CN1150450A - 包含金属离子螯合配合物和阴离子官能聚合物的洗涤剂粉末组合物 - Google Patents
包含金属离子螯合配合物和阴离子官能聚合物的洗涤剂粉末组合物 Download PDFInfo
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- CN1150450A CN1150450A CN 95193528 CN95193528A CN1150450A CN 1150450 A CN1150450 A CN 1150450A CN 95193528 CN95193528 CN 95193528 CN 95193528 A CN95193528 A CN 95193528A CN 1150450 A CN1150450 A CN 1150450A
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- 239000000843 powder Substances 0.000 title claims abstract description 49
- 239000003599 detergent Substances 0.000 title claims abstract description 30
- 239000000203 mixture Substances 0.000 title claims abstract description 28
- 125000000129 anionic group Chemical group 0.000 title claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 title claims description 5
- 239000002184 metal Substances 0.000 title claims description 5
- 239000013522 chelant Substances 0.000 title description 2
- 229920001002 functional polymer Polymers 0.000 title description 2
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 14
- 239000011777 magnesium Substances 0.000 claims abstract description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- 125000000524 functional group Chemical group 0.000 claims abstract description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000004411 aluminium Substances 0.000 claims abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 3
- 239000011575 calcium Substances 0.000 claims abstract description 3
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 239000011701 zinc Substances 0.000 claims abstract description 3
- 239000003352 sequestering agent Substances 0.000 claims description 30
- 239000000126 substance Substances 0.000 claims description 19
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- -1 methylene phosphonic acid Chemical compound 0.000 claims description 13
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 7
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 claims description 3
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 claims description 3
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 claims description 3
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- 150000003009 phosphonic acids Chemical class 0.000 claims description 3
- NIONDZDPPYHYKY-SNAWJCMRSA-N (2E)-hexenoic acid Chemical compound CCC\C=C\C(O)=O NIONDZDPPYHYKY-SNAWJCMRSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 claims description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims description 2
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- VKZRWSNIWNFCIQ-WDSKDSINSA-N (2s)-2-[2-[[(1s)-1,2-dicarboxyethyl]amino]ethylamino]butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)NCCN[C@H](C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-WDSKDSINSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000011734 sodium Substances 0.000 description 6
- 159000000000 sodium salts Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 229960005261 aspartic acid Drugs 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid Substances OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 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 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229920006318 anionic polymer Polymers 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- CKLJMWTZIZZHCS-UHFFFAOYSA-N D-OH-Asp Natural products OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- CKLJMWTZIZZHCS-UWTATZPHSA-N L-Aspartic acid Natural products OC(=O)[C@H](N)CC(O)=O CKLJMWTZIZZHCS-UWTATZPHSA-N 0.000 description 2
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- MXYOPVWZZKEAGX-UHFFFAOYSA-N 1-phosphonoethylphosphonic acid Chemical compound OP(=O)(O)C(C)P(O)(O)=O MXYOPVWZZKEAGX-UHFFFAOYSA-N 0.000 description 1
- JJJOZVFVARQUJV-UHFFFAOYSA-N 2-ethylhexylphosphonic acid Chemical compound CCCCC(CC)CP(O)(O)=O JJJOZVFVARQUJV-UHFFFAOYSA-N 0.000 description 1
- PSZAEHPBBUYICS-UHFFFAOYSA-N 2-methylidenepropanedioic acid Chemical compound OC(=O)C(=C)C(O)=O PSZAEHPBBUYICS-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- XWPSVCZJPUMSMF-UHFFFAOYSA-N C(C(=O)O)(=O)O.NCC(O)C(=O)O Chemical compound C(C(=O)O)(=O)O.NCC(O)C(=O)O XWPSVCZJPUMSMF-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229940024606 amino acid Drugs 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229940105329 carboxymethylcellulose Drugs 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
- LSJWUSSUFZMXQM-UHFFFAOYSA-N ethoxy(dimethyl)azanium;chloride Chemical compound [Cl-].CCO[NH+](C)C LSJWUSSUFZMXQM-UHFFFAOYSA-N 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229940095686 granule product Drugs 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
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- 229940071676 hydroxypropylcellulose Drugs 0.000 description 1
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- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 108010064470 polyaspartate Proteins 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- GJAWHXHKYYXBSV-UHFFFAOYSA-N pyridinedicarboxylic acid Natural products OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000033912 thigmotaxis Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical class CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- 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
- C11D1/62—Quaternary ammonium 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
- C11D3/16—Organic compounds
- C11D3/168—Organometallic compounds or orgometallic complexes
-
- 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
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
-
- 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
- C11D3/36—Organic compounds containing phosphorus
- C11D3/361—Phosphonates, phosphinates or phosphonites
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3245—Aminoacids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
本发明涉及利用喷雾干燥制备的自由流动洗涤剂粉末，该粉末包含：(a)10％-90％重量的配合物，该配合物含有(i)螯合剂，和(ii)选自由镁，钙，锶，锌和铝及其混合物组成的一组金属的金属离子；(b)10％-90％重量的聚合物，该聚合物含有阴离子官能团。
Description
本发明涉及主要包含配合螯合剂和阴离子聚合物的洗涤剂粉末。此粉末可以很容易利用喷雾干燥进行制备。
洗涤剂组份和组合物多年来一直使用不同的喷雾干燥技术制造的。典型情况下，不同的洗涤剂活性物质溶解或分散在水溶液中，水溶液在高压下泵送到喷雾器，例如喷咀或转盘。
然后利用干燥气体，通常是热空气从雾化液滴中除去过量的水。再后干液滴就形成自由流动的颗粒产物。绝大多数以此种方法制备的颗粒产物都含有有机物和无机物。
一种先有技术公开了主要洗涤剂活性物是配合螯合剂的洗涤剂组分：1981年3月31日发布的US4259200公开了螯合剂与金属离子的配合物。据说该配合物在漂白组合物中具有改进的化学稳定性。获得包含金属/螯合剂配合物的散粒产品的不同方法也公开了，其中包括利用如四硼酸盐，三磷酸盐，硫酸盐等无机盐的喷雾干燥。
事实上，为了保护螯合剂免于在漂白剂存在时发生降解，螯合剂常常与镁进行预配位。可是由于会发生水溶液的沉淀，难于制备大于3∶1的镁：螯合剂的摩尔比。喷雾干燥过程中的沉淀迅速导致喷咀的堵塞。此外，主要由螯合剂/镁配合物组成的粉末具有很低的溶解速度。
现已发现，加入含有阴离子官能团的各种聚合物可以避免沉淀问题，可以利用喷雾干燥在较高的螯合剂与镁的摩尔比下进行制备，和大大地增加所得粉末的溶解速度。
阴离子聚合物的加入也能够制备有机物含量很高的，优选地大于80％的粉末。这样的用其他方法难于制备的粉末也为处理和加工有机聚合物提供了方便的方法。
发明概述
本发明涉及通过喷雾干燥制备的自由流动的洗涤剂粉末，该粉末包括：
(a)10％-90％重量的配合物，该配合物包括
(a)(i)螯合剂和
(a)(ii)选自由镁，钙，锶，锌和铝及其混合物组成的一组金属的金属离子，其特征在于该粉末还包括
(b)10％-90％重量的聚合物，该聚合物包含阴离子的官能团。
优选地该粉末包含小于20％，更优选地小于10％重量(干基)的除了(a)(ii)金属离子以外的无机组分。最优选地是铝硅酸盐和碳酸盐(干基)的总含量小于10％重量。
螯合剂优选地选自由膦酸，琥珀酸，膦酸盐或琥珀酸盐，或它们的混合物组成的一组物质，更优选的螯合剂是二亚乙基三胺五(亚甲基膦酸)，或乙二胺-N-N′-二琥珀酸(disuccimiacid)，或它们的盐，或它们的混合物。优选的金属离子是镁。金属离子与螯合剂的摩尔比优选地大于3∶1。
聚合物可以包含羧酸盐官能团，特别是脂肪羧酸例如丙烯酸，马来酸，乙烯酸，衣康酸，中康酸，富马酸，乌头酸，柠康酸，亚甲丙二酸和它们的混合物的均聚物和共聚物的水溶性盐。
优选的聚合物是分子量2000-100000的马来酸和丙烯酸的共聚物。
自由流动的洗涤剂粉末也可以含有阳离子表面活性剂。当有阳离子表面活性剂存在时，阳离子表面活性剂可以以1％-80％重量存在，优选地可以以2％-20％重量的二甲基乙氧氯化铵存在。发明详述
本发明的主要组分是螯合剂和含有阴离子官能团的聚合物。现在将较详细地给出这些组分的实例。螯合剂
适合于本发明使用的螯合剂可以选自本领域技术人员所熟知的很宽范围的化学品。合适的螯合剂的实例是膦酸，琥珀酸和它们的盐。
多膦酸盐是亚乙基二膦酸的钠盐和钾盐；乙烷1-羟基-1，1-二膦酸的钠盐和钾盐；乙烷，1，1，2-三膦酸的钠盐和钾盐。特别适合的螯合剂的实例是乙二胺四(亚甲基膦酸)和二亚乙基三胺五(亚甲基膦酸)。
另一个优选的螯合剂是乙二胺-N，N′-二琥珀酸(disuccimiacid)(EDDS)或其碱金属，碱土金属，铵，或取代铵的盐，或它们的混合物。优选的EDDS化合物是游离酸形态和它们的钠盐或镁盐。这样的优选的EDDS的钠盐的实例包括NaEDDS，Na2EDDS和Na4EDDS。这样的优选的EDDS镁盐的实例包括MgEDDS和Mg2EDDS。根据本发明在组合物中包含镁盐是最优选的。酸式的EDDS的结构如下：
例如EDDS可以由易于购得的，便宜的原料如马来酐和乙二胺按如下合成得到：
由市售得到的原料合成EDDS的方法更完全的公开可参见在1964年11月24日发布的Kazerian和Ramsay的美国专利3,158,635。
由于有两个不对称的碳原子，所以由马来酐和乙二胺合成EDDS可生成三种旋光异构体，[R，R]，[S，S]和[S，R]的混合物。EDDS的生物降解是旋光异构体特有的，[S，S]的异构体降解是最快和最充分的，基于这一原因，在本发明的组合物中含有[S，S]异构体是最优选的。
可以由L-天冬氨酸和1，2-二溴乙烷合成EDDS的[S，S]异构体，反应如下：
L-天冬氨酸和1，2-二溴乙烷反应生成EDDS的[S，S]异构体的更完全的公开可参见无机化学(Inorganic Chemistry)，Vol7(1968)，pp.2405-2412中由Neal和Rose所写的乙二胺二琥珀酸的立体定向配体和它们的配合物一文。
下面给出了适合于本发明使用的羧酸盐和其它螯合剂的具体例子。
-亚氨基二醋酸-N-2-羟丙基磺酸
-天冬氨酸N-羧甲基-N-2羟丙基-3-磺酸
-β-氨基丙酸N，N-二乙酸
-天冬氨酸-N，N二乙酸
-天冬氨酸N-一乙酸
-亚氨基二琥珀酸
-氨基酸基螯合剂例如
异丝氨酸二乙酸(ISDA)
2-膦酰基丁烷-1，2，4-三羧酸GADS
也可用作螯合剂的有：烷基亚氨基二乙酸；吡啶二羧酸；羟基-1，1-亚乙基二膦酸(HEDP)和衍生物。聚合物和/或共聚物
本发明的聚合物和共聚物也可选自广泛的有机聚合物，某些有机聚合物还可起改进去垢能力作为增洁剂的作用。在这样的聚合物中值得提及的是羧基-低级烷基纤维素钠，低级烷基纤维素钠和羟基-低级烷基纤维素钠，例如羧基甲基纤维素钠，甲基纤维素钠和羟基丙基纤维素钠，聚丙烯酸酯，聚天冬氨酸酯；以及各种共聚物，例如马来酸和丙烯酸的共聚物。这样的聚合物的分子量范围很广，但是大多数的分子量在2,000-100,000的范围内。
在1967年3月7日发布的Diehl的美国专利提出了聚合的聚羧酯增洁剂。这种物质包括脂肪羧酸例如马来酸，衣康酸，中康酸，富马酸，乌头酸，柠康酸和亚甲基丙二酸的均聚物和共聚物的水溶性盐。
采用具有分子量2000-100000的马来酸和丙烯酸的共聚物，羧基甲基纤维素以及它们的混合物对于本发明是最优选的。
本发明喷雾干燥粉末中任选的成分是阳离子表面活性剂。有用的阳离子表面活性剂包括通式为R4R5R6R7N+X-的水溶性的季铵化合物，式中R4是具10-20个碳原子，优选地具有12-18个碳原子的烷基，R5是C1-C20烷基，R6和R7各自是C1-C7的烷基，优选地是甲基；X-是阴离子，例如氯根。这种三甲基铵化合物的例子包括氯化C12-14烷基三甲基铵，氯化C12-14烷基二甲基乙氧基铵和N-甲硫酸C12-14烷基三甲基铵。加工
制造本发明的喷雾干燥粉末方法的主要步骤是螯合剂与金属离子的配合物的制备。这一步骤优选是将金属离子的盐以所需要的比例溶解在螯合剂的溶液而做到的。金属离子与螯合剂的摩尔比优选地至少是1∶1，本发明允许待制备的摩尔比大于3∶1，最优选的摩尔比约是5∶1。尽管可以使用任何的金属盐，但硫酸镁是最优选的。
阴离子聚合物加到含有配合物连同任何其它任选成分的溶液中。然后所得到的淤浆或溶液利用常规方法进行喷雾干燥。
使用转盘雾化器是最优选的喷雾干燥法。成品洗涤剂组合物的制造
在本发明的最简单实施方案中，自由流动喷雾干燥粉末与其它的洗涤剂粉末混合，以形成最终粒状洗涤剂产品。喷雾干燥粉末迅速溶解水中，以便尽可能早地使螯合剂和聚合物释放入洗涤过程中，这是本发明的一个很重要的优点。成品的洗涤剂组合物的组分可以选自范围很广的洗涤剂活性物。常见的实例包括表面活性剂，增洁剂，漂白剂，漂白活化剂，酶，光学增亮剂，脱垢聚合物，染料迁移抑制剂，软化粘土，香料等等。
另外本发明的喷雾干燥粉末还可以例如通过附加的粒化，结块，压实步骤进一步进行加工。1992年10月14日发布的EP508543叙述了特别优选的方法。在此种申请中，公开了构造或“规整”高活性表面活性剂糊状物，然后在洗涤剂粉末存在下进行造粒的一种方法。已经预见到，喷雾干燥粉末既可以成为规整步骤的组分，也可以成为造粒步骤的组分，或者同时成为这两个步骤的组分。使用此方法与本发明喷雾干燥粉末相结合能够生产具有表面活性剂含量至少为40％重量，而堆积密度至少为600克/升的自由流动的洗涤剂颗粒。
实例(全部％都是以重量计)例1
制备下列自由流动的粉末组合物：
丙烯酸/马来酸共聚物(分子量＝5000) 72％
二亚乙基三胺五(亚甲基膦酸) 10％
MgSO4 10％
水 8％
100％
将共聚物钠盐的40％活性溶液，膦酸的25％活性溶液和硫酸盐粉末(MgSO4·7H2O)混合，制备组合物，得到淤浆。
然后淤浆通过在塔顶装有并流空气入口和转盘(15000转/分)的连续喷雾干燥器进行处理。从塔底排出后，两台串联的流化床对喷雾干燥产物提供了进一步的干燥和冷却。
通过振动筛分级(除去细小颗粒和过粗颗粒)后，所得到喷雾干燥粉末具有450克/升的堆密度(利用再注杯法测量)例2
利用与例1相同的方法制备下列自由流动粉末组合物，和例1不同的是，用乙二胺-N，N′-二琥珀酸的33％活性溶液来代替二亚乙基三胺五(亚甲基膦酸)：
丙烯酸/马来酸共聚物(分子量＝5000) 43.5％
乙二胺-N，N′-二琥珀酸 15.5％
MgSO4 31％
水 10％
100％得到的粉末是自由流动的，具有460克/升的堆积密度。例3
下列自由流动的粉末组合物也是利用与例1相同的方法制备的：
丙烯酸/马来酸共聚物(分子量50000) 42.0％
乙二胺-N，N′-二琥珀酸 24.5％
MgSO4 24.5％
水 9.0％
100％所得到的粉末是自由流动的，具有450克/升的堆积密度。例4
下列自由流动的粉末组合物是利用与例1相同的方法制备的：
丙烯酸/马来酸共聚物(分子量＝50000) 62.0％
乙二胺-N，N′-二琥珀酸 14.0％
MgSO4 14.0％
水 10.0％
100％所得到的粉末是自由流动的，具有430克/升的堆积密度。
Claims (12)
1、自由流动的洗涤剂粉末，是通过喷雾干燥制备的，该粉末包括：
(a)10％-90％重量的配合物，该配位化合物包括
(a)(i)螯合剂和
(a)(ii)选自由镁，钙，锶，锌和铝，及其混合物的一组金属的金属离子，其特征在于该粉末还包括
(b)10％-90％的聚合物，该聚合物含有阴离子的官能团。
2、根据权利要求1的自由流动洗涤剂粉末，其特征是除(a)(ii)金属离子外它还包含小于20％重量(干基)的无机组分。
3、根据权利要求2的自由流动洗涤剂粉末，其特征在于除(a)(ii)金属离子外它还包含小于10％重量(干基)的无机组分。
4、根据权利要求1-3的任一自由流动的洗涤剂粉末，其特征在于它还包含小于10％重量(干基)的铝硅酸盐和碳酸盐。
5、根据权利要求1的自由流动的洗涤剂粉末，其中(a)(i)螯合剂选自由膦酸，琥珀酸，膦酸盐或琥珀酸盐，及其混合物组成的一组物质，和金属离子是镁。
6、根据权利要求5的自由流动洗涤剂粉末，其中(a)(i)螯合剂选自由二亚乙基三胺五(亚甲基膦酸)，或乙二胺-N，N′-二琥珀酸，或它们的盐，或它们的混合物组成的一组物质。
7、根据权利要求1-6的任一自由流动的洗涤剂粉末，其中(a)(ii)金属离子与(a)(i)螯合剂的摩尔比是大于3∶1。
8、根据权利要求1的自由流动洗涤剂粉末，其中聚合物(b)含有羧基的官能团。
9、根据权利要求8的自由流动的洗涤剂粉末，其中聚合物(b)选自由脂肪羧酸例如丙烯酸，马来酸，乙烯酸，衣康酸，中康酸，富马酸，乌头酸，柠康酸，亚甲基丙二酸和它们的混合物的均聚物和共聚物的水溶盐组成的一组物质。
10、根据权利要求9的自由流动洗涤剂粉末，其中聚合物(b)是具有分子量2000-100000的马来酸和丙烯酸的共聚物。
11、根据权利要求1的自由流动的洗涤剂粉末，该粉末还包含1％-80％重量的阳离子表面活性剂。
12、根据权利要求11的自由流动洗涤剂粉末，该粉末包含2％-20％重量的氯化二甲基乙氧基铵。
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| EP94201092A EP0678572A1 (en) | 1994-04-20 | 1994-04-20 | Detergent powder compositions |
| EP94201092.7 | 1994-04-20 |
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| CN1150450A true CN1150450A (zh) | 1997-05-21 |
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| EP (1) | EP0678572A1 (zh) |
| JP (1) | JPH09512300A (zh) |
| CN (1) | CN1150450A (zh) |
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| BR (1) | BR9507326A (zh) |
| CA (1) | CA2187517A1 (zh) |
| PE (1) | PE996A1 (zh) |
| TW (1) | TW341597B (zh) |
| WO (1) | WO1995029216A1 (zh) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111788293A (zh) * | 2018-02-23 | 2020-10-16 | 荷兰联合利华有限公司 | 包含氨基多羧酸盐和有机酸的洗涤剂固体组合物 |
| CN112074593A (zh) * | 2018-05-04 | 2020-12-11 | 巴斯夫欧洲公司 | 颗粒或粉末及其制备方法 |
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| DK0796911T3 (da) † | 1996-03-23 | 2002-09-30 | Procter & Gamble | Spraytørret detergentbestanddel, der omfatter chelateringsmiddel |
| US6599989B2 (en) | 1998-03-03 | 2003-07-29 | Nippon Skokubai Co., Ltd. | Water-absorbent agents containing polycarboxylic amine chelating agents |
| DE19937345A1 (de) * | 1999-08-11 | 2001-02-15 | Basf Ag | Mischpulver oder Mischgranulat auf Basis von Glycin-N,N-diessigsäure |
| GB9929840D0 (en) * | 1999-12-16 | 2000-02-09 | Unilever Plc | Detergent compositions |
| GB0011678D0 (en) * | 2000-05-15 | 2000-07-05 | Unilever Plc | Detergent compositions |
| GB0013501D0 (en) * | 2000-06-02 | 2000-07-26 | Unilever Plc | Detergent compositions |
| EP1803801A1 (de) * | 2006-01-03 | 2007-07-04 | Basf Aktiengesellschaft | Mischpulver oder Mischgranulat auf Basis von Glutaminsäure-N,N-diessigsäure und ihren Salzen |
| US20110241235A1 (en) * | 2009-09-23 | 2011-10-06 | Rohan Govind Murkunde | Process for preparing spray-dried particles |
| EP2338970A1 (en) * | 2009-12-18 | 2011-06-29 | The Procter & Gamble Company | A spray-drying process |
| WO2011076769A1 (en) | 2009-12-24 | 2011-06-30 | Akzo Nobel Chemicals International B.V. | Coated particles of a glumatic acid n,n-diacetate chelating agent |
| EP2380962B1 (en) * | 2010-04-23 | 2016-03-30 | The Procter and Gamble Company | Particle |
| EP2383329A1 (en) * | 2010-04-23 | 2011-11-02 | The Procter & Gamble Company | Particle |
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| CH642678A5 (de) * | 1979-04-06 | 1984-04-30 | Unilever Nv | Bleich- und reinigungsmittel. |
| FR2493294A1 (fr) * | 1980-11-04 | 1982-05-07 | Air Liquide | Compositions stabilisantes pour produits peroxydes |
| US4614646A (en) * | 1984-12-24 | 1986-09-30 | The Dow Chemical Company | Stabilization of peroxide systems in the presence of alkaline earth metal ions |
| US4959409A (en) * | 1988-01-14 | 1990-09-25 | The Procter & Gamble Company | Amino-functional compounds as builder/dispersants in detergent compositions |
| US4846993A (en) * | 1988-07-11 | 1989-07-11 | Ecolab Inc. | Zero phosphate warewashing detergent composition |
| HUT64391A (en) * | 1990-11-14 | 1993-12-28 | Procter & Gamble | Nonphosphated dishwashing compositions with oxygen belach systems and method for producing them |
| DE4213036A1 (de) * | 1992-04-21 | 1993-10-28 | Henkel Kgaa | Granulares, alkalisches, phosphatfreies Reinigungsadditiv |
| US5318728A (en) * | 1992-11-30 | 1994-06-07 | The Procter & Gamble Company | Low sudsing polyhydroxy fatty acid amide detergents |
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1994
- 1994-04-20 EP EP94201092A patent/EP0678572A1/en not_active Ceased
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1995
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- 1995-04-20 WO PCT/US1995/004799 patent/WO1995029216A1/en active Application Filing
- 1995-04-20 AU AU24602/95A patent/AU2460295A/en not_active Abandoned
- 1995-04-20 CA CA 2187517 patent/CA2187517A1/en not_active Abandoned
- 1995-04-20 BR BR9507326A patent/BR9507326A/pt not_active Application Discontinuation
- 1995-04-20 CN CN 95193528 patent/CN1150450A/zh active Pending
- 1995-04-20 PE PE26682295A patent/PE996A1/es not_active Application Discontinuation
- 1995-07-19 TW TW084107455A patent/TW341597B/zh active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111788293A (zh) * | 2018-02-23 | 2020-10-16 | 荷兰联合利华有限公司 | 包含氨基多羧酸盐和有机酸的洗涤剂固体组合物 |
| CN112074593A (zh) * | 2018-05-04 | 2020-12-11 | 巴斯夫欧洲公司 | 颗粒或粉末及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09512300A (ja) | 1997-12-09 |
| BR9507326A (pt) | 1997-09-30 |
| WO1995029216A1 (en) | 1995-11-02 |
| CA2187517A1 (en) | 1995-11-02 |
| PE996A1 (es) | 1996-02-21 |
| EP0678572A1 (en) | 1995-10-25 |
| TW341597B (en) | 1998-10-01 |
| AU2460295A (en) | 1995-11-16 |
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