JPH02153903A - Production of highly hygroscopic resin - Google Patents
Production of highly hygroscopic resinInfo
- Publication number
- JPH02153903A JPH02153903A JP30817888A JP30817888A JPH02153903A JP H02153903 A JPH02153903 A JP H02153903A JP 30817888 A JP30817888 A JP 30817888A JP 30817888 A JP30817888 A JP 30817888A JP H02153903 A JPH02153903 A JP H02153903A
- Authority
- JP
- Japan
- Prior art keywords
- ether
- water
- compound
- glycol
- crosslinking
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011347 resin Substances 0.000 title claims abstract description 32
- 229920005989 resin Polymers 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229920000642 polymer Polymers 0.000 claims abstract description 38
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 18
- -1 ether compound Chemical class 0.000 claims abstract description 17
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 8
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000000524 functional group Chemical group 0.000 claims abstract description 4
- 239000002250 absorbent Substances 0.000 claims description 13
- 230000002745 absorbent Effects 0.000 claims description 11
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 4
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 3
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims 1
- QMGJMGFZLXYHCR-UHFFFAOYSA-N 1-(2-butoxypropoxy)butane Chemical compound CCCCOCC(C)OCCCC QMGJMGFZLXYHCR-UHFFFAOYSA-N 0.000 claims 1
- WONYMNWUJVKVII-UHFFFAOYSA-N 3,5-diiodothyropropionic acid Chemical compound IC1=CC(CCC(=O)O)=CC(I)=C1OC1=CC=C(O)C=C1 WONYMNWUJVKVII-UHFFFAOYSA-N 0.000 claims 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims 1
- 150000007942 carboxylates Chemical group 0.000 abstract description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004593 Epoxy Substances 0.000 abstract description 3
- 229920002472 Starch Polymers 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 229920000578 graft copolymer Polymers 0.000 abstract description 3
- 239000008107 starch Substances 0.000 abstract description 3
- 235000019698 starch Nutrition 0.000 abstract description 3
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 abstract description 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 abstract description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 abstract description 2
- 150000004645 aluminates Chemical class 0.000 abstract description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 abstract 1
- 229910052782 aluminium Inorganic materials 0.000 abstract 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 description 31
- 238000010521 absorption reaction Methods 0.000 description 25
- 238000011282 treatment Methods 0.000 description 20
- 239000000499 gel Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 11
- 239000002270 dispersing agent Substances 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 7
- 239000007788 liquid Substances 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical group [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 229920002125 Sokalan® Polymers 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 229940015043 glyoxal Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 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
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- MTVLEKBQSDTQGO-UHFFFAOYSA-N 2-(2-ethoxypropoxy)propan-1-ol Chemical compound CCOC(C)COC(C)CO MTVLEKBQSDTQGO-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
- RQZUWSJHFBOFPI-UHFFFAOYSA-N 2-[1-[1-(oxiran-2-ylmethoxy)propan-2-yloxy]propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COC(C)COCC1CO1 RQZUWSJHFBOFPI-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 1
- SEFYJVFBMNOLBK-UHFFFAOYSA-N 2-[2-[2-(oxiran-2-ylmethoxy)ethoxy]ethoxymethyl]oxirane Chemical compound C1OC1COCCOCCOCC1CO1 SEFYJVFBMNOLBK-UHFFFAOYSA-N 0.000 description 1
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 229940024546 aluminum hydroxide gel Drugs 0.000 description 1
- SMYKVLBUSSNXMV-UHFFFAOYSA-K aluminum;trihydroxide;hydrate Chemical compound O.[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-K 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 238000003898 horticulture Methods 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 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
- HDMGAZBPFLDBCX-UHFFFAOYSA-N potassium;sulfooxy hydrogen sulfate Chemical compound [K+].OS(=O)(=O)OOS(O)(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は高吸水性樹脂の製法に係わり、詳しくは吸水速
度、吸水量及びゲル強度が共に大きい吸水性樹脂の工業
的製法に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Field of Application> The present invention relates to a method for producing a super absorbent resin, and more particularly to an industrial method for producing a water absorbent resin that has high water absorption rate, water absorption amount, and gel strength.
〈従来の技術〉
高吸水性樹脂は、その驚異的に多い吸水量及び多少の圧
力を受けても一度吸水した液は離水しないという優れた
保持力から、従来、バルブや吸水紙に代わる液吸収素材
として、おむつ、生理用品等の衛生用品メーカーの注目
を集め実用化されてきたものであり、近年、その用途は
農業、園芸、食品、メディカル等に幅広く拡がりつつあ
る。<Prior art> Super water-absorbing resin has been used as an alternative to valves and water-absorbing paper due to its surprisingly large amount of water absorption and its excellent retention ability, which means that once absorbed, the liquid will not separate from water even when subjected to some pressure. As a material, it has attracted the attention of manufacturers of sanitary products such as diapers and sanitary products, and has been put into practical use.In recent years, its uses have been expanding to a wide range of fields, including agriculture, horticulture, food, and medical care.
ところで、高吸水性樹脂には、吸水量が多いことのみな
らず、速やかに吸水することが要求される。−このため
、吸水性樹脂に一定の処理を施して、吸水速度をさらに
大きくする等の改良が一般に行われている。例えば、粉
末状の吸水性高分子の粒子表面を架橋剤にて架橋する種
々の改良法が提案されている（特公昭５９−８８９８号
公報、特開昭５８−４２８０２号公報、特公昭６１−４
８５２１号公報、特公昭６０−１８８９０号公報参照）
。これらの方法は、いずれも適量の架橋剤を用いること
により、粒子に表面処理を施し、粒子表面の架橋密度を
大きくして、吸水によって膨潤した粒子間の凝集、凝着
を起こり難くすると共に、吸水初期の段階における粒子
表面のゲル化を防止して、吸水速度を改良することによ
り、大きな吸水量と共に大きな吸水速度を有する高吸水
性樹脂を得ることを目的とするものである。By the way, super absorbent resins are required not only to absorb a large amount of water, but also to absorb water quickly. - For this reason, improvements such as subjecting water-absorbing resins to certain treatments to further increase their water-absorbing speed are generally being carried out. For example, various improved methods have been proposed in which the particle surfaces of powdered water-absorbing polymers are cross-linked using a cross-linking agent (Japanese Patent Publications No. 59-8898, JP-A-58-42802, JP-B No. 61-1988). 4
(Refer to Publication No. 8521 and Special Publication No. 18890/1989)
. In each of these methods, by using an appropriate amount of a crosslinking agent, particles are surface-treated to increase the crosslinking density on the particle surface, thereby making it difficult for particles swollen by water absorption to coagulate and adhere, and The purpose of this invention is to obtain a super water-absorbent resin that has both a large water absorption amount and a high water absorption rate by preventing gelation of the particle surface at the initial stage of water absorption and improving the water absorption rate.
これら従来の表面架橋法にあっては、メタノール等の揮
発性の有機溶媒中に吸水性の高分子化合物を分散させた
液に、架橋剤を添加することにより架橋を行なっていた
。In these conventional surface crosslinking methods, crosslinking is carried out by adding a crosslinking agent to a liquid in which a water-absorbing polymer compound is dispersed in a volatile organic solvent such as methanol.
〈発明が解決しようとする課題〉
しかしながら、分散媒として有機溶媒を多量に用いる上
記従来の製法にあっては、火災、爆発等の危険性があり
、このため作業上の安全性に問題があった。<Problems to be Solved by the Invention> However, the conventional manufacturing method described above, which uses a large amount of organic solvent as a dispersion medium, has the risk of fire, explosion, etc., and therefore poses problems in work safety. Ta.
また、有機溶媒の回収が水質汚濁等の公害を防止す、る
上で必要になるため製造コストがかさむという問題もあ
った。Furthermore, since recovery of the organic solvent is necessary to prevent pollution such as water pollution, there is also the problem of increased manufacturing costs.
ところで、上記従来製法を開示した公報には、分散剤と
してメタノール、エタノール、ケトン、エチレングリコ
ール、プロピレングリコール、グリセリン、ジエチレン
グリコール等の親水性有機溶剤を用いることにより吸水
速度が大きい高吸水性樹脂を得ることが可能である旨記
載されているが、本発明者等による確認試験によれば各
公報において開示されているほどの品質を有するものは
得られなかった。本発明者等がこの原因を検討した結果
、架橋処理の際に、吸水性高分子化合物の粒子同士が凝
集してダマ状になるため樹脂表面を均一に架橋すること
ができないことに因ることが判った。By the way, the publication disclosing the above-mentioned conventional production method states that a super absorbent resin with a high water absorption rate can be obtained by using a hydrophilic organic solvent such as methanol, ethanol, ketone, ethylene glycol, propylene glycol, glycerin, or diethylene glycol as a dispersant. However, according to confirmation tests conducted by the present inventors, it was not possible to obtain a product having the quality disclosed in each publication. The inventors investigated the cause of this problem and found that it is because the particles of the water-absorbing polymer compound aggregate and form lumps during cross-linking treatment, making it impossible to uniformly cross-link the resin surface. It turns out.
本発明は以上の事情に鑑みなされたものであって、その
目的とするところは、樹脂表面を均一に架橋することに
より、吸水速度及び吸水量が共に大きく、しかも大きな
ゲル強度を有する吸水性樹脂を、低廉且つ安全に製造す
る方法を提供することにある。The present invention has been made in view of the above circumstances, and its purpose is to create a water-absorbing resin that has high water absorption rate and water absorption amount, and high gel strength by uniformly crosslinking the resin surface. The purpose of the present invention is to provide a method for manufacturing the same at low cost and safely.
く課題を解決するための手段〉
上記目的を達成するための本発明に係る吸水性樹脂の製
法においては、分散剤としてエーテル化合物を用いるこ
とにより、架橋処理の際の吸水性高分子化合物の粒子の
凝集を防止してこれを均一に分散させ、粒子表面を均一
に架橋し得るようにした。Means for Solving the Problems> In the method for producing a water-absorbing resin according to the present invention to achieve the above object, an ether compound is used as a dispersant, so that particles of a water-absorbing polymer compound during crosslinking treatment are By preventing agglomeration of the particles and uniformly dispersing them, the particle surfaces can be uniformly crosslinked.
即ち、本発明に係る高吸水性樹脂の製法は、カルボキシ
ル基及び／又はカルボキシレート部分を有する粉末状の
吸水性高分子化合物を、水及びエーテル化合物の存在下
、前記吸水性高分子化合物と反応し得る２個以上の官能
基を有する架橋剤にて処理するものである。That is, the method for producing a superabsorbent resin according to the present invention involves reacting a powdery water-absorbing polymer compound having a carboxyl group and/or a carboxylate moiety with the water-absorbing polymer compound in the presence of water and an ether compound. It is treated with a crosslinking agent having two or more functional groups that can be used.
以下、本発明に係る製法を詳細に説明する。Hereinafter, the manufacturing method according to the present invention will be explained in detail.
本発明において用い得る吸水性高分子化合物としては、
カルボキシル基及び／又はカルボキシレート部分を有す
る重合体であれば良く、例えば澱粉／アクリルニトリル
グラフト共重合体の加水分解物、澱粉／アクリル酸グラ
フト共重合体の部分中和物、酢酸ビニル／アクリル酸エ
ステル共重合体のケン化物、カルボキシメチルセルロー
ス、イソブチレン／無水マレイン酸共重合体、ポリアク
リル酸の部分中和物及びこれらの各重合体の架橋物等を
挙げることができる。主鎖にアクリル酸又はアクリル酸
塩の七ツマー単位を有する重合体又は共重合体からなる
ポリアクリル酸系の吸水性高分子化合物が特に好ましい
。Water-absorbing polymer compounds that can be used in the present invention include:
Any polymer having carboxyl groups and/or carboxylate moieties may be used, such as hydrolysates of starch/acrylic nitrile graft copolymers, partially neutralized starch/acrylic acid graft copolymers, vinyl acetate/acrylic acid Examples include saponified products of ester copolymers, carboxymethylcellulose, isobutylene/maleic anhydride copolymers, partially neutralized products of polyacrylic acid, and crosslinked products of each of these polymers. Particularly preferred is a polyacrylic acid-based water-absorbing polymer compound consisting of a polymer or copolymer having heptad units of acrylic acid or acrylate in its main chain.
かかる主鎖にアクリル酸又はアクリル酸塩のモノマー単
位を有する重合体又は共重合体からなるポリアクリル酸
系の重合体としては、例えばポリアクリル酸、ポリアク
リル酸塩、アクリル酸とアクリル酸塩との共重合体等が
挙げられる。ここで、ポリアクリル酸塩及びアクリル酸
塩の塩部分としては、ナトリウム塩、カリウム塩等のア
ルカリ金属塩、アンモニウム塩等の有機塩基塩を挙げる
ことができる。また、親水性等の特性を改良するために
、主鎖にアクリル酸又はアクリル酸塩のモノマー単位を
有する重合体とアクリルアミド、Ｎ−ビニルピロリドン
、２−ヒドロキシエチルメタクリレート等との共重合体
であってもよい。なお、架橋したものが好ましく、架橋
物の製造に際しては、公知の架橋手段を用いることがで
きる。例えば、Ｎ−メチロールアクリルアミド等の架橋
性上ツマ−との共重合体を加熱したり、或いはペルオキ
ソ硫酸カリウム等の酸化性を有する触媒を用いることに
より、又は２個以上の重合性不飽和結合を有する架橋剤
として例えばＮ、Ｎ’ −メチレンビスアクリルアミド
、エチレングリコールジアクリレート等を重合の際に添
加する方法がある。Examples of polyacrylic acid-based polymers consisting of polymers or copolymers having monomer units of acrylic acid or acrylate in the main chain include polyacrylic acid, polyacrylate, and acrylic acid and acrylate. Examples include copolymers of. Here, examples of the polyacrylate and the salt portion of the acrylate include alkali metal salts such as sodium salt and potassium salt, and organic base salts such as ammonium salt. In addition, in order to improve properties such as hydrophilicity, copolymers of polymers having acrylic acid or acrylate monomer units in the main chain with acrylamide, N-vinylpyrrolidone, 2-hydroxyethyl methacrylate, etc. You can. Note that crosslinked products are preferable, and known crosslinking means can be used for producing crosslinked products. For example, by heating a copolymer with a crosslinkable polymer such as N-methylolacrylamide, or by using an oxidizing catalyst such as potassium peroxosulfate, or by removing two or more polymerizable unsaturated bonds. There is a method of adding, for example, N,N'-methylenebisacrylamide, ethylene glycol diacrylate, etc. as a crosslinking agent during polymerization.
しかし、通常はアクリル酸及び／又はアクリル酸塩の水
溶液に、必要に応じて他の共重合性モノマー及び上記の
架橋剤を添加して重合させる方法が採られており、この
方法で得られる重合体は乾燥すると塊状に固化するので
、高吸水性樹脂素材に適した大きさの粒径に粉砕機を用
いて粉砕する。However, a method is usually adopted in which other copolymerizable monomers and the above-mentioned crosslinking agents are added as necessary to an aqueous solution of acrylic acid and/or acrylates, and the polymers obtained by this method are When the coalescence is dried, it solidifies into a lump, so it is crushed using a crusher to a particle size suitable for the super absorbent resin material.
タイラーふるいにおいて、５〜４００メツシュ通過物が
好ましく、１０〜２００メツシュ通過物がさらに好まし
い。なお、乳化重合又は懸濁重合により得られる重合体
は小さな球状をなしており、そのまま用いても良く、さ
らに粉砕して微細化して用いても良い。In the Tyler sieve, a material passing through a 5 to 400 mesh is preferred, and a material passing through a 10 to 200 mesh is more preferred. In addition, the polymer obtained by emulsion polymerization or suspension polymerization has a small spherical shape, and may be used as it is, or may be further pulverized to make it finer.
本発明において水を添加するのは、架橋深度即ち高吸水
性樹脂の架橋部分の粒子表面からの深さを均一化するた
めであり、好ましい水の添加量はポリマー１００ｆｆｌ
量部当り１〜５０重量部である。The reason why water is added in the present invention is to equalize the crosslinking depth, that is, the depth from the particle surface of the crosslinked part of the super absorbent resin, and the preferable amount of water added is 100ffl of the polymer.
The amount is 1 to 50 parts by weight.
１重量部未満の場合、添加効果が充分でない一方、５０
重量部を越えた場合、粒子の内部深くまで架橋されてし
まうため、ゲル強度は大きくなるものの吸水量が小さく
なり、吸水量及びゲル強度の両方を満足する高吸水性樹
脂を得ることができず、また水の量が多くなればなるほ
ど、乾燥により多くの時間および熱量を要するため工業
的製法として不向きだからである。If the amount is less than 1 part by weight, the effect of addition is not sufficient;
If the amount exceeds 1 part by weight, the particles will be cross-linked deep inside, so although the gel strength will increase, the amount of water absorption will decrease, making it impossible to obtain a superabsorbent resin that satisfies both water absorption and gel strength. Moreover, the larger the amount of water, the more time and heat required for drying, making it unsuitable as an industrial production method.
本発明において分散剤として用い得るエーテル化合物と
しては、ジエチレングリコール、プロピレングリコール
、ジプロピレングリコール、トリプロピレングリコール
、テトラエチレングリコール等のモノアルキルエーテル
またはジアルキルエーテルが例示され、具体的には、ジ
エチレングリコールメチルエーテル、ジプロピレングリ
コールメチルエーテル、ジエチレングリコールジエチル
エーテル、ジエチレングリコールジエチルエーテル、ジ
エチレングリコールジブチルエーテル、プロピレングリ
コールメチルエーテル、プロピレングリコールエチルエ
ーテル、ジプロピレングリコールメチルエーテル、ジプ
ロピレングリコールエチルエーテル、トリプロピレング
リコールメチルエーテル、テトラエチレングリコールジ
メチルエーテル等が挙げられる。Examples of the ether compound that can be used as a dispersant in the present invention include monoalkyl ethers or dialkyl ethers such as diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and tetraethylene glycol. Specifically, diethylene glycol methyl ether, Dipropylene glycol methyl ether, diethylene glycol diethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, tripropylene glycol methyl ether, tetraethylene glycol dimethyl ether etc.
なお、エチレングリコールのアルキルエーテルは、毒性
がある点で、好ましくない。Note that alkyl ethers of ethylene glycol are not preferred because they are toxic.
本発明において、かかる特定のエーテル化合物を選択し
たのは、本発明者等による実験結果に基くものであり、
他の親水性有機溶剤を用いたのでは、架橋処理の際に凝
集によるダマが発生しやすく均一な架橋処理が困難にな
るとの理由による。In the present invention, such specific ether compounds were selected based on experimental results by the present inventors.
This is because using other hydrophilic organic solvents tends to cause lumps due to aggregation during the crosslinking process, making uniform crosslinking difficult.
好ましい使用量はポリマー１００重量部当り０６０５〜
１０重量部である。０．０５重量部未満の場合、架橋処
理の際にダマが発生するために添加効果が小さくなる一
方、
１０ｆｆｉｆｆｉ部を越えて添加した場合、粉末のベト
ッキが出てきて流動性が低下し、ハンドリング性が著し
く悪化する。なお、この特定のエーテル化合物の使用量
は、水１００重量部に対して２〜５０重量部であること
が望ましい。これは、２重量部未満の場合、有意な添加
効果を得ることができない一方、５０重量部を越えた場
合、増量効果をさほど期待できないからである。なお、
好ましい配合量は５〜３０重量部である。The preferred amount used is 0.605 to 100 parts by weight of polymer.
It is 10 parts by weight. If the amount is less than 0.05 parts by weight, lumps will be generated during crosslinking treatment and the effect of addition will be reduced. If more than 10 ffiffi parts are added, a sticky powder will appear, reducing fluidity and making handling difficult. Sexuality deteriorates significantly. Note that the amount of this specific ether compound used is preferably 2 to 50 parts by weight per 100 parts by weight of water. This is because if the amount is less than 2 parts by weight, no significant effect can be obtained, while if it exceeds 50 parts by weight, no significant increase in weight can be expected. In addition,
The preferred amount is 5 to 30 parts by weight.
本発明において用い得る２以上の官能基を有する架橋剤
としては、吸水性高分子化合物が有するカルボキシル基
及び／又はカルボキシレート部分と反応し得るものであ
れば良い。かかる架橋剤としては、例えばアルデヒド化
合物（例えばグルタルア−ルデヒド、グリオキザール等
）イソシアネ−ト（例えば２．４−トリレンジイソシア
ネート、ヘキサメチレンジイソシアネート等）、ハロエ
ポキシ化合物（例えばエピクロルヒドリン、エビブロモ
ヒドリン）、エポキシ化合物（例えばエチレングリコー
ルジグリシジルエーテル、ジエチレングリコールジグリ
シジルエーテル、ポリエチレングリコールジグリシジル
エーテル、プロピレングリコールジグリシジルエーテル
、ジプロピレングリコールジグリシジルエーテル、ポリ
プロピレングリコールジグリシジルエーテル、グリセリ
ンジグリシジルエーテル、ポリグリセリンポリグリシジ
ルエーテル、ペンタエリトリトールポリグリシジルエー
テル、ソルビトールポリグリシジルエーテル）および多
価の金属化合物を挙げることができる。これらの架橋剤
の中では、エポキシ化合物およびアルミニウム塩とアル
ミン酸塩またはアルミニウム塩とアルカリ金属水酸化物
との反応により形成された水酸化アルミニウムゲル（特
開昭６２−２５０７２号公報参照）が最も好ましい。The crosslinking agent having two or more functional groups that can be used in the present invention may be any crosslinking agent as long as it can react with the carboxyl group and/or carboxylate moiety of the water-absorbing polymer compound. Examples of such crosslinking agents include aldehyde compounds (e.g. glutaraldehyde, glyoxal, etc.), isocyanates (e.g. 2,4-tolylene diisocyanate, hexamethylene diisocyanate, etc.), haloepoxy compounds (e.g. epichlorohydrin, shrimp bromohydrin), epoxy Compounds (e.g. ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, polyglycerin polyglycidyl ether, Pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether) and polyvalent metal compounds may be mentioned. Among these crosslinking agents, aluminum hydroxide gel formed by the reaction of an epoxy compound and an aluminum salt and an aluminate or an aluminum salt and an alkali metal hydroxide (see Japanese Patent Application Laid-Open No. 62-25072) is the most popular. preferable.
上記架橋剤は、求める吸水特性、ゲル強度等に応じて適
宜の量を用い得るが、吸水性高分子化合物１００重量部
に対して０．００１〜１０重量部を用いるのが一般的で
あり、好ましい使用量は０．００５〜５重量部である。The crosslinking agent may be used in an appropriate amount depending on the desired water absorption properties, gel strength, etc., but it is generally used in an amount of 0.001 to 10 parts by weight per 100 parts by weight of the water absorbing polymer compound. The preferred amount used is 0.005 to 5 parts by weight.
ここで、架橋剤が一般的に０．００１〜１０重量部使用
されるのは、０．００１重量部未満の場合、架橋効果が
充分にあられれず、また架橋処理の際に粉末状の吸水性
樹脂が凝集してダマ状の塊になり、均一に架橋処理する
ことが困難になる一方、１０重量部を越える場合、架橋
密度が大きくなり過ぎ、吸水量が低下するからである。Here, the crosslinking agent is generally used in an amount of 0.001 to 10 parts by weight, because if it is less than 0.001 part by weight, the crosslinking effect will not be sufficiently achieved, and during the crosslinking treatment, the powdery water absorbent This is because the resin aggregates into lump-like lumps, making it difficult to crosslink uniformly, while if it exceeds 10 parts by weight, the crosslinking density becomes too high and the amount of water absorption decreases.
本発明に係る高吸水性樹脂の製法においては、特定のエ
ーテル化合物と水との存在下、粉末状の吸水性高分子化
合物を架橋剤にて架橋処理をした後、乾燥する。具体的
には種々の方法が考えられるが、混合機に吸水性高分子
化合物を収容し、これに分散剤と架橋剤とを水に溶解又
は分散させた液を攪拌しながら滴下又はスプレーし、充
分に混合して架橋処理した後、乾燥機で乾燥する方法が
例示される。In the method for producing a superabsorbent resin according to the present invention, a powdery water-absorbing polymer compound is crosslinked with a crosslinking agent in the presence of a specific ether compound and water, and then dried. Specifically, various methods can be considered, such as placing a water-absorbing polymer compound in a mixer, dropping or spraying a liquid in which a dispersant and a crosslinking agent are dissolved or dispersed in water while stirring; An example of this method is to thoroughly mix and crosslink, and then dry in a dryer.
なお、上記混合機は、本発明においては特に限定されず
、ナウターミキサ−リボンブレンダーコニカルブレンダ
ー、ヘンシェルミキサー ライカイ器等の慣用の混合機
を用いることができる。The above-mentioned mixer is not particularly limited in the present invention, and a conventional mixer such as a Nauta mixer, a ribbon blender, a conical blender, a Henschel mixer, or the like can be used.
また、架橋処理後に行う乾燥には、慣用の乾燥機、例え
ば熱風循環乾燥機、減圧乾燥機等を用いることができる
。Further, for drying after the crosslinking treatment, a conventional dryer such as a hot air circulation dryer, a vacuum dryer, etc. can be used.
上記架橋処理において、架橋反応温度は特に限定されず
、架橋剤の種類、目標とする吸水特性及びゲル強度等に
応じて適宜の温度で行うことができる。In the above-mentioned crosslinking treatment, the crosslinking reaction temperature is not particularly limited, and can be carried out at an appropriate temperature depending on the type of crosslinking agent, target water absorption characteristics, gel strength, etc.
また、乾燥温度は、室温〜１５０℃、好ましくは７０−
１２０℃である。なお、架橋処理と乾燥処理とを同時に
行なってもよい。In addition, the drying temperature is room temperature to 150°C, preferably 70°C to 150°C.
The temperature is 120°C. Note that the crosslinking treatment and the drying treatment may be performed simultaneously.
さらに、混合時の流動性、架橋特性等を改良するために
、塩化カルシウム、硝酸亜鉛等を添加してもよい。Furthermore, calcium chloride, zinc nitrate, etc. may be added to improve fluidity during mixing, crosslinking properties, etc.
〈実施例〉
以下に、本発明方法の実施例及び比較例を示すが、本発
明は下記の実施例に限定されるものではないことは勿論
である。下記において、９６は重量％を示し、また吸水
性樹脂の性能試験は下記の方法により行なった。<Examples> Examples and comparative examples of the method of the present invention are shown below, but it goes without saying that the present invention is not limited to the following examples. In the following, 96 indicates weight %, and the performance test of the water absorbent resin was conducted by the following method.
ａ）吸水量の測定
ひだ折りした市販のコーヒーフィルタに試料Ｘ （ｇ）
を入れ、０．９％食塩水に１０分間浸漬した後、コーヒ
ーフィルタを含めて重ｕＹ（ｇ）を測定する。別途また
、０．９％食塩水を吸水した前記コーヒーフィルタの重
ｆｉ１Ｚ（ｇ）を測定する。これらの測定値Ｘ−Ｚより
、下記の式に基づいて吸水量（倍）を求めた。a) Measurement of water absorption amount Sample X (g) is placed on a folded commercially available coffee filter.
After soaking in 0.9% saline solution for 10 minutes, the weight uY (g) including the coffee filter is measured. Separately, the weight fi1Z (g) of the coffee filter that has absorbed 0.9% saline is measured. From these measured values X-Z, the water absorption amount (times) was determined based on the following formula.
吸水量（倍）−（Ｙ−Ｚ）／Ｘ
ｂ）ゲル強度の測定
２００ ｍｌのビーカーに０．９％食塩水９７．５ｇを
加え、マグネチックスターラで攪拌しながら、吸水性高
分子化合物２．５ｇを添加してゲル化させる。生成した
ゲルを２４時間放置した後、初めに３／１６インチ直径
のＪＩＳ規格玉軸受用鋼球を、次にそれよりｌ／１６イ
ンチずつ大きくなった同鋼球を順次ゲル表面に載せる。Water absorption amount (times) - (Y-Z) / Add .5g and allow to gel. After the gel is left to stand for 24 hours, first a JIS standard ball bearing steel ball with a diameter of 3/16 inch is placed on the surface of the gel, and then steel balls larger in diameter of 1/16 inch are sequentially placed on the gel surface.
この操作を鋼球がゲル内に沈降するまで継続する。但し
、沈降しなかった鋼球は除去してから次の鋼球を載せる
ようにする。このようにして、沈降しなかった鋼球の最
大直径をもってゲル強度とした。This operation is continued until the steel balls settle into the gel. However, the steel balls that have not settled should be removed before placing the next steel ball. In this way, the maximum diameter of the steel balls that did not settle was defined as the gel strength.
■ 供試吸水性高分子化合物の調製
８０％アクリル酸７５重量部、４８．６％水酸化ナトリ
ウム４８．０重量部及びイオン交換水４８．６重量部を
混合して中和度７０％のアクリル酸塩水溶液を調製した
。このアクリル酸塩水溶液１０２８ｇに、１％Ｎ、Ｎ’
−メチレンビスアクリルアミド水溶液５ｇを添加して
窒素置換した後、２％ベルオキソニ硫酸塩に２ Ｓ２
ｏｓ水溶液３６ｇ、２％ピロ亜硫酸塩に２ Ｓ２０ｓ水
溶液２１．６ｇ及び４０％グリオキサール水溶液を水で
５０倍に薄めた希釈液１４．４ｇを添加して混合液を得
た。次いで、この混合液を、縦４８ｃｍ。■ Preparation of test water-absorbing polymer compound 75 parts by weight of 80% acrylic acid, 48.0 parts by weight of 48.6% sodium hydroxide, and 48.6 parts by weight of ion-exchanged water were mixed to prepare acrylic with a neutralization degree of 70%. An aqueous acid salt solution was prepared. To 1028 g of this acrylate aqueous solution, 1% N, N'
- After adding 5 g of methylene bisacrylamide aqueous solution and purging with nitrogen, 2 S2
A mixed solution was obtained by adding 21.6 g of 2S20s aqueous solution and 14.4 g of a diluted solution of 40% glyoxal aqueous solution diluted 50 times with water to 36 g of os aqueous solution and 2% pyrosulfite. Next, spread this mixture into a length of 48 cm.
横３７印のバット（内面テフロンコーティング）に注入
し、４２℃の熱風循環乾燥器内で２０分間重合して、厚
さ５〜６ ｍｍの含水ゲルを得た。得られた含水ゲルを
表面温度１３０℃のドラムドライアで乾燥してフレーク
状の樹脂とし、この樹脂をビンミルで粉砕した後、分級
し、１６〜２００メツシユの粉末状の吸水性高分子化合
物を得た。The mixture was poured into a vat with 37 horizontal marks (Teflon coating on the inside) and polymerized for 20 minutes in a hot air circulation dryer at 42°C to obtain a hydrogel with a thickness of 5 to 6 mm. The obtained hydrous gel was dried in a drum dryer with a surface temperature of 130°C to obtain a flaky resin, and this resin was ground in a bottle mill and then classified to obtain a powdery water-absorbing polymer compound of 16 to 200 meshes. Ta.
■ 実施例１〜５及び比較例１〜４
■で得られた粉末状の吸水性高分子化合物を、第１表に
示す組成を有する処理液を所定量用いて処理した。即ち
、容ｆｆ１ｌｆｆの小型攪拌機に前述■の調製で得た粉
末状の吸水性高分子化合物１００ｇを入れ、分散剤種の
みを異にする第１表に示す処理液２４．０５ｇを攪拌し
ながら滴下した。この滴下は徐々に行なうことが肝要で
あり、本実施例における滴下時間は１分間であった。滴
下終了後、さらに５分間攪拌を継続し、架橋処理におけ
るダマの発生の有無等を観察した。(2) Examples 1 to 5 and Comparative Examples 1 to 4 The powdered water-absorbing polymer compound obtained in (1) was treated using a predetermined amount of a treatment liquid having the composition shown in Table 1. That is, 100 g of the powdered water-absorbing polymer compound obtained in the above-mentioned preparation (2) was placed in a small stirrer with a volume of ff1lff, and 24.05 g of the treatment solution shown in Table 1, which differed only in the type of dispersant, was added dropwise while stirring. did. It is important to perform this dropping gradually, and the dropping time in this example was 1 minute. After the dropwise addition was completed, stirring was continued for another 5 minutes, and the presence or absence of lumps during the crosslinking treatment was observed.
■ 実施例６〜１１
■で得られた粉末状の吸水性高分子化合物を、第２表に
示すように分散剤の種類および水と分散剤との配合割合
が異なる種々の架橋処理液を用いて処理した。即ち、容
ｆｆ１ｌＮの小型攪拌機に■の調整で得られた粉末状の
吸水性高分子化合物１００ｇを入れ、第２表にその組成
を示す架橋処理液を攪拌しながら滴下した。この滴下も
■の場合と同様に徐々に行なうことが肝要であり、本実
施例では１分間で滴下した。滴下終了後、さらに５分間
攪拌を継続し、得られた樹脂を乾燥機にて含水率が約７
％になるまで１４０℃の温度で乾燥した。 以上の処理
をして得られた高吸水性樹脂としての各試料について吸
水量（倍）及びゲル強度（インチ）を測定した。■ Examples 6 to 11 The powdered water-absorbing polymer compounds obtained in (1) were treated with various crosslinking solutions having different types of dispersants and different mixing ratios of water and dispersants, as shown in Table 2. Processed. That is, 100 g of the powdered water-absorbing polymer compound obtained in the adjustment in (2) was placed in a small stirrer having a capacity of ff11N, and the crosslinking treatment solution whose composition is shown in Table 2 was added dropwise while stirring. It is important to perform this dropping gradually as in case ①, and in this example, the dropping was carried out over 1 minute. After dropping, stirring was continued for another 5 minutes, and the resulting resin was dried in a dryer until the moisture content was approximately 7.
% at a temperature of 140°C. The water absorption amount (times) and gel strength (in inches) were measured for each sample as a super absorbent resin obtained through the above treatment.
■ 実施例１２
架橋処理液として、第３表に示される架橋処理液を用い
たこと以外は、実施例６〜１１と同様にして、■で得ら
れた粉末状の吸水性高分子化合物を処理し、吸水量（倍
）及びゲル強度（インチ）を測定した。■ Example 12 The powdered water-absorbing polymer compound obtained in (■) was treated in the same manner as Examples 6 to 11, except that the cross-linking treatment liquid shown in Table 3 was used as the cross-linking treatment liquid. Then, water absorption (times) and gel strength (inch) were measured.
（以下、余白）
第１表に示すように、特定のエーテル化合物を分散剤と
して含有する架橋処理液を用いた場合（実施例１〜５）
は、ダマが発生せず、供試高分子化合物の均一な架橋処
理をすることができた。(Hereinafter, blank space) As shown in Table 1, when a crosslinking treatment liquid containing a specific ether compound as a dispersant was used (Examples 1 to 5)
The test polymer compound was able to be crosslinked uniformly without any lumps.
これに対して、メタノール、アセトン、プロピレングリ
コール、グリセリンを分散剤として用いた場合（比較例
１〜４）は、ダマが発生した。特に、メタノールを分散
剤として用いた比較例１では、凝集・凝着がはなはだし
く起こり、攪拌不能になった。また、第２表および第３
表に示すように、種々の特定エーテル化合物を使用し、
また処方を種々変更して架橋処理を行った（実施例６〜
１２）ものはいずれも、吸水量が多く、ゲル強度が大き
かった。On the other hand, when methanol, acetone, propylene glycol, or glycerin was used as a dispersant (Comparative Examples 1 to 4), lumps were generated. In particular, in Comparative Example 1 in which methanol was used as a dispersant, agglomeration and aggregation occurred so much that stirring became impossible. Also, Table 2 and 3
As shown in the table, using various specific ether compounds,
In addition, crosslinking treatment was carried out by changing the formulation in various ways (Example 6 to
12) All of them had a large amount of water absorption and high gel strength.
〈発明の効果〉
以上説明したように、本発明に係る高吸水性樹脂の製法
においては、特定のエーテル化合物と水とを共存せしめ
て、カルボキシル基及び／又はカルボキシレート部分を
有する粉末状の吸水性高分子化合物を架橋処理するので
、その処理時に、吸水性高分子化合物がダマ状に凝集せ
ず、均一な架橋処理が可能となると共に、優れた吸水性
能を有する高吸水性樹脂を製造することができる。即ち
、本発明方法により得られる高吸水性樹脂は、例えば、
水のみならず塩類を含有する溶液、例えば尿、血液等の
体液等に対しても大きな吸水速度を示し、速やかにこれ
らを吸収することができる。また、吸水後のゲル強度が
大きいので、安定した形状で水分を保持することができ
るという保水性に優れる。さらに、吸水時にいわゆるマ
マコ現象を起こすことが無いので、吸水速度が大きい。<Effects of the Invention> As explained above, in the method for producing a superabsorbent resin according to the present invention, a specific ether compound and water are allowed to coexist to form a water-absorbing powder having carboxyl groups and/or carboxylate moieties. Since the water-absorbing polymer compound is cross-linked, the water-absorbing polymer compound does not aggregate into lumps during the treatment, making uniform cross-linking possible, and producing a super-absorbent resin with excellent water-absorbing performance. be able to. That is, the superabsorbent resin obtained by the method of the present invention is, for example,
It exhibits a high water absorption rate not only for water but also for solutions containing salts, such as body fluids such as urine and blood, and can rapidly absorb these. In addition, since the gel strength after water absorption is high, it has excellent water-retaining properties that allow it to retain water in a stable shape. Furthermore, since the so-called mamako phenomenon does not occur when water is absorbed, the water absorption rate is high.
またさらに、ゲル強度等の特性が充分でない吸水性高分
子化合物であっても、本発明に係る製法を用いて均一に
架橋することにより、ゲル強度が大きな吸水性樹脂を製
造することができる。Furthermore, even if a water-absorbing polymer compound does not have sufficient properties such as gel strength, it is possible to produce a water-absorbing resin with high gel strength by uniformly crosslinking it using the production method according to the present invention.
しかも、本発明方法によれば、効率的且つ低順に吸水性
能に優れた吸水性樹脂を製造することができる。即ち、
架橋工程にアルコール等の有機溶媒を多量に用いること
がないため、溶媒の回収工程等を必要とせず、生産性を
高めることが可能になると共に、架橋処理工程において
、ダマを生じることなく均一に架橋処理することができ
るため、生産コストの低減を図ることができ、簡易且つ
安全な製造が可能になる。Moreover, according to the method of the present invention, water-absorbing resins with excellent water-absorbing performance can be produced efficiently and in descending order. That is,
Since large amounts of organic solvents such as alcohol are not used in the crosslinking process, there is no need for a solvent recovery process, which makes it possible to increase productivity, and the crosslinking process can be performed uniformly without creating lumps. Since crosslinking treatment can be performed, production costs can be reduced, and simple and safe manufacturing becomes possible.
以上のように、本発明は種々の優れた特有の効果を奏す
るものである。As described above, the present invention has various excellent and unique effects.
特許出願人 積水化成品工業株式会社代 理 人Patent applicant: Sekisui Plastics Co., Ltd. Reason Man
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30817888A JPH0639487B2 (en) | 1988-12-06 | 1988-12-06 | Super absorbent resin manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30817888A JPH0639487B2 (en) | 1988-12-06 | 1988-12-06 | Super absorbent resin manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02153903A true JPH02153903A (en) | 1990-06-13 |
| JPH0639487B2 JPH0639487B2 (en) | 1994-05-25 |
Family
ID=17977849
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30817888A Expired - Fee Related JPH0639487B2 (en) | 1988-12-06 | 1988-12-06 | Super absorbent resin manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0639487B2 (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06200046A (en) * | 1992-01-28 | 1994-07-19 | Sanyo Chem Ind Ltd | Preparation of modified highly water-absorptive resin and resin |
| US5389722A (en) * | 1992-06-05 | 1995-02-14 | Nippon Shokubai Co., Ltd. | Hydrophilic resin and method for production thereof |
| EP0755413A1 (en) * | 1994-04-11 | 1997-01-29 | Hoechst Celanese Corporation | Superabsorbent polymers and products therefrom |
| US6265488B1 (en) | 1998-02-24 | 2001-07-24 | Nippon Shokubai Co., Ltd. | Production process for water-absorbing agent |
| US6297319B1 (en) | 1998-11-05 | 2001-10-02 | Nippon Shokubai Co., Ltd. | Water-absorbing agent and production process therefor |
| US6372852B2 (en) | 1998-03-31 | 2002-04-16 | Nippon Shokubai Co., Ltd | Water-absorbing composition and production process for water-absorbing agent |
| EP1712584A2 (en) | 1997-06-18 | 2006-10-18 | Nippon Shokubai Co., Ltd. | Water-absorbent resin granule-containing composition and production process |
| US7312278B2 (en) | 2001-06-08 | 2007-12-25 | Nippon Shokubai Co., Ltd. | Water-absorbing agent and production process therefor, and sanitary material |
| EP1682194B1 (en) † | 2003-10-31 | 2008-07-09 | Basf Se | Blood- and/or body fluid-absorbing polymer particles |
| EP3009474B1 (en) | 2014-10-16 | 2017-09-13 | Evonik Degussa GmbH | Method for the production of water soluble polymers |
| EP3381970A1 (en) | 2017-03-31 | 2018-10-03 | Formosa Plastics Corporation | Superabsorbent polymer and the method of fabricating the same |
| EP3381972A1 (en) | 2017-03-31 | 2018-10-03 | Formosa Plastics Corporation | Superabsorbent polymer and the method of fabricating the same |
| EP3954717A1 (en) | 2020-08-10 | 2022-02-16 | Formosa Plastics Corporation | Superabsorbent polymer and method for producing the same |
| EP4317260A1 (en) | 2022-08-04 | 2024-02-07 | Formosa Plastics Corporation | Superabsorbent polymer and method for producing the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0839986A (en) * | 1994-07-29 | 1996-02-13 | Masaharu Hosoi | Correcting tool for writing way |
-
1988
- 1988-12-06 JP JP30817888A patent/JPH0639487B2/en not_active Expired - Fee Related
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06200046A (en) * | 1992-01-28 | 1994-07-19 | Sanyo Chem Ind Ltd | Preparation of modified highly water-absorptive resin and resin |
| JPH0674331B2 (en) * | 1992-01-28 | 1994-09-21 | 三洋化成工業株式会社 | Process for producing modified super absorbent resin and resin |
| US5389722A (en) * | 1992-06-05 | 1995-02-14 | Nippon Shokubai Co., Ltd. | Hydrophilic resin and method for production thereof |
| EP0755413A1 (en) * | 1994-04-11 | 1997-01-29 | Hoechst Celanese Corporation | Superabsorbent polymers and products therefrom |
| EP0755413A4 (en) * | 1994-04-11 | 1999-11-17 | Hoechst Celanese Corp | Superabsorbent polymers and products therefrom |
| EP1712584A2 (en) | 1997-06-18 | 2006-10-18 | Nippon Shokubai Co., Ltd. | Water-absorbent resin granule-containing composition and production process |
| US6265488B1 (en) | 1998-02-24 | 2001-07-24 | Nippon Shokubai Co., Ltd. | Production process for water-absorbing agent |
| US6372852B2 (en) | 1998-03-31 | 2002-04-16 | Nippon Shokubai Co., Ltd | Water-absorbing composition and production process for water-absorbing agent |
| US6297319B1 (en) | 1998-11-05 | 2001-10-02 | Nippon Shokubai Co., Ltd. | Water-absorbing agent and production process therefor |
| US7312278B2 (en) | 2001-06-08 | 2007-12-25 | Nippon Shokubai Co., Ltd. | Water-absorbing agent and production process therefor, and sanitary material |
| EP1682194B1 (en) † | 2003-10-31 | 2008-07-09 | Basf Se | Blood- and/or body fluid-absorbing polymer particles |
| US7867623B2 (en) | 2003-10-31 | 2011-01-11 | Basf Aktiengesellschaft | Polymeric particles capable of absorbing blood and/or body fluids |
| US8071222B2 (en) | 2003-10-31 | 2011-12-06 | Basf Se | Polymeric particles capable of absorbing blood and/or body fluids |
| EP1682194B2 (en) † | 2003-10-31 | 2017-03-29 | Basf Se | Blood- and/or body fluid-absorbing polymer particles |
| EP3009474B1 (en) | 2014-10-16 | 2017-09-13 | Evonik Degussa GmbH | Method for the production of water soluble polymers |
| EP3381970A1 (en) | 2017-03-31 | 2018-10-03 | Formosa Plastics Corporation | Superabsorbent polymer and the method of fabricating the same |
| EP3381972A1 (en) | 2017-03-31 | 2018-10-03 | Formosa Plastics Corporation | Superabsorbent polymer and the method of fabricating the same |
| EP3954717A1 (en) | 2020-08-10 | 2022-02-16 | Formosa Plastics Corporation | Superabsorbent polymer and method for producing the same |
| US11673116B2 (en) | 2020-08-10 | 2023-06-13 | Formosa Plastics Corporation | Method for producing superabsorbent polymer |
| EP4317260A1 (en) | 2022-08-04 | 2024-02-07 | Formosa Plastics Corporation | Superabsorbent polymer and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0639487B2 (en) | 1994-05-25 |
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