JP4968657B2 - Hydrogel - Google Patents
Hydrogel Download PDFInfo
- Publication number
- JP4968657B2 JP4968657B2 JP2005218104A JP2005218104A JP4968657B2 JP 4968657 B2 JP4968657 B2 JP 4968657B2 JP 2005218104 A JP2005218104 A JP 2005218104A JP 2005218104 A JP2005218104 A JP 2005218104A JP 4968657 B2 JP4968657 B2 JP 4968657B2
- Authority
- JP
- Japan
- Prior art keywords
- alkyl group
- general formula
- hydrogel
- compound represented
- group
- 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.)
- Expired - Fee Related
Links
- 239000000017 hydrogel Substances 0.000 title claims description 60
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 59
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 59
- 229920005989 resin Polymers 0.000 claims description 48
- 239000011347 resin Substances 0.000 claims description 48
- 238000007127 saponification reaction Methods 0.000 claims description 46
- 125000000217 alkyl group Chemical group 0.000 claims description 35
- 229920001577 copolymer Polymers 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 23
- 239000000178 monomer Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- 150000000180 1,2-diols Chemical class 0.000 claims description 18
- 229920001567 vinyl ester resin Polymers 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 229910001964 alkaline earth metal nitrate Inorganic materials 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 150000002823 nitrates Chemical class 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 239000000499 gel Substances 0.000 claims description 6
- IGDCJKDZZUALAO-UHFFFAOYSA-N 2-prop-2-enoxypropane-1,3-diol Chemical compound OCC(CO)OCC=C IGDCJKDZZUALAO-UHFFFAOYSA-N 0.000 claims description 4
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 230000000911 decarboxylating effect Effects 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 123
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 36
- 238000000034 method Methods 0.000 description 34
- 238000006116 polymerization reaction Methods 0.000 description 33
- 239000000853 adhesive Substances 0.000 description 25
- 230000001070 adhesive effect Effects 0.000 description 25
- -1 aldehyde compound Chemical class 0.000 description 23
- 239000000243 solution Substances 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 12
- 238000007334 copolymerization reaction Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 10
- MWWXARALRVYLAE-UHFFFAOYSA-N 2-acetyloxybut-3-enyl acetate Chemical compound CC(=O)OCC(C=C)OC(C)=O MWWXARALRVYLAE-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002685 polymerization catalyst Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000007664 blowing Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 125000002843 carboxylic acid group Chemical group 0.000 description 4
- 238000006567 deketalization reaction Methods 0.000 description 4
- 125000004185 ester group Chemical group 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229910017053 inorganic salt Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 125000000542 sulfonic acid group Chemical group 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000006114 decarboxylation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229920000858 Cyclodextrin Polymers 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- VIRPYONDKXQHHU-HWKANZROSA-N [(e)-4-acetyloxybut-3-enyl] acetate Chemical compound CC(=O)OCC\C=C\OC(C)=O VIRPYONDKXQHHU-HWKANZROSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 239000001913 cellulose Chemical class 0.000 description 2
- 229920002678 cellulose Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- SQTUYFKNCCBFRR-UHFFFAOYSA-N (2,4-dimethoxyphenyl)boronic acid Chemical compound COC1=CC=C(B(O)O)C(OC)=C1 SQTUYFKNCCBFRR-UHFFFAOYSA-N 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical class 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- LANDRZNMJOEVQO-UHFFFAOYSA-N 3-ethenoxypropane-1,2-diol Chemical compound OCC(O)COC=C LANDRZNMJOEVQO-UHFFFAOYSA-N 0.000 description 1
- UAIRLKNEZWEEJO-UHFFFAOYSA-N 3-prop-1-en-2-yloxypropane-1,2-diol Chemical compound CC(=C)OCC(O)CO UAIRLKNEZWEEJO-UHFFFAOYSA-N 0.000 description 1
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 1
- SQXNZBLNWGWIHZ-UHFFFAOYSA-N 4-ethenyl-2,2-dimethyl-1,3-dioxolane Chemical compound CC1(C)OCC(C=C)O1 SQXNZBLNWGWIHZ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 244000007835 Cyamopsis tetragonoloba Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- HETCEOQFVDFGSY-UHFFFAOYSA-N Isopropenyl acetate Chemical compound CC(=C)OC(C)=O HETCEOQFVDFGSY-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-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
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920001218 Pullulan Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- UVJZGFKZGQSKDV-OUKQBFOZSA-N [(e)-1,3-diphenylprop-2-enyl] acetate Chemical compound C=1C=CC=CC=1C(OC(=O)C)\C=C\C1=CC=CC=C1 UVJZGFKZGQSKDV-OUKQBFOZSA-N 0.000 description 1
- VZUAUHWZIKOMFC-ONEGZZNKSA-N [(e)-4-acetyloxybut-2-enyl] acetate Chemical compound CC(=O)OC\C=C\COC(C)=O VZUAUHWZIKOMFC-ONEGZZNKSA-N 0.000 description 1
- WLQXPAUZYVXSNE-UHFFFAOYSA-N [Ca].O[N+]([O-])=O Chemical compound [Ca].O[N+]([O-])=O WLQXPAUZYVXSNE-UHFFFAOYSA-N 0.000 description 1
- JJJBUGDRBSGCTD-UHFFFAOYSA-N [Sr].[N+](=O)(O)[O-] Chemical compound [Sr].[N+](=O)(O)[O-] JJJBUGDRBSGCTD-UHFFFAOYSA-N 0.000 description 1
- 239000003655 absorption accelerator Substances 0.000 description 1
- 125000002339 acetoacetyl group Chemical group O=C([*])C([H])([H])C(=O)C([H])([H])[H] 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- RZJRJXONCZWCBN-UHFFFAOYSA-N alpha-octadecene Natural products CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000017531 blood circulation Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- ITMIAZBRRZANGB-UHFFFAOYSA-N but-3-ene-1,2-diol Chemical compound OCC(O)C=C ITMIAZBRRZANGB-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001720 carbohydrates Chemical class 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
- 239000000969 carrier Substances 0.000 description 1
- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 1
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- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropyl acetate Chemical class CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
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- 150000002825 nitriles Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
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- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001290 polyvinyl ester Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- 235000019423 pullulan Nutrition 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- TZYULTYGSBAILI-UHFFFAOYSA-M trimethyl(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC=C TZYULTYGSBAILI-UHFFFAOYSA-M 0.000 description 1
- ZQYKGADTDCTWSZ-UHFFFAOYSA-N trimethyl-[(prop-2-enoylamino)methyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CNC(=O)C=C ZQYKGADTDCTWSZ-UHFFFAOYSA-N 0.000 description 1
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 1
- CCVMLEHYQVSFOM-UHFFFAOYSA-N trimethyl-[2-(prop-2-enoylamino)ethyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCNC(=O)C=C CCVMLEHYQVSFOM-UHFFFAOYSA-N 0.000 description 1
- NFUDTVOYLQNLPF-UHFFFAOYSA-M trimethyl-[3-(2-methylprop-2-enoyloxy)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCCC[N+](C)(C)C NFUDTVOYLQNLPF-UHFFFAOYSA-M 0.000 description 1
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明はハイドロゲルに関し、さらに詳しくは生体に対する粘着力が大きく、保水性に優れ、粘着力の経時低下が少ないハイドロゲルに関する。 The present invention relates to a hydrogel, and more particularly to a hydrogel having a large adhesive force to a living body, excellent water retention, and little decrease in adhesive force over time.
ポリビニルアルコール（以下、ＰＶＡと略記する。）を用いた高分子ハイドロゲルは、含水率、強度、生体への親和性などに優れることから、ソフトコンタクトレンズ材料、創傷被覆材、経皮吸収製剤の基材、眼、皮膚、関節などの生体ゲル代替材料、生体電極材料、酵素や菌体の固定化担体、保冷用熱媒体、アクチュエーター材料など、広範な用途への応用が検討、実用化されている。
かかるＰＶＡ系ハイドロゲルの製造法としては、ＰＶＡ水溶液を凍結乾燥あるいは繰り返し凍結・融解する方法や、アルデヒド化合物等を架橋剤として用いる方法、ホウ素等の金属化合物によって配位結合や水素結合を形成させる方法、紫外線、放射線等を照射する方法などが知られている。しかし、これらの方法で得られたＰＶＡ系ハイドロゲルは粘着力が不充分であり、創傷被覆材、経皮吸収製剤の基材、生体電極材料等の生体表面への粘着力が必要な用途に対しては適用が困難であった。
Polymer hydrogels using polyvinyl alcohol (hereinafter abbreviated as PVA) are excellent in moisture content, strength, affinity for living body, etc. Application to a wide range of applications such as base materials, biogel substitute materials such as eyes, skin and joints, bioelectrode materials, enzyme and fungus immobilization carriers, heat insulation media for cold storage, actuator materials, etc. have been studied and put into practical use. Yes.
As a method for producing such a PVA-based hydrogel, a PVA aqueous solution is freeze-dried or repeatedly freeze-thawed, a method using an aldehyde compound or the like as a cross-linking agent, and a coordination bond or hydrogen bond is formed by a metal compound such as boron. A method, a method of irradiating ultraviolet rays, radiation, and the like are known. However, PVA hydrogels obtained by these methods have insufficient adhesive strength, and are used for applications that require adhesive strength to living body surfaces such as wound dressings, base materials for transdermally absorbable preparations, and bioelectrode materials. On the other hand, it was difficult to apply.
そこで、これらの課題を解決するために、水、ＰＶＡおよび二価の金属塩を主成分とする粘着性ハイドロゲル組成物（例えば、特許文献１参照。）や、水、ＰＶＡおよびシクロデキストリンを主成分とする粘着性ハイドロゲル組成物（例えば、特許文献２参照。）などが提案されている。
しかしながら、本発明者が特許文献１、２に記載の粘着性ハイドロゲル組成物について詳細に検討を行ったところ、生体に対する粘着力についてはかなり改善されているものの、保水性が不充分であるため長時間にわたって使用する場合には経時で水分が蒸発し、それとともに粘着力が低下することが判明した。
すなわち、生体に対する粘着力が大きく、保水性に優れ、粘着力の経時低下が少ないハイドロゲルが望まれるところである。
However, when the inventor conducted detailed studies on the adhesive hydrogel composition described in Patent Documents 1 and 2, the adhesive strength against a living body was considerably improved, but water retention was insufficient. It has been found that when used over a long period of time, the water evaporates over time and the adhesive strength decreases with it.
That is, a hydrogel that has high adhesive strength to a living body, excellent water retention, and little decrease in adhesive strength with time is desired.
しかるに、本発明者はかかる事情に鑑み鋭意研究を重ねた結果、側鎖に下記一般式（１）で表される１，２−ジオール構造単位を含有するＰＶＡ系樹脂（Ａ）とアルカリ土類金属の硝酸塩（Ｂ）を含有し、ＰＶＡ系樹脂（Ａ）に対するアルカリ土類金属の硝酸塩（Ｂ）の含有割合（重量％）が４０〜２５０％であるハイドロゲルが上記目的に合致することを見出し、本発明を完成した。
However, as a result of intensive studies in view of such circumstances, the present inventor has found that the PVA resin (A) containing 1,2-diol structural unit represented by the following general formula (1) in the side chain and alkaline earth containing a metal nitrate salt of (B), the hydrogel PVA-based content ratio of the resin (a) an alkaline earth metal nitrate for (B) (wt%) is 40 to 250% matches the above object The present invention has been completed.
本発明のハイドロゲルは生体に対する粘着力が大きく、保水性に優れ、粘着力の経時低下が少ないため長期間にわたり良好な粘着力を保持することから、創傷被覆材、経皮吸収製剤の基材、生体電極材料等の材料として好適である。 Since the hydrogel of the present invention has high adhesive strength to living organisms, excellent water retention, and has low adhesive strength over time, it retains good adhesive strength over a long period of time. It is suitable as a material such as a bioelectrode material.
まず、本発明で用いられる側鎖に下記一般式（１）で表される１，２−ジオール構造単位を含有するＰＶＡ系樹脂（Ａ）について詳しく説明する。
上記一般式（１）において、Ｒ1、Ｒ2、Ｒ3はそれぞれ独立して水素又はアルキル基である。該アルキル基としては特に限定されないが、例えばメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基等の炭素数１〜４のアルキル基が好ましい。かかるアルキル基は必要に応じて、ハロゲン基、水酸基、エステル基、カルボン酸基、スルホン酸基等の置換基を有していてもよい。また、Ｒ4は、単結合またはアルキル基を有していてもよい炭素数１〜３のアルキレン基を示し、ｎは０又は正の整数を示す。
First, the PVA resin (A) containing a 1,2-diol structural unit represented by the following general formula (1) in the side chain used in the present invention will be described in detail.
In the above general formula (1), R 1 , R 2 and R 3 are each independently hydrogen or an alkyl group. Although it does not specifically limit as this alkyl group, For example, C1-C4 alkyl groups, such as a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, are preferable. Such an alkyl group may have a substituent such as a halogen group, a hydroxyl group, an ester group, a carboxylic acid group, or a sulfonic acid group, if necessary. R 4 represents a single bond or an alkylene group having 1 to 3 carbon atoms which may have an alkyl group, and n represents 0 or a positive integer.
かかるＰＶＡ系樹脂（Ａ）を得るに当たっては、特に限定されないが、（ｉ）ビニルエステル系モノマーと下記一般式（２）で示される化合物との共重合体をケン化する方法、
［式中、Ｒ1、Ｒ2、Ｒ3はそれぞれ独立して水素又はアルキル基であり、Ｒ4は単結合またはアルキル基を有していてもよい炭素数１〜３のアルキレン基であり、Ｒ5およびＲ6は、それぞれ独立して水素またはＲ7−ＣＯ−（式中、Ｒ7は、アルキル基である）である。］
In obtaining such a PVA resin (A), although not particularly limited, (i) a method of saponifying a copolymer of a vinyl ester monomer and a compound represented by the following general formula (2),
[Wherein, R 1 , R 2 and R 3 are each independently hydrogen or an alkyl group, R 4 is a C 1-3 alkylene group which may have a single bond or an alkyl group, R 5 and R 6 are each independently hydrogen or R 7 —CO— (wherein R 7 is an alkyl group). ]
（ｉｉ）ビニルエステル系モノマーと下記一般式（３）で示される化合物との共重合体をケン化する方法、
［式中、Ｒ1、Ｒ2、Ｒ3はそれぞれ独立して水素又はアルキル基であり、Ｒ4は単結合またはアルキル基を有していてもよい炭素数１〜３のアルキレン基であり、Ｒ5およびＲ6は、それぞれ独立して水素またはＲ7−ＣＯ−（式中、Ｒ7は、アルキル基である）である。］
(Ii) a method for saponifying a copolymer of a vinyl ester monomer and a compound represented by the following general formula (3);
[Wherein, R 1 , R 2 and R 3 are each independently hydrogen or an alkyl group, R 4 is a C 1-3 alkylene group which may have a single bond or an alkyl group, R 5 and R 6 are each independently hydrogen or R 7 —CO— (wherein R 7 is an alkyl group). ]
（ｉｉｉ）ビニルエステル系モノマーと下記一般式（４）で示される化合物との共重合体をケン化及び脱炭酸する方法、
［式中、Ｒ1、Ｒ2、Ｒ3はそれぞれ独立した水素又はアルキル基である。］
(Iii) a method of saponifying and decarboxylating a copolymer of a vinyl ester monomer and a compound represented by the following general formula (4),
[Wherein R 1 , R 2 and R 3 are each independently hydrogen or an alkyl group. ]
（ｉｖ）ビニルエステル系モノマーと下記一般式（５）で示される化合物との共重合体をケン化及び脱ケタール化する方法、などが好ましく用いられる。
［式中、Ｒ1、Ｒ2、Ｒ3、Ｒ8、Ｒ9はそれぞれ独立した水素又はアルキル基である。］
(Iv) A method of saponifying and deketalizing a copolymer of a vinyl ester monomer and a compound represented by the following general formula (5) is preferably used.
[Wherein R 1 , R 2 , R 3 , R 8 and R 9 are each independently hydrogen or an alkyl group. ]
なお、本発明で用いられるビニルエステル系モノマーとしては、ギ酸ビニル、酢酸ビニル、プロピオン酸ビニル、バレリン酸ビニル、酪酸ビニル、イソ酪酸ビニル、ピバリン酸ビニル、カプリン酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル、安息香酸ビニル、バーサチック酸ビニル等が挙げられるが、経済的にみて中でも酢酸ビニルが好ましく用いられる。
以下、かかる（ｉ）、（ｉｉ）、（ｉｉｉ）及び（ｉｖ）の方法について説明する。
The vinyl ester monomers used in the present invention include vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate. , Vinyl benzoate, vinyl versatate, and the like, among which vinyl acetate is preferably used from an economical viewpoint.
Hereinafter, the methods (i), (ii), (iii) and (iv) will be described.
［（ｉ）の方法］
本発明で用いられる上記一般式（２）で示される化合物において、Ｒ1、Ｒ2、Ｒ3は上記一般式（１）と同様のものが挙げられ、Ｒ4は単結合またはアルキル基を有していてもよい炭素数１〜３のアルキレン基であり、Ｒ5およびＲ6は、それぞれ独立して水素またはＲ7−ＣＯ−（式中、Ｒ7は、アルキル基、好ましくはメチル基、プロピル基、ブチル基、ヘキシル基またはオクチル基であり、かかるアルキル基は必要に応じて、ハロゲン基、水酸基、エステル基、カルボン酸基、スルホン酸基等の置換基を有していてもよい）である。
[Method (i)]
In the compound represented by the general formula (2) used in the present invention, R 1 , R 2 and R 3 are the same as those in the general formula (1), and R 4 has a single bond or an alkyl group. R 5 and R 6 are each independently hydrogen or R 7 —CO— (wherein R 7 is an alkyl group, preferably a methyl group, A propyl group, a butyl group, a hexyl group or an octyl group, and the alkyl group may optionally have a substituent such as a halogen group, a hydroxyl group, an ester group, a carboxylic acid group, or a sulfonic acid group) It is.
式（２）で示される化合物としては、具体的に３，４−ジヒドロキシ−１−ブテン、３，４−ジアシロキシ−１−ブテン、３−アシロキシ−４−ヒドロキシ−１−ブテン、４−アシロキシ−３−ヒドロキシ−１−ブテン、３，４−ジアシロキシ−２−メチル−１−ブテン、４，５−ジヒドロキシ−１−ペンテン、４，５−ジアシロキシ−１−ペンテン、４，５−ジヒドロキシ−３−メチル−１−ペンテン、４，５−ジアシロキシ−３−メチル−１−ペンテン、５，６−ジヒドロキシ−１−ヘキセン、５，６−ジアシロキシ−１−ヘキセンなどが挙げられる。なかでも、共重合反応性および工業的な取り扱いにおいて優れるという点で、Ｒ1、Ｒ2、Ｒ3が水素、Ｒ4が単結合、Ｒ5、Ｒ6がＲ7−ＣＯ−でありＲ7がアルキル基である３，４−ジアシロキシ−１−ブテンが好ましく、そのなかでも特にＲ7がメチル基である３，４−ジアセトキシ−１−ブテンがより好ましい。
なお、３，４−ジアセトキシ−１−ブテンは、工業生産用ではイーストマンケミカル社、試薬レベルではアクロス社の製品を市場から入手することができる。また、ブタジエン法により１，４−ブタンジオールを製造する過程で生じる３，４−ジアセトキシー１−ブテンを使用することも可能である。
Specific examples of the compound represented by the formula (2) include 3,4-dihydroxy-1-butene, 3,4-diacyloxy-1-butene, 3-acyloxy-4-hydroxy-1-butene, and 4-acyloxy- 3-hydroxy-1-butene, 3,4-diacyloxy-2-methyl-1-butene, 4,5-dihydroxy-1-pentene, 4,5-diasiloxy-1-pentene, 4,5-dihydroxy-3- Examples include methyl-1-pentene, 4,5-diacyloxy-3-methyl-1-pentene, 5,6-dihydroxy-1-hexene, and 5,6-diasiloxy-1-hexene. Among these, R 1 , R 2 and R 3 are hydrogen, R 4 is a single bond, R 5 and R 6 are R 7 —CO—, and R 7 is excellent in copolymerization reactivity and industrial handling. 3,4-diacyloxy-1-butene in which is an alkyl group is preferred, and 3,4-diacetoxy-1-butene in which R 7 is a methyl group is particularly preferred.
As for 3,4-diacetoxy-1-butene, products from Eastman Chemical Company for industrial production and Acros Company at the reagent level can be obtained from the market. It is also possible to use 3,4-diacetoxy-1-butene produced in the process of producing 1,4-butanediol by the butadiene method.
かかるビニルエステル系モノマーと３，４−ジアシロキシ−１−ブテンとを共重合するに当たっては、特に制限はなく、塊状重合、溶液重合、懸濁重合、分散重合、またはエマルジョン重合等の公知の方法を採用することができるが、通常は溶液重合が行われる。
共重合時のモノマー成分の仕込み方法としては特に制限されず、一括仕込み、分割仕込み、連続仕込み等任意の方法が採用されるが、式（２）で示される化合物に由来する構造単位がポリビニルエステル系ポリマーの分子鎖中に均一に分布させられる点から滴下重合が好ましく、特にはＨＡＮＮＡ法に基づく重合方法が好ましい。
There are no particular limitations on the copolymerization of the vinyl ester monomer and 3,4-diacyloxy-1-butene, and any known method such as bulk polymerization, solution polymerization, suspension polymerization, dispersion polymerization, or emulsion polymerization may be used. Although it can be employed, solution polymerization is usually performed.
The method for charging the monomer component at the time of copolymerization is not particularly limited, and any method such as batch charging, split charging, continuous charging, etc. is adopted, but the structural unit derived from the compound represented by formula (2) is a polyvinyl ester. Drop polymerization is preferred from the viewpoint of being uniformly distributed in the molecular chain of the polymer, and a polymerization method based on the HANNA method is particularly preferred.
かかる共重合で用いられる溶媒としては、通常、メタノール、エタノール、イソプロピルアルコール、ｎ−プロパノール、ブタノール等の低級アルコールやアセトン、メチルエチルケトン等のケトン類等が挙げられ、工業的には、メタノールが好適に使用される。
溶媒の使用量は、目的とする共重合体の重合度に合わせて、溶媒の連鎖移動定数を考慮して適宜選択すればよく、例えば、溶媒がメタノールの時は、Ｓ（溶媒）／Ｍ（モノマー）＝０．０１〜１０（重量比）、好ましくは０．０５〜３（重量比）程度の範囲から選択される。
Examples of the solvent used in such copolymerization include usually lower alcohols such as methanol, ethanol, isopropyl alcohol, n-propanol and butanol, and ketones such as acetone and methyl ethyl ketone, and industrially preferred is methanol. used.
The amount of the solvent used may be appropriately selected in consideration of the chain transfer constant of the solvent in accordance with the degree of polymerization of the target copolymer. For example, when the solvent is methanol, S (solvent) / M ( Monomer) = 0.01 to 10 (weight ratio), preferably 0.05 to 3 (weight ratio).
共重合に当たっては重合触媒が用いられ、かかる重合触媒としては、例えばアゾビスイソブチロニトリル、過酸化アセチル、過酸化ベンゾイル、過酸化ラウリル等の公知のラジカル重合触媒やアゾビスジメチルバレロニトリル、アゾビスメトキシジメチルバレロニトリル、ｔ−ブチルパーオキシネオデカネート、ジーｎ―プロピルパーオキシジカーボネート等の低温活性ラジカル重合触媒等が挙げられ、重合触媒の使用量は、触媒の種類により異なり一概には決められないが、重合速度に応じて任意に選択される。例えば、アゾイソブチロニトリルや過酸化アセチルを用いる場合、ビニルエステル系モノマーに対して０．０１〜０．２モル％が好ましく、特には０．０２〜０．１５モル％が好ましい。
また、共重合反応の反応温度は、使用する溶媒や圧力により３０℃〜沸点程度で行われ、より具体的には、３５〜１５０℃、好ましくは４０〜７５℃の範囲で行われる。
For the copolymerization, a polymerization catalyst is used. Examples of the polymerization catalyst include known radical polymerization catalysts such as azobisisobutyronitrile, acetyl peroxide, benzoyl peroxide, lauryl peroxide, azobisdimethylvaleronitrile, azo Examples include low-temperature active radical polymerization catalysts such as bismethoxydimethylvaleronitrile, t-butylperoxyneodecanate, and di-n-propylperoxydicarbonate, and the amount of polymerization catalyst used varies depending on the type of catalyst. Although not determined, it is arbitrarily selected depending on the polymerization rate. For example, when azoisobutyronitrile or acetyl peroxide is used, 0.01 to 0.2 mol% is preferable with respect to the vinyl ester monomer, and 0.02 to 0.15 mol% is particularly preferable.
Moreover, the reaction temperature of a copolymerization reaction is performed at about 30 degreeC-a boiling point by the solvent and pressure to be used, More specifically, it is 35-150 degreeC, Preferably it is carried out in 40-75 degreeC.
得られた共重合体は次いでケン化されるのであるが、かかるケン化にあたっては上記で得られた共重合体をアルコール等の溶媒に溶解し、アルカリ触媒又は酸触媒を用いて行われる。代表的な溶媒としては、２０℃での誘電率３２以下の溶媒が使用され、具体的にはメタノール、エタノール、プロパノール、ｔｅｒｔ−ブタノール、酢酸メチル、酢酸エチル、ベンゼン、キシレン、アセトン、トリクロロエチレン、イソプロピルアセテート等が挙げられるが、工業的にはメタノールやメタノール／酢酸メチルの混合液が特に好ましく用いられる。アルコール中の共重合体の濃度は系の粘度により適宜選択されるが、通常は１０〜６０重量％の範囲から選ばれる。ケン化に使用される触媒としては、水酸化ナトリウム、水酸化カリウム、ナトリウムメチラート、ナトリウムエチラート、カリウムメチラート、リチウムメチラート等のアルカリ金属の水酸化物やアルコラートの如きアルカリ触媒、硫酸、塩酸、硝酸、メタスルフォン酸、ゼオライト、カチオン交換樹脂等の酸触媒が挙げられる。 The obtained copolymer is then saponified. In the saponification, the copolymer obtained as described above is dissolved in a solvent such as alcohol, and the reaction is carried out using an alkali catalyst or an acid catalyst. As a typical solvent, a solvent having a dielectric constant of 32 or less at 20 ° C. is used. Specifically, methanol, ethanol, propanol, tert-butanol, methyl acetate, ethyl acetate, benzene, xylene, acetone, trichloroethylene, isopropyl Acetates and the like can be mentioned, but industrially, methanol or a mixed solution of methanol / methyl acetate is particularly preferably used. The concentration of the copolymer in the alcohol is appropriately selected depending on the viscosity of the system, but is usually selected from the range of 10 to 60% by weight. Catalysts used for saponification include alkali catalysts such as alkali metal hydroxides and alcoholates such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, potassium methylate, lithium methylate, etc., sulfuric acid, Examples include acid catalysts such as hydrochloric acid, nitric acid, metasulfonic acid, zeolite, and cation exchange resin.
かかるケン化触媒の使用量については、ケン化方法、目標とするケン化度等により適宜選択されるが、アルカリ触媒を使用する場合は通常、ビニルエステル系モノマーおよび式（２）で示される化合物の合計量１モルに対して０．１〜３０ミリモル、好ましくは２〜１７ミリモルの割合が適当である。
また、ケン化反応の反応温度は特に限定されないが、１０〜６０℃が好ましく、より好ましくは２０〜５０℃である。
The amount of the saponification catalyst used is appropriately selected depending on the saponification method, the target degree of saponification, etc. When an alkali catalyst is used, the vinyl ester monomer and the compound represented by the formula (2) are usually used. A ratio of 0.1 to 30 mmol, preferably 2 to 17 mmol, is suitable for 1 mol of the total amount.
Moreover, although the reaction temperature of saponification reaction is not specifically limited, 10-60 degreeC is preferable, More preferably, it is 20-50 degreeC.
［（ｉｉ）の方法］
本発明で用いられる上記一般式（３）で示される化合物において、Ｒ1、Ｒ2、Ｒ3は上記一般式（１）と同様のものが挙げられ、Ｒ4は単結合またはアルキル基を有していてもよい炭素数１〜３のアルキレン基であり、Ｒ5およびＲ6は、それぞれ独立して水素またはＲ7−ＣＯ−（式中、Ｒ7は、アルキル基、好ましくはメチル基、プロピル基、ブチル基、ヘキシル基またはオクチル基であり、かかるアルキル基は必要に応じて、ハロゲン基、水酸基、エステル基、カルボン酸基、スルホン酸基等の置換基を有していてもよい）である。
[Method (ii)]
In the compound represented by the general formula (3) used in the present invention, R 1 , R 2 and R 3 are the same as those in the general formula (1), and R 4 has a single bond or an alkyl group. R 5 and R 6 are each independently hydrogen or R 7 —CO— (wherein R 7 is an alkyl group, preferably a methyl group, A propyl group, a butyl group, a hexyl group or an octyl group, and the alkyl group may optionally have a substituent such as a halogen group, a hydroxyl group, an ester group, a carboxylic acid group, or a sulfonic acid group) It is.
式（３）で示される化合物としては、具体的にはグリセリンモノアリルエーテル、２，３−ジアセトキシ−１−アリルオキシプロパン、２−アセトキシ−１−アリルオキシ−３−ヒドロキシプロパン、３−アセトキシ−１−アリルオキシ−２−ヒドロキシプロパン、グリセリンモノビニルエーテル、グリセリンモノイソプロペニルエーテル、などが挙げられる。なかでも、共重合反応性および工業的な取り扱いにおいて優れるという点で、Ｒ1、Ｒ2、Ｒ3が水素、Ｒ4がメチレン、Ｒ5、Ｒ6が水素であるグリセリンモノアリルエーテルや、Ｒ1、Ｒ2、Ｒ3が水素、Ｒ4がメチレン、Ｒ5、Ｒ6がＲ7−ＣＯ−でありＲ7がメチル基である２，３−ジアセトキシ−１−アリルオキシプロパンが好ましく、そのなかでもグリセリンモノアリルエーテルがより好ましい。 Specific examples of the compound represented by the formula (3) include glycerin monoallyl ether, 2,3-diacetoxy-1-allyloxypropane, 2-acetoxy-1-allyloxy-3-hydroxypropane, and 3-acetoxy-1 -Allyloxy-2-hydroxypropane, glycerin monovinyl ether, glycerin monoisopropenyl ether, and the like. Among them, glycerin monoallyl ether in which R 1 , R 2 and R 3 are hydrogen, R 4 is methylene, R 5 and R 6 are hydrogen, and R is excellent in copolymerization reactivity and industrial handling. 1,3-diacetoxy-1-allyloxypropane, wherein R 1 , R 2 and R 3 are hydrogen, R 4 is methylene, R 5 and R 6 are R 7 —CO— and R 7 is a methyl group, Of these, glycerin monoallyl ether is more preferable.
かかるビニルエステル系モノマーと一般式（３）で示される化合物とを共重合およびケン化するに当たっては、上記（ｉ）の方法と同様に行われる。
なお、重合触媒の使用量については、アゾビスイソブチロチトリルや過酸化アセチルを用いる場合、ビニルエステル系モノマーに対して０．０５〜０．７モル％とすることが好ましく、特には０．１〜０．５モル％とすることが好ましい。
The copolymerization and saponification of the vinyl ester monomer and the compound represented by the general formula (3) are performed in the same manner as in the above method (i).
In addition, about the usage-amount of a polymerization catalyst, when using azobisisobutyrotitryl and an acetyl peroxide, it is preferable to set it as 0.05-0.7 mol% with respect to a vinyl-ester type monomer, Especially 0.1. It is preferable to set it as 1-0.5 mol%.
［（ｉｉｉ）の方法］
本発明で用いられる上記一般式（４）で示される化合物において、Ｒ1、Ｒ2、Ｒ3は上記一般式（１）と同様のものが挙げられる。中でも入手の容易さ、良好な共重合性を有する点で、Ｒ1、Ｒ2、Ｒ3が水素であるビニルエチレンカーボネートが好適である。
[Method (iii)]
In the compound represented by the general formula (4) used in the present invention, examples of R 1 , R 2 and R 3 are the same as those in the general formula (1). Among them, vinyl ethylene carbonate in which R 1 , R 2 , and R 3 are hydrogen is preferable because it is easily available and has good copolymerizability.
ビニルエステル系モノマーと一般式（４）で示される化合物とを共重合およびケン化するに当たっては、上記（ｉ）の方法と同様に行われる。
なお、共重合反応の反応温度は、使用する溶媒によるが、４０℃〜沸点程度とすることが好ましく、ケン化反応の反応温度は１０〜１５０℃（さらには１０〜６０℃、特には２０〜５０℃）が好ましい。
The copolymerization and saponification of the vinyl ester monomer and the compound represented by the general formula (4) is carried out in the same manner as in the above method (i).
The reaction temperature of the copolymerization reaction depends on the solvent used, but is preferably about 40 ° C. to the boiling point, and the reaction temperature of the saponification reaction is 10 to 150 ° C. (more preferably 10 to 60 ° C., particularly 20 to 20 ° C. 50 ° C.) is preferred.
脱炭酸については、通常、ケン化後に特別な処理を施すことなく、上記ケン化条件下で該ケン化とともに脱炭酸が行われ、エチレンカーボネート環が開環することで１，２−ジオール成分に変換される。
また、一定圧力下（常圧〜１×１０7Ｐａ）で且つ高温下（５０〜２００℃）でビニルエステル部分をケン化することなく、脱炭酸を行うことも可能であり、かかる場合、脱炭酸を行った後、上記ケン化を行うこともできる。
As for decarboxylation, usually, without any special treatment after saponification, decarboxylation is performed together with the saponification under the above saponification conditions, and the ethylene carbonate ring is opened to form a 1,2-diol component. Converted.
It is also possible to perform decarboxylation without saponifying the vinyl ester moiety under a constant pressure (normal pressure to 1 × 10 7 Pa) and at a high temperature (50 to 200 ° C.). The saponification can also be performed after carbonation.
［（ｉｖ）の方法］
本発明で用いられる上記一般式（５）で示される化合物において、Ｒ1、Ｒ2、Ｒ3は上記一般式（１）と同様のものが挙げられ、Ｒ8、Ｒ9はそれぞれ独立して水素又はアルキル基であり、該アルキル基としては特に限定されないが、例えばメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基等の炭素数１〜４のアルキル基が好ましい。かかるアルキル基は必要に応じて、ハロゲン基、水酸基、エステル基、カルボン酸基、スルホン酸基等の置換基を有していてもよい。中でも入手の容易さ、良好な共重合性を有する点で、Ｒ1、Ｒ2、Ｒ3が水素で、Ｒ8、Ｒ9がメチル基である２，２−ジメチル−４−ビニル−１，３−ジオキソランが好適である。
[Method (iv)]
In the compound represented by the general formula (5) used in the present invention, R 1 , R 2 and R 3 are the same as those in the general formula (1), and R 8 and R 9 are each independently It is hydrogen or an alkyl group, and the alkyl group is not particularly limited. For example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, etc. An alkyl group of 4 is preferred. Such an alkyl group may have a substituent such as a halogen group, a hydroxyl group, an ester group, a carboxylic acid group, or a sulfonic acid group, if necessary. Among these, 2,2-dimethyl-4-vinyl-1, in which R 1 , R 2 , and R 3 are hydrogen and R 8 and R 9 are methyl groups in terms of easy availability and good copolymerizability. 3-dioxolane is preferred.
ビニルエステル系モノマーと上記一般式（５）で示される化合物とを共重合およびケン化するに当たっては、上記（ｉ）の方法と同様に行われる。
なお、共重合反応の反応温度は、使用する溶媒によるが、４０℃〜沸点程度とすることが好ましく、ケン化反応の反応温度は１０〜１５０℃（さらには１０〜６０℃、特には２０〜５０℃）が好ましい。
The copolymerization and saponification of the vinyl ester monomer and the compound represented by the general formula (5) is performed in the same manner as in the method (i).
The reaction temperature of the copolymerization reaction depends on the solvent used, but is preferably about 40 ° C. to the boiling point, and the reaction temperature of the saponification reaction is 10 to 150 ° C. (more preferably 10 to 60 ° C., particularly 20 to 20 ° C. 50 ° C.) is preferred.
上記共重合体のケン化物の脱ケタール化については、上記ケン化がアルカリ触媒を用いて行われる場合は、ケン化した後、更に酸触媒を用いて水系溶媒（水、水／アセトン、水／メタノール等の低級アルコール混合溶媒等）中で脱ケタール化が行われ、１，２−ジオール成分に変換される。脱ケタール化に用いられる酸触媒としては、酢酸、塩酸、硫酸、硝酸、メタスルフォン酸、ゼオライト、カチオン交換樹脂等が挙げられる。
また、上記ケン化が酸触媒を用いて行われる場合は、通常、ケン化後に特別な処理を施すことなく、上記ケン化条件下で該ケン化とともに脱ケタール化が行われ、１，２−ジオール成分に変換される。
Regarding the deketalization of the saponification product of the copolymer, when the saponification is carried out using an alkali catalyst, after saponification, an aqueous solvent (water, water / acetone, water / Deketalization is performed in a mixed solvent of lower alcohol such as methanol) and the like, and converted into a 1,2-diol component. Examples of the acid catalyst used for deketalization include acetic acid, hydrochloric acid, sulfuric acid, nitric acid, metasulfonic acid, zeolite, and cation exchange resin.
When the saponification is carried out using an acid catalyst, the deketalization is usually carried out together with the saponification under the above saponification conditions without any special treatment after saponification. Converted to diol component.
また、本発明に用いるＰＶＡ系樹脂（Ａ）においては、本発明の目的を阻害しない範囲においてその他の不飽和モノマーを共重合性成分として共重合することもできる。該不飽和モノマーとして、例えばエチレンやプロピレン、イソブチレン、α−オクテン、α−ドデセン、α−オクタデセン等のα−オレフィン等のオレフィン類、アクリル酸、メタクリル酸、クロトン酸、マレイン酸、無水マレイン酸、イタコン酸等の不飽和酸類あるいはその塩あるいはモノ又はジアルキルエステル等、アクリロニトリル、メタアクリロニトリル等のニトリル類、ジアセトンアクリルアミド、アクリルアミド、メタクリルアミド等のアミド類、エチレンスルホン酸、アリルスルホン酸、メタアリルスルホン酸等のオレフィンスルホン酸あるいはその塩、アルキルビニルエーテル類、ジメチルアリルビニルケトン、Ｎ−ビニルピロリドン、塩化ビニル、塩化ビニリデン、ポリオキシエチレン（メタ）アリルエーテル、ポリオキシプロピレン（メタ）アリルエーテル等のポリオキシアルキレン（メタ）アリルエーテル、ポリオキシエチレン（メタ）アクリレート、ポリオキシプロピレン（メタ）アクリレート等のポリオキシアルキレン（メタ）アクリレート、ポリオキシエチレン（メタ）アクリルアミド、ポリオキシプロピレン（メタ）アクリルアミド等のポリオキシアルキレン（メタ）アクリルアミド、ポリオキシエチレン（１−（メタ）アクリルアミド−１，１−ジメチルプロピル）エステル、ポリオキシエチレンビニルエーテル、ポリオキシプロピレンビニルエーテル、ポリオキシエチレンアリルアミン、ポリオキシプロピレンアリルアミン、ポリオキシエチレンビニルアミン、ポリオキシプロピレンビニルアミン等が挙げられる。 In addition, in the PVA resin (A) used in the present invention, other unsaturated monomers can be copolymerized as a copolymerizable component as long as the object of the present invention is not impaired. Examples of the unsaturated monomer include olefins such as ethylene, propylene, isobutylene, α-octene, α-dodecene, α-olefin such as α-octadecene, acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, Unsaturated acids such as itaconic acid or salts thereof, mono- or dialkyl esters, nitriles such as acrylonitrile and methacrylonitrile, amides such as diacetone acrylamide, acrylamide and methacrylamide, ethylene sulfonic acid, allyl sulfonic acid, methallyl sulfone Olefin sulfonic acids such as acids or their salts, alkyl vinyl ethers, dimethylallyl vinyl ketone, N-vinyl pyrrolidone, vinyl chloride, vinylidene chloride, polyoxyethylene (meth) allyl ether, polyoxy Polyoxyalkylene (meth) allyl ether such as lopyrene (meth) allyl ether, polyoxyalkylene (meth) acrylate such as polyoxyethylene (meth) acrylate, polyoxypropylene (meth) acrylate, polyoxyethylene (meth) acrylamide, Polyoxyalkylene (meth) acrylamide such as polyoxypropylene (meth) acrylamide, polyoxyethylene (1- (meth) acrylamide-1,1-dimethylpropyl) ester, polyoxyethylene vinyl ether, polyoxypropylene vinyl ether, polyoxyethylene Examples include allylamine, polyoxypropylene allylamine, polyoxyethylene vinylamine, and polyoxypropylene vinylamine.
更に、Ｎ−アクリルアミドメチルトリメチルアンモニウムクロライド、Ｎ−アクリルアミドエチルトリメチルアンモニウムクロライド、Ｎ−アクリルアミドプロピルトリメチルアンモニウムクロライド、２−アクリロキシエチルトリメチルアンモニウムクロライド、２−メタクリロキシエチルトリメチルアンモニウムクロライド、２−ヒドロキシ−３−メタクリロイルオキシプロピルトリメチルアンモニウムクロライド、アリルトリメチルアンモニウムクロライド、メタアリルトリメチルアンモニウムクロライド、３−ブテントリメチルアンモニウムクロライド、ジメチルジアリルアンモニウムクロリド、ジエチルジアリルアンモニウムクロライド等のカチオン基含有モノマー、アセトアセチル基含有モノマー、酢酸イソプロペニル、１−メトキシビニルアセテート、１，４−ジアセトキシ−２−ブテン、エチレンカーボネート等も挙げられる。又、重合温度を１００℃以上にすることにより、ＰＶＡ主鎖中に１，２−ジオールを１．６〜３．５モル％程度導入したものを使用することが可能である。 Further, N-acrylamidomethyltrimethylammonium chloride, N-acrylamidoethyltrimethylammonium chloride, N-acrylamidopropyltrimethylammonium chloride, 2-acryloxyethyltrimethylammonium chloride, 2-methacryloxyethyltrimethylammonium chloride, 2-hydroxy-3- Cationic group-containing monomers such as methacryloyloxypropyltrimethylammonium chloride, allyltrimethylammonium chloride, methallyltrimethylammonium chloride, 3-butenetrimethylammonium chloride, dimethyldiallylammonium chloride, diethyldiallylammonium chloride, acetoacetyl group-containing monomer, isopropenyl acetate , 1-me Alkoxy vinyl acetate, 1,4-diacetoxy-2-butene, may also be mentioned ethylene carbonate. Further, by setting the polymerization temperature to 100 ° C. or higher, it is possible to use a product in which about 1.6 to 3.5 mol% of 1,2-diol is introduced into the PVA main chain.
かくして得られるＰＶＡ系樹脂（Ａ）のケン化度は、９５モル％以上（さらには９７モル％以上、特には９８モル％以上であることが好ましく、かかるケン化度が９５モル％未満では１価乃至２価の金属塩と配合した際のハイドロゲル生成が困難となるため好ましくない。 The saponification degree of the PVA-based resin (A) thus obtained is 95 mol% or more (more preferably 97 mol% or more, particularly 98 mol% or more, and if the saponification degree is less than 95 mol%, 1 Since hydrogel formation becomes difficult when blended with a valent or divalent metal salt, it is not preferable.
本発明のＰＶＡ系樹脂（Ａ）の平均重合度（ＪＩＳ Ｋ６７２６に準拠して測定）は１５０〜４５００（さらには３００〜２８００、特には５００ 〜２６００）のものが好ましく、かかる平均重合度が１５０未満ではハイドロゲルの粘着力、柔軟性が不十分となる場合があり、４５００を超えるものは１，２−ジオール構造単位を多く導入することが困難となる場合があるため、好ましくない。 The average degree of polymerization (measured according to JIS K6726) of the PVA-based resin (A) of the present invention is preferably 150 to 4500 (more preferably 300 to 2800, particularly 500 to 2600), and the average degree of polymerization is 150. If it is less than 1, the adhesive strength and flexibility of the hydrogel may be insufficient, and those exceeding 4500 are not preferable because it may be difficult to introduce a large amount of 1,2-diol structural units.
また、本発明のＰＶＡ系樹脂（Ａ）中の一般式（１）で表される１，２−ジオール構造単位の含有量は、０．５〜３０モル％（さらには１．０〜１５モル％、特には１．５〜１０モル％）のものが好ましく、かかる含有量が０．５未満では本発明の効果である粘着性・柔軟性の維持、保水力の改善が充分ではなく、３０モル％を超えるものはポリビニルアルコール系樹脂の重合度が低くなりすぎたりするためか、ハイドロゲルの強度、粘着力が低くなる場合があるため、好ましくない。 Further, the content of the 1,2-diol structural unit represented by the general formula (1) in the PVA resin (A) of the present invention is 0.5 to 30 mol% (more preferably 1.0 to 15 mol). %, Especially 1.5 to 10 mol%), and when the content is less than 0.5, the adhesiveness and flexibility, which are the effects of the present invention, are not sufficiently improved, and the water retention is not sufficient. Those exceeding mol% are not preferable because the polymerization degree of the polyvinyl alcohol resin becomes too low, or the strength and adhesive strength of the hydrogel may be lowered.
次に、本発明で用いられるアルカリ土類金属の硝酸塩（Ｂ）について説明する。
アルカリ土類金属の硝酸塩（Ｂ）としては、硝酸ベリリウム、硝酸マグネシウム、硝酸カルシウム、硝酸ストロンチウム、硝酸バリウムなどのアルカリ土類金属の硝酸塩が挙げられる。
これらのアルカリ土類金属の硝酸塩（Ｂ）の中でも、硝酸マグネシウム、硝酸カルシウムが側鎖１，２―ジオールを有するポリビニルアルコールの結晶性を低下させる効果やジオール成分との相互作用が強く、金属塩を従来のポリビニルアルコールに比べ、より多く内包させることが出来る為か、ハイドロゲルの保水性、柔軟性、粘着性向上、ゲル強度向上の点で好適に用いられる。
It will now be described alkaline earth metal nitrate salts used in the present invention (B).
Examples of the alkaline earth metal nitrate salt of (B), nitric acid beryllium, magnesium nitrate, calcium nitrate, nitric acid strontium, an alkaline earth metal sulfate salts, such as barium nitrate.
Among these alkaline earth metal nitrate salt of (B), magnesium nitrate acid, the interaction between effects and diol component nitric acid calcium reduces the crystallinity of the polyvinyl alcohol having a side chain 1,2-diol It is strong and can be preferably used in terms of water retention, flexibility, adhesion improvement, and gel strength improvement of the hydrogel because it can contain more metal salt than conventional polyvinyl alcohol.
本発明は、上述の一般式（１）で表される１，２−ジオール構造単位を含有するＰＶＡ系樹脂（Ａ）とアルカリ土類金属の硝酸塩（Ｂ）を含有してなるハイドロゲルであり、かかるＰＶＡ系樹脂（Ａ）に対する金属塩（Ｂ）の含有割合（重量％）は、４０〜２５０％、好ましくは４０〜１７０％、更に好ましくは４０〜１５０％である。金属塩（Ｂ）の含有量がＰＶＡ（Ａ）に対して１％未満となる場合、ハイドロゲルの強度、保水性、粘着力の経時変化の低減効果等が低くなり、また２５０％を超えるとハイドロゲルの柔軟性が低下する場合があるため好ましくない。
The present invention is a hydrogel comprising a PVA-based resin (A) and the alkaline earth metal nitrate salt containing a 1,2-diol structural unit represented by the above general formula (1) (B) The content (% by weight) of the metal salt (B) relative to the PVA resin (A) is 40 to 250%, preferably 40 to 170%, and more preferably 40 to 150%. When the content of the metal salt (B) is less than 1% with respect to the PVA (A), the hydrogel strength, water retention, the effect of reducing changes in adhesive strength with time, etc. are reduced, and when the content exceeds 250%. This is not preferable because the flexibility of the hydrogel may be reduced.
次に本発明のハイドロゲルの製造法について説明する。
ＰＶＡ系樹脂の水溶液を調整する際に、該ＰＶＡ水溶液中に各種無機塩を添加させながら溶解作業を行う必要がある。通常、未変性ＰＶＡは、鹸化度９５モル％以上になると常温水には、溶解し難くなる。従って、このような常温で溶解し難いＰＶＡを無機塩存在下で溶解するには、温度を９７℃以上に上げたり、オートクレーブや高圧クッカー等を使用して１１０℃程度で溶解しなければならないという問題があった。しかし、本発明の側鎖１，２―ジオールを有するＰＶＡならば、無機塩存在下でも、オートクレーブや高圧クッカーを用いなくても充分に溶解することが可能性であり、また、従来のＰＶＡの様な溶解時の発泡の問題なく、無機塩含有ＰＶＡ水溶液の調整時の作業性を大幅に改善することが可能となった。
本発明のハイドロゲルの製造法は特に限定されないが、例えばＰＶＡ系樹脂（Ａ）とアルカリ土類金属の硝酸塩（Ｂ）を含有する水溶液を冷却ゲル化させる方法が好ましく用いられる。
かかる冷却ゲル化法による本発明のハイドロゲルの製造法において、ＰＶＡ系樹脂（Ａ）とアルカリ土類金属の硝酸塩（Ｂ）を含有する水溶液の濃度は１０〜８０％（重量％）（さらには２５〜７５％、特には４０〜７５％）であることが好ましい。かかる濃度が１０重量％未満ではハイドロゲルの保水性、強度、粘着力が低くなりすぎる場合があり、逆に８０重量％を超えるとハイドロゲルの粘着性が低下したり、柔軟性が低下する場合があるため好ましくない。
Next, the manufacturing method of the hydrogel of this invention is demonstrated.
When adjusting the aqueous solution of the PVA-based resin, it is necessary to perform a dissolving operation while adding various inorganic salts to the PVA aqueous solution. Normally, unmodified PVA becomes difficult to dissolve in normal temperature water when the saponification degree is 95 mol% or more. Therefore, in order to dissolve such PVA that is difficult to dissolve at room temperature in the presence of an inorganic salt, the temperature must be raised to 97 ° C. or higher or dissolved at about 110 ° C. using an autoclave, a high-pressure cooker, or the like. There was a problem. However, the PVA having a side chain 1,2-diol of the present invention can be sufficiently dissolved even in the presence of an inorganic salt without using an autoclave or a high-pressure cooker. It was possible to significantly improve the workability at the time of preparing the inorganic salt-containing PVA aqueous solution without the problem of foaming during such dissolution.
Preparation of hydrogels of the present invention is not particularly limited, for example, a method of an aqueous solution containing a PVA-based resin (A) and the alkaline earth metal nitrate salt of (B) is cooled gel is preferably used.
In the preparation of hydrogels of the present invention by such cooling gelation method, the concentration of the aqueous solution containing the PVA-based resin (A) and the alkaline earth metal nitrate salt of (B) 10 to 80% (wt%) (more Is preferably 25 to 75%, particularly 40 to 75%). If the concentration is less than 10% by weight, the water retention, strength, and adhesive strength of the hydrogel may be too low. On the other hand, if the concentration exceeds 80% by weight, the hydrogel's adhesiveness may decrease or the flexibility may decrease. This is not preferable.
かかる水溶液を使用目的に応じた任意の形状の容器や鋳型中に、あるいは金属板、ガラス板、プラスチック板やフィルム上に流延した後、低温条件下に置くことで本発明のハイドロゲルが得られる。その場合の温度は４０℃〜−３０℃（さらには２５〜−２０℃、特には８〜−１０℃）であることが好ましい。かかる温度が４０℃より高いとハイドロゲルの生成が困難となる場合があり、逆に−３０℃より低温の場合は工業的な生産性の面において問題となる場合があるため好ましくない。 The hydrogel of the present invention can be obtained by casting the aqueous solution in a container or mold of any shape according to the purpose of use, or after casting it on a metal plate, glass plate, plastic plate or film, and then placing it under low temperature conditions. It is done. The temperature in that case is preferably 40 ° C. to −30 ° C. (further 25 to −20 ° C., particularly 8 to −10 ° C.). When the temperature is higher than 40 ° C., it may be difficult to form a hydrogel. On the other hand, when the temperature is lower than −30 ° C., it may be problematic in terms of industrial productivity.
かくして得られたハイドロゲルは、ゲル強度を向上させる目的で各種後処理を施してもよい。かかる後処理としては、冷却状態で真空乾燥し水分含有量を調整する方法、一旦融解させた後、再び冷却ゲル化させ、そのサイクルを繰り返して結晶化度を向上させる方法、氷点以上の温度に一定時間保持して結晶成長させる方法、放射線、電子線、紫外線を照射して架橋密度を上げる方法などが挙げられ、これらを組み合せることも可能である。 The hydrogel thus obtained may be subjected to various post-treatments for the purpose of improving the gel strength. As such post-treatment, a method of adjusting the water content by vacuum drying in a cooled state, a method of once melting and then cooling and gelling again, repeating the cycle to improve the crystallinity, and a temperature above the freezing point Examples include a method of growing crystals by holding for a certain period of time, a method of increasing the crosslink density by irradiating with radiation, electron beam, or ultraviolet ray, and these can be combined.
本発明におけるハイドロゲルは、上述したように一般式（１）で表される１，２−ジオール構造単位を含有するＰＶＡ系樹脂（Ａ）と、アルカリ土類金属の硝酸塩（Ｂ）および水を含有するものであり、固体でありながら分子間に多量の水分を安定して含有するため、弾力性と柔軟性を有するものである。
かかるハイドロゲル中の水の含有量は、通常、２０〜９０％（重量％）である。
また、かかるハイドロゲルは保水性および粘着力保持性に優れており、後述で定義される離水率が２０％以下、好ましくは１７％以下である。また、後述で定義される３６時間後の粘着面積保持率が６０％以上、好ましくは７０％以上である。
なお、ハイドロゲルの構造および大きさは特に限定されないが、例えば粒径１〜１０ｍｍの粒状物として、あるいは厚さ０．５〜５ｍｍのシート状物として使用される。
Hydrogel in the present invention, the PVA-based resin containing a 1,2-diol structural unit represented by the general formula (1) as described above (A), alkaline earth metal nitrate salt of (B) and water Since it contains a solid and contains a large amount of moisture stably between molecules, it has elasticity and flexibility.
The content of water in the hydrogel is usually 20 to 90% (% by weight).
Such hydrogel is excellent in water retention and adhesive strength retention, and the water separation rate defined below is 20% or less, preferably 17% or less. Moreover, the adhesion area retention after 36 hours defined later is 60% or more, preferably 70% or more.
The structure and size of the hydrogel are not particularly limited. For example, the hydrogel is used as a granular material having a particle size of 1 to 10 mm, or as a sheet material having a thickness of 0.5 to 5 mm.
本発明のハイドロゲルは保水性および生体への粘着性に優れるものであるが、さらにこれらの特性を向上させるためにグリセリン、エチレングリコールなどの多価アルコール類、シクロデキストリン、プルラン、グアガムなどの多糖類、ゼラチン、カルボキシメチルセルロースなどのセルロース誘導体、デンプン類、ポリアクリル酸およびそのナトリウム塩、ポリエチレングリコール、ポリビニルピロリドン、ポリアクリルアミドなどの水溶性高分子類を併用することも可能である。また、ゲル強度や硬度を向上させるため、シリカ、クレー、タルク、炭酸カルシウムなどの無機粉体、天然繊維、合成繊維などの短繊維、あるいはその織物や不織布などをハイドロゲル製造時に水溶液中に共存させることで、これらの材料とハイドロゲルからなる複合材料とすることも可能である。 The hydrogel of the present invention is excellent in water retention and adhesiveness to a living body, but in order to further improve these properties, polyhydric alcohols such as glycerin and ethylene glycol, cyclodextrins, pullulans, guar gums and the like It is also possible to use saccharides, cellulose, cellulose derivatives such as carboxymethylcellulose, water-soluble polymers such as starches, polyacrylic acid and its sodium salt, polyethylene glycol, polyvinylpyrrolidone and polyacrylamide. To improve gel strength and hardness, inorganic powders such as silica, clay, talc and calcium carbonate, short fibers such as natural fibers and synthetic fibers, or woven fabrics and non-woven fabrics coexist in an aqueous solution during hydrogel production. By making it, it is also possible to set it as the composite material which consists of these materials and hydrogel.
また、本発明のハイドロゲルを経皮吸収製剤の基材あるいは創傷被覆材として適用させる場合には、ハイドロゲル中に経皮吸収性薬剤、経皮吸収促進剤、消毒剤、抗菌剤、血行改善薬、生理活性物質などを含有させれば良く、その製造法としては、ゲル化前の水溶液に薬剤を添加しゲル化させる方法が好ましい。
その他、本発明の目的を阻害しない範囲において、吸水性樹脂、ｐＨ調節剤、界面活性剤、防腐剤、防黴剤、消泡剤、多価アルコール等を添加することも可能である。
また、本発明のハイドロゲルの用途として生体研究用、生体治療用、生体診断用等の生体電極用のイオン導電性粘着剤、及び経皮吸収製剤用、冷却治療用等の含水貼附剤の基剤として用いられたり、帯電を防止能を有するハイドロゲル組成物にも有効である。
In addition, when the hydrogel of the present invention is applied as a base material or a wound dressing for a percutaneous absorption preparation, a percutaneous absorption agent, a percutaneous absorption accelerator, a disinfectant, an antibacterial agent, and blood circulation improvement are contained in the hydrogel. A drug, a physiologically active substance, or the like may be contained, and the production method is preferably a method in which a drug is added to an aqueous solution before gelation and gelled.
In addition, it is also possible to add a water-absorbing resin, a pH adjuster, a surfactant, an antiseptic, an antifungal agent, an antifoaming agent, a polyhydric alcohol, and the like as long as the object of the present invention is not impaired.
In addition, the hydrogel of the present invention can be used for ionic conductive pressure-sensitive adhesives for biological electrodes for biological research, biological treatment, biodiagnosis and the like, and water-containing adhesives for transdermal absorption preparations, cooling treatments, etc. It is also effective for a hydrogel composition that is used as a base or has an ability to prevent electrification.
以下に、本発明を実施例を挙げて説明するが、本発明はかかる実施例のみに限定されるものではない。
尚、例中、「部」、「％」とあるのは、断りのない限り重量基準を意味する。
Hereinafter, the present invention will be described with reference to examples. However, the present invention is not limited to the examples.
In the examples, “parts” and “%” mean weight basis unless otherwise specified.
製造例１：ＰＶＡ系樹脂（Ａ１）
還流冷却器、滴下漏斗、撹拌機を備えた反応缶に、酢酸ビニル１０００ｇ、メタノール５０ｇ、３，４−ジアセトキシ−１−ブテン１２０ｇ（６モル％対仕込み酢酸ビニル）を仕込み、アゾビスイソブチロニトリルを０．０３モル％（対仕込み酢酸ビニル）投入し、撹拌しながら窒素気流下で温度を上昇させ重合を開始した酢酸ビニルの重合率が７２％となった時点で、ｍ−ジニトロベンゼンを所定量添加して重合を終了し、続いて、メタノール蒸気を吹き込む方法により未反応の酢酸ビニルモノマーを系外に除去し共重合体のメタノール溶液を得た。
次いで、該溶液をメタノールで希釈し、濃度４０％に調整してニーダーに仕込み、溶液温度を４０℃に保ちながら、水酸化ナトリウムの２％メタノール溶液を共重合体中の酢酸ビニル構造単位及び３，４−ジアセトキシ−１−ブテン構造単位の合計量１モルに対して８ミリモルとなる割合で加えてケン化を行った。ケン化が進行すると共にケン化物が析出し、粒子状となった時点で、濾別し、メタノールでよく洗浄して熱風乾燥機中で乾燥し、ＰＶＡ系樹脂（Ａ１）を得た。
得られたＰＶＡ系樹脂（Ａ１）のケン化度は、残存酢酸ビニル及び３，４−ジアセトキシ−１−ブテンの加水分解に要するアルカリ消費量で分析を行ったところ、９９．５モル％であり、平均重合度は、ＪＩＳ Ｋ ６７２６に準して分析を行ったところ、１４５０であった。また、１，２−ジオール構造単位の含有量は1Ｈ−ＮＭＲ（内部標準物質；テトラメチルシラン）で測定して算出したところ６．２モル％であった。なお、ＮＭＲ測定には日本ブルカー社製「ＡＶＡＮＣＥ ＤＰＸ４００」を用いた。
Production Example 1: PVA resin (A1)
A reaction vessel equipped with a reflux condenser, a dropping funnel, and a stirrer was charged with 1000 g of vinyl acetate, 50 g of methanol, and 120 g of 3,4-diacetoxy-1-butene (6 mol% vs. charged vinyl acetate), and azobisisobutyro Nitrile was added in an amount of 0.03 mol% (compared with vinyl acetate), and the temperature was raised in a nitrogen stream while stirring to start polymerization. When the polymerization rate of vinyl acetate reached 72%, m-dinitrobenzene was added. A predetermined amount was added to complete the polymerization, and then unreacted vinyl acetate monomer was removed from the system by a method of blowing methanol vapor to obtain a methanol solution of the copolymer.
Next, the solution was diluted with methanol, adjusted to a concentration of 40%, charged into a kneader, and a 2% methanol solution of sodium hydroxide was added to the vinyl acetate structural unit and 3% in the copolymer while keeping the solution temperature at 40 ° C. The saponification was carried out at a ratio of 8 mmol per 1 mol of the total amount of 1,4-diacetoxy-1-butene structural units. When saponification progressed and saponified product was precipitated and became particulate, it was separated by filtration, washed well with methanol and dried in a hot air dryer to obtain PVA resin (A1).
The saponification degree of the obtained PVA-based resin (A1) was 99.5 mol% when analyzed by the alkali consumption required for hydrolysis of residual vinyl acetate and 3,4-diacetoxy-1-butene. The average degree of polymerization was 1450 when analyzed according to JIS K 6726. The content of the 1,2-diol structural unit was 6.2 mol% when calculated by 1 H-NMR (internal standard substance: tetramethylsilane). In addition, “AVANCE DPX400” manufactured by Nippon Bruker Co., Ltd. was used for NMR measurement.
製造例２：ＰＶＡ系樹脂（Ａ２）
製造例１において、ケン化の途中でサンプルを抜き取ることによりＰＶＡ系樹脂（Ａ２）（部分鹸化物：ケン化度 ９７．５モル％）を得た。
Production Example 2: PVA resin (A2)
In Production Example 1, a PVA-based resin (A2) (partially saponified product: degree of saponification: 97.5 mol%) was obtained by extracting a sample during the saponification.
製造例３：ＰＶＡ系樹脂（Ａ３）
還流冷却器、滴下漏斗、撹拌機を備えた反応缶に、酢酸ビニル１３００ｇ、メタノール
１９０ｇ、３，４−ジアセトキシ−１−ブテン６０．５ｇ（２．２８モル％対仕込み酢酸ビニル）を仕込み、アゾビスイソブチロニトリルを０．０６モル％（対仕込み酢酸ビニル）投入し、撹拌しながら窒素気流下で温度を上昇させ、６７℃で重合を開始したと同時に３，４−ジアセトキシー１−ブテンの５．４％メタノール溶液を均一に滴下仕込みを行ない酢酸ビニルの重合率が８５．３％となった時点で、ｍ−ジニトロベンゼンを所定量添加して重合を終了し、続いて、メタノール蒸気を吹き込む方法により未反応の酢酸ビニルモノマーを系外に除去し共重合体のメタノール溶液を得た。
次いで、該溶液をメタノールで希釈し、濃度４０％に調整してニーダーに仕込み、溶液温度を４０℃に保ちながら、水酸化ナトリウムの２％メタノール溶液を共重合体中の酢酸ビニル構造単位及び３，４−ジアセトキシ−１−ブテン構造単位の合計量１モルに対して ９ミリモルとなる割合で加えてケン化を行った。ケン化が進行すると共にケン化物が析出し、粒子状となった時点で、濾別し、メタノールでよく洗浄して熱風乾燥機中で乾燥し、ＰＶＡ系樹脂（Ａ３）を得た。
得られたＰＶＡ系樹脂（Ａ３）のケン化度は、残存酢酸ビニル及び３，４−ジアセトキシ−１−ブテンの加水分解に要するアルカリ消費量で分析を行ったところ、９９．６モル％であり、平均重合度は、ＪＩＳ Ｋ ６７２６に準して分析を行ったところ、１３２０であった。また、１，２−ジオール構造単位の含有量は1Ｈ−ＮＭＲで測定して算出したところ３．２モル％であった。
Production Example 3: PVA resin (A3)
A reaction vessel equipped with a reflux condenser, a dropping funnel and a stirrer was charged with 1300 g of vinyl acetate, 190 g of methanol, and 60.5 g of 3,4-diacetoxy-1-butene (2.28 mol% with respect to vinyl acetate charged). Bisisobutyronitrile was added in an amount of 0.06 mol% (vs. vinyl acetate), and the temperature was increased under a nitrogen stream while stirring. The polymerization was started at 67 ° C. and at the same time 3,4-diacetoxy-1-butene When a 5.4% methanol solution was uniformly added dropwise and the polymerization rate of vinyl acetate reached 85.3%, a predetermined amount of m-dinitrobenzene was added to complete the polymerization, and then methanol vapor was supplied. Unreacted vinyl acetate monomer was removed out of the system by a blowing method to obtain a methanol solution of the copolymer.
Next, the solution was diluted with methanol, adjusted to a concentration of 40%, charged into a kneader, and a 2% methanol solution of sodium hydroxide was added to the vinyl acetate structural unit and 3% in the copolymer while keeping the solution temperature at 40 ° C. The saponification was carried out by adding 9 mmol per 1 mol of the total amount of 1,4-diacetoxy-1-butene structural units. When saponification progressed and saponified substance precipitated and became particulate, it was filtered, washed well with methanol and dried in a hot air dryer to obtain a PVA resin (A3).
The saponification degree of the obtained PVA-based resin (A3) was 99.6 mol% when analyzed by the alkali consumption required for hydrolysis of residual vinyl acetate and 3,4-diacetoxy-1-butene. The average degree of polymerization was 1320 when analyzed according to JIS K 6726. The content of 1,2-diol structural unit was 3.2 mol% when calculated by measurement with 1 H-NMR.
製造例４：ＰＶＡ系樹脂（Ａ４）
製造例１において、３，４−ジアセトキシ−１−ブテンの配合量を３００ｇ（１５モル％対仕込み酢酸ビニル）とし、水酸化ナトリウムの２％メタノール溶液の添加量を、共重合体中の酢酸ビニル構造単位および３，４−ジアセトキシ−１−ブテン構造単位の合計量１モルに対して１１ ミリモルとなる割合にした以外は、製造例１と同様に重合およびケン化を行ない、ケン化度 ９９．２モル％、平均重合度９５０、１，２−ジオール構造単位の含有量１４．９モル％のＰＶＡ系樹脂（Ａ４）を得た。
Production Example 4: PVA resin (A4)
In Production Example 1, the blending amount of 3,4-diacetoxy-1-butene was 300 g (15 mol% with respect to the charged vinyl acetate), and the addition amount of a 2% methanol solution of sodium hydroxide was changed to vinyl acetate in the copolymer. Polymerization and saponification were carried out in the same manner as in Production Example 1 except that the amount was 11 mmol per 1 mol of the total amount of the structural unit and 3,4-diacetoxy-1-butene structural unit. A PVA resin (A4) having 2 mol%, an average degree of polymerization of 950, and a content of 1,2-diol structural units of 14.9 mol% was obtained.
製造例５：ＰＶＡ系樹脂（Ａ５）
還流冷却器、滴下漏斗、撹拌機を備えた反応缶に、酢酸ビニル１５００ｇ、メタノール
１５０ｇ、グリセリンモノアリルエーテル１３８ｇ（６モル％対仕込み酢酸ビニル）を仕込み、アゾビスイソブチロニトリルを０．３モル％（対仕込み酢酸ビニル）投入し、撹拌しながら窒素気流下で温度を上昇させ、重合を開始した。酢酸ビニルの重合率が８１％となった時点で、ｍ−ジニトロベンゼンを所定量添加して重合を終了し、続いて、メタノール蒸気を吹き込む方法により未反応の酢酸ビニルモノマーを系外に除去し共重合体のメタノール溶液を得た。
次いで、該溶液をメタノールで希釈し、濃度５５％に調整してニーダーに仕込み、溶液温度を４０℃に保ちながら、水酸化ナトリウムの２％メタノール溶液を共重合体中の酢酸ビニル構造単位１モルに対して６ミリモルとなる割合で加えてケン化を行った。ケン化が進行すると共にケン化物が析出し、粒子状となった時点で、濾別し、メタノールでよく洗浄して熱風乾燥機中で乾燥し、ＰＶＡ系樹脂（Ａ５）を得た。
得られたＰＶＡ系樹脂（Ａ５）のケン化度は、９７．８モル％であり、平均重合度は、４６０であった。また、１，２−ジオール構造単位の含有量は５．８モル％であった。
Production Example 5: PVA resin (A5)
A reaction vessel equipped with a reflux condenser, a dropping funnel and a stirrer was charged with 1500 g of vinyl acetate, 150 g of methanol, and 138 g of glyceryl monoallyl ether (6 mol% with respect to the charged vinyl acetate), and 0.3% of azobisisobutyronitrile. Mol% (vs. vinyl acetate charged) was added and the temperature was raised under a nitrogen stream while stirring to initiate polymerization. When the vinyl acetate polymerization rate reaches 81%, a predetermined amount of m-dinitrobenzene is added to complete the polymerization, and then unreacted vinyl acetate monomer is removed from the system by blowing methanol vapor. A methanol solution of the copolymer was obtained.
Next, the solution was diluted with methanol, adjusted to a concentration of 55%, charged into a kneader, and while maintaining the solution temperature at 40 ° C., a 2% methanol solution of sodium hydroxide was added to 1 mol of vinyl acetate structural unit in the copolymer. The saponification was carried out at a ratio of 6 mmol with respect to the amount. When saponification progressed and saponified product was precipitated and became particulate, it was filtered off, washed well with methanol and dried in a hot air dryer to obtain a PVA resin (A5).
The saponification degree of the obtained PVA resin (A5) was 97.8 mol%, and the average polymerization degree was 460. The content of the 1,2-diol structural unit was 5.8 mol%.
製造例６：ＰＶＡ系樹脂（Ａ６）
還流冷却器、滴下漏斗、撹拌機を備えた反応缶に、酢酸ビニル１３００ｇ、メタノール１９０ｇ、ビニルエチレンカーボネート４０．１ｇ（２．２８モル％対仕込み酢酸ビニル）を仕込み、アゾビスイソブチロニトリルを０．０６モル％（対仕込み酢酸ビニル）投入し、撹拌しながら窒素気流下で温度を上昇させ、６７℃で重合を開始したと同時にビニルエチレンカーボネートを含む１０．１７％メタノール溶液を仕込みHANNA法に従って重合を行ない、重合率８５．３％までに１１６ｍｌ仕込んだ。酢酸ビニルの重合率が８５．３％となった時点で、ｍ−ジニトロベンゼンを所定量添加して重合を終了し、続いて、メタノール蒸気を吹き込む方法により未反応の酢酸ビニルモノマーを系外に除去し共重合体のメタノール溶液を得た。
次いで、該溶液をメタノールで希釈し、濃度３０％に調整してニーダーに仕込み、溶液温度を４０℃に保ちながら、水酸化ナトリウムの２％メタノール溶液を共重合体中の酢酸ビニル構造単位１モルに対して９ミリモルとなる割合で加えてケン化を行った。ケン化が進行すると共にケン化物が析出し、粒子状となった時点で、濾別し、メタノールでよく洗浄して熱風乾燥機中で乾燥し、ＰＶＡ系樹脂（Ａ６）を得た。
得られたＰＶＡ系樹脂（Ａ６）のケン化度は、９９．６モル％であり、平均重合度は、１３６０であった。また、１，２−ジオール構造単位の含有量は３．１モル％であった。
Production Example 6: PVA resin (A6)
A reactor equipped with a reflux condenser, a dropping funnel, and a stirrer was charged with 1300 g of vinyl acetate, 190 g of methanol, and 40.1 g of vinyl ethylene carbonate (2.28 mol% with respect to the charged vinyl acetate), and azobisisobutyronitrile was added. 0.06 mol% (vs. charged vinyl acetate) was added, the temperature was increased under nitrogen flow while stirring, and polymerization was started at 67 ° C. At the same time, a 10.17% methanol solution containing vinyl ethylene carbonate was added and HANNA method Polymerization was conducted according to the above, and 116 ml was charged to a polymerization rate of 85.3%. When the polymerization rate of vinyl acetate reached 85.3%, a predetermined amount of m-dinitrobenzene was added to complete the polymerization, and then unreacted vinyl acetate monomer was removed from the system by blowing methanol vapor. Removal of the copolymer gave a methanol solution of the copolymer.
Next, the solution was diluted with methanol, adjusted to a concentration of 30%, charged into a kneader, and while maintaining the solution temperature at 40 ° C., a 2% methanol solution of sodium hydroxide was added to 1 mol of vinyl acetate structural units in the copolymer. The saponification was carried out at a ratio of 9 mmol with respect to the amount. When saponification progressed and saponified substance precipitated and became particulate, it was filtered, washed well with methanol and dried in a hot air dryer to obtain a PVA resin (A6).
The saponification degree of the obtained PVA-based resin (A6) was 99.6 mol%, and the average polymerization degree was 1360. The content of 1,2-diol structural unit was 3.1 mol%.
製造例７：ＰＶＡ系樹脂（Ａ７）
還流冷却器、滴下漏斗、撹拌機を備えた反応缶に、酢酸ビニル１０００ｇ、メタノール１００ｇ、２，２−ジメチル−４−ビニル−１，３−ジオキソラン１４．９ｇ（１モル％対仕込み酢酸ビニル）を仕込み、アゾビスイソブチロニトリルを０．０４５モル％（対仕込み酢酸ビニル）投入し、撹拌しながら窒素気流下で温度を上昇させ、６５℃で重合を開始した。酢酸ビニルの重合率が９０％となった時点で、ｍ−ジニトロベンゼンを所定量添加して重合を終了し、続いて、メタノール蒸気を吹き込む方法により未反応の酢酸ビニルモノマーを系外に除去し共重合体のメタノール溶液を得た。
次いで、該溶液をメタノールで希釈し、濃度３０％に調整してニーダーに仕込み、溶液温度を４０℃に保ちながら、水酸化ナトリウムの２％メタノール溶液を共重合体中の酢酸ビニル構造単位１モルに対して９ミリモルとなる割合で加えてケン化を行った。ケン化が進行すると共にケン化物が析出し、遂には粒子状となった。かかるケン化物を３Ｎの塩酸（水／メタノール＝１／１の混合溶媒）中に分散させ、６０℃で脱ケタール化を行ない、生成したＰＶＡ系樹脂（Ａ７）を濾別し、メタノールでよく洗浄して熱風乾燥機中で乾燥し、目的物を得た。
得られたＰＶＡ系樹脂（Ａ７）のケン化度は、９９．３モル％であり、平均重合度は、１１１０であった。また、１，２−ジオール構造単位の含有量は０．９５モル％であった。
Production Example 7: PVA resin (A7)
In a reaction vessel equipped with a reflux condenser, a dropping funnel, and a stirrer, 1000 g of vinyl acetate, 100 g of methanol, 14.9 g of 2,2-dimethyl-4-vinyl-1,3-dioxolane (1 mol% to charged vinyl acetate) The azobisisobutyronitrile was added in an amount of 0.045 mol% (vs. prepared vinyl acetate), the temperature was raised under a nitrogen stream while stirring, and polymerization was started at 65 ° C. When the polymerization rate of vinyl acetate reaches 90%, a predetermined amount of m-dinitrobenzene is added to complete the polymerization, and then unreacted vinyl acetate monomer is removed from the system by blowing methanol vapor. A methanol solution of the copolymer was obtained.
Next, the solution was diluted with methanol, adjusted to a concentration of 30%, charged into a kneader, and while maintaining the solution temperature at 40 ° C., a 2% methanol solution of sodium hydroxide was added to 1 mol of vinyl acetate structural units in the copolymer. The saponification was carried out at a ratio of 9 mmol with respect to the amount. Saponification progressed as saponification progressed, and finally became particulate. This saponified product is dispersed in 3N hydrochloric acid (mixed solvent of water / methanol = 1/1), deketalized at 60 ° C., and the resulting PVA resin (A7) is filtered off and washed thoroughly with methanol. And it dried in the hot air dryer, and obtained the target object.
The saponification degree of the obtained PVA resin (A7) was 99.3 mol%, and the average polymerization degree was 1110. The content of 1,2-diol structural unit was 0.95 mol%.
実施例１
ＰＶＡ系樹脂（Ａ１）１００部および硝酸カルシウム（Ｂ）１３０部を含む濃度６５％の水溶液（８０℃で１時間加熱溶解）を調製し、かかる水溶液をＰＥＴフィルム上に流延し、これを−１０℃のフリーザー中に一昼夜おいてゲル化させ、厚さ約１ｍｍ、重量固形分６４％のハイドロゲルシートを得た。かかるシートを用いて、以下の項目を評価した。結果を表１に示す。
Example 1
A 65% strength aqueous solution (heat-dissolved at 80 ° C. for 1 hour) containing 100 parts of PVA resin (A1) and 130 parts of calcium nitrate (B) was prepared, and this aqueous solution was cast on a PET film. Gelation was carried out in a freezer at 10 ° C. all day and night to obtain a hydrogel sheet having a thickness of about 1 mm and a weight solid content of 64%. Using the sheet, the following items were evaluated. The results are shown in Table 1.
（離水率）
得られたハイドロゲルシートを５ｃｍ×５ｃｍに切り出し、２３℃、５５％ＲＨの恒温恒湿器中に４８時間吊り下げ、離水率（％）を測定した。なお、離水率（％）の算出にあたっては、試験前のハイドロゲルシートの重量（Ｙ1）および試験後のハイドロゲルシートの重量（Ｙ2）（いずれもｇ）を求め、下式にて離水率（％）を求めた。
離水率（％）＝[（Ｙ1―Ｙ2）／Ｙ1]×１００
(Water separation rate)
The obtained hydrogel sheet was cut into 5 cm × 5 cm, suspended in a constant temperature and humidity chamber at 23 ° C. and 55% RH for 48 hours, and the water separation rate (%) was measured. In calculating the water separation rate (%), the weight of the hydrogel sheet before the test (Y 1 ) and the weight of the hydrogel sheet after the test (Y 2 ) (both are g) were calculated, and the water separation rate ( %).
Water separation rate (%) = [(Y 1 −Y 2 ) / Y 1 ] × 100
（粘着面積保持率）
得られたハイドロゲルシートを５ｃｍ×５ｃｍに切り出し、被験者１０名の肩に貼付し３６時間後と４８時間後のハイドロゲルシートと皮膚との粘着面積（Ｘ）（ｃｍ2）を測定、下式にて粘着面積保持率（％）を算出した。表１には１０名の平均値を示す。
粘着面積保持率（％）＝（Ｘ／２５）×１００
(Adhesive area retention rate)
The obtained hydrogel sheet was cut out to 5 cm × 5 cm, stuck on the shoulders of 10 subjects, and the adhesion area (X) (cm 2 ) between the hydrogel sheet and the skin after 36 hours and 48 hours was measured. The adhesion area retention rate (%) was calculated. Table 1 shows the average value of 10 people.
Adhesive area retention rate (%) = (X / 25) × 100
実施例２〜７
実施例１において、ＰＶＡ系樹脂（Ａ１）に替えて、製造例２〜７によるＰＶＡ系樹脂（Ａ２〜Ａ７）を用いた以外は実施例１と同様にしてハイドロゲルシートを得て、同様に評価を行った。結果を表１に示す。
Examples 2-7
In Example 1, it replaced with PVA-type resin (A1), obtained the hydrogel sheet similarly to Example 1 except having used PVA-type resin (A2-A7) by manufacture examples 2-7, and evaluated similarly. Went. The results are shown in Table 1.
実施例８
実施例１において、ＰＶＡ系樹脂（Ａ１）１００部、硝酸カルシウム（Ｂ）２００部とした以外は実施例１と同様にしてハイドロゲルシート得て、同様に評価を行った。結果を表１に示す。
Example 8
A hydrogel sheet was obtained in the same manner as in Example 1 except that 100 parts of PVA resin (A1) and 200 parts of calcium nitrate (B) were used. The results are shown in Table 1.
実施例９
実施例１において、硝酸カルシウム（Ｂ）に替えて硝酸マグネシウム（Ｂ）を用いた以外は実施例１と同様にしてハイドロゲルシートを得て、同様に評価を行った。結果を表１に示す。
Example 9
In Example 1, a hydrogel sheet was obtained in the same manner as in Example 1 except that magnesium nitrate (B) was used instead of calcium nitrate (B), and evaluation was performed in the same manner. The results are shown in Table 1.
比較例１
実施例１において、硝酸カルシウム（Ｂ）を用いなかった以外は実施例１と同様にしたがハイドロゲルシートは得られなかったので、評価は出来なかった。
Comparative Example 1
Example 1 was the same as Example 1 except that calcium nitrate (B) was not used. However, no hydrogel sheet was obtained, so evaluation could not be performed.
比較例２
実施例１において、ＰＶＡ系樹脂（Ａ１）に替えて、ケン化度９９．９モル％、平均重合度１４００の未変性ＰＶＡ系樹脂を用い無機塩含有のＰＶＡ水溶液を調整時に高圧クッカーを用いて１１０℃、４０分かけて溶解作業を行った以外は実施例１と同様にしてハイドロゲルシートを得て、同様に評価を行った。結果を表１に示す。
Comparative Example 2
In Example 1, in place of the PVA-based resin (A1), an inorganic salt-containing PVA aqueous solution was prepared using an unmodified PVA-based resin having a saponification degree of 99.9 mol% and an average polymerization degree of 1400, using a high-pressure cooker. A hydrogel sheet was obtained and evaluated in the same manner as in Example 1 except that the melting operation was performed at 110 ° C. for 40 minutes. The results are shown in Table 1.
〔表１〕樹脂組成物の特性
[Table 1] Properties of resin composition
本発明のハイドロゲルは生体に対する粘着力が大きく、保水性に優れ、粘着力の経時低下が少ないため長時間にわたり良好な粘着力が得られることから、創傷被覆材、経皮吸収剤の基材、生体電極材料等の材料として非常に有用である。
Since the hydrogel of the present invention has high adhesive strength to living organisms, excellent water retention, and less adhesive strength with time, good adhesive strength can be obtained over a long period of time. It is very useful as a material such as a bioelectrode material.
Claims (10)
Ｒ6はそれぞれ独立して水素又はＲ7−ＣＯ−（式中、Ｒ7はアルキル基である）である］ The hydrogel according to claim 1, wherein the polyvinyl alcohol resin (A) is obtained by saponifying a copolymer of a vinyl ester monomer and a compound represented by the general formula (2).
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| JP5178303B2 (en) * | 2007-04-27 | 2013-04-10 | 日本合成化学工業株式会社 | Rice hull molded body and method for producing the same |
| JP5235364B2 (en) * | 2007-09-05 | 2013-07-10 | 日本合成化学工業株式会社 | Method for producing polyvinyl alcohol resin having 1,2-diol structure in side chain |
| JP5091011B2 (en) * | 2008-05-29 | 2012-12-05 | 日本合成化学工業株式会社 | Hairdresser |
| JP5335326B2 (en) * | 2008-08-29 | 2013-11-06 | 株式会社クラレ | Production method of polyvinyl alcohol film |
| EP2426172B1 (en) * | 2009-04-28 | 2014-05-14 | The Nippon Synthetic Chemical Industry Co., Ltd. | Polyvinyl alcohol based resin composition |
| JP2013124317A (en) * | 2011-12-15 | 2013-06-24 | Kuraray Co Ltd | Polyvinyl alcohol-based polymer and method for producing hydrolyzable cellulose using the same |
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| JP2824460B2 (en) * | 1988-03-11 | 1998-11-11 | 株式会社ビーエムジー | Adhesive PVA hydrogel composition |
| JPH04272935A (en) * | 1991-02-28 | 1992-09-29 | Japan Synthetic Rubber Co Ltd | Production of transparent gel |
| JPH04283511A (en) * | 1991-03-13 | 1992-10-08 | Sansho Kaken Kk | Two-agent type skin spreading material |
| JPH04338326A (en) * | 1991-05-15 | 1992-11-25 | Sansho Kaken Kk | Material for skin application |
| JP3916941B2 (en) * | 2000-12-15 | 2007-05-23 | 日本合成化学工業株式会社 | New vinyl alcohol resin and its use |
| JP2002241433A (en) * | 2000-12-15 | 2002-08-28 | Nippon Synthetic Chem Ind Co Ltd:The | Novel vinyl alcohol resin and its use |
| JP4079723B2 (en) * | 2002-08-20 | 2008-04-23 | 日本合成化学工業株式会社 | Melt molded product |
| JP4079806B2 (en) * | 2003-03-20 | 2008-04-23 | 日本合成化学工業株式会社 | Polyvinyl alcohol resin having 1,2-glycol bond in side chain and method for producing the same |
| JP2005120115A (en) * | 2003-10-14 | 2005-05-12 | Nippon Synthetic Chem Ind Co Ltd:The | Polyvinyl alcohol resin composition |
| JP4653992B2 (en) * | 2004-09-29 | 2011-03-16 | 日本合成化学工業株式会社 | Polyvinyl alcohol-based hydrogel, adsorption separation agent and adsorption separation method using the same |
| JP5078268B2 (en) * | 2005-03-22 | 2012-11-21 | 日本合成化学工業株式会社 | Resin composition and use thereof |
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