups, what has been said in section (a1) applies analogously. The HLB value of the (a2) fraction is between 8, 5 and 12, preferably between 9 and 11.5.
Das unter (a3) aufgeführte nichtionische Tensid leitet sich von gesättigten primären Alkylaminen mit 10 bis 18, vorzugsweise 12 bis 18 C-Atomen ab, wobei solche Alkylamine besonders bevorzugt sind, deren Alkylgruppen zu mehr als 50 %, insbesondere zu mehr als 65 % aus solchen mit 12 bis 14 C-Atomen bestehen. Geeignet sind neben Synthesealkohol-Gemischen aus Cocosalkoholen gewonnene Gemische, von denen die Fraktion mit 10 und weniger C-Atomen weitgehend abgetrennt wurde. Die durchschnittliche Anzahl der Glykolethergruppen beträgt 1 bis 3, insbesondere 2. Auch im diesem Falle kann das Ethoxylatgemisch Anteile mit niedrigerem und höherem Ethoxylierungsgrad enthalten, entsprechend einer sich zwangsläufig einstellenden statistischen Verteilung. Der HLB-Wert der (a3)-Fraktion liegt im Bereich von 4 bis 8, vorzugsweise von 5,5 bis 7,5.The nonionic surfactant listed under (a3) is derived from saturated primary alkylamines having 10 to 18, preferably 12 to 18, carbon atoms, with particular preference being given to those alkylamines whose alkyl groups are more than 50%, in particular more than 65% exist with 12 to 14 carbon atoms. In addition to synthetic alcohol mixtures, mixtures obtained from coconut alcohols are suitable, from which the fraction with 10 and fewer carbon atoms has been largely separated. The average number of glycol ether groups is 1 to 3, in particular 2. Also in this case the ethoxylate mixture can contain parts with a lower and a higher degree of ethoxylation, corresponding to an inevitably established statistical distribution. The HLB value of the (a3) fraction is in the range from 4 to 8, preferably from 5.5 to 7.5.
Das Gewichtsverhältnis (a1) : (a2) : (a3) beträgt 1 : (2 -6) : (0,8 -2,5), vorzugsweise 1 : (3 -5) : (1 - 2), wobei in dem bevorzugten Bereich ein besonders ausgewogenes Verhältnis hinsichtlich des Reinigungsvermögens besteht, insbesondere gegenüber fettigen und öligen Anschmutzungen.The weight ratio (a1): (a2): (a3) is 1: (2 -6): (0.8 -2.5), preferably 1: (3 -5): (1 - 2), in which preferred range there is a particularly balanced ratio with regard to the cleaning ability, in particular with respect to greasy and oily soiling.
Die Komponente (b) besteht aus anionischen Tensiden vom Suifonat-Typ bzw. Sulfat-Typ. Brauchbar sind insbesondere Alkylbenzolsufonate mit linearen Alkylresten, die 10 bis 13, insbesondere 12 C-Atome aufweisen. Weitere bevorzugte Aniontenside sind primäre Alkylsulfate, die sich von linearen Alkoholen mit 12 bis 18 C-Atomen ableiten sowie alpha-Sulfofettsäurealkylester, die sich von gesättigten Fettsäuren mit 12 bis 18, insbesondere 14 bis 18 C-Atomen und Alkanolen mit 1 bis 3 C-Atomen, insbesondere Methanol ableiten. Auch Gemische der vorgenannten Aniontenside sind geeignet, insbesondere Mischungen aus Alkylbenzolsulfonaten und Fettalkoholsulfaten im Gewichtsverhältnis 3 : 1 bis 1 : 3 sowie Alkylbenzolsulfonaten und alpha-Sulfofettsäureestern im Verhältnis 3 : 1 bis 1 : 3. Die genannten Aniontenside kommen im allgmeinen in Form ihrer Natriumsalze zum Einsatz.Component (b) consists of anionic surfactants of the suifonate type or sulfate type. Alkylbenzenesulfonates with linear alkyl radicals which have 10 to 13, in particular 12, C atoms are particularly useful. Further preferred anionic surfactants are primary alkyl sulfates, which are derived from linear alcohols with 12 to 18 carbon atoms, and alpha-sulfofatty acid alkyl esters, which are derived from saturated fatty acids with 12 to 18, in particular 14 to 18, carbon atoms and alkanols with 1 to 3 carbon atoms. Derive atoms, especially methanol. Mixtures of the aforementioned anionic surfactants are also suitable, in particular mixtures of alkylbenzenesulfonates and fatty alcohol sulfates in a weight ratio of 3: 1 to 1: 3 and alkylbenzenesulfonates and alpha-sulfofatty acid esters in a ratio of 3: 1 to 1: 3. The anionic surfactants mentioned are generally in the form of their sodium salts Commitment.
Weitere geeignete Aniontenside, die gegebenenfalls anwesend sein können, sind Aikansuifonate, wie sie durch Sulfochlorierung oder Sulfoxidation aus Paraffinkohlenwasserstoffen mit 12 bis 18 bzw. 14 bis 16 C-Atomen erhältlich sind. Brauchbar sind auch die aus endständigen Olefinen durch Sulfonierung mit Schwefeltrioxid und nachfolgende Hydrolyse erhältlichen Olefinsulfonate. Auch andere bekannte Tenside vom Sulfonat-bzw. Sulfat-Typ können gegebenenfalls anwesend sein, jedoch treten sie in ihrer Bedeutung hinter den vorgenannten Typen zurück. Brauchbar sind ferner Seifen von gesättigten bzw. ungesättigten Fettsäuren mit 12 bis 18 C-Atomen, allerdings verbessern derartige Zusätze die Eigenschaften des Waschmittels nicht wesentlich, weshalb die Mittel vorzugsweise seifenfrei sind.Other suitable anionic surfactants, which may be present, are aikansuifonate, as can be obtained by sulfochlorination or sulfoxidation from paraffin hydrocarbons having 12 to 18 or 14 to 16 carbon atoms. The olefin sulfonates obtainable from terminal olefins by sulfonation with sulfur trioxide and subsequent hydrolysis can also be used. Other known surfactants from sulfonate or. Sulphate types may be present, but their importance is less than that of the aforementioned types. Soaps of saturated or unsaturated fatty acids with 12 to 18 carbon atoms can also be used, but such additives do not significantly improve the properties of the detergent, which is why the detergents are preferably soap-free.
Der Gehalt der Mittel an anionischen Tensiden ist geringer als ihr Gehalt an nichtionsichen Tensiden. Vorzugsweise beträgt das Gewichtsverhältnis von nichtionischer Komponente (a) zu anionischer Komponente (b) 4 : 1 bis 4 : 3, insbesondere 3 : 1 bis 3 : 2. In diesem Bereich ist die Waschkraft sowohl gegenüber fettartigen wie mineralischen Verschmutzungen besonders ausgeprägt. Der Gehalt des Mittels an den vorgenannten Tensiden beträgt dabei insgesamt 10 bis 25 Gew.-%, vorzugsweise 12 bis 20 Gew.-%.The content of the anionic surfactants is lower than their nonionic surfactant content. The weight ratio of nonionic component (a) to anionic component (b) is preferably 4: 1 to 4: 3, in particular 3: 1 to 3: 2. In this range, the detergency is both greasy and mineral Soiling is particularly pronounced. The content of the agent in the aforementioned surfactants is a total of 10 to 25% by weight, preferably 12 to 20% by weight.
Als Gerüstsalze (Komponente c), die in Anteiten von 35 bis 50 Gew.-% vorliegen, kommen synthetische, gebundenes Wasser enthaltende Natriumalumosilikate, vorzugsweise vom Zeolith A-Typ in Frage. Brauchbar sind femer Zeolith NaX sowie dessen Gemische mit Zeolith NaA, wobei der Anteil des Zeoliths NaX in derartigen Gemischen zweckmäßigerweise unter 30 %, insbesondere unter 20 %, bezogen auf den Zeolithanteil, liegt. Geeignete Zeolithe weisen keine Teilchen mit einer Größe über 30 Mikron auf und bestehen zu wenigstens 80 % aus Teilchen einer Größe von weniger als 10 Mikron. Ihr Calciumbindevermögen, das nach den Angaben der DE 24 12 837 bestimmt wird, liegt im Bereich von 100 bis 200 mg CaO/g.Suitable framework salts (component c), which are present in proportions of 35 to 50% by weight, are synthetic sodium aluminosilicates containing bound water, preferably of the zeolite A type. It is also possible to use zeolite NaX and mixtures thereof with zeolite NaA, the proportion of zeolite NaX in such mixtures advantageously being less than 30%, in particular less than 20%, based on the proportion of zeolite. Suitable zeolites have no particles larger than 30 microns and consist of at least 80% particles smaller than 10 microns. Their calcium binding capacity, which is determined according to the information in DE 24 12 837, is in the range from 100 to 200 mg CaO / g.
Ein weiterer obligatorischer Bestandteil der Komponente (c) besteht aus einer homopolymeren und/oder copolymeren Carbonsäure bzw. deren Natrium-oder Kaliumsalz, wobei die Natriumsalze bevorzugt sind. Geeignete Homopolymere sind Polyacrylsäure, Polymethacrylsäure und Polyma-[einsäure. Geeignete Copolymere sind solche der Acrylsäure oder Methacrylsäure mit Maleinsäure bzw. Copolymere der Acrylsäure, Methacrylsäure oder Maleinsäure mit Vinylethern, wie Vinylmethylether bzw.A further mandatory component of component (c) consists of a homopolymeric and / or copolymeric carboxylic acid or its sodium or potassium salt, the sodium salts being preferred. Suitable homopolymers are polyacrylic acid, polymethacrylic acid and polymic acid. Suitable copolymers are those of acrylic acid or methacrylic acid with maleic acid or copolymers of acrylic acid, methacrylic acid or maleic acid with vinyl ethers, such as vinyl methyl ether or
Vinylethylether, ferner mit Vinylestem, wie Vinylacetat oder Vinylpropionat, Acrylamid, Methacrylamid sowie mit Ethylen, Propylen oder Styrol. In solchen copolymeren Säuren, in denen eine der Komponenten keine Säurefunktion aufweist, beträgt deren Anteil im Interesse einer ausreichenden Wasserlöslichkeit nicht mehr als 70 Molprozent, vorzugsweise weniger als 60 Molprozent. Als besonders geeignet haben sich Copolymere der Acrylsäure mit Maleinsäure erwiesen, wie sie beispielsweise in EP 25 551-B1 sowie in der Zeitschrift "Tenside", 16 (1979), Seiten 82 -89, näher charakterisiert sind. Es handelt sich dabei um Copolymerisate, die 40 bis 90 Gew.-% Acrylsäure bzw. Methacrylsäure und 60 bis 10 Gew.-% Maleinsäure enthalten. Besonders bevorzugt sind solche Copolymere, in denen 45 bis 85 Gew.-% Acrylsäure und 55 bis 15 Gew.-% Maleinsäure anwesend sind. Das Molekulargewicht der Homo- bzw. Copolymeren beträgt im allgemeinen 1 000 bis 150 000, vorzugsweise 1 500 bis 100 000.Vinyl ethyl ether, also with vinyl esters, such as vinyl acetate or vinyl propionate, acrylamide, methacrylamide and with ethylene, propylene or styrene. In those copolymeric acids in which one of the components has no acid function, the proportion thereof in the interest of sufficient water solubility is not more than 70 mole percent, preferably less than 60 mole percent. Copolymers of acrylic acid with maleic acid have proven to be particularly suitable, as are described in more detail, for example, in EP 25 551-B1 and in the journal "Tenside", 16 (1979), pages 82-89. These are copolymers which contain 40 to 90% by weight of acrylic acid or methacrylic acid and 60 to 10% by weight of maleic acid. Copolymers in which 45 to 85% by weight of acrylic acid and 55 to 15% by weight of maleic acid are present are particularly preferred. The molecular weight of the homo- or copolymers is generally 1,000 to 150,000, preferably 1,500 to 100,000.
Ein weiterer Bestandteil der Komponente (c) besteht aus Natriumsilikat der Zusammensetzung Na20 : Si02 = 1 : 2 bis 1 : 3,5, vorzugsweise 1 : 2,5 bis 1 : 3,3. Auch Gemische von Silikaten mit unterschiedlichem Alkaligehalt können verwendet werden, beispielsweise ein Gemisch aus Na2O : Si02 = 1 : 2 und Na2O : SiO2 = 1 : 2,5 bis 3,3.Another component of component (c) consists of sodium silicate with the composition Na20: SiO2 = 1: 2 to 1: 3.5, preferably 1: 2.5 to 1: 3.3. Mixtures of silicates with different alkali contents can also be used, for example a mixture of Na 2 O: Si0 2 = 1: 2 and Na 2 O: SiO 2 = 1: 2.5 to 3.3.
Der Gehalt der Mittel an Zeolith beträgt 10 bis 40 Gew.-%, vorzugsweise 12 bis 20 Gew.-%, an polymeren bzw. copolymeren Carbonsäuren bzw. deren Salzen 0,5 bis 5, vorzugsweise 0.8 bis 4 Gew.-% und an Natriumsilikat 1 bis 7 Gew.-%, vorzugsweise 2 bis 6 Gew.-%.The zeolite content of the compositions is 10 to 40% by weight, preferably 12 to 20% by weight, of polymeric or copolymeric carboxylic acids or their salts 0.5 to 5, preferably 0.8 to 4% by weight and on Sodium silicate 1 to 7% by weight, preferably 2 to 6% by weight.
Weitere geeignete Gerüstsalze sind Natriumcarbonat und -sofern gegen die Mitverwendung untergeordneter Mengen an Phosphaten keine Bedenken bestehen -Polyphosphate, insbesondere Pentanatriumtripolyphosphat. Dessen Anteil kann unter den genannten Voraussetzungen bis zu 25 Gew.-%, vorzugsweise 5 bis 22 Gew.-% betragen. In Fällen, wo Phosphate nicht eingesetzt werden können, kommt auch ein Ersatz durch Natriumnitrilotriacetat in Anteilen von beispielsweise 2 bis 10 Gew.-% in Frage. Auch andere bekannte wasserlösliche Phosphatsubstitute können gegebenenfalls mitverwendet werden, beispielsweise Polyacetale der Glyoxylsäure in Form der Natriumsalze.Other suitable skeletal salts are sodium carbonate and, in so far as there are no concerns about the use of minor amounts of phosphates, polyphosphates, in particular pentasodium tripolyphosphate. Under the conditions mentioned, its proportion can be up to 25% by weight, preferably 5 to 22% by weight. In cases where phosphates cannot be used, replacement by sodium nitrilotriacetate in proportions of, for example, 2 to 10% by weight is also possible. Other known water-soluble phosphate substitutes can optionally also be used, for example polyacetals of glyoxylic acid in the form of the sodium salts.
Zu den Gerüstsalzen (c) zählen ferner die meist in vergleichsweise geringer Menge anwesenden, als sogenannte Co-Builder, Stabilisatoren, Fällungsvsrhüter (Threshold-Substanzen) wirkenden Sequestrierungsmittel aus der Klasse der Aminopolycarbonsäuren und Polyphosphonsäuren. Zu den Aminopolycarbonsäuren zählen die Ethylendiamintetraessigsäure, die Diethylentriaminpentaessigsäure sowie deren höhere Homologen. Geeignete Polyphosphonsäuren sind 1-Hydroxyethan-1,1-diphosphonsäure, Aminotri-(methylenphosphonsäure), Ethylendiaminteira-(methylenphosphonsäure) und deren höhere Homologen, wie z. B. Diethylentriamintetra-(methylenphosphonsäure). Die vorgenannten Polycarbonsäuren bzw. Polyphosphonsäuren kommen üblicherweise in Form der Natrium-bzw. Kaliumsalze zur Anwendung. Ihre Einsatzmenge beträgt im allgemeinen 0,1 bis 5 Gew.-%, vorzugsweise 0,2 bis 1 Gew.-%.The framework salts (c) also include the sequestering agents from the class of aminopolycarboxylic acids and polyphosphonic acids, which are usually present in comparatively small amounts and act as so-called co-builders, stabilizers, precipitation inhibitors (threshold substances). The aminopolycarboxylic acids include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and their higher homologues. Suitable polyphosphonic acids are 1-hydroxyethane-1,1-diphosphonic acid, aminotri- (methylenephosphonic acid), ethylenediaminteira- (methylenephosphonic acid) and their higher homologs, such as. B. Diethylenetriamine tetra (methylenephosphonic acid). The aforementioned polycarboxylic acids or polyphosphonic acids usually come in the form of the sodium or. Potassium salts for use. The amount used is generally 0.1 to 5% by weight, preferably 0.2 to 1% by weight.
Zu den sonstigen üblichen Waschmittelbestandteilen (Komponente d) zählen vergrauungsverhütende Stoffe, optische Aufheller, Enzyme, Bleichmittel und Bleichaktivatoren, Schauminhibitoren, Farb-und Duftstoffe, Biocide, Neutralsalze sowie Stoffe, welche die Pulverbeschaffenheit verbessern.The other usual detergent ingredients (component d) include anti-graying substances, optical brighteners, enzymes, bleaching agents and bleach activators, foam inhibitors, colorants and fragrances, biocides, neutral salts and substances which improve the quality of the powder.
Geeignete Vergrauungsverhüter sind Celluloseether, wie Carboxymethylcellulose, Methylcellulose, Hydroxyalkylcellulosen und Mischether, wie Methylhydroxyethylcellulose, Methylhydroxypropylcellulose und Methyl-Carboxymethylcellulose. Geeignet sind ferner Gemische verschiedener Celluloseether, insbesondere Gemische aus Carboxymethylcellulose und Methylcellulose.Suitable graying inhibitors are cellulose ethers, such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl celluloses and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose and methyl carboxymethyl cellulose. Mixtures of various cellulose ethers, in particular mixtures of carboxymethyl cellulose and methyl cellulose, are also suitable.
Geeignete optische Aufheller sind Alkalisalze der 4,4-Bis-(2"-anilino-4"-morpholino-1,3,5-triazinyl-6"-amino)-stilben-2,2'-disulfonsäure oder gleichartig aufgebaute Verbindungen, die anstelle der Morpholinogruppe eine Diethanolaminogruppe tragen. Weiterhin kommen Aufheller vom Typ der substituierten Diphenylstyryle in Frage, z. B. die Alkalisalze des 4,4'-Bis--(2-sulfostyryl)-diphenyls, 4,4'-Bis-(4-chlor-3-sulfostyryl)-diphenyls und 4-(4-Chlorstyryl-4'-(2-su!fostyry!)-diphenyis.Suitable optical brighteners are alkali metal salts of 4,4-bis- (2 "-anilino-4" -morpholino-1,3,5-triazinyl-6 "-amino) -stilbene-2,2'-disulfonic acid or compounds of the same structure, which carry a diethanolamino group instead of the morpholino group. Brighteners of the substituted diphenylstyryl type, for example the alkali metal salts of 4,4'-bis - (2-sulfostyryl) -diphenyl, 4,4'-bis- ( 4-chloro-3-sulfostyryl) diphenyls and 4- (4-chlorostyryl-4 '- (2-su! Fostyry!) - diphenyis.
Als Enzyme kommen solche aus der Klasse der Proteasen, Lipasen und Amylasen bzw. deren Gemische in Frage. Besonders geeignet sind aus Bakterienstämmen oder Pilzen, wie Bacillus subtilis, Bacillus licheniformis und Streptomyces griseus gewonnene enzymatische Wirkstoffe. Die Enzyme können in Hüllsubstanzen eingebettet sien, um sie gegen vorzeitige Zersetzung zu schützen.Enzymes from the class of proteases, lipases and amylases or mixtures thereof are possible. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. The enzymes can be embedded in coating substances to protect them against premature decomposition.
Als Bleichkomponente kommen die üblicherweise in Wasch-und Bleichmitteln verwendeten Perhydrate und Perverbindungen in Frage. Zu den Perhydraten zählen bevorzugt Natriumperborat, das als Tetrahydrat oder auch als Monohydrat vorliegen kann, ferner die Perhydrate des Natriumcarbonats (Natriumpercarbonat), des Natriumpyrophosphats (Perpyrophosphat), des Natriumsilikats (Persilikat) sowie des Harnstoffes. Diese Perhydrate kommen bevorzugt zusammen mit Bleichaktivatoren zum Einsatz.The perhydrates and per-compounds commonly used in washing and bleaching agents are suitable as bleaching components. The perhydrates preferably include sodium perborate, which can be present as a tetrahydrate or as a monohydrate, furthermore the perhydrates of sodium carbonate (sodium percarbonate), sodium pyrophosphate (perpyrophosphate), sodium silicate (persilicate) and urea. These perhydrates are preferably used together with bleach activators.
Bevorzugt kommt Natriumperborat-tetrahydrat in Verbindung mit Bleichaktivatoren als Bleichkomponente in Frage. Zu den Bleichaktivatoren zählen insbesondere N-Acylverbindungen und O-Acylverbindungen. Beispiele für geeignete N-Acylverbindungen sind mehrfach acylierte Alkylendiamine, wie Tetraacetylmethylendiamin, Tetraacetylethylendiamin und deren höhere Homologen, sowie acylierte Glykolurile, wie Tetraacetylglykoluril. Weitere Beispiele sind Na-Cyanamid, N-Alkyl-N-sulfonylcarbonamide, N-Acylhydantoine, N-acylierte cyclische Hydrazide, Triazole, Urazole, Diketopiperazine, Sulfurylamide, Cyanurate und Imidazoline. Als 0-Acylverbindungen kommen neben Carbonsäureanhydriden, wie Phthalsäureanhydrid und Estern, wie Na-(iso)-nonanoylphenolsulfonat, insbesondere acylierte Zucker, wie Glucosepentaacetat in Frage. Bevorzugte Bleichaktivatoren sind Tetraacetylethylendiamin und Glucosepentaacetat. Auch die Bleichaktivatoren können zwecks Vermeidung von Wechselwirkungen mit den Perverbindungen, insbesondere während der Lagerung pulverförmiger Gemische, mit Hüllsubstanzen überzogen sein.Sodium perborate tetrahydrate in combination with bleach activators is preferred as the bleaching component. The bleach activators include in particular N-acyl compounds and O-acyl compounds. Examples of suitable N-acyl compounds are multiply acylated alkylenediamines, such as tetraacetylmethylene diamine, tetraacetylethylenediamine and their higher homologues, and acylated glycolurils, such as tetraacetylglycoluril. Further examples are Na-cyanamide, N-alkyl-N-sulfonylcarbonamides, N-acylhydantoins, N-acylated cyclic hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides, cyanurates and imidazolines. In addition to carboxylic acid anhydrides, such as phthalic anhydride and esters, such as Na (iso) nonanoylphenol sulfonate, in particular acylated sugars such as glucose pentaacetate are suitable as 0-acyl compounds. Preferred bleach activators are tetraacetylethylene diamine and glucose pentaacetate. The bleach activators can also be coated with coating substances in order to avoid interactions with the per compounds, especially during the storage of powdery mixtures.
Geeignete Schauminhibitoren sind Organopolysiloxane und deren Gemische mit mikrofeiner, gegebenenfalls silanierter Kieselsäure, Paraffine, Wachse, Mikrokristallinwachse und deren Gemische mit silanierter Kieselsäure sowie gesättigte Fettsäuren mit 18 bis 24 C-Atomen bzw. deren Alkaliseifen. Auch Gemische verschiedener Schauminhibitoren, z. B. aus Silikonen und Paraffinen sind brauchbar.Suitable foam inhibitors are organopolysiloxanes and their mixtures with microfine, optionally silanized silica, paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica and saturated fatty acids with 18 to 24 carbon atoms or their alkali soaps. Mixtures of various foam inhibitors, e.g. B. from silicones and paraffins are useful.
Als weitere Bestandteile kommen Neutralsalze, insbesondere Natriumsulfat sowie als Stabilisator für Perverbindungen wirkendes Magnesiumsilikat in Betracht. Weitere Waschhilfsmittel sind Zusätze, welche die Pulverstruktur verbessern, z. B. Alkalisalze oder Toluol-, Cumol-oder Xylolsulfonsäure.Neutral salts, in particular sodium sulfate, and magnesium silicate acting as a stabilizer for per compounds also come into consideration as further constituents. Other washing aids are additives that improve the powder structure, e.g. B. alkali salts or toluene, cumene or xylene sulfonic acid.
Die der Komponente (d) angehörenden Bestandteile können in Mengen vorliegen, die in bekannten Waschmittelzusammensetzungen allgemein üblich sind. Der Anteil der Vergrauungsinhibitoren beträgt im allgemeinen 0,2 bis 2 Gew.-%, der Anteil der optischen Aufheller 0,05 bis 0,5 Gew.-%. Der Anteil der Enzyme richtet sich in erster Linie nach ihrer Aktivität. Technische Enzympräparate, die üblicherweise mit Stabilisatoren, Calciumsalzen und Verschnittmitteln vermischt und auf eine bestimmte Aktivität eingestellt werden, kommen üblicherweise in Anteilen von 0,1 bis 2 Gew.-% zum Einsatz. Der Anteil an Perborat beträgt üblicherweise 5 bis 25 Gew.-%. Die Einsatzmengen an Bleichaktivatoren orientiert sich ebenfalls an deren Wirksamkeit. Hochwirksame Aktivatoren, wie Tetraacetylethylendiamin, werden üblicherweise in Mengen von 0,5 bis 5 Gew.-% verwendet. Analog gilt dies auch für Schauminhibitoren, deren Anteil im Falle hochwirksamer Silikonentschäumer allgemein 0,01 bis 0,5 Gew.-%, im Falle wachsartiger bzw. paraffinischer Stoffe bzw. höhermolekularer Fettsäuren bis 2 Gew.-% betragen kann. Der Anteil an Natriumsulfat kann bis 25 Gew.-%, in besonderen Fällen auch noch mehr betragen.The components belonging to component (d) can be present in amounts which are generally customary in known detergent compositions. The proportion of graying inhibitors is generally 0.2 to 2% by weight, the proportion of optical brighteners 0.05 to 0.5% by weight. The proportion of enzymes depends primarily on their activity. Technical enzyme preparations, which are usually mixed with stabilizers, calcium salts and blending agents and adjusted to a specific activity, are usually used in proportions of 0.1 to 2% by weight. The proportion of perborate is usually 5 to 25% by weight. The amounts of bleach activators used are also based on their effectiveness. Highly effective activators, such as tetraacetylethylenediamine, are usually used in amounts of 0.5 to 5% by weight. This also applies analogously to foam inhibitors, the proportion of which can generally be from 0.01 to 0.5% by weight in the case of highly effective silicone defoamers, and up to 2% by weight in the case of waxy or paraffinic substances or higher molecular weight fatty acids. The proportion of sodium sulfate can be up to 25% by weight, in special cases even more.
Die erfindungsgemäßen Mittel liegen als körnige Pulver bzw. Pulvergemische vor, die in geeigneter Weise durch Granulieren, Sprühtrocknen, Sprühmischen, Homogenisieren oder. durch eine Kombination dieser Arbeitsweisen erhältlich sind. Da die Komponente (a) aus flüssigen, zum Kleben neigenden Verbindungen besteht, die sich aufgrund ihrer Neigung zum "Pluming" nur bedingt für eine Sprühtrocknung eignen, ist es erforderlich, daß sie an einer Trägersubstanz adsorbiert ist. Als Trägersubstanz eignen sich die Gerüstsalze (c), insbesondere Zeolith, Phosphate, Silikate, Nitrilotriacetat sowie deren Gemische, ferner sprühgetrocknete Gemische aus Gerüstsalzen (c), anionischen Tensiden (b) und sonstigen Bestandteilen (d), soweit diese unter den Bedingungen der Sprühtrocknung beständig sind. Aus Gerüstsalzen bestehende Trägersubstanzen können außerdem Neutralsalze, wie Natriumsulfat, Vergrauungsverhüter, Mg-Silikat sowie zusätzliche Adsorptionsmittel, wie feinteilige Kieselsäure, feinteiliges Aluminiumoxid, Smektittone, Schichtsilikate und Bentonite enthalten. Anstelle von sprühgetrockneten Gemischen können auch durch Aufbaugranulation hergestellte Gerüstsalzgemische als Trägersubstanz für die Komponente (a) dienen. Nach dem Aufbringen der nichtionischen Komponente (a) auf diese Trägermaterialien können die Granulate noch mit adsorbierenden, das Kleben verhindernden Überzügen versehen sein, was beispielsweise durch Pudem mit den vorgenannten feinteiligen Adsorptionsmitteln erfolgen kann.The agents according to the invention are in the form of granular powders or powder mixtures which can be suitably granulated, spray-dried, spray-mixed, homogenized or. can be obtained through a combination of these working methods. Since component (a) consists of liquid compounds which tend to stick and which, owing to their tendency to "pluming", are only suitable for spray drying to a limited extent, it is necessary for them to be adsorbed on a carrier substance. As a carrier the skeleton salts (c), in particular zeolite, phosphates, silicates, nitrilotriacetate and their mixtures, are also spray-dried mixtures of skeleton salts (c), anionic surfactants (b) and other constituents (d), provided that these are stable under the conditions of spray drying . Carrier substances consisting of skeletal salts can also contain neutral salts, such as sodium sulfate, graying inhibitors, Mg silicate and additional adsorbents, such as finely divided silica, finely divided aluminum oxide, smectite clays, layered silicates and bentonites. Instead of spray-dried mixtures, it is also possible to use framework salt mixtures prepared by build-up granulation as the carrier substance for component (a). After the nonionic component (a) has been applied to these carrier materials, the granules can also be provided with adsorbing coatings which prevent them from sticking, which can be done, for example, by means of the aforementioned fine-particle adsorbents.
Eine besonders bevorzugte Ausführungsform der Erfindung besteht darin, daß 30 bis 100 Gew.- % der Komponente (c) in Form eines Granulates - (c1) vorliegen, enthaltend den Zeolith, das Salz der polymeren bzw. copolymeren Carbonsäure und das Natriumsilikat bzw. einen Teil des insgesamt anwesenden Natriumsilikats. Geeignete Granulate - (c1) weisen die folgende Zusammensetzung auf (in Gew.-%, bezogen auf Grunulat):
- 60 -80 %, insbesondere 65 -75 % Zeolith,
- 3 -20 %, insbesondere 4 -15 % Polycarbonsäure-Salz,
- 0,1 -2 %, insbesondere 0,15 - 1 % Natriumsilikat,
- 8 -18 %, insbesondere 10 -16 % Wasser, das bei einer Trocknungstemperatur von 145 °C entfembar ist,
- 0,5 -5 %, vorzugsweise 2 -4 % Dispersionsstabilisator.
- 60 -80%, especially 65 -75% zeolite,
- 3 -20%, especially 4 -15% polycarboxylic acid salt,
- 0.1-2%, especially 0.15-1% sodium silicate,
- 8 -18%, in particular 10 -16% water, which can be removed at a drying temperature of 145 ° C.,
- 0.5 -5%, preferably 2 -4% dispersion stabilizer.
Unter Dispersionsstabilisatoren sind Verbindungen zu verstehen, die dazu verwendet werden, wäßrige bzw. pastenförmige Zeolithaufschlämmungen zu stabilisieren. Sie werden im allgemeinen diesen Aufschlämmungen während ihrer Herstellung bzw. feuchten Filterkuchen zugesetzt und verbleiben auch bei der Weiterverarbeitung in den Zeolithen. Es sei hierzu auf DE 25 27 388 verwiesen. Beispiele für derartige Stabilisatoren sind Neutralsalze, wie Natriumsulfat, nichtionische Tenside aus der Klasse der ethoxylierten Fettalkohole mit 12 bis 18 C-Atomen und 3 bis 10 Glykolethergruppen sowie polymere und copolymere Carbonsäuren. Vorzugsweise besteht der Dispersionsstabilisator aus dem unter (a1) aufgeführten nichtionischen Tensid bzw. einem Teil desselben.Dispersion stabilizers are to be understood as meaning compounds which are used to stabilize aqueous or pasty zeolite slurries. They are generally added to these slurries during their manufacture or moist filter cake and remain in the zeolites even during further processing. For this purpose, reference is made to DE 25 27 388. Examples of such stabilizers are neutral salts, such as sodium sulfate, nonionic surfactants from the class of ethoxylated fatty alcohols with 12 to 18 carbon atoms and 3 to 10 glycol ether groups, and polymeric and copolymeric carboxylic acids. The dispersion stabilizer preferably consists of the nonionic surfactant listed under (a1) or a part thereof.
Das Granulat, das vorzugsweise durch Sprühtrocknung hergestellt wird und in der Patentanmeldung P 34 44 960 (D 7180) näher beschrieben ist, weist eine mittlere Korngröße von 0,2 bis 1,2 mm auf und enthält weniger als 2 Gew.-% an staubförmigen Anteilen (Komgröße unter 0,05 mm) sowie nicht mehr als 5 Gew.-% an Grobanteilen (Komgröße über 2 mm). Sein Schüttgewicht beträgt 400 bis 700 g/l. Es zeichnet sich durch ein sehr hohes Adsorptionsvermögen für flüssige bzw. pastenförmige Stoffe aus und eignet sich daher besonders als Trägersubstanz für die nichtionischen Tenside (Komponente a).The granulate, which is preferably produced by spray drying and is described in more detail in patent application P 34 44 960 (D 7180), has an average grain size of 0.2 to 1.2 mm and contains less than 2% by weight of dust-like Proportions (grain size less than 0.05 mm) and no more than 5% by weight of coarse parts (grain size more than 2 mm). Its bulk density is 400 to 700 g / l. It is characterized by a very high adsorption capacity for liquid or paste-like substances and is therefore particularly suitable as a carrier for the nonionic surfactants (component a).
In einer weiteren bevorzugten Ausführungsform liegt daher das erfindungsgemäße Mittel als ein Gemisch mehrerer Teilpulver vor. Als Teilpulver kommen in Frage:
- (I) Ein Teilpulver, bestehend aus dem zuvor beschriebenen Granulat aus Zeolith, (co- )polymerem carbonsaurem Salz, Natriumsilikat, Wasser, dem nichtionischen Dispersionsstabilisator sowie der an diesem Granulat adsorbierten nichtionischen Tensidkomponente (a).
- (11) Ein Teilpulver, bestehend aus der anionischen Tensidkomponente (b), den nicht in dem Granulat enthaltenen Gerüstsalzen der Komponente (c) sowie weiteren Waschmittelbestandteilen (d), sowiet diese sich für eine Sprühtrocknung eignen. Hierzu zählen Komplexbildner, Vergrauungsinhibitoren, optische Aufheller, Neutralsalze.
- (III) Ein oder mehrere Teilpulver, die solche Bestandteile enthalten, die aus Stabilitätsgründen nicht in unmittelbaren Kontakt mit den Bestandteilen der Teilpulver (1) und - (11) gebracht bzw. nicht sprühgetrocknet werden sollen. Diese Bestandteile umfassen Bleichmittel, Bleichaktivatoren, Schauminhibitoren, Enzyme, Duftstoffe und Biocide. Diese Stoffe werden im allgemeinen gesondert aufbereitet bzw. in eine geeignete Pulver-oder Granulatform überführt und mit den übrigen Teilpulvem vermischt. Flüssige Bestandteile, wie Parfümöle, können auch auf andere kömige Teilpulver, z. B. das Perborat, aufgesprüht und mit diesem zusammen dem Gemisch zugesetzt werden. Auch die Schauminhibitoren werden vorzugsweise auf eine adsorbierend wirkende Trägersubstanz aufgebracht bzw. in ein wasserlösliches Hüllmaterial eingebettet, um sie gegen Wechselwirkungen mit anderen Pulverbestandteilen und den daraus resultierenden Wirkungsverlust zu schützen.
- (I) A partial powder consisting of the granules of zeolite described above, (co) polymeric carboxylic acid salt, sodium silicate, water, the nonionic dispersion stabilizer and the nonionic surfactant component (a) adsorbed on these granules.
- (11) A partial powder consisting of the anionic surfactant component (b), the skeleton salts of component (c) not contained in the granules and further detergent components (d), as far as these are suitable for spray drying. These include complexing agents, graying inhibitors, optical brighteners, neutral salts.
- (III) One or more partial powders which contain such constituents which, for reasons of stability, should not be brought into direct contact with the constituents of the partial powders (1) and - (11) or should not be spray-dried. These ingredients include bleaches, bleach activators, foam inhibitors, enzymes, fragrances and biocides. These substances are generally prepared separately or converted into a suitable powder or granulate form and mixed with the other partial powders. Liquid components, such as perfume oils, can also be used on other granular partial powders, e.g. B. the perborate, sprayed and added to the mixture together with this. Foam inhibitors are also preferred applied to an adsorbent carrier or embedded in a water-soluble coating material in order to protect it against interactions with other powder components and the resulting loss of activity.
Gegenstand der Erfindung ist ferner ein Verfahren zur Herstellung der erfindungsgemäßen Waschmittel. Dieses Verfahren besteht darin, daß man ein Granulat der Zusammensetzung (in Gew.-%)
- 60 -80 %, insbesondere 65 -75 % Zeolith,
- 3 -20 %, insbesondere 4 -15 % Polycarbonsäure-Salz,
- 0,1 -2 %, insbesondere 0,15 -1 % Natriumsilikat,
- 8 -18 %, insbesondere 10 -16 % Wasser, das bei einer Trocknungstemperatur von 145 °C entfernbar ist,
- 0,5 -5 %, vorzugsweise 2 - 4 % Dispersionsstabilisator
durch Sprühtrocknung herstellt, das Granulat mit dem nichtionischen Tensidgemisch (a) imprägniert und das erhaltene Teilpulver (I) mit einem sprühgetrockneten Teilpulver (11) gemäß vorstehend angegebener Zusammensetzung sowie weiteren Teilpulvern (111) gemäß vorstehend angegebener Zusammensetzung vermischt.The invention further relates to a method for producing the detergents according to the invention. This method consists in that a granulate of the composition (in% by weight)
- 60 -80%, especially 65 -75% zeolite,
- 3 -20%, especially 4 -15% polycarboxylic acid salt,
- 0.1-2%, in particular 0.15-1% sodium silicate,
- 8 -18%, in particular 10 -16% water, which can be removed at a drying temperature of 145 ° C.
- 0.5 -5%, preferably 2-4% dispersion stabilizer
is produced by spray drying, the granules are impregnated with the nonionic surfactant mixture (a) and the partial powder (I) obtained is mixed with a spray-dried partial powder (11) having the composition given above and further partial powders (111) having the composition given above.
Bei der Herstellung des Teilpulvers (I) ist darauf zu achten, daß dessen Gehalt an Natriumsilikat begrenzt ist. Sofern aus anwendungstechnischen Gründen der Gehalt an Natriumsilikat im Waschmittel wesentlich höher liegt, sollte der überschießende Anteil den übrigen Teilpulvern, insbesondere dem sprühgetrockneten Teilpulver (11) zugeschlagen werden. Höhere Anteile an Natriumsilikat in diesem Granulat als angegeben erhöhen dessen Zerfallzeit bzw. verschlechtern seine Löslichkeit in der Waschlauge. Dadurch verzögert sich die Freisetzung des nichtionischen Tensides, was zu einer Verschlechterung des Waschergebnisses führen kann. Diese Unterteilung des insgesamt anwesenden Natriumsilikats auf zwei verschiedene Teilpulver ist ein weiterer Aspekt der Erfindung.When producing the partial powder (I), care must be taken to ensure that its sodium silicate content is limited. If the content of sodium silicate in the detergent is considerably higher for technical reasons, the excess portion should be added to the other partial powders, in particular the spray-dried partial powder (11). Higher proportions of sodium silicate in these granules than specified increase its disintegration time or impair its solubility in the wash liquor. This delays the release of the non-ionic surfactant, which can lead to a deterioration in the washing result. This subdivision of the total sodium silicate present into two different partial powders is a further aspect of the invention.
Weiter Angaben über die Herstellung der Granulates und seine Imprägnierung mit nichtionischen Tensiden sind der DE 34 44 960 (D 7180) zu entnehmen, auf die hier ausdrücklich Bezug genommen wird.Further information on the production of the granules and their impregnation with nonionic surfactants can be found in DE 34 44 960 (D 7180), to which reference is expressly made here.
Die erfindungsgemäßen Mittel zeichnen sich durch ein hohes Waschvermögen, insbesondere durch eine ausgezeichnete Reinigungskraft gegenüber hartnäckigen fettartigen Anschmutzungen, beispielsweise solchen aus Speise-und Soßenresten, Hautfett, Lippenstift und Wimperntusche aus. Trotz ihres vergleichsweise hohen Gehaites an flüssigen nichtionischen Tensiden sind sie hervorragend schütt-und rieselfähig und neigen nicht zum Durchfetten von Kartonageverpackungen. Sofern sie nach der bevorzugten Verfahrensweise hergestellt werden, d. h. Adsorbieren des nichtionischen Tensids an dem zuvor hergestellten Granulat aus Zeolith, Polymersäure und Natriumsilikat, wird die Entstehung von Aerosolen in der Abluft der Sprühtürme vollständig vermieden.The agents according to the invention are characterized by a high washing capacity, in particular by an excellent cleaning power against stubborn greasy soiling, for example those from food and sauce residues, skin fat, lipstick and mascara. Despite their comparatively high content of liquid non-ionic surfactants, they are extremely pourable and free-flowing and do not tend to grease cardboard packaging. If they are made according to the preferred procedure, i. H. Adsorbing the non-ionic surfactant on the previously prepared granules of zeolite, polymeric acid and sodium silicate completely avoids the formation of aerosols in the exhaust air from the spray towers.
Nach den Angaben der Patentschrift DE 33 44 960 (D 7180) wurde durch Sprühtrocknung ein saugfähiges Granulat folgender Zusammensetzung hergestellt (GT = Gewichtsteile):
Der verwendete Zeolith wies eine Partikelgröße von 1 bis 8 Mikron auf, wobei der Anteil über 8 Mikron 6 Gew.-% betrug. Anteile über 20 Mikron lagen nicht vor. Als Polycarbonsäure wurde ein Copolymerisat aus Acrylsäure und Maleinsäure - (Molverhältnis 7 : 3) mit einem mittleren Molekulargewicht von 70 000 in Form des Natriumsalzes zum Einsatz gebracht. Als ethoxylierter Fettalkohol wurde ein mit 5 Mol Ethylenoxid (EO) umgesetzter Talgalkohol (30 % Cetylalkohol, 70 % Stearylalkohol) verwendet (entspricht einem Teil der Komponente a1).The zeolite used had a particle size of 1 to 8 microns, the proportion over 8 microns being 6% by weight. There were no portions above 20 microns. A copolymer of acrylic acid and maleic acid (molar ratio 7: 3) with an average molecular weight of 70,000 in the form of the sodium salt was used as the polycarboxylic acid. Tallow alcohol reacted with 5 mol ethylene oxide (EO) (30% cetyl alcohol, 70% stearyl alcohol) was used as the ethoxylated fatty alcohol (corresponds to part of component a1).
Das durch Siebanalyse ermittelte Kornspektrum ergab die folgende Gewichtsverteilung:
67,6 Gewichtsteile des Granulates wurden in einer Sprühmischapparat, bestehend aus einer gegen die Horizontale geneigten, mit Mischorganen und Sprühdüsen ausgerüsteten zylindrischen Trommel (LÖDIGE-Mischer) mit einer geschmolzenen Mischung nichtionischer Tenside besprüht. Die Temperatur des Granulats betrug 20 °C, die der Tensidschmelze 50 °C. Das Tensidgemisch bestand aus 4,1 Gewichtsteilen Talgalkohol mit 5 EO (restlicher Anteil der Komponente at), 20 Gewichtsteilen eines Laurylalkohol-Myristylalkohol-Gemisches (2 : 1) mit 5 EO - (Komponente a2) und 8,3 Gewichtsteilen Cocosalkylamin + 2 EO (C12-C18-Gemisch, mittlere Kettenlänge C,3,5). Nach dem Abkühlen wurde eine nichtklebendes, kömiges Produkt erhalten, dessen Rieselfähigkeit trotz eines Gehaltes an insgesamt 34 Gew.-% flüssigem nichtionischem Tensid ausgezeichnet war. Das Schüttgewicht betrug 740 g/l.67.6 parts by weight of the granules were sprayed with a molten mixture of nonionic surfactants in a spray mixer consisting of a cylindrical drum (LÖDIGE mixer) equipped with mixing elements and spray nozzles inclined to the horizontal. The temperature of the granules was 20 ° C, that of the surfactant melt 50 ° C. The surfactant mixture consisted of 4.1 parts by weight of tallow alcohol with 5 EO (remaining part of component at), 20 parts by weight of a lauryl alcohol-myristyl alcohol mixture (2: 1) with 5 EO - (component a2) and 8.3 parts by weight of cocoalkylamine + 2 EO (C 12 -C 18 mixture, average chain length C, 3 , 5 ). After cooling, a non-sticky, granular product was obtained, the flowability of which was excellent despite a total content of 34% by weight of liquid nonionic surfactant. The bulk density was 740 g / l.
30 Gewichtsteile des mit dem nichtionischen Tensid imprägnierten Granulats (Teilpulver t) wurde mit 54,7 Gewichsteilen eines sprühgetrockneten Pulvers (Teilpulver II) vermischt, enthaltend Natriumdodecylbenzolsulfonat, Natriumtripolyphosphat, Natrium-Ethylendiamintetra-methylenphosphat (EDTMP), Celluloseether, Natriumsilikat, optische Aufheller und Natriumsulfat. An weiteren Pulverbestandteilen wurden granulierte Enzyme granulierter Silikonentschäumer, Natriumperborat und granuliertes Tetraacetylethylendiamin (TAED) zugemischt. Diese pulverförmigen bzw. granularen Bestandteile werden unter dem Begriff "Teilpulver III" zusammengefaßt, deren Anteil insgesamt 15,3 Gewichtsteile beträgt.30 parts by weight of the granules impregnated with the nonionic surfactant (partial powder t) were mixed with 54.7 parts by weight of a spray-dried powder (partial powder II) containing sodium dodecylbenzenesulfonate, sodium tripolyphosphate, sodium ethylenediaminetetra-methylene phosphate (EDTMheller) and sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, cellulose ether, sodium sulfate, sodium sulfate, sodium sulfate, cellulose ether, sodium sulfate, sodium sulfate, cellulose ether, sodium sulfate, sodium sulfate, cellulose ether, sodium sulfate, sodium sulfate, cellulose ether, sodium sulfate, cellulose ether, sodium sulfate, cellulose ether, sodium sulfate, cellulose ether, sodium sulfate, cellulose ether, sodium sulfate, cellulose ether, sodium sulfate, cellulose ether, sodium sulfate, cellulose ether, sodium sulfate, cellulose ether, sodium sulfate, cellulose ether, sodium sulfate, cellulose ether, sodium sulfate, cellulose ether, cellulose ether, sodium sulfate, cellulose ether, sodium sulfate, cellulose ether, sodium sulfate, cellulose ether, cellulose ether, sodium sulfate, cellulose ether, sodium sulfate, respectively, and cellulose ether . Granulated enzymes of granulated silicone defoamers, sodium perborate and granulated tetraacetylethylenediamine (TAED) were added to further powder components. These powdery or granular constituents are summarized under the term "partial powder III", the proportion of which is a total of 15.3 parts by weight.
Die Zusammensetzung des Mittels lautete (in Gew.-%)
Es wurden Vergleichsversuche mit künstlich angeschmutzten Textilproben durchgeführt. Die unter reproduzierbaren Bedingungen auf Baumwolltextilien aufgebrachten Anschmutzungen bestanden aus Make-up-Creme, Wimperntusche und Lippenstift. Die Proben wurden zusammen mit 3 kg Ballastwäsche in handelsüblichen Haushaltswaschmaschinen (Aufnahmefähigkeit 4 kg Trockenwäsche) eingebracht und bei Temperaturen von 60 °C und 95 °C gewaschen (Pflegeleichtprogramm bzw. Kochwaschprogramm sowie 20 Minuten Vorwäsche bei 25 °C). Die Waschdauer einschließlich Aufheizung im Hauptwaschgang betrug 40 Minuten, die Waschmittelkonzentration 7,5 g/I, das Verhältnis von Textilmenge (in kg) zu Waschlauge (in Liter) betrug 1 : 5, die Wasserhärte des Leitungswasser 16 °dH (160 mg CaO pro Liter). Nach dreimaligem Nachspülen wurde geschleudert, getrocknet und der Remissionswert der Proben photometrisch ermittelt. Die Ergebnisse (Tabelle 11) sind Mittelwerte aus 5 Waschversuchen mit jeweils 6 Abmusterungen.Comparative tests were carried out with artificially soiled textile samples. The soiling applied to cotton textiles under reproducible conditions consisted of make-up cream, mascara and lipstick. The samples were placed together with 3 kg ballast washing in commercial household washing machines (absorption capacity 4 kg dry laundry) and washed at temperatures of 60 ° C and 95 ° C (easy care program or cook wash program and 20 minutes prewash at 25 ° C). The washing time including heating in the main wash cycle was 40 minutes, the detergent concentration 7.5 g / l, the ratio of the amount of textile (in kg) to the wash liquor (in liters) was 1: 5, the water hardness of the tap water was 16 ° dH (160 mg CaO per Liter). After rinsing three times, the product was spun, dried and the reflectance value of the samples was determined photometrically. The results (Table 11) are mean values from 5 washing tests with 6 samples each.
Zum Vergleich wurden Waschmittel herangezogen, die bei sonst unveränderter Zusammensetzung folgende Tenside enthielten (siehe Tabelle I):
Die Talgalkohol-bzw. Cocosalkylreste waren hinsichtlich ihrer qualitativen und quantitativen Zusammensetzung mit den im Beispiel eingesetzten identisch. Die Zusammensetzungen Versuch 1 und 2 entsprechen den Tensidzusammensetzungen handelsüblicher Hochleistungswaschmittel. Versuch 3 und 4 entsprechen Mitteln gemäß US 3 925 224.The tallow alcohol or. The qualitative and quantitative composition of coconut alkyl residues was identical to that used in the example. The compositions of experiments 1 and 2 correspond to the surfactant compositions of commercially available high-performance detergents. Trials 3 and 4 correspond to agents according to US 3 925 224.
Die Ergebnisse sind Tabelle II zu entnehmen. Die Note 1 bedeutet die höchste, 6 die - schlechteste Bewertung. Die verbesserte Waschkraft der erfindungsgemäßen Mittel kommt insbesondere im 60 °C-Waschbereich zum Ausdruck.
Claims (10)
wobei das Gewichtsverhältnis von (a1) : (a2) : (a3) = 1 : (2 -6) : (0,8 -2,5) beträgt und der Anteil der Komponente (a) den Anteil der Komponente (b) übertrifft.1. Granular detergent with improved cleaning ability against oil and fat-containing soiling, comprising a surfactant combination of (a) water-insoluble to partially soluble, nonionic, polyglycol ether group-containing surfactants, which are adsorbed to a granular carrier material, and (b) water-soluble surfactants from sulfonate Type and / or sulfate type, further comprising (c) skeleton salts and (d) other common detergent components, characterized in that component (a) consists of the following components
the weight ratio of (a1): (a2): (a3) = 1: (2 -6): (0.8 -2.5) and the proportion of component (a) exceeds the proportion of component (b) .
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3514364 | 1985-04-20 | ||
DE19853514364 DE3514364A1 (en) | 1985-04-20 | 1985-04-20 | GRINNY DETERGENT WITH IMPROVED CLEANING CAPACITY |
Publications (2)
Publication Number | Publication Date |
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EP0200953A2 true EP0200953A2 (en) | 1986-11-12 |
EP0200953A3 EP0200953A3 (en) | 1989-05-31 |
Family
ID=6268721
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP86105031A Withdrawn EP0200953A3 (en) | 1985-04-20 | 1986-04-11 | Granular detergent |
Country Status (4)
Country | Link |
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US (1) | US4675124A (en) |
EP (1) | EP0200953A3 (en) |
JP (1) | JPS61247798A (en) |
DE (1) | DE3514364A1 (en) |
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WO1990000189A1 (en) * | 1988-07-02 | 1990-01-11 | Henkel Kommanditgesellschaft Auf Aktien | Washing agent additives with improved dispersibility |
EP0436240A1 (en) * | 1989-12-04 | 1991-07-10 | Unilever N.V. | Process for preparing a high bulk density detergent composition having improved dispensing properties |
EP0544492A1 (en) * | 1991-11-26 | 1993-06-02 | Unilever Plc | Particulate detergent compositions |
WO1994013771A1 (en) * | 1992-12-15 | 1994-06-23 | Henkel Kommanditgesellschaft Auf Aktien | Granulated washing and cleaning agents with a high surfactant content |
WO1994014946A1 (en) * | 1992-12-23 | 1994-07-07 | Henkel Kommanditgesellschaft Auf Aktien | Granulated washing and/or cleaning agents |
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EP0227720A1 (en) * | 1985-06-22 | 1987-07-08 | Henkel Kommanditgesellschaft auf Aktien | Washing agent for low washing temperatures |
DE3626224A1 (en) * | 1986-08-02 | 1988-02-04 | Henkel Kgaa | CLEANING SUPPLIES |
DE3643895A1 (en) * | 1986-12-22 | 1988-06-30 | Henkel Kgaa | LIQUID NON-ionic surfactant blends |
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DE3716543A1 (en) * | 1987-05-16 | 1988-11-24 | Basf Ag | USE OF WATER-SOLUBLE COPOLYMERS, WHICH CONTAIN MONOMERS WITH AT LEAST TWO ETHYLENICALLY UNSATURATED DOUBLE BINDINGS IN DETERGENT AND CLEANING AGENTS |
DE3812530A1 (en) * | 1988-04-15 | 1989-10-26 | Henkel Kgaa | PROCESS FOR INCREASING THE DENSITY OF SPREADY DRY, PHOSPHATE-REDUCED DETERGENT |
DE3818426A1 (en) * | 1988-05-31 | 1989-12-07 | Basf Ag | METHOD FOR PRODUCING WATER-SOLUBLE POLYMERISATS AND THEIR USE |
DE3818829A1 (en) * | 1988-06-03 | 1989-12-14 | Henkel Kgaa | KOENIGES ADSORPTIONSMITTEL WITH IMPROVED SPOONING BEHAVIOR |
DE4010533A1 (en) * | 1990-04-02 | 1991-10-10 | Henkel Kgaa | Prodn. of high-density detergent granules |
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US5804543A (en) * | 1994-10-11 | 1998-09-08 | The Procter & Gamble Company | Detergent compositions with optimized surfactant systems to provide dye transfer inhibition benefits |
US5565422A (en) * | 1995-06-23 | 1996-10-15 | The Procter & Gamble Company | Process for preparing a free-flowing particulate detergent composition having improved solubility |
US6080713A (en) * | 1997-12-04 | 2000-06-27 | Crutcher; Terry | Method for cleaning hydrocarbon-containing greases and oils from fabric in laundry washing applications |
US6146427A (en) * | 1997-12-04 | 2000-11-14 | Crutcher; Terry | Method for cleaning hydrocarbon-containing greases and oils from fabric in laundry washing applications |
FR2776299B1 (en) * | 1998-03-18 | 2002-07-12 | Dior Christian Parfums | USE OF A CLEANING COMPOSITION FOR CLEANING LIPSTICK CARTRIDGE DEVICES, AND A METHOD AND APPARATUS COMPRISING APPLICATION THEREOF |
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GB0111862D0 (en) * | 2001-05-15 | 2001-07-04 | Unilever Plc | Granular composition |
GB0111863D0 (en) * | 2001-05-15 | 2001-07-04 | Unilever Plc | Granular composition |
JP2003119496A (en) * | 2001-10-12 | 2003-04-23 | Yushiro Chem Ind Co Ltd | Cleanser composition |
WO2007134822A1 (en) * | 2006-05-24 | 2007-11-29 | Harald Weirich | Binding agents and detergent builders modified with vegetable oils and vegetable oil derivatives |
DE102006054436A1 (en) * | 2006-11-16 | 2008-05-21 | Henkel Kgaa | Firm, textile and / or skin care composition |
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Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0240356A1 (en) * | 1986-04-04 | 1987-10-07 | Unilever Plc | Detergent powders and process for preparing them |
EP0270240A2 (en) * | 1986-10-31 | 1988-06-08 | Unilever Plc | Detergent powders and process for preparing them |
EP0270240A3 (en) * | 1986-10-31 | 1990-01-03 | Unilever Plc | Detergent powders and process for preparing them |
EP0273377A2 (en) * | 1986-12-31 | 1988-07-06 | Henkel Kommanditgesellschaft auf Aktien | Phosphate-free detergent with a reduced foaming tendency |
EP0273377A3 (en) * | 1986-12-31 | 1990-10-31 | Henkel Kommanditgesellschaft auf Aktien | Phosphate-free detergent with a reduced foaming tendency |
EP0288858A1 (en) * | 1987-04-25 | 1988-11-02 | Henkel Kommanditgesellschaft auf Aktien | Laundry prespotting agent for oil and fatty greases |
EP0354331A1 (en) * | 1988-07-02 | 1990-02-14 | Henkel Kommanditgesellschaft auf Aktien | Detergent additive with improved flushing property |
WO1990000189A1 (en) * | 1988-07-02 | 1990-01-11 | Henkel Kommanditgesellschaft Auf Aktien | Washing agent additives with improved dispersibility |
EP0436240A1 (en) * | 1989-12-04 | 1991-07-10 | Unilever N.V. | Process for preparing a high bulk density detergent composition having improved dispensing properties |
US5324455A (en) * | 1989-12-04 | 1994-06-28 | Lever Brothers Company, Division Of Conopco, Inc. | Process for preparing a high bulk density detergent composition having improved dispensing properties |
EP0544492A1 (en) * | 1991-11-26 | 1993-06-02 | Unilever Plc | Particulate detergent compositions |
WO1994013771A1 (en) * | 1992-12-15 | 1994-06-23 | Henkel Kommanditgesellschaft Auf Aktien | Granulated washing and cleaning agents with a high surfactant content |
WO1994014946A1 (en) * | 1992-12-23 | 1994-07-07 | Henkel Kommanditgesellschaft Auf Aktien | Granulated washing and/or cleaning agents |
Also Published As
Publication number | Publication date |
---|---|
DE3514364A1 (en) | 1986-10-23 |
EP0200953A3 (en) | 1989-05-31 |
US4675124A (en) | 1987-06-23 |
JPS61247798A (en) | 1986-11-05 |
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