TW500728B - Hydrophobically modified cellulose ethers, preparation process thereof, and composition containing the same - Google Patents
Hydrophobically modified cellulose ethers, preparation process thereof, and composition containing the same Download PDFInfo
- Publication number
- TW500728B TW500728B TW088105857A TW88105857A TW500728B TW 500728 B TW500728 B TW 500728B TW 088105857 A TW088105857 A TW 088105857A TW 88105857 A TW88105857 A TW 88105857A TW 500728 B TW500728 B TW 500728B
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- TW
- Taiwan
- Prior art keywords
- cellulose
- cellulose ether
- scope
- item
- patent application
- Prior art date
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- 229920003086 cellulose ether Polymers 0.000 title claims abstract description 53
- 239000000203 mixture Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 24
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 23
- 229920002678 cellulose Polymers 0.000 claims description 23
- 239000001913 cellulose Substances 0.000 claims description 23
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 22
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 22
- 238000006467 substitution reaction Methods 0.000 claims description 14
- -1 alkenyl acetophenone dimer Chemical class 0.000 claims description 13
- 230000004048 modification Effects 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 9
- 230000002209 hydrophobic effect Effects 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 4
- 239000012459 cleaning agent Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 3
- 229910052799 carbon Inorganic materials 0.000 claims 3
- 238000000576 coating method Methods 0.000 abstract description 13
- 239000011248 coating agent Substances 0.000 abstract description 8
- 239000003599 detergent Substances 0.000 abstract description 5
- 239000000539 dimer Substances 0.000 abstract description 5
- 239000002270 dispersing agent Substances 0.000 abstract description 5
- 238000005553 drilling Methods 0.000 abstract description 3
- 239000003973 paint Substances 0.000 abstract description 2
- 239000003921 oil Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000000123 paper Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 4
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- 239000001856 Ethyl cellulose Substances 0.000 description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000008186 active pharmaceutical agent Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000002079 cooperative effect Effects 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 229920001249 ethyl cellulose Polymers 0.000 description 3
- 235000019325 ethyl cellulose Nutrition 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 229920000609 methyl cellulose Polymers 0.000 description 3
- 239000001923 methylcellulose Substances 0.000 description 3
- 235000010981 methylcellulose Nutrition 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- 241000157282 Aesculus Species 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 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 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 125000004181 carboxyalkyl group Chemical group 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 235000010181 horse chestnut Nutrition 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000003752 hydrotrope Substances 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- NONOKGVFTBWRLD-UHFFFAOYSA-N isocyanatosulfanylimino(oxo)methane Chemical compound O=C=NSN=C=O NONOKGVFTBWRLD-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229940023144 sodium glycolate Drugs 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- JEJAMASKDTUEBZ-UHFFFAOYSA-N tris(1,1,3-tribromo-2,2-dimethylpropyl) phosphate Chemical compound BrCC(C)(C)C(Br)(Br)OP(=O)(OC(Br)(Br)C(C)(C)CBr)OC(Br)(Br)C(C)(C)CBr JEJAMASKDTUEBZ-UHFFFAOYSA-N 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B13/00—Preparation of cellulose ether-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/20—Post-etherification treatments of chemical or physical type, e.g. mixed etherification in two steps, including purification
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
- C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
- C11D3/226—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin esterified
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Polymers & Plastics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Emergency Medicine (AREA)
- Molecular Biology (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Detergent Compositions (AREA)
- Paper (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
500728
纖 素 改 經濟部智慧財產局員工消費合作社印製 發明背景 :π:關於經疏水性改質之纖維素趟及其使用。 溶液y 基甲基纖料,特別廣泛用於處理水性 …I變性質。使用之對象物包 化妝品製劑、清潔冑 h j如食-、樂劑、 紙張塗層混合物、建築材織品、印刷墨水、 聚合作用之添加劑 貝接者劑、塗科、陶㈣料及 藉由接附不同之取代基至纖維素經基上改質 ==,纖維素酸之溶解度或疏水性特別會被影響。 關於醣頒的疏水性改質已有許多文獻揭橥。 美國專利第仙277號敘述非離子性纖維素謎之改質,例 如甲基纖維素、甲基與丙其鳙始:I , u m▲素、題丙基纖維素及特別 疋姓乙基纖維素,其係使用具有1()至24個碳垸基長度之環 乳坑。根據料利,改質之優點在於即使疏水性改質之 維素醚僅有少量’仍可使得水溶液之黏度增加,使纖維 醚之劑量可減少。祕改質之纖維素料料塗料。該政 質係使用纖維素醚作爲起始物進行,其反應時間較長至2至 5小時。然而,並枝用環氧化物因其對健康有害。 在法國專利第95138號中,羧甲基經乙基纖維素係藉^ 0.1至4重量計之含量具有8至25個碳數找基改質,該乂 物亦可應用於塗料。烷基反應物可爲由化物、画化氫或] 氧化物,其中所有的化合物均對環境及健康有害。声乙 化、疏水性改質及羧曱基化依序進行,因此反應時間長 超過4小時。 -4 - 本纸張尺度適用中國國家標準(CNS)A4規格(210 X 297公f
(請先閱讀背面之注意事項再本頁) -裝 丄 · -I線. 500728 A7 經濟部智慧財產局員工消費合作社印製 五、發明說明(2 ) 美國專利第53 02196號敘述藉由具有3至24個碳原子之含 氟烷基改質之纖維素醚,該氟之含量爲〇 〇5至5 c/❶重量計。 该纖維素醚特別係羥乙基纖維素,羥乙基羧甲基纖維素或 甲基海乙基纖維素。含氟燒基反應物較佳爲環氧化物,溴 化物或全氟烯烴。該產物亦發展於塗料。該反應較久,改 貝需6小時的反應時間。 在歐洲專利申請案第384167號中,纖維素醚,特別是輕乙 基纖維素,以具有至少10個碳之芳烷基改質,含量爲每莫 耳纖維素醚之葡萄糖重覆單位中含〇·0〇1至〇 1莫耳。燒基 反應物可爲例如卣化物、環氧乙烷、酸、(硫)異氰酸鹽或 卣化氫。該產物可用於乳液塗料。該製造過程亦具長反應 時間,爲6或長達1 2小時。 1 發明概述 疏水性改質之纖維素醚已被發明,其係根據獨立項申請 專利範圍第1項之界定,而附屬項之申請專利範圍係揭示發 明之較佳實施態樣〇 ^ 本發明介紹一新型之疏水性改質之纖維素醚,其中改質 劑爲烯基乙晞酮二聚物。纖維素醚較佳爲幾甲基纖維素^ 羧甲基纖維素鈉(CMC,NaCMC)。 ' 5 以烯基乙烯酮二聚物改質之纖維素醚易於製造,方法& 全,簡單及快速。此改質亦可改良纖維素醚於水中之分7 性。 刀政 本發明適用於任何以水爲基底之塗料。其疏水性基圈 得物質之性質爲有益的,例如清潔劑、紙張塗層混合物、 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注音?事項再1¾本頁} •裝 -1Ρ1Γ 本 訂· --線< 500728 A7 一_______B7_____ 五、發明說明(3 ) 分散劑及油性鑽孔泥漿。 發明詳述 根據本發明,烯基乙烯酮二聚物(AKD)使用於改質纖維 素醚。AKD的通式爲
Ri -CH = C-CH-R2
I I ο - c = o 其中R 1及R2爲具有5至22燒基或烯基鏈,較佳爲1 3至2 0個 碳。111及112亦可被取代或於鏈中含有雜原子。^^及!^特 別爲直缝並含有1 4至1 8個碳。 AKD與纖維素或纖維素醚之經基團反應,形成下式: Ο R2 0
II I II
Ri-CH2-C-CH_C-0-纖維素(醚) 高溫如3 0至12(TC可增強反應,較佳爲5 0至9 0 ,最佳 爲60至85°C。較佳之溫度係爲AKD先融化時。高溫及鹼性 ρ Η可改良AKD與纖維素醚之反應性。AKD可與取代基,例 如纖維素醚内之羧甲基基團反應。AKD亦可與其他含有0Η 基團之化合物反應,這些基團包括在製備CMC時產生的水 、醇及甘醇酸鈉。所得之化合物亦對產物之疏水性具有影 響。 經反應之AKD於纖維素醚之濃度可使用氣相層析法分析 (請先閱讀背面之注意事項再 11¾本頁) 丨裝 .線· 經濟部智慧財產局員工消費合作社印製 -6 500728 A7 _B7__ 五、發明說明(4 ) ,而未反應之AKD或與其他含OH基團之化合物反應之AKD 可以適當之溶劑萃取。樣品經水解導致烷基乙烯酮基團之 裂解。經反應之AKD以適當之溶劑萃取並且用氣相層析法 分析。 AKD可爲固態或分散於水或其他溶劑中。 AKD於纖維素醚中之含量可爲0.001至1 0 %重量計,該含 量較佳爲〇.〇1至2%重量計。 纖維素醚分子量(Mw)可爲10 000至1 000 000,較佳爲20 000 至700 00。纖維素醚可爲例如烷基、羥烷基或羧烷基取代, 或爲該等經取代之醚類混合物。 根據本發明,經AKD改質之纖維素醚可用於任何水基底 之塗料,其可用於例如紙張或木板之塗層混合物、於紙張 或木板製造時之溼e n d、塗料、建築材料、接著劑、油性 鑽孔泥漿、清潔劑、化妝用產品及作爲分散劑。 纖維素醚較佳爲羧甲基纖維素(CMC),其經取代之程度 (D S,也就是葡萄糖環中經取代之羥基平均數目)可爲例如 0.2至2.0,較佳爲0.4至1.5,最佳爲0.4至1.2,其分子量 較佳爲40 000至500 000。其可塗用於所有上述之物品。 纖維素醚亦可爲例如羥乙基纖維素(HEC),其分子量可爲 例如90 000至1 300 000,莫耳取代(MS)爲1 · 5至4。HEC可 用於塗料,建築材料,特別是化妝品製劑。 纖維素醚亦可爲例如經丙基纖維素(HPC),其分子量可爲 例如80 000至1 150 000,莫耳取代(MS)爲1.5至4。HPC可 用於食品,醫療製劑,特別是塗料。 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項本頁)
-I線- 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明(5 經濟部智慧財產局員工消費合作社印製 有許多的文獻係關於纖維素醚之製備…般而言,纖維 j係由木材基底或㈣絲底之生材質與反應介質,例 :或酮混合,並以鹼性物質如氫氧化鈉鹼化,而活化纖 :素,再加入醚化之化合物使其反應,最後的產物並經中 和。右需要,可將黏度降低。副產物例如反應中產生之鹽 ’當製備純纖維素醚時,可以例如醇類清洗,但亦可留在 刀中或除去伤(精製或粗製纖維素醚)。所使用之溶劑 ,,二刀離,並將產物乾燥。粒子大小及體密度可藉由將產物 研磨成粉末或將其顆粒化而調整,產物亦可過筛。 纖維素醚可藉由不同方法以AKD改質。AKD可於製造時 炙任何階段加入至纖維素醚,例如於鹼化作用,醚化作用 或乾燥。AKD可以固體型式加入或作爲分散冑。高溫及驗 性p Η可改良AKD與纖維素醚之反應性。 AKD亦可以如下之加入至纖維素醚。而纖維素醚可被包 覆,例如以固態AKD或AKD分散液。此方法中,適量之 AKD噴灑至纖維素醚之表面,或與其混合。產物以高溫處 理以起始反應。 根據本發明之經疏水性改質之纖維素醚之製造既簡單又 快速’並不需要複雜的溶劑或長時間。此外,AKD爲安全 之化學物質,並不會燃燒亦不具爆炸性;因此,於製備時 並不會導致危險,亦不會危害環境。AKD並不危險或刺激 ,並不引起過敏;因此,對於製程操作人員或最後使用者 並不顯現任何之危險性。 疏水性改質之纖維素醚特別用於清潔劑組合物。纖維素 (請先閱讀背面之注意事項再 本頁) 丨襄 士 訂: ,線· 8- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 500728 A7 五、發明說明(6 ) 酸較佳爲羧甲基纖維素(CMC),其取代程度較佳爲〇 4-〇 6。 Μ組合物通常包括約〇·1- 5 %重量計之纖維素基底之纖維處 理成份’較佳爲0.5-4%,最佳爲〇·75 _ 3%。該清潔組合物 可以是液態、糊狀物或顆粒型。該組合物包括約i _ 8 〇 %重 量計,較佳爲5-50%之清潔性界面活性劑,其可爲陰離子 、非離子、兩性離子或陽離子型。組合物可包括〇丨_ 8 〇 % 重I计之清潔劑增效劑,較佳爲1 _ 1 〇 %液態型及1 _ 5 〇 %顆 粒型。清潔劑增效劑可包括例如磷酸鹽與不同的有機及非 有機性之非磷增效劑。除清潔劑、增效劑及纖維性基底材 料外’清潔組合物亦可包括例如酵素及酵素穩定劑、泡沫 促進劑及泡沫抑制劑、抗去光及抗腐蝕劑、土壤懸浮劑、 土壤釋出劑、殺蟲劑、p Η調整劑、非促進劑驗性來源,螯 合劑、有機及非有機充填劑、溶劑、水溶助長劑、光增量 劑、染劑及香料。 顆粒清潔組合物通常由結合基底原料爲泥漿物並喷霧乾 燥此泥漿物至低殘餘水量。剩下的原料乾燥時可預混,或 於液毖噴灑最後的顆粒。液態清潔組合物可以預混原料於 任何想要的方式。 纖維及織物於含有疏水性改質之纖維素醚清洗溶液中之 洗滌’接著漂洗及乾燥,給予纖維及織物之外觀益處。此 益處可包括改良全部的外觀,減少起毛球/起絨毛狀,抗光 澤消极、改良磨損之抗性,及/或增進柔軟度。 實施例 所有的實施例使用烷基乙烯酮二聚物,烷基基團的長度 本纸張尺度適用中國國家標準(CNS)A4規格(2〗〇χ 297公釐)
頁 訂 -9 - 500728 A7B7 五、發明說明(7 ) 爲 16 至 18 個後(Raisio Chemicals 公司)。 實例1 (請先閱讀背面之注意事項再本頁) 將100克具有平均分子量爲180 000及取代程度爲0.65之 CMC(Metsa Speciality Chemicals 公司)放入鋼製容器,再將 1 克之具有AKD含量1 0 %重量計之烷基乙烯酮二聚物分散液 以50克水稀釋後喷灑於CMC上,同時攪拌粉末。產物於80 °C下乾燥至溼度低於8 %。終產物之AKD含量爲0.1 %重量 實例2至6 使用如上述之方法製備下列之疏水性改質之CMC樣品(實 例2至6) ·· 表1 實例 CMC之分子量 CMC之取代程度 CMC中AKD含量, %重量計 2 60 000 0.72 0.05 3 300 000 0.80 0.05 4 220 000 0.87 0.1 5 305 000 1.15 1.0 6 80 000 0.75 0.01 經濟部智慧財產局員工消費合作社印製
實例5含已與CMC反應之0.02%重量計之AKD 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 500728 A7 B7 經濟部智慧財產局員工消費合作社印制π 五、發明說明(8 ) 實例7 將100克具有平均分子量爲40 000及取代程度爲〇·79之CMC 放入鋼製圓筒,加入5克之固態烷基乙晞酮二聚物。粉末於 烘箱中於60 °C下攪動120分鐘及於105°C下攪動15分鐘。終 產物之AKD含量爲5.0%重量計。 實例8 具有平均分子量爲400 000及取代程度爲〇·86,及AKD含 量10.0%重量計之疏水性改質之CMC,以根據實例7所述之 方法製備。 實例9 47克的木漿(Metsa_Botnia),175克的乙醇,及20克的水 於供有混合器及氮氣密閉的玻璃燒戒中混合,該燒瓶置於 水浴中。1 8克的氫氧化鋼以1 8克的水稀釋後加入,將纖維 素於2 0 °C下驗化3 0分鐘。2 2克的單氣醋酸以6克的水稀釋 後,加入具有AKD含量2 0 %重量計之垸基乙烯酮二聚物分 散液1.25克,並使溫度於55分鐘内升至65°C。纖維素於65 °C醚化6 0分鐘。回收乙醇並將產物於8 〇。(;乾燥至歷度低於 8 %。終產物之AKD含量爲0·3%重量計,平均分子量爲15〇 000 ’敌乙基基團之D S爲0.57。樣品所含〇 〇2 %重量計之 AKD與纖維素反應。 實例1 0至1 5 實例1 0至1 5以根據實例9所述之方法製備。實例1 〇及! 5 中’產物於酯化後以氫氟酸中和。於實例1 〇中AKD於中和 後加入並於70°C反應5分鐘。 -11- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公爱) (請先閱讀背面之注意事 — 1 裝i謹 項再本頁) 訂- -線- 500728 A7 _B7 五、發明說明(9 ) 表2 實例 CMC之分子量 CMC之取代程度 CMC中AKD含量,%重量計 10 180 000 0.46 0.6 11 120 000 0.48 0.6 12 140 000 0.52 0.06 13 150 000 0.55 1.1 14 140 000 0.56 2.7 15 270 000 0.52 0.06 (請先閱讀背面之注意事項 實例12含< 0.01 %重量計之已與CMC反應之AKD 實例1 6 100克的木漿(MetsS-Botnia),1270克的異丙醇,及162克 的水於供有混合器及氮氣密閉的玻璃燒瓶中混合,該燒瓶 置於水浴中。4 0克的氫氧化鋼以4 0克的水稀釋後加入,將 纖維素於2 0 °C下鹼化9 0分鐘。4 4克的單氣醋酸以1 1克的 水稀釋後,加入具有AKD含量1 0 %重量計之烷基乙晞酮二 聚物分散液1克,並使溫度於4 5分鐘内升至7 0 °C。纖維素 於7 0 °C醚化9 0分鐘,並將CMC以氫氯酸中和。反應之副產 物,氯化鈉及甘醇酸,以7 5 %甲醇清洗,而產物於8 0 °C嚇 乾燥至溼度低於8%。終產物之AKD含量爲0.08%重量計, 平均分子量爲270 000,羧甲基基團之DS爲0.59。 實例1 7至1 9 實例1 7至1 9以根據實例1 6所述之方法製備。實例1 9中, A K D於驗化時加入。 -12- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) -線- 經濟部智慧財產局員工消費合作社印製 500728 A7 B7 五、發明說明(10 ) 表3 實例 生材料 CMC之分子量 CMC之取代程度 CMC中AKD含量 ,%重量計 17 木漿 (Metsa- Botnia) 60 000 0.77 0.07 18 木漿 (Borregaard) 240 000 0.89 0.07 19 棉籽絨 (Buckeye, Temming) 380 000 0.80 0.7 實例2 0 (請先閱讀背面之注意事項再 11¾本頁)
根據本發明之顆粒清潔劑組合物具有下列之基礎配方: 線. 經濟部智慧財產局員工消費合作社印製 -13- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 500728 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明(11 ) 表4 成份 Wt.% c12直鏈烷基苯磺酸酯 9.31 C14-15貌基醚(0.35EO)橫酸酯 12.74 沸石增進劑 27.79 碳酸鈉 27.31 PEG 4000 1.60 分散劑 2.26 〇12-13乙氧醇酯(9 EO) 1.5 過硼酸鈉 1.03 土壤釋出聚合物 0.41 酵素 0.59 疏水性改質之纖維素醚 3.0 香料、增亮劑、泡沫抑制劑、其他 差額量 微量物、水、硫酸鹽 100% (請先閱讀背面之注意事項再本頁)
· · ;線· 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐)
Claims (1)
- 500728 A8 B8 第88105857號專利申請案 中文申請專利範圍修正本(90年I2月)益 公 申請範圍% ^ 條 一種疏水性改質之纖維素醚,其特徵在於疏水改質係使 用具有通式如下之烷基或烯基乙晞酮二聚物進行: Ri-CH = C-CH-R 0 - c = o 其中1及112為具.有5至22碳數之烷基或烯基鏈; 其中纖維素醚具有下列通式: Ο R2 0 II I II RrCHyC-CH-C-O-纖維素(醚) 其中Ri及R2之定義同前; 其中纖維素醚之分子量為1 0,000至〖,〇〇〇,〇〇〇 •,且 其中烷基或缔基乙婦酮二聚物於纖維素鍵之含量為 〇 · 〇 0 1至-1 0 %重量計。 • 2·根據申請專利範圍第i項之改質纖維素醚,其中及尺2 為具有I3至2〇碳數之烷基或、缔多鏈。 3·根據申請專利範圍第2項之改質纖維素醚,其中汉1及尺2 為具有14至18碳數之烷基或烯基鏈。 4.根據中請專利範圍第i項之改質纖維㈣,其中纖維素酸500728之分子量為20,000至700,〇〇〇。 5 ·根據申請專利範圍第4項之改質纖維素醚,其中纖維素醚 之分子量為40,000至500,〇〇〇。 6·根據申請專利範圍第1項之改質纖維素醚,其中烷基或烯 基乙缔酮二聚物於纖維素醚之含量為001至2%重^計 〇 7·根據申請專利範圍第1至6項中任一項之改質 其中纖維素醚為羧基甲基纖維素。 / μ 8. 根據申請專利範圍第7項之改質纖維素醚,其中羧基甲基 纖維素取代度為0.2至2。 9. 根據申請專利範圍第8項之改質纖維素醚,其 纖維素取代度為0.4至1.5。 1〇·根據申請專利範圍第9項之改質纖維素_, 纖維素取代度為0.4^2。 11· 一種製備疏水性改質之纖維素醚之方法,特徵在於 於30至120°c高溫及鹼性pH下, -纖維素醚可與烷基或烯基乙埽酮二聚物反應,或 -纖維素或其衍生物可與烷基或烯基乙缔酮二聚物反應 ’其後該產物可轉化成纖維素醚。 12· —種欲與水混合之組合物,特徵在於該組合物包含根據 申請專利範圍第1項之疏水性改質之纖維素醚,其中該纖 維素醚係為羧基甲基纖維素:,其取代程度為〇2至2〇, 分子量為40,000至500,000 ,且含量為〇丨至5重量百分 比。線500728 8 8 8 8 A BCD ~、申請專利範圍 13·根據申請專利範圍第12項之組合物,其係用作清潔劑。 14·根據申請專利範圍第12項之組合物,其中羧基甲基纖維 素之取代程度為0.4至0.6。 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公董)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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FI981149A FI107385B (fi) | 1998-05-25 | 1998-05-25 | Modifioitujen selluloosaeetterien valmistus |
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TW500728B true TW500728B (en) | 2002-09-01 |
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TW088105857A TW500728B (en) | 1998-05-25 | 1999-04-13 | Hydrophobically modified cellulose ethers, preparation process thereof, and composition containing the same |
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US (2) | US6600033B1 (zh) |
EP (2) | EP0998498B9 (zh) |
JP (1) | JP4468579B2 (zh) |
KR (1) | KR100362421B1 (zh) |
CN (1) | CN1191278C (zh) |
AR (1) | AR016721A1 (zh) |
AT (1) | ATE444312T1 (zh) |
AU (1) | AU3422399A (zh) |
BR (1) | BR9906504B1 (zh) |
CA (1) | CA2297904C (zh) |
CO (1) | CO5050321A1 (zh) |
DE (1) | DE69941472D1 (zh) |
ES (1) | ES2333186T3 (zh) |
FI (1) | FI107385B (zh) |
HK (1) | HK1027823A1 (zh) |
HU (1) | HUP0100160A3 (zh) |
PL (1) | PL200907B1 (zh) |
TR (1) | TR200000242T1 (zh) |
TW (1) | TW500728B (zh) |
WO (2) | WO1999061478A1 (zh) |
ZA (1) | ZA200000301B (zh) |
Families Citing this family (19)
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FI19992519A (fi) * | 1999-11-25 | 2001-05-26 | Neste Chemicals Oy | Menetelmä nukleofiilisten yhdisteiden asetoasetyloimiseksi |
US6528643B1 (en) * | 2000-05-05 | 2003-03-04 | Hercules Incorporated | Esterified polysaccharide products and B-lactone ring opened ketene dimer products containing the compositions, and process of making the same |
US6677427B1 (en) | 2000-06-13 | 2004-01-13 | Hercules Incorporated | Enzyme-catalyzed polyamides and compositions and processes of preparing and using the same |
US6528644B1 (en) | 2001-09-26 | 2003-03-04 | Hercules Incorporated | Acetoacetylated saccharides and process of making the same |
GB0227242D0 (en) * | 2002-11-21 | 2002-12-31 | Unilever Plc | Improvements relating to fabric laundering |
JP5007985B2 (ja) * | 2004-06-25 | 2012-08-22 | 国立大学法人 東京大学 | ポリマーブラシ化合物及びその調製方法 |
GB0419689D0 (en) | 2004-09-04 | 2004-10-06 | Unilever Plc | Improvements relating to fabric laundering |
WO2007056070A2 (en) * | 2005-11-04 | 2007-05-18 | Hercules Incorporated | Ether derivatives of raw cotton linters for water-borne coatings |
EP2085070A1 (en) * | 2008-01-11 | 2009-08-05 | Procter & Gamble International Operations SA. | Cleaning and/or treatment compositions |
EP2302025B1 (en) * | 2009-09-08 | 2016-04-13 | The Procter & Gamble Company | A laundry detergent composition comprising a highly water-soluble carboxmethyl cellulose particle |
CN102443067B (zh) * | 2011-10-28 | 2013-03-20 | 东北林业大学 | 一种羰基化改性纳米纤维素的制备方法 |
CN104629508B (zh) * | 2015-03-11 | 2018-03-06 | 马清浩 | 一种耐水耐擦洗内外墙乳胶漆 |
DE17784205T1 (de) | 2016-09-28 | 2019-11-28 | Cp Kelco Oy | Waschmittelzusammensetzungen mit polysacchariden mit extrem niedrigem molekulargewicht |
CN108048236B (zh) * | 2017-12-01 | 2020-11-06 | 纳爱斯浙江科技有限公司 | 一种含有羧甲基纤维素的液体洗涤剂及其制备方法 |
JP2019099822A (ja) * | 2017-12-06 | 2019-06-24 | 花王株式会社 | 繊維製品用洗浄剤組成物 |
US11872711B2 (en) | 2019-05-10 | 2024-01-16 | The Gillette Company Llc | Lubricating member for razor cartridges |
CN110563855A (zh) * | 2019-10-12 | 2019-12-13 | 山东省食品发酵工业研究设计院 | 一种自组装纳米粒子材料——十八烷酰十八烷酸普鲁兰多糖酯的合成方法 |
CN111995691A (zh) * | 2020-08-21 | 2020-11-27 | 南京林业大学 | 纤维素醚类衍生物、制备方法及用途 |
EP4269548A1 (en) | 2022-04-27 | 2023-11-01 | Dalli-Werke GmbH & Co. KG | Detergent composition with antiscalants |
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US2627477A (en) * | 1949-10-06 | 1953-02-03 | Hercules Powder Co Ltd | Higher alkyl ketene dimer emulsion |
SE361908B (zh) * | 1972-07-14 | 1973-11-19 | Kema Nord Ab | |
JPS50120836A (zh) * | 1974-03-08 | 1975-09-22 | ||
US4228277A (en) | 1979-02-12 | 1980-10-14 | Hercules Incorporated | Modified nonionic cellulose ethers |
GB8621680D0 (en) * | 1986-09-09 | 1986-10-15 | Du Pont | Filler compositions |
US4826970A (en) | 1987-09-17 | 1989-05-02 | Hercules Incorporated | Carboxymethyl hydrophobically modified hydroxyethylcellulose |
BR9000379A (pt) | 1989-01-31 | 1990-12-04 | Union Carbide Chem Plastic | Polissacarideo soluvel em agua,processo para producao de um polissacarideo soluvel em agua,composicao de latex e processo para producao de uma composicao de latex |
DE4028746A1 (de) | 1990-09-11 | 1992-03-12 | Hoechst Ag | Modifizierte celluloseether und ihre verwendung in dispersionsfarben |
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1998
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1999
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- 1999-04-08 BR BRPI9906504-5A patent/BR9906504B1/pt not_active IP Right Cessation
- 1999-04-08 CN CNB998008354A patent/CN1191278C/zh not_active Expired - Fee Related
- 1999-04-08 EP EP99914585A patent/EP0998498B9/en not_active Expired - Lifetime
- 1999-04-08 TR TR2000/00242T patent/TR200000242T1/xx unknown
- 1999-04-08 JP JP2000550882A patent/JP4468579B2/ja not_active Expired - Lifetime
- 1999-04-08 WO PCT/FI1999/000295 patent/WO1999061478A1/en active Application Filing
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- 1999-04-08 DE DE69941472T patent/DE69941472D1/de not_active Expired - Lifetime
- 1999-04-08 AT AT99914585T patent/ATE444312T1/de not_active IP Right Cessation
- 1999-04-08 US US09/463,499 patent/US6600033B1/en not_active Expired - Fee Related
- 1999-04-08 KR KR1020007000597A patent/KR100362421B1/ko not_active IP Right Cessation
- 1999-04-08 US US09/463,498 patent/US20030040622A1/en not_active Abandoned
- 1999-04-08 WO PCT/FI1999/000296 patent/WO1999061479A1/en active IP Right Grant
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- 1999-04-08 EP EP09157060A patent/EP2078733A1/en not_active Withdrawn
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