CN1252235C - 改进的粒料配方 - Google Patents
改进的粒料配方 Download PDFInfo
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- CN1252235C CN1252235C CN00103661.0A CN00103661A CN1252235C CN 1252235 C CN1252235 C CN 1252235C CN 00103661 A CN00103661 A CN 00103661A CN 1252235 C CN1252235 C CN 1252235C
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- water
- pellet
- methyl
- disintegrating agent
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- 239000008187 granular material Substances 0.000 title description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 68
- 239000008188 pellet Substances 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 230000002745 absorbent Effects 0.000 claims abstract description 20
- 239000002250 absorbent Substances 0.000 claims abstract description 20
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- 238000000034 method Methods 0.000 claims abstract description 10
- -1 agrochemistry Substances 0.000 claims description 31
- 239000003599 detergent Substances 0.000 claims description 20
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- 229920001155 polypropylene Polymers 0.000 claims description 15
- 239000001913 cellulose Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
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- 239000000178 monomer Substances 0.000 claims description 10
- 239000003814 drug Substances 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 4
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 claims description 4
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 229910052728 basic metal Inorganic materials 0.000 claims description 3
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
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- 239000000052 vinegar Substances 0.000 claims 3
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- 239000000499 gel Substances 0.000 description 15
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
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- 235000019832 sodium triphosphate Nutrition 0.000 description 4
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- 238000002955 isolation Methods 0.000 description 3
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 3
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- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 2
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229920000881 Modified starch Polymers 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
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- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
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- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 2
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- 239000000344 soap Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
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- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 235000002723 Dioscorea alata Nutrition 0.000 description 1
- 235000007056 Dioscorea composita Nutrition 0.000 description 1
- 235000009723 Dioscorea convolvulacea Nutrition 0.000 description 1
- 235000005362 Dioscorea floribunda Nutrition 0.000 description 1
- 235000004868 Dioscorea macrostachya Nutrition 0.000 description 1
- 235000005361 Dioscorea nummularia Nutrition 0.000 description 1
- 235000005360 Dioscorea spiculiflora Nutrition 0.000 description 1
- 244000281702 Dioscorea villosa Species 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000006350 Ipomoea batatas var. batatas Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 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 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 235000007244 Zea mays Nutrition 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000002785 anti-thrombosis Effects 0.000 description 1
- 229960004676 antithrombotic agent Drugs 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
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- 235000005822 corn Nutrition 0.000 description 1
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- 239000013530 defoamer Substances 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
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- 235000011187 glycerol Nutrition 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- AUCNMQYOQYTGPE-UHFFFAOYSA-N n-(hydroxymethyl)-n-methylprop-2-enamide Chemical compound OCN(C)C(=O)C=C AUCNMQYOQYTGPE-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229940100486 rice starch Drugs 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920005613 synthetic organic polymer Polymers 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
- 239000002023 wood Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/20—Pills, tablets, discs, rods
- A61K9/2004—Excipients; Inactive ingredients
- A61K9/2022—Organic macromolecular compounds
- A61K9/205—Polysaccharides, e.g. alginate, gums; Cyclodextrin
- A61K9/2054—Cellulose; Cellulose derivatives, e.g. hydroxypropyl methylcellulose
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/20—Pills, tablets, discs, rods
- A61K9/2004—Excipients; Inactive ingredients
- A61K9/2022—Organic macromolecular compounds
- A61K9/2027—Organic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyvinyl pyrrolidone, poly(meth)acrylates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Medicinal Chemistry (AREA)
- Epidemiology (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Pharmacology & Pharmacy (AREA)
- Molecular Biology (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
- Medicinal Preparation (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
本发明涉及能迅速有效地崩解在水介质中的粒料形式化学组合物以及一种制备该粒料的方法。该粒料包含:(a)至少一种具有药物、农业化学、水处理、水软化、织物软化或洗涤活性的组分;(b)至少一种崩解剂,包括一种或多种凝胶形成时间为30秒或更低的交联聚丙烯酸酯吸水聚合物;和(c)至少一种在粒料与水接触时将水输送到粒料中的水输送剂。
Description
本发明涉及在水介质中能够迅速有效地崩解的改进的粒料形式化学组合物。“粒料”是指任何固体配方,包括(但不限于)片、砖、条、粒、球、或块、以及在储存时,尤其是在高湿度条件下因材料粘着在一起而得到的聚集材料。
人们熟知,例如在医药和农业领域中,且最近在其它领域,如洗涤剂中使用粒料形式的化学组合物。粒料相对颗粒组合物可产生某些优点;它们无尘,无需测定,因压缩而占空间较少,且各成分在转移和储存时无需隔离。但粒料在使用时,存在溶解或崩解方面的问题。在制造工艺中必须进行权衡,一方面,粒料压力要足够高以保证粒料形成良好且耐处理,但另一方面粒料压力又要足够低以得到合适的溶解性/分散性分布。为了解决这种问题,已知可以使用一种能提高粒料的内聚作用而无需高粒料压力或能够提高片剂分散性的加工助剂。
具体回顾能提高分散性的这些添加剂,药物科学杂志,61卷,№11,1972,1695-1711页给出了各种已知的崩解剂;例如,以下各种物质:(i)通过析出气体造成崩解的物质,如在柠檬酸或酒石酸的存在下的碳酸氢钠;(ii)能够促进吸水的物质,如淀粉、胶态二氧化硅、羧甲基纤维素和米淀粉;(iiii)能膨胀的物质,如交联聚丙烯酸、交联阿拉伯胶、羧甲基纤维素;(iv)能提高多孔性的物质,如马铃薯和玉米淀粉;最后是(v)能经历物理化学键接的物质,如微结晶纤维素和高岭土。
许多已有技术专利文件也涉及包含崩解剂的洗涤剂片。这些文件的例子包括:EP-A-0799886,公开了使用淀粉衍生物、纤维素化合物、聚乙烯基吡咯烷酮化合物、膨润土化合物、藻酸盐、明胶和果胶作为崩解剂;以及EP-A-0522766,列举了玉米、玉蜀黍、米和马铃薯淀粉和淀粉衍生物、纤维素和纤维素衍生物以及各种合成有机聚合物,如聚乙二醇、交联聚乙烯基吡咯烷酮和能够膨胀的无机物,如膨润土作为崩解剂。
EP-A-0481547介绍了包括外层、隔绝层和内层的机器洗碗多层洗涤剂片。该片剂首先由外层,然后由内层顺序释放出洗涤剂成分,而且这两次溶解之间的时间可由隔离外层和内层的隔绝层的厚度以及其中成分的选择来控制。该隔绝层中的一种成分是崩解剂,优选包括马来酸/丙烯酸共聚物或其盐、乙烯马来酸酐交联聚合物和聚乙二醇之一。
EP-A-0238341确定螯合剂,如次氨基三乙酸或二乙二胺四乙酸或由烯属不饱和单体(如,不饱和羧酸、磺酸或膦酸单体)形成的低分子量阴离子聚合物作为崩解剂。此外,该文件在讨论背景技术文件EP-A-0075818和EP-A-0037026内容时提出,其中公开的常规不溶性水可膨胀崩解助剂,如高分子量碳水化合物,如淀粉、纤维素粉末,如碎木、或聚乙烯基吡咯烷酮等不会产生令人满意的崩解作用或崩解作用在低温下非常慢。在使用纤维素和纤维素衍生物时,可以看出另一缺点,即在能够有效促进崩解的用量(如,占片剂的约5%重量)下,该片剂易破碎。该问题可通过加入加工助剂,如能够将片剂颗粒“粘着”在一起的粘合剂来解决,但这却增加了成本并降低了可用于活性成分的片剂体积。
在用于自动洗碗洗涤剂组合物时,片剂的溶解或崩解通常要加以控制,这样可保证溶解有规律但不会太快,从而避免在预洗时消耗太多的洗涤剂组合物。但在主洗碗周期中,剩余片剂迅速溶解是有利的,这样剩余的片剂固体不会在餐具上产生问题。相反,对用于洗衣的洗涤剂组合物的一个关键要求是,洗涤剂组合物释放越多越好,这样可在洗涤的起始阶段得到该洗涤剂组合物。如果洗碗机没有预洗周期,情况也是这样。由于洗涤水中的钙和镁硬度离子已存在于洗涤周期开始时,因此有螯合成分往往会浓度太低并与这些硬度离子一起沉淀的高风险。这导致在待洗衣物上形成不溶性积垢,且可用于清洗的洗涤剂组合物中活性物质的量下降。如果洗涤剂组合物中有某些助洗剂,如三聚磷酸钠(STPP),这种问题更加严重,因为Ca/STPP沉淀物会形成非常难以去除的积垢。片剂的尺寸和应用条件也影响片剂的分散性分布;例如,用于洗衣的片剂通常比用于自动洗碗机或用于水软化的要大很多;洗衣时,40-55克片剂,而洗碗和水软化时,20-25克片剂。这与洗衣片剂往往被埋藏在待洗衣物中有关,意味着相对其它应用来说,特别难以满足对洗衣用片剂的溶解性要求。
申请人以前在法国专利申请9807643中已经公开,与水接触时崩解或溶解非常迅速的粒料配方因此适用于要求这些活性成分迅速释放的各种合成。这些粒料包含:(a)至少一种具有药物、农业化学、水处理、水软化、织物软化或洗涤活性的组分;和(b)至少一种崩解剂,包括一种或多种凝胶形成时间为30秒或更低的交联聚丙烯酸酯吸水聚合物。
这些粒料具有足够的强度,不会在储存、运输或处理时破碎,而且能够在各种气候条件下(包括温度和湿度波动)进行储存。特别理想的是,这些粒料对水但不对湿度敏感。它们还必须具有良好的活性,这要求活性成分的含量要高,而且它们能够在不同温度和很宽应用条件下,例如在一定范围的水硬度(在用于洗涤剂时)下表现出这种良好的活性。
申请人已经发现,这些粒料甚至可进一步优化。申请人已经看出,片剂崩解的速率随着片剂中崩解剂的量的增加而提高,但如果该片剂包含,例如2%重量或更高的这些崩解剂,则会在该片剂与水接触时形成凝胶,这抑制水渗入片剂的中心,即,这种凝胶可延缓崩解。
因此,本发明的目的是提供具有进一步提高的崩解速率且能够克服由凝胶形成而产生的难题的粒料配方。
因此,本发明提供了一种粒料形式的化学组合物,包含:(a)至少一种具有药物、农业化学、水软化、织物软化或洗涤活性的组分;(b)至少一种崩解剂,包括一种或多种凝胶形成时间为30秒或更低的交联聚丙烯酸酯吸水聚合物;和(c)至少一种在粒料与水接触时将水输送到粒料中的水输送剂。
水输送剂的用途是将水迅速夹带到粒料中心,这样片剂内的交联聚丙烯酸酯吸水聚合物可膨胀,从而有助于粒料快速崩解。如果没有这种水输送剂,那么靠近粒料表面的吸水聚合物会与水接触膨胀,而且如果该聚合物的浓度例如为粒料的2%重量或更高,它们会形成凝胶,从而有效地阻止水进一步渗透到粒料内。优选的水输送剂包括一种或多种无定形纤维素、微结晶纤维素、改性纤维素和合成中空纤维。水输送剂以小粒径为有利,例如200μm或更低,优选80μm或更低。
交联聚丙烯酸酯吸水聚合物(崩解剂)的量一般占粒料配方的0.5-2.0%重量,优选1.0-1.5%重量,且水输送剂的量可占粒料配方的0.5-5.0%重量,优选2.0-3%重量。特别有利的组合物包含占粒料1.0%重量的交联聚丙烯酸酯吸水聚合物和2.0%重量的微结晶纤维素。
特别有利的是,该交联聚丙烯酸酯吸水聚合物的凝胶形成时间为10秒或更低。
在本发明的另一实施方案中,粒料的崩解速率可进一步通过改性该崩解剂,即在加入粒料之前用水进行喷洒而提高。水的量可以是5-50%重量/重量(w/w),优选5-20%w/w。
本发明还涉及一种通过向其中加入以下物质来提高粒料形式化学组合物崩解速率的方法:
(a)至少一种具有药物、农业化学、水处理、水软化、织物软化或洗涤活性的组分;
(b)至少一种崩解剂,包括一种或多种凝胶形成时间为30秒或更低的交联聚丙烯酸酯吸水聚合物;和
(c)至少一种在粒料与水接触时将水输送到粒料中的水输送剂。“提高崩解速率”是指,与不含一种或多种其凝胶形成时间为30秒或更低的交联聚丙烯酸酯吸水聚合物与水输送剂的混合物的粒料相比,按照本发明的粒料的崩解时间较少。
用于本发明的交联聚丙烯酸酯吸水聚合物一般通过选自以下物质的至少一种水溶性烯属不饱和单体的自由基聚合反应和交联作用而得到:(甲基)丙烯酸、(甲基)丙烯酸的碱金属或铵盐、(甲基)丙烯酸酯、马来酸、马来酸酐和(甲基)丙烯酰胺。
交联反应可使用以下三种方法的至少一种来进行:
(i)通过与包含至少两个双键的共聚单体进行自由基聚合反应而交联。这些共聚单体的例子包括:三羟甲基丙烷二(三)(甲基)丙烯酸酯、N,N-亚甲基双(甲基)丙烯酰胺、乙二醛双丙烯酰胺、二(甲基)丙烯酸乙二醇酯;
(ii)通过与所谓官能单体的自由基聚合反应而交联,所述官能单体包含一个双键(有共聚活性)和至少一个能够在官能团与主水溶性单体的化学活性部分之间进行交联反应的官能团。这种交联剂的例子包括:N-羟甲基(甲基)丙烯酰胺、和(甲基)丙烯酸缩水甘油酯;和
(iii)通过加入非可聚合的官能交联剂而交联,所述官能交联剂包含至少两个能够与水溶性单体的化学活性部分进行反应的官能团。这种交联剂的例子包括:乙二醛、乙二醇、(聚)乙二醇二缩水甘油醚、(聚)丙二醇二缩水甘油醚、(二)甘油聚缩水甘油醚、聚甘油聚缩水甘油醚、表氯醇、乙二胺和乙酸锌。
生产吸水聚合物所需的交联剂的量通常为基于水溶性烯属不饱和单体总重的0.001-10%重量,最优选0.01-5%重量。
用于本发明的交联聚丙烯酸酯吸水聚合物可通过任何合适的自由基聚合方法而制成。最常用的溶液型聚合法(也称作凝胶法)是EP-A-0530438所公开的那些,而典型的反相悬浮聚合法例如描述于EP-A-0258120。用于本发明的交联聚丙烯酸酯吸水聚合物的基本特征在于,它们的凝胶形成时间低于30秒。
除了包含至少一种具有药物、农业化学、水处理、水软化、织物软化或洗涤活性的组分,该组合物还可包含其它的成分,例如包括一种或多种以下物质:加工助剂、助剂、涂料、酶、助洗剂、积垢抑制剂、乳化剂、表面活性剂、皂、分散剂、沸石、去脂剂、消泡剂、磷酸盐、膦酸盐、碳酸盐、碳酸氢盐、柠檬酸盐、柠檬酸、有机螯合剂、漂白剂、荧光增白剂、填料、增量剂、去污剂、抗絮凝剂、抗凝剂、抗漂剂、稀释剂和载体。
现在参考以下实施例来描述本发明。
所用的测试方法用于模拟实际应用。使用典型洗衣洗涤剂组合物的洗涤剂片是使用常规的压片设备制成的。将测试片剂同时载有崩解剂和水输送剂,然后测试这些测试片剂的崩解效率,并与仅载有崩解剂、或仅载有水输送剂、或既没有崩解剂也没有水输送剂的类似对比片剂进行比较。所用的洗衣洗涤剂组合物详见下表1:
表1
成分 | 洗涤剂组成 |
阴离子表面活性剂 | 5-15% |
非离子表面活性剂 | 5-15% |
皂 | <5% |
沸石 | >30% |
聚合物助洗剂 | <5% |
膦酸盐 | <5% |
漂白剂 | 5-15% |
所测试的崩解剂是凝胶形成时间为5秒的交联聚丙烯酸酯吸水聚合物。该物质得自Norso Haas SA(法国)。
崩解剂的凝胶形成时间使用以下方法测定,本领域通常称作涡流试验或涡流膨胀速率试验。
将分析级氯化钠溶解在去矿化水中至最终溶液的盐浓度为0.9%重量,制备出氯化钠水溶液。该0.9%重量氯化钠水溶液是用于表征吸水聚合物的参照测试液(“测试液”)。在温控房间(20℃)中,将交联聚丙烯酸酯吸水聚合物(3克)加入内径55毫米的烧杯(200毫升)中。将该烧杯放在电磁搅拌器上,然后放入磁力棒(45毫米×8毫米)进行搅拌。搅拌速率固定在600+/-20rpm,然后将烧杯迅速装上测试液(100克)。在加完测试液时,将其计为时间0并从这时进行测定。在搅拌涡流由于吸水聚合物形成凝胶而消失时,停止时间测定。对于特别快的胶凝聚合物,可能需要颠倒将聚合物和测试液加入烧杯中的顺序。
使用以下测试方法来测定测试片剂和对比片剂的崩解速率。
使用常规的压片设备,制备出包含表1所给洗涤剂组合物的测试片剂和对比片剂。每种片剂的崩解速率测定如下:将16-17℃的冷自来水(4.5升)放入支架上的5升烧杯中,然后加入预称重的片剂。在400rpm下,使用磁力棒和磁力棒搅拌设备,搅拌该溶液10或5分钟。测试周期结束时,将残余物放入杯中,在80℃炉中干燥2小时,然后再称重。百分残余物计算如下:
测试结果在下表2中给出:
表2
剩余片剂的百分数
实施例 | 添加剂 | 10分钟之后的残余物百分数 | 评述 |
1 | 无(对比) | 61 | 片剂难以溶解 |
2 | 1.5%崩解剂(对比) | 33 | 崩解速率中等 |
3 | 3%水输送剂(对比) | 47 | 崩解速率中等 |
4 | 5%水输送剂(对比) | 2 | 易碎片剂 |
5 | 1%崩解剂+1%水输送剂(实验测试) | 29 | 优异的片剂,良好的崩解速率 |
6 | 1%崩解剂+2%水输送剂(实验测试) | 18 | 优异的片剂,崩解速率快 |
7 | 1%崩解剂+3%水输送剂(实验测试) | 0 | 优异的片剂,且崩解速率优异 |
5分钟之后的残余物百分数 | |||
8 | 5%水输送剂(对比) | 56 | 易碎片剂 |
9 | 1%崩解剂*+2%水输送剂(实验测试) | 26 | 优异的片剂且崩解速率优异 |
*表示该崩解剂在加入片剂之前进行改性,即用20%w/w去离子水喷洒。
由这些结果可以看出,同时包含崩解剂与水输送剂的片剂(实施例5-6)可得到优异的片剂,且明显比仅包含这两种成分之一的片剂崩解要快。
此外,如果用20%w/w去离子水处理该崩解剂(实施例9),那么可进一步提高崩解速率。
Claims (8)
1.粒料形式的化学组合物,包含:
(a)至少一种具有药物、农业化学、水处理、水软化、织物软化或洗涤活性的组分;
(b)至少一种崩解剂,包括一种或多种凝胶形成时间为30秒或更低的交联聚丙烯酸醋吸水聚合物;和
(c)至少一种在粒料与水接触时将水输送到粒料中的水输送剂,
所述水输送剂选自无定形纤维素、微结晶纤维素、改性纤维素和合成中空纤维中的一种或多种。
2.根据权利要求1的化学组合物,其中所述崩解剂通过选自以下物质的至少一种水溶性烯属不饱和单体的自由基聚合反应和交联作用而得到:(甲基)丙烯酸、(甲基)丙烯酸的碱金属或铵盐、(甲基)丙烯酸醋、马来酸、马来酸酐和(甲基)丙烯酰胺。
3.根据权利要求1的化学组合物,其中崩解剂的量占所述粒料组合物重量的0.52.0%且水输送剂的量占0.5-5.0%。
4.根据权利要求1的化学组合物,其中所述崩解剂在形成粒料之前用水进行处理。
5.提高粒料形式化学组合物崩解速率的方法,包括将以下物质加到一起的
步骤:
(a)至少一种具有药物、农业化学、水处理、水软化、织物软化或洗涤活性的组分;
(b)至少一种崩解剂,包括一种或多种凝胶形成时间为30秒或更低的交联聚丙烯酸酯吸水聚合物;和
(c)至少一种在粒料与水接触时将水输送到粒料中的水输送剂,
所述水输送剂选自无定形纤维素、微结晶纤维素、改性纤维素和合成中空纤维中的一种或多种。
6.根据权利要求5的方法,其中所述崩解剂通过选自以下物质的至少一种水溶性烯属不饱和单体的自由基聚合反应和交联作用而得到:(甲基)丙烯酸、(甲基)丙烯酸的碱金属或铵盐、(甲基)丙烯酸醋、马来酸、马来酸酐和(甲基)丙烯酰胺。
7.根据权利要求5的方法,其中崩解剂的量占所述粒料组合物重量的0.5-2.0%且水输送剂的量占0.5-5.0%。
8.根据权利要求5的方法,其中所述崩解剂在形成粒料之前用水进行处理。
Applications Claiming Priority (3)
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FR99/02791 | 1999-03-05 | ||
FR9902791 | 1999-03-05 | ||
US09/507,852 US6254892B1 (en) | 1999-03-05 | 2000-02-22 | Pellet formulations |
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CN1266081A CN1266081A (zh) | 2000-09-13 |
CN1252235C true CN1252235C (zh) | 2006-04-19 |
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CN00103661.0A Expired - Fee Related CN1252235C (zh) | 1999-03-05 | 2000-03-01 | 改进的粒料配方 |
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US (1) | US6254892B1 (zh) |
EP (1) | EP1035196B1 (zh) |
JP (1) | JP2000302933A (zh) |
CN (1) | CN1252235C (zh) |
AU (1) | AU1758500A (zh) |
CA (1) | CA2299952A1 (zh) |
DE (1) | DE60000022T2 (zh) |
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Publication number | Priority date | Publication date | Assignee | Title |
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EP1167433A1 (de) * | 2000-06-19 | 2002-01-02 | Mifa Ag Frenkendorf | Mit unlöslichem Sprengmittel coprozessiertes Polysaccharidprodukt, Herstellungsverfahren und Verwendung davon |
EP1184449A1 (en) * | 2000-09-04 | 2002-03-06 | The Procter & Gamble Company | Carpet cleaning composition comprising an absorbent gelling material |
US7550156B2 (en) * | 2001-11-23 | 2009-06-23 | Rohm And Haas Company | Optimised pellet formulations |
EP1314776B1 (en) * | 2001-11-23 | 2007-05-23 | Rohm And Haas Company | Optimised pellet formulations |
US20090032063A1 (en) * | 2007-07-30 | 2009-02-05 | Haas Geoffrey R | Solid cleaning composition and method of use |
US20110303872A1 (en) * | 2010-06-14 | 2011-12-15 | Basf Se | Water-Absorbing Polymer Particles with Improved Color Stability |
WO2016168224A1 (en) | 2015-04-14 | 2016-10-20 | The Procter & Gamble Company | Solid conditioning composition |
US10329519B2 (en) | 2016-10-19 | 2019-06-25 | The Procter & Gamble Company | Consumer product composition comprising a polyethyleneglycol carrier, silicone conditioner, and particulate spacer material |
EP3793526B1 (de) * | 2018-05-16 | 2024-02-14 | Basf Se | Poly(meth)acrylsäure-popcornpolymerisate als sprengmittel für tabletten |
US11852971B2 (en) | 2019-10-29 | 2023-12-26 | Samsung Sdi Co., Ltd. | Compound, photosensitive resin composition including the same, photosensitive resin layer, color filter and display device |
CN113955865B (zh) * | 2021-10-22 | 2022-06-21 | 南京大学 | 一种绿色高效抑制二氧化硅成垢的羟乙基纤维素改性阻垢剂及其制备方法 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH552343A (de) * | 1971-02-10 | 1974-08-15 | Sarea Ag | Pilliertes saatgut. |
DE3011998C2 (de) | 1980-03-28 | 1982-06-16 | Henkel KGaA, 4000 Düsseldorf | Verfahren zur Herstellung eines lagerstabilen, leichtlöslichen Granulates mit einem Gehalt an Bleichaktivatoren |
DE3268039D1 (en) | 1981-09-28 | 1986-01-30 | Basf Ag | Granular bleach activator |
US4461759A (en) * | 1983-01-03 | 1984-07-24 | Verex Laboratories, Inc. | Constant release rate solid oral dosage formulations of veropamil |
GB8606804D0 (en) | 1986-03-19 | 1986-04-23 | Warwick International Ltd | Particulate bleach activator composition |
GB8724763D0 (en) * | 1987-10-22 | 1987-11-25 | Aps Research Ltd | Sustained-release formulations |
US5229131A (en) * | 1990-02-05 | 1993-07-20 | University Of Michigan | Pulsatile drug delivery system |
US5133892A (en) | 1990-10-17 | 1992-07-28 | Lever Brothers Company, Division Of Conopco, Inc. | Machine dishwashing detergent tablets |
GB9114184D0 (en) | 1991-07-01 | 1991-08-21 | Unilever Plc | Detergent composition |
DK173111B1 (da) * | 1996-04-03 | 2000-01-31 | Cleantabs As | Tøjvasketabletter |
DE19714657C1 (de) * | 1997-04-09 | 1999-01-07 | Benckiser Nv | Wasserlöslicher, wasserenthärtender Builder |
ZA993473B (en) * | 1998-06-17 | 2000-01-10 | Rohm & Haas | Pellet formulations. |
GB2339574A (en) * | 1998-07-15 | 2000-02-02 | Procter & Gamble | Disintegrating components |
-
2000
- 2000-02-21 DE DE60000022T patent/DE60000022T2/de not_active Expired - Fee Related
- 2000-02-21 AU AU17585/00A patent/AU1758500A/en not_active Abandoned
- 2000-02-21 EP EP00301335A patent/EP1035196B1/en not_active Expired - Lifetime
- 2000-02-22 US US09/507,852 patent/US6254892B1/en not_active Expired - Fee Related
- 2000-02-29 CA CA002299952A patent/CA2299952A1/en not_active Abandoned
- 2000-03-01 CN CN00103661.0A patent/CN1252235C/zh not_active Expired - Fee Related
- 2000-03-06 JP JP2000060708A patent/JP2000302933A/ja not_active Withdrawn
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AU1758500A (en) | 2000-09-07 |
JP2000302933A (ja) | 2000-10-31 |
EP1035196A1 (en) | 2000-09-13 |
US6254892B1 (en) | 2001-07-03 |
DE60000022D1 (de) | 2001-12-06 |
DE60000022T2 (de) | 2002-03-14 |
EP1035196B1 (en) | 2001-10-31 |
CN1266081A (zh) | 2000-09-13 |
CA2299952A1 (en) | 2000-09-05 |
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