JP4553572B2 - UV curable adhesive and its adhesive - Google Patents
UV curable adhesive and its adhesive Download PDFInfo
- Publication number
- JP4553572B2 JP4553572B2 JP2003382366A JP2003382366A JP4553572B2 JP 4553572 B2 JP4553572 B2 JP 4553572B2 JP 2003382366 A JP2003382366 A JP 2003382366A JP 2003382366 A JP2003382366 A JP 2003382366A JP 4553572 B2 JP4553572 B2 JP 4553572B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- group
- curable adhesive
- ultraviolet curable
- 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 - Lifetime
Links
- 239000000853 adhesive Substances 0.000 title claims description 57
- 230000001070 adhesive effect Effects 0.000 title claims description 57
- 150000001875 compounds Chemical class 0.000 claims description 65
- 239000004593 Epoxy Substances 0.000 claims description 51
- 125000003700 epoxy group Chemical group 0.000 claims description 46
- 125000002723 alicyclic group Chemical group 0.000 claims description 30
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 26
- -1 cycloalkyl ester Chemical class 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 19
- 239000004925 Acrylic resin Substances 0.000 claims description 18
- 229920000178 Acrylic resin Polymers 0.000 claims description 18
- 125000005843 halogen group Chemical group 0.000 claims description 18
- 239000003505 polymerization initiator Substances 0.000 claims description 18
- 238000010538 cationic polymerization reaction Methods 0.000 claims description 17
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 10
- 150000001768 cations Chemical class 0.000 claims description 8
- 239000011342 resin composition Substances 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 238000006735 epoxidation reaction Methods 0.000 claims description 6
- 229920005862 polyol Polymers 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 2
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 20
- 229920005989 resin Polymers 0.000 description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 239000010408 film Substances 0.000 description 11
- 239000010419 fine particle Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 229910017048 AsF6 Inorganic materials 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 7
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 239000010409 thin film Substances 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 125000002091 cationic group Chemical group 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- CABDEMAGSHRORS-UHFFFAOYSA-N oxirane;hydrate Chemical compound O.C1CO1 CABDEMAGSHRORS-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 3
- 229940081735 acetylcellulose Drugs 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229920002301 cellulose acetate Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical group C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- FRQGUZFVAWVQLA-UHFFFAOYSA-N 4-cyclohex-3-en-1-ylcyclohexene Chemical group C1C=CCCC1C1CC=CCC1 FRQGUZFVAWVQLA-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- PUHCWRBJAFJNPG-UHFFFAOYSA-N ethaneperoxoic acid;ethyl acetate Chemical compound CC(=O)OO.CCOC(C)=O PUHCWRBJAFJNPG-UHFFFAOYSA-N 0.000 description 2
- 150000002432 hydroperoxides Chemical class 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 150000004967 organic peroxy acids Chemical class 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- YSBPNMOAQMQEHE-UHFFFAOYSA-N (2-methyloxiran-2-yl)methyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1(C)CO1 YSBPNMOAQMQEHE-UHFFFAOYSA-N 0.000 description 1
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- UHHSHIQBMDUHIY-UHFFFAOYSA-N (3-methyl-7-oxabicyclo[4.1.0]heptan-4-yl) 3,4-dimethyl-7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1C2OC2CC(C)C1(C)C(=O)OC1CC2OC2CC1C UHHSHIQBMDUHIY-UHFFFAOYSA-N 0.000 description 1
- 125000006686 (C1-C24) alkyl group Chemical group 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- XYPISWUKQGWYGX-UHFFFAOYSA-N 2,2,2-trifluoroethaneperoxoic acid Chemical compound OOC(=O)C(F)(F)F XYPISWUKQGWYGX-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-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
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- GLVYLTSKTCWWJR-UHFFFAOYSA-N 2-carbonoperoxoylbenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1C(O)=O GLVYLTSKTCWWJR-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- PPPFYBPQAPISCT-UHFFFAOYSA-N 2-hydroxypropyl acetate Chemical compound CC(O)COC(C)=O PPPFYBPQAPISCT-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 description 1
- UFERIGCCDYCZLN-UHFFFAOYSA-N 3a,4,7,7a-tetrahydro-1h-indene Chemical compound C1C=CCC2CC=CC21 UFERIGCCDYCZLN-UHFFFAOYSA-N 0.000 description 1
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- YKXAYLPDMSGWEV-UHFFFAOYSA-N 4-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCO YKXAYLPDMSGWEV-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- DQSJGBWCBXHQCT-UHFFFAOYSA-N 6-cyclohexyloxy-6-oxohexanoic acid Chemical compound OC(=O)CCCCC(=O)OC1CCCCC1 DQSJGBWCBXHQCT-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- RBHIUNHSNSQJNG-UHFFFAOYSA-N 6-methyl-3-(2-methyloxiran-2-yl)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CC2(C)OC2CC1C1(C)CO1 RBHIUNHSNSQJNG-UHFFFAOYSA-N 0.000 description 1
- NHJIDZUQMHKGRE-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-yl 2-(7-oxabicyclo[4.1.0]heptan-4-yl)acetate Chemical compound C1CC2OC2CC1OC(=O)CC1CC2OC2CC1 NHJIDZUQMHKGRE-UHFFFAOYSA-N 0.000 description 1
- BNDNAARXJVXTED-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-yl 4-methyl-7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1OC(=O)C1(C)CC2OC2CC1 BNDNAARXJVXTED-UHFFFAOYSA-N 0.000 description 1
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 1
- OXQXGKNECHBVMO-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptane-4-carboxylic acid Chemical compound C1C(C(=O)O)CCC2OC21 OXQXGKNECHBVMO-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910021630 Antimony pentafluoride Inorganic materials 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
- KILHTNUQHUACHR-UHFFFAOYSA-N C(C(=C)C)(=O)OC=CC(C)=C Chemical compound C(C(=C)C)(=O)OC=CC(C)=C KILHTNUQHUACHR-UHFFFAOYSA-N 0.000 description 1
- XQEZVCBQRYTPAO-UHFFFAOYSA-N C(CC)(=O)OC=C.CC(=C)C1=CC=CC=C1 Chemical compound C(CC)(=O)OC=C.CC(=C)C1=CC=CC=C1 XQEZVCBQRYTPAO-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
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- 238000002955 isolation Methods 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
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- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
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Landscapes
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は紫外線照射により硬化し、密着性、シール性、接着強度に優れた硬化物を形成することのできる紫外線硬化型接着剤、及びこの接着剤を使用した接着体に関する。 The present invention relates to an ultraviolet curable adhesive that can be cured by ultraviolet irradiation to form a cured product having excellent adhesion, sealing properties, and adhesive strength, and an adhesive body using the adhesive.
近年、液晶や有機ELが用いられた表示装置が各種携帯機器に搭載され、携帯機器の小型化、薄型化、軽量化が進められている。液晶や有機ELが用いられた表示装置の基板や表示部分には、ガラス、アルミニウム等の金属、PET等の合成樹脂、アセチルセルロース等の半合成樹脂が使用されている。これら材料の中、樹脂で薄膜状のフィルムや、異種材料を簡便に短時間でしかも強力に接着させる接着剤が望まれている。 In recent years, display devices using liquid crystal or organic EL have been mounted on various portable devices, and miniaturization, thinning, and weight reduction of portable devices have been promoted. A substrate or a display portion of a display device using liquid crystal or organic EL uses glass, a metal such as aluminum, a synthetic resin such as PET, or a semi-synthetic resin such as acetylcellulose. Among these materials, a thin film film made of a resin and an adhesive that easily and strongly bonds different types of materials in a short time are desired.
従来、簡便で短時間に硬化し、接着させるために紫外線硬化型の接着剤が使用されてきた。紫外線硬化型接着剤としては、エポキシ基やビニル基を有するカチオン重合性化合物及び紫外線照射によりカチオンを発生するカチオン重合開始剤を含むカチオン重合型と、ラジカル重合性不飽和基を有するラジカル重合性化合物及び紫外線照射によりラジカルを発生するラジカル重合開始剤を含むものが知られている。 Conventionally, an ultraviolet curable adhesive has been used to cure and bond easily in a short time. Examples of the ultraviolet curable adhesive include a cationic polymerizable compound having an epoxy group or a vinyl group and a cationic polymerizable type containing a cationic polymerization initiator that generates a cation by ultraviolet irradiation, and a radical polymerizable compound having a radical polymerizable unsaturated group. In addition, those containing a radical polymerization initiator that generates radicals upon irradiation with ultraviolet rays are known.
しかしながら、ラジカル重合型の接着剤は硬化速度が比較的速いという特徴がある反面、材料への密着性、加工性が不十分であり、また酸素による硬化阻害があるため、表面の硬化性に劣り、窒素封入などの設備は必要である等の問題がある。 However, radical polymerization type adhesives are characterized by a relatively fast curing speed, but they are inferior in surface curability due to insufficient adhesion to materials and processability, and inhibition of curing by oxygen. However, there is a problem that facilities such as nitrogen sealing are necessary.
一方、カチオン重合型の接着剤は、ラジカル重合型の接着剤と比較して、材料への密着性、加工性が良好であり窒素封入などの設備も必要としないなどの利点がある反面、硬化速度が遅いという問題があった。オキセタニル基を含む脂環式化合物を用いてこの問題を解決した技術が開示されている(特許文献1参照)が、硬化物の接着強度の良いものが望まれている。とりわけフィルム等の薄膜の接着で密着性の良い接着剤が望まれている。 On the other hand, cationic polymerization type adhesives have advantages such as better adhesion to materials and workability compared to radical polymerization type adhesives, and do not require equipment such as nitrogen encapsulation. There was a problem that the speed was slow. A technique that solves this problem by using an alicyclic compound containing an oxetanyl group is disclosed (see Patent Document 1), but a cured product having good adhesive strength is desired. In particular, an adhesive having good adhesion by bonding a thin film such as a film is desired.
また、従来より異種材料の接着で硬化速度が速く、かつ十分な接着強度を持つ接着剤の提供が望まれていた。
本発明の課題は、窒素封入などの設備を必要としない紫外線照射により、速やかに硬化することができ、密着性、とりわけフィルム等の薄膜の密着性、および異種材料間の密着性に優れた紫外線硬化型接着剤を提供することにある。 The problem of the present invention is that it can be cured quickly by ultraviolet irradiation that does not require equipment such as nitrogen encapsulation, and has excellent adhesion, particularly adhesion of thin films such as films, and adhesion between different materials. It is to provide a curable adhesive.
本発明者は、鋭意検討を行なった結果、脂環式エポキシ基2個を有しエステル結合を有していない脂環式エポキシ化合物を用いることにより密着性、とりわけフィルム等の薄膜の密着性、および異種材料間の密着性に優れた紫外線硬化型接着剤を見出し本発明に至った。 As a result of intensive studies, the inventor of the present invention uses an alicyclic epoxy compound having two alicyclic epoxy groups and not having an ester bond, particularly adhesion of a thin film such as a film, In addition, the present inventors have found an ultraviolet curable adhesive having excellent adhesion between different materials and have reached the present invention.
すなわち、本発明の第1は、(i)(A)脂環式エポキシ基2個を有しエステル結合を有していない脂環式エポキシ化合物10〜99重量部、(B)上記(A)とは異なるエポキシ化合物1〜90重量部、((A)と(B)の合計は100重量部)からなる組成物100重量部に対して、(D′)分子中にエポキシ基、又はエポキシ基と水酸基を有するとともに、共重合モノマー成分としてメタクリル酸の炭素数1〜24のアルキル又はシクロアルキルエステルを含むアクリル樹脂1〜85重量部を含有させた樹脂組成物100重量部に対し、(C)紫外線照射によりカチオンを発生するカチオン重合開始剤を0.1〜20重量部配合してなる紫外線硬化型接着剤か、又は(ii)(A)脂環式エポキシ基2個を有しエステル結合を有していない脂環式エポキシ化合物10〜99重量部、(B′)少なくともβ−(3,4−エポキシシクロヘキシル)エチルトリメトキシシランを含む上記(A)とは異なるエポキシ化合物1〜90重量部、((A)と(B′)の合計は100重量部)からなる組成物100重量部に対して、(E)水酸基を分子中に2〜4個持つカプロラクトン変性ポリオール化合物を1〜50重量部含有させた樹脂組成物100重量部に対し、(C)紫外線照射によりカチオンを発生するカチオン重合開始剤を0.1〜20重量部配合してなる紫外線硬化型接着剤であって、前記(A)脂環式エポキシ基2個を有しエステル結合を有していない脂環式エポキシ化合物が以下の一般式(1)、(3)または(5)で表されるエポキシ化合物である紫外線硬化型接着剤、である。
本発明の第2は、一般式(1)、(3)または(5)で表わされる脂環式エポキシ化合物におけるR1〜R18の全てが水素原子である本発明第1に記載の紫外線硬化型接着剤、である。 A second aspect of the present invention is the ultraviolet curable adhesive according to the first aspect of the present invention, wherein all of R1 to R18 in the alicyclic epoxy compound represented by the general formula (1), (3) or (5) are hydrogen atoms. Agent.
本発明の第3は、一般式(1)、(3)または(5)で表わされる脂環式エポキシ化合物が、それぞれ対応するジオレフィン化合物を水分含有量が0.8重量%以下の有機過カルボン酸でエポキシ化して得られるものである本発明第1または2に記載の紫外線硬化型接着剤、である。 The third of the present invention have the general formula (1), (3) or (5) an alicyclic epoxy compound represented by the corresponding diolefin compound moisture content over organic 0.8 wt% or less The ultraviolet curable adhesive according to the first or second aspect of the present invention, which is obtained by epoxidation with a carboxylic acid.
本発明の第4は、有機過カルボン酸が有機溶剤溶液である本発明第3に記載の紫外線硬化型接着剤、である。 A fourth aspect of the present invention is the ultraviolet curable adhesive according to the third aspect , wherein the organic percarboxylic acid is an organic solvent solution.
本発明の第5は、複数の被接着体を、本発明第1〜4いずれか一項に記載の紫外線硬化型接着剤で接着して得られたことを特徴とする接着体、である。
なお、本明細書では、上記の発明のほか、[1](A)脂環式エポキシ基2個を有しエステル結合を有していない脂環式エポキシ化合物、(B)上記(A)とは異なるエポキシ化合物(C)紫外線照射によりカチオンを発生するカチオン重合開始剤からなる紫外線硬化型接着剤、[2](A)脂環式エポキシ基2個を有しエステル結合を有していない脂環式エポキシ化合物10〜99重量部、(B)上記(A)と異なるエポキシ化合物1〜90重量部、((A)と(B)の合計は100重量部)からなる組成物100重量部に対し、(C)紫外線照射によりカチオンを発生するカチオン重合開始剤0.01〜20重量部を配合してなる前記[1]に記載の紫外線硬化型接着剤、[3](A)及び(B)の合計100重量部に対して、(D)分子中にエポキシ基、又はエポキシ基と水酸基を有するアクリル樹脂1〜85重量部を含有させた樹脂組成物100重量部に対し、(C)を0.1〜20重量部配合してなる前記[1]に記載の紫外線硬化型接着剤、[4](A)及び(B)の合計100重量部に対して、(E)水酸基を分子中に2〜4個持つカプロラクトン変性ポリオール化合物を1〜50重量部含有させた樹脂組成物100重量部に対し、(C)を0.1〜20重量部配合してなる前記[1]に記載の紫外線硬化型接着剤についても説明する。
The fifth of the present invention, a plurality of adherends, a bonding material, characterized in that the obtained bonded with an ultraviolet curing adhesive as claimed in any one invention first 1-4.
In the present specification, in addition to the above invention, [1] (A) an alicyclic epoxy compound having two alicyclic epoxy groups and no ester bond, (B) the above (A) and Is a different epoxy compound (C) UV curable adhesive comprising a cationic polymerization initiator that generates cations upon UV irradiation, [2] (A) a fat having two alicyclic epoxy groups and no ester bond To 100 parts by weight of a composition comprising 10 to 99 parts by weight of a cyclic epoxy compound, (B) 1 to 90 parts by weight of an epoxy compound different from the above (A), and (the sum of (A) and (B) is 100 parts by weight) On the other hand, (C) the ultraviolet curable adhesive according to the above [1], comprising 0.01 to 20 parts by weight of a cationic polymerization initiator that generates cations by ultraviolet irradiation, [3] (A) and (B ) For a total of 100 parts by weight of (D) Said [1] which mix | blends 0.1-20 weight part of (C) with respect to 100 weight part of resin compositions which contained 1-85 weight part of acrylic resin which has an epoxy group or an epoxy group and a hydroxyl group in [1]. ] [4] 1 to 50 caprolactone-modified polyol compounds having 2 to 4 hydroxyl groups in the molecule with respect to 100 parts by weight of the total of [4] (A) and (B). The ultraviolet curable adhesive described in [1] above, which is obtained by blending 0.1 to 20 parts by weight of (C) with respect to 100 parts by weight of the resin composition contained in parts by weight, will also be described.
本発明の紫外線硬化型接着剤は、カチオン重合開始剤の存在下、窒素封入等の設備を必要とすることなく、低照射量の紫外線照射によっても、速やかに、効率よくカチオン重合により硬化させることができ、かつフィルム等の薄膜の接着、すなわち、PETフィルム/PETフィルム等の接着や、異種材料間の接着、すなわち、ガラス等の無機材料とPET,アセチルセルロース等の樹脂、及びその薄膜、アルミニウム等の金属材料とPET等の樹脂及びその薄膜の接着において密着性に優れている。 The ultraviolet curable adhesive of the present invention can be quickly and efficiently cured by cationic polymerization even in the presence of a cationic polymerization initiator, without requiring facilities such as nitrogen encapsulation, and even by irradiation with a low dose of ultraviolet light. Bonding of thin films such as films, that is, bonding of PET films / PET films, bonding between different materials, that is, inorganic materials such as glass and resins such as PET and acetylcellulose, and their thin films, aluminum Excellent adhesion in adhesion of metal materials such as PET and resin such as PET and its thin film.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明で用いられる脂環式エポキシ基を2個有し、エステル結合を有していない脂環式エポキシ化合物の代表的なものとしては、一般式(1)、(3)又は(5)で表わされるエポキシ化合物である。例えば、一般式(1)のエポキシ化合物は、ビシクロヘキシル−3,3'−ジエン骨格を持つ一般式(2)で表わされる不飽和化合物を有機過カルボン酸、ハイドロパーオキサイド類によって酸化させることにより製造される。 Typical examples of the alicyclic epoxy compound having two alicyclic epoxy groups and having no ester bond used in the present invention are those represented by the general formula (1), (3) or (5). It is an epoxy compound represented. For example, an epoxy compound of the general formula (1) is obtained by oxidizing an unsaturated compound represented by the general formula (2) having a bicyclohexyl-3,3′-diene skeleton with an organic percarboxylic acid or a hydroperoxide. Manufactured.
また、一般式(3)で表されるエポキシ化合物は、シクロオクタジエン骨格を
持つ一般式(IV)で表わされる不飽和化合物を有機過カルボン酸、ハイドロパーオキサイド類によって酸化させることにより製造される。
The epoxy compound represented by the general formula (3) is produced by oxidizing an unsaturated compound represented by the general formula (IV) having a cyclooctadiene skeleton with an organic percarboxylic acid or a hydroperoxide. .
っても異なっていてもよい。これらは、水素原子、ハロゲン原子、あるいは酸素原子もしくはハロゲン原子を含んでよい炭化水素基、又は置換基を有してよいアルコキシ基である。
さらに、一般式(5)で表されるエポキシ化合物は、脂環式インデン骨格を持つ一般式(VI)で表わされる不飽和化合物をハイドロパーオキサイド類や有機過カルボン酸によって酸化させることにより製造される。 Furthermore, the epoxy compound represented by the general formula (5) is produced by oxidizing the unsaturated compound represented by the general formula (VI) having an alicyclic indene skeleton with a hydroperoxide or an organic percarboxylic acid. The
中でも、一般式(1)〜(4)におけるR1〜R18が水素原子であるエポキシ化合物が工業的に製造されているので、好ましい。 Among them, since the epoxy compound R 1 to R 18 is a hydrogen atom in the general formula (1) to (4) are industrially produced, preferred.
使用し得るハイドロパーオキサイド類としては、過酸化水素、ターシャリブチルハイドロパーオキサイド、クメンハイドロパーオキサイド等がある。 Hydroperoxides that can be used include hydrogen peroxide, tertiary butyl hydroperoxide, cumene hydroperoxide, and the like.
使用し得る有機過酸としては、有機過カルボン酸、より具体的には、過ギ酸、
過酢酸、過プロピオン酸、過安息香酸、トリフルオロ過酢酸、または、過フタル酸等があるが、中でも、工業的に大量に使用されている過酢酸を使用することが好ましい。
Organic peracids that can be used include organic percarboxylic acids, more specifically, formic acid,
There are peracetic acid, perpropionic acid, perbenzoic acid, trifluoroperacetic acid, and perphthalic acid. Among them, it is preferable to use peracetic acid that is used industrially in large quantities.
なお、有機過カルボン酸の中でも対応するアルデヒドの空気または酸素による酸化で得られるものは水分含有率が低く、具体的には、水分含有率0.8重量%以下であり、本発明におけるエポキシ化合物を製造する際、特に好ましい。その理由は、水分が実質的に存在していないため、エポキシ基が開環して水酸基になったり、水分存在下で起こり易い有機過カルボン酸から生じたカルボン酸とエポキシ基とのエステル化反応が抑制され、エポキシ化率の高いものが得られるからである。酸化反応の際には必要に応じて触媒を用いることもできる。例えば有機過酸の場合、炭酸ソーダなどのアルカリや硫酸などの酸を触媒として用い得る。 Among the organic percarboxylic acids, those obtained by oxidation of the corresponding aldehyde with air or oxygen have a low water content, specifically, the water content is 0.8% by weight or less, and the epoxy compound in the present invention It is particularly preferable when manufacturing. The reason is that, since water is not substantially present, the epoxy group is ring-opened to form a hydroxyl group, or an esterification reaction between a carboxylic acid and an epoxy group generated from an organic percarboxylic acid that easily occurs in the presence of moisture. This is because a high epoxidation rate is obtained. In the oxidation reaction, a catalyst can be used as necessary. For example, in the case of an organic peracid, an alkali such as sodium carbonate or an acid such as sulfuric acid can be used as a catalyst.
また、ハイドロパーオキサイド類の場合、タングステン酸と苛性ソーダの混合物を過酸化水素とあるいは有機酸を過酸化水素と、あるいはモリブデンヘキサカルボニルをターシャリブチルハイドロパーオキサイドと使用して触媒効果を得ることができる。過酸化水素及びタングステン酸とナトリウムなどのアルカリ金属塩及びリン酸又はリン酸エステル類、リン酸塩、ホスホン酸及びアルキルアンモニウムと硫酸などの無機酸との塩を用いて酸化することもできる。酸化反応は、触媒、溶媒使用の有無や反応温度を調整して行なう。 In the case of hydroperoxides, a catalytic effect can be obtained by using a mixture of tungstic acid and caustic soda with hydrogen peroxide, organic acid with hydrogen peroxide, or molybdenum hexacarbonyl with tertiary butyl hydroperoxide. it can. It can also be oxidized using alkali metal salts such as hydrogen peroxide and tungstic acid and sodium, and salts of phosphoric acid or phosphate esters, phosphates, phosphonic acids and alkylammonium and inorganic acids such as sulfuric acid. The oxidation reaction is carried out by adjusting the presence or absence of a catalyst and a solvent and the reaction temperature.
用いる酸化剤の反応性によって使用できる反応温度域は定まる。 The reaction temperature range that can be used is determined by the reactivity of the oxidizing agent used.
好ましい酸化剤である過酢酸についていえば0〜70℃、好ましくは、10〜60℃、さらに好ましくは、20〜50である。0℃以下では反応が遅く、70℃では過酢酸の分解が起きるので、好ましくない。 Speaking of peracetic acid which is a preferable oxidizing agent, it is 0-70 degreeC, Preferably, it is 10-60 degreeC, More preferably, it is 20-50. The reaction is slow at 0 ° C. or lower, and peracetic acid is decomposed at 70 ° C., which is not preferable.
また、ハイドロパーオキサイドの1例であるターシャルブチルハイドロパーオキサイド/モリブデン二酸化物ジアセチルアセトナート系では、同じ理由で20℃〜150℃、好ましくは、25〜120℃である。 Moreover, in the tertiary butyl hydroperoxide / molybdenum dioxide diacetylacetonate system which is an example of hydroperoxide, it is 20 degreeC-150 degreeC for the same reason, Preferably it is 25-120 degreeC.
酸化剤として、上記のような水分含有率が低い有機過カルボン酸を使用する場合、有機過カルボン酸の安定化のために溶媒を使用することもできる。有機過カルボン酸が過酢酸の場合であれば酢酸エチルがしばしば用いられる。 When the organic percarboxylic acid having a low water content as described above is used as the oxidizing agent, a solvent can be used for stabilizing the organic percarboxylic acid. If the organic percarboxylic acid is peracetic acid, ethyl acetate is often used.
上記一般式(1)、(3)、または(5)で表される各エポキシ化合物の中でも、それぞれ対応する上記一般式(2)、(4)、または(6)で表される各ジオレフィン化合物を実質的に水分を含まない、具体的には、水分含有量0.8重量%以下、好ましくは0.6重量%以下の有機過カルボン酸を使用して得られたものが高いエポキシ化率を有しており、長期間にわたって絶縁油における安定性を保持できるという点で好ましい。この実質的に水分を含まない有機過カルボン酸は、アルデヒド類、例えば、アセトアルデヒドの空気酸化により製造されるものであり、例えば、過酢酸についてはドイツ公開特許公報1418465号や特開昭54−3006に記載された方法により製造される。この方法によれば、過酸化水素から有機過カルボン酸を合成し、溶媒により抽出して有機過カルボン酸を製造する場合に比べて、連続して大量に高濃度の有機過カルボン酸を合成できるために、実質的に安価に得ることができる。 Among the epoxy compounds represented by the general formula (1), (3), or (5), the corresponding diolefins represented by the general formula (2), (4), or (6), respectively. High epoxidation of compounds obtained using organic percarboxylic acids that are substantially free of moisture, specifically 0.8% by weight or less, preferably 0.6% by weight or less Therefore, it is preferable in that the stability of the insulating oil can be maintained over a long period of time. This organic percarboxylic acid substantially free of water is produced by air oxidation of aldehydes, for example, acetaldehyde. For example, peracetic acid is disclosed in German Patent Publication No. 1418465 and Japanese Patent Laid-Open No. 54-30006. Manufactured by the method described in 1. above. According to this method, it is possible to synthesize organic percarboxylic acid in a large amount continuously, compared with the case where organic percarboxylic acid is synthesized from hydrogen peroxide and extracted with a solvent to produce organic percarboxylic acid. Therefore, it can be obtained substantially inexpensively.
上記のような水分を含まない有機過カルボン酸を使用して一般式(1)、(3)または(5)で表される各エポキシ化合物を製造する技術は、それぞれ、特願2002−260490号、特願2002−351437号各明細書に記載されている。具体的には、下記のような方法である。 Techniques for producing each epoxy compound represented by the general formula (1), (3) or (5) using the organic percarboxylic acid not containing water as described above are disclosed in Japanese Patent Application No. 2002-260490, respectively. And Japanese Patent Application No. 2002-351437. Specifically, the method is as follows.
エポキシ化剤の量には厳密な制限がなく、それぞれの場合における最適量は使用する個々のエポキシ化剤や脂環式オレフィン化合物の反応性、目的とするエポキシ化の割合等の可変要因によって決まる。 There is no strict limitation on the amount of epoxidizing agent, and the optimum amount in each case depends on variable factors such as the reactivity of the individual epoxidizing agent and cycloaliphatic olefin compound used, and the desired epoxidation ratio. .
エポキシ化反応は、装置や原料物性に応じて溶媒使用の有無や反応温度を調節して行う。溶媒としては、原料粘度の低下、エポキシ化剤の希釈による安定化などの目的で使用することができ、過酢酸の場合であればエステル類、芳香族化合物、エーテル類などを用いることができる。特に好ましい溶媒は、酢酸エチル、ヘキサン、シクロヘキサン、トルエン、ベンゼン等であり、とりわけ、酢酸エチルが好ましい。反応温度は用いるエポキシ化剤と不飽和基含有化合物の反応性によって定まる。 The epoxidation reaction is carried out by adjusting the presence or absence of a solvent and the reaction temperature according to the apparatus and the physical properties of the raw material. As the solvent, it can be used for the purpose of lowering the viscosity of the raw material, stabilizing by diluting the epoxidizing agent, and in the case of peracetic acid, esters, aromatic compounds, ethers and the like can be used. Particularly preferred solvents are ethyl acetate, hexane, cyclohexane, toluene, benzene and the like, and ethyl acetate is particularly preferred. The reaction temperature is determined by the reactivity of the epoxidizing agent used and the unsaturated group-containing compound.
例えば、好ましいエポキシ化剤である過酢酸を使用する場合の反応温度は20〜70℃が好ましい。20℃未満では反応が遅く、70℃を超える温度では過酢酸が発熱を伴って分解するので、好ましくない。 For example, the reaction temperature when using peracetic acid, which is a preferred epoxidizing agent, is preferably 20 to 70 ° C. If it is less than 20 ° C., the reaction is slow, and if it exceeds 70 ° C., peracetic acid decomposes with heat generation, which is not preferable.
エポキシ化剤は不飽和基1モルに対して望ましくは1.0〜3.0モル、より望ましくは1.05〜1.5モル加える。経済性及び副反応の問題から、3.0倍モルを超えることは通常不利である。 The epoxidizing agent is preferably added in an amount of 1.0 to 3.0 mol, more preferably 1.05 to 1.5 mol per mol of the unsaturated group. From the viewpoint of economy and side reaction, it is usually disadvantageous to exceed 3.0 times mole.
反応で得られた粗液の特別な操作は必要なく、例えば粗液を1〜5時間攪拌し、熟成させればよい。得られた粗液からのエポキシ化合物の単離は適当な方法、例えば貧溶媒で沈殿させる方法、エポキシ化物を熱水中に攪拌の下で投入し溶媒を蒸留除去する方法、直接脱溶媒法などで行うことができる。
本発明における(B)上記(A)と異なるエポキシ化合物は、分子中にエポキシ基を1個以上、好ましくは1〜2個有する化合物である。このエポキシ基は脂環式エポキシ基でも脂環式エポキシ基以外のエポキシ基でもよく、分子中に脂環式エポキシ基を有する化合物の具体例としては、リモネンジオキサイド、ジ(3,4−エポキシシクロヘキシル)アジペート、(3,4−エポキシシクロヘキシル)メチル−3,4−エポキシシクロヘキサンカルボキシレート、(3,4−エポキシ−6−メチルシクロヘキシル)メチル−3,4−エポキシ−6−メチルシクロヘキサンカルボキシレート、エチレン−1,2−ジ(3,4−エポキシシクロヘキサンカルボン酸)エステルなどが挙げられ、中でも3,4−エポキシシクロヘキシルメチル−3,4−エポキシシクロヘキサンカルボキシレート、3,4−エポキシシクロヘキシルメチルアルコール、3,4−エポキシシクロヘキシルエチルトリメトキシシランが好ましい。尚、これらの化合物は単独で又は2種以上組合わせて使用することができる。なお、本発明における、「(B)上記(A)と異なるエポキシ化合物」には、エステル型脂環エポキシ化合物を使用しても差し支えない。
No special operation is required for the crude liquid obtained by the reaction. For example, the crude liquid may be aged by stirring for 1 to 5 hours. Isolation of the epoxy compound from the obtained crude liquid is an appropriate method, for example, a method of precipitating with a poor solvent, a method of pouring the epoxidized product into hot water with stirring and removing the solvent by distillation, a direct desolvation method, etc. Can be done.
(B) The epoxy compound different from the above (A) in the present invention is a compound having one or more, preferably 1-2 epoxy groups in the molecule. This epoxy group may be an alicyclic epoxy group or an epoxy group other than the alicyclic epoxy group. Specific examples of the compound having an alicyclic epoxy group in the molecule include limonene dioxide, di (3,4-epoxy). (Cyclohexyl) adipate, (3,4-epoxycyclohexyl) methyl-3,4-epoxycyclohexanecarboxylate, (3,4-epoxy-6-methylcyclohexyl) methyl-3,4-epoxy-6-methylcyclohexanecarboxylate, And ethylene-1,2-di (3,4-epoxycyclohexanecarboxylic acid) ester, among others, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl alcohol, 3,4-epoxycyclohexyl Trimethoxysilane is preferred. In addition, these compounds can be used individually or in combination of 2 or more types. In the present invention, an ester type alicyclic epoxy compound may be used for “(B) an epoxy compound different from the above (A)”.
一方、分子中に脂環式エポキシ基以外のエポキシ基を有する化合物としては、ビスフェノールA型、F型に代表される各種ビスフェノール型のジグリシジルエーテル(市販品としては、エピコート828,806(ジャパンエポキシレジン社製)YD−128(東都化成製)など)、ビスフェノール型エポキシ樹脂の核水添品(市販品としては、HBE−100(新日本理化製)、YX−4000(ジャパンエポキシレジン社製)など)が挙げられる。その他に、シクロヘキサンジメタノールのジグリシジルエーテルなどの環状脂肪族骨格を持ったグリシジルエーテル(市販品としては、DME−100(新日本理化製)など)、ノボラック型フェノール樹脂のグリシジルエーテル、DCPDなどを共重合させたノボラック型フェノール樹脂のグリシジルエーテル、ナフタレンなどの多環芳香族のグリシジルエーテル、脂環骨格に末端エポキシを持つエポキシ樹脂(市販品としては、EHPE−3150,EHPE−3150CE(ダイセル化学工業製)など)、エポキシ基を持ったシリコン樹脂(市販品としては、A−186(日本ユニカー製)、KBM303、KBM403、KBM42(信越化学工業製)など)も挙げられる。 On the other hand, as a compound having an epoxy group other than an alicyclic epoxy group in the molecule, various bisphenol type diglycidyl ethers typified by bisphenol A type and F type (Epicoat 828,806 (Japan Epoxy as commercial products) YD-128 (manufactured by Resin Co., Ltd.), etc.), hydrogenated products of bisphenol type epoxy resin (commercially available products are HBE-100 (manufactured by Nippon Nippon Chemical Co., Ltd.), YX-4000 (manufactured by Japan Epoxy Resin Co., Ltd.) Etc.). In addition, glycidyl ether having a cycloaliphatic skeleton such as diglycidyl ether of cyclohexanedimethanol (commercially available products such as DME-100 (manufactured by Nippon Nippon Chemical Co., Ltd.)), glycidyl ether of novolac type phenol resin, DCPD, etc. Polycyclic aromatic glycidyl ether such as glycidyl ether and naphthalene of copolymerized novolak type phenol resin, epoxy resin having terminal epoxy on alicyclic skeleton (commercially available products are EHPE-3150, EHPE-3150CE (Daicel Chemical Industries, Ltd.) Etc.), and silicon resins having an epoxy group (commercially available products such as A-186 (manufactured by Nihon Unicar), KBM303, KBM403, KBM42 (manufactured by Shin-Etsu Chemical Co., Ltd.)).
本発明における(D)エポキシ基を有するアクリル樹脂、又は、エポキシ基と水酸基を有するアクリル樹脂は、エポキシ基を含むモノマーを重合するか、又は、エポキシ基を含むモノマーと水酸基を含むモノマーを共重合することで得ることが出来る。エポキシ基を含むモノマーとしては、グリシジルエーテル又は、類似の末端エポキシを持つ化合物、脂環エポキシなど有する(メタ)アクリル酸エステルなどを挙げることができる。具体例としては、グリシジルメタクリレート、2−メチル−グリシジルメタクリレート、エポキシ化イソプレニルメタクリレート、CYM M−100及び、CYM A−400(ダイセル化学工業製)などが挙げられる
一方、水酸基を含むモノマーとしては、ヒドロキシエチル(メタ)アクリレート、ヒドロキシプロピル(メタ)アクリレート、及びこれらの水酸基含有アクリレートをカプロラクトン変性したモノマー(商品名FM−1、FM−3、FM−10、FA−1、FA−3でダイセル化学工業より市販されている。)が挙げられる。
In the present invention, (D) the acrylic resin having an epoxy group, or the acrylic resin having an epoxy group and a hydroxyl group is polymerized with a monomer containing an epoxy group, or a copolymer containing a monomer containing an epoxy group and a monomer containing a hydroxyl group. You can get it. Examples of the monomer containing an epoxy group include glycidyl ether, a compound having a similar terminal epoxy, and a (meth) acrylic acid ester having an alicyclic epoxy. Specific examples include glycidyl methacrylate, 2-methyl-glycidyl methacrylate, epoxidized isoprenyl methacrylate, CYM M-100, and CYM A-400 (manufactured by Daicel Chemical Industries). Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and monomers obtained by caprolactone modification of these hydroxyl group-containing acrylates (trade names FM-1, FM-3, FM-10, FA-1, FA-3, Daicel Chemical) Commercially available from industry).
本発明における(D)エポキシ基を有するアクリル樹脂、又は、エポキシ基と水酸基を有するアクリル樹脂には、モノマーとして、エポキシ基を含むモノマーと水酸基を含むモノマーの他、通常のアルキルアクリレート単量体を共重合に使用することができる。 In the acrylic resin having an epoxy group (D) in the present invention or an acrylic resin having an epoxy group and a hydroxyl group, as a monomer, in addition to a monomer containing an epoxy group and a monomer containing a hydroxyl group, a normal alkyl acrylate monomer is used. Can be used for copolymerization.
共重合に使用することができる通常のアルキルアクリレート単量体としては、メチルアクリレート、メチルメタクリレート、エチルアクリレート、エチルメタクリレート、n−,i−又はt−ブチルアクリレート、n−,i−もしくはt−ブチルメタアクリレート、ヘキシルアクリレート、ヘキシルメタクリレート、オクチルアクリレート、オクチルメタクリレート、ラウリルアクリレート、ラウリルメタクリレート、ステアリルアクリレート、ステアリルメタクリレート、シクロヘキシルアクリレート、シクロヘキシルメタクリレート等の如きアクリル酸又はメタクリル酸の炭素数1〜24のアルキル又はシクロアルキルエステル;2−ヒドロキシエチルアクリレート、2−ヒドロキシエチルメタクリレート、2−ヒドロキシプロピルアクリレート、2−ヒドロキシプロピルメタクリレート、4−ヒドロキシブチルアクリレート、4−ヒドロキシブチルメタクリレートなどのアクリル酸又はメタクリル酸の炭素数1〜8個のヒドロキシアルキルエステル;アクリル酸、メタクリル酸、マレイン酸、イタコン酸、クロトン酸などのα,β−エチレン性不飽和カルボン酸;アクリルアミド、メタクリルアミド、N−メチルアクリルアミド、N−エチルメタクリルアミド、ジアセトンアクリルアミド、N−メチロールアクリルアミド、N−メチロールメタクリルアミド、N−メトキシメチルアクリルアミド、N−ブトキシメチルアクリルアミドなどのアクリルアミドもしくはメタクリルアミド又はこれらの誘導体;スチレン、ビニルトルエン、α−メチルスチレンなどの芳香族ビニル単量体;プロピオン酸ビニル、酢酸ビニル、アクリロニトリル、メタクリロニトリル、ビニルピバレート、ベオバモノマー(シェル化学社製、分岐脂肪酸のビニルエステル)、サイラプレーンFM0711、同FM0721、同FM0725(以上、いずれもチッソ社製、末端にメタクリロイル基を有するポリジメチルシロキサンマクロモノマー)、その他ビニル単量体を挙げることができる。 Usual alkyl acrylate monomers that can be used for copolymerization include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-, i- or t-butyl acrylate, n-, i- or t-butyl. C1-C24 alkyl or cyclohexane of acrylic acid or methacrylic acid such as methacrylate, hexyl acrylate, hexyl methacrylate, octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, etc. Alkyl ester; 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acetate Rate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate and other acrylic or methacrylic acid hydroxyalkyl esters having 1 to 8 carbon atoms; acrylic acid, methacrylic acid, maleic acid, itaconic acid, Α, β-ethylenically unsaturated carboxylic acids such as crotonic acid; acrylamide, methacrylamide, N-methylacrylamide, N-ethylmethacrylamide, diacetoneacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-methoxymethyl Acrylamide or methacrylamide such as acrylamide, N-butoxymethylacrylamide or derivatives thereof; aromatic vinyl such as styrene, vinyltoluene, α-methylstyrene Vinyl propionate, vinyl acetate, acrylonitrile, methacrylonitrile, vinyl pivalate, Veova monomer (manufactured by Shell Chemical Co., Ltd., vinyl ester of branched fatty acid), silaplane FM0711, FM0721, FM0721 Polydimethylsiloxane macromonomer having a methacryloyl group) and other vinyl monomers.
本発明における(D)エポキシ基を有するアクリル樹脂、又は、エポキシ基と水酸基を有するアクリル樹脂をモノマーから製造する際には、重合開始剤を用いることができる。重合開始剤としては、過硫酸カリウム、過硫酸アンモニウム、過酸化ベンゾイル、過酸化水素、ジ−t−ブチルパーオキシド、ジクミルパーオキシド、2、4−ジクロロベンゾイルパーオキシド、デカノイルパーオキシド、ラウリルパーオキシド、クメンヒドロパーオキシド、t−ブチルヒドロパーオキシド、アセチルパーオシキド、メチルエチルケトンパーオキシド、コハク酸パーオキシド、ジセチルパーオキシジカーボネート、t−ブチルパーオキシアセテート、AIBN(2、2'−アゾビスイソブチロニトリル)、ABN−E(2,2'−アゾビス(2−メチルブチロニトリル))、ABN−V(2,2'−アゾビス(2、4−ジメチルバレロニトリル))、パーブチルO(t−ブチルパーオキシ2−エチルヘキサノエート)などを使用することができる。 In producing the acrylic resin having an epoxy group (D) or the acrylic resin having an epoxy group and a hydroxyl group in the present invention from a monomer, a polymerization initiator can be used. Polymerization initiators include potassium persulfate, ammonium persulfate, benzoyl peroxide, hydrogen peroxide, di-t-butyl peroxide, dicumyl peroxide, 2,4-dichlorobenzoyl peroxide, decanoyl peroxide, lauryl peroxide. Oxide, cumene hydroperoxide, t-butyl hydroperoxide, acetyl peroxide, methyl ethyl ketone peroxide, succinic acid peroxide, dicetyl peroxydicarbonate, t-butyl peroxyacetate, AIBN (2, 2′-azobis) Isobutyronitrile), ABN-E (2,2′-azobis (2-methylbutyronitrile)), ABN-V (2,2′-azobis (2,4-dimethylvaleronitrile)), perbutyl O ( t-Butylperoxy 2-ethylhexanoate) Rukoto can.
重合開始剤の使用量は、モノマー100重量部に対して、1〜10重量部、好ましくは、3〜6重量部である。重合開始剤は、一部あらかじめ反応器に仕込んでおいても良いし、モノマーに配合しても、又は配合せず別々に滴下しても良い。また、モノマーを仕込んだ後に開始剤を追加仕込みにしても良い。 The usage-amount of a polymerization initiator is 1-10 weight part with respect to 100 weight part of monomers, Preferably, it is 3-6 weight part. A part of the polymerization initiator may be charged in the reactor in advance, or may be added to the monomer or dropped separately without being added. Further, an initiator may be additionally charged after the monomer is charged.
好ましい重合温度は、90〜130℃で、より好ましくは、100〜120℃である。温度が、130℃以上では、重合が不安定になり高分子量の化合物が多く生成し好ましくない。一方、90℃以下では、重合時間が長くなり好ましくない。 A preferable polymerization temperature is 90 to 130 ° C, and more preferably 100 to 120 ° C. When the temperature is 130 ° C. or higher, the polymerization becomes unstable and a large amount of high molecular weight compounds are produced, which is not preferable. On the other hand, if it is 90 ° C. or less, the polymerization time becomes long, which is not preferable.
本発明における(D)エポキシ基を有するアクリル樹脂、又は、エポキシ基と水酸基を有するアクリル樹脂中のエポキシ基の量は、オキシラン酸素濃度として、カチオン重合性を有するエポキシ化合物及びカチオン種と反応する官能基を有するアクリル樹脂を合計した際に、6〜11%、好ましくは、7.5〜9.5%である。又、エポキシ基の他に水酸基も有するアクリル樹脂中の水酸基の量は、水酸基価として1〜300の範囲が好ましく、更に、1.5〜250の範囲がより好ましい。 In the present invention, (D) the amount of epoxy group in the acrylic resin having an epoxy group or the acrylic resin having an epoxy group and a hydroxyl group is a functional group that reacts with an epoxy compound having a cationic polymerizable property and a cationic species as an oxirane oxygen concentration. When the acrylic resin having a group is added up, it is 6 to 11%, preferably 7.5 to 9.5%. Moreover, the amount of the hydroxyl group in the acrylic resin having a hydroxyl group in addition to the epoxy group is preferably from 1 to 300 as a hydroxyl value, and more preferably from 1.5 to 250.
本発明における(C)カチオン重合開始剤は、紫外線照射によりカチオン種を発生して重合を開始させる化合物であり、例えば、下記式(I)〜(XV)で示されるヘキサフルオロアンチモネート塩、ペンタフルオロヒドロキシアンチモネート塩、ヘキサフルオロホスフェート塩、ヘキサフルオロアルゼネート塩及びその他のカチオン重合開始剤を挙げることができる。 The (C) cationic polymerization initiator in the present invention is a compound that initiates polymerization by generating cationic species by irradiation with ultraviolet rays. For example, a hexafluoroantimonate salt represented by the following formulas (I) to (XV), penta Mention may be made of fluorohydroxyantimonate salts, hexafluorophosphate salts, hexafluoroarsenate salts and other cationic polymerization initiators.
、X- はPF6-、SbF6- 又はAsF6- を表わす。)
本発明における(E)水酸基を分子中に2〜4個持つカプロラクトン変性ポリオール化合物としては、以下のものが例示される。水酸基を2個持つものとしては、PCL−205,PCL−212、PCL−240、PCL−L208AL,PCL−L220AL,PCL−220EC、PCL−CD220PL、PCL−CD210HL(いずれもダイセル化学工業(株)より市販されている)などが挙げられる。水酸基を3個持つものとしては、PCL−303、PCL−308,PCL−L320AL(いずれもダイセル化学工業(株)より市販されている)、水酸基を4個持つものとしては、PCL−410,PCL−420D(いずれもダイセル化学工業(株)より市販されている)などが挙げられる。 Examples of the caprolactone-modified polyol compound having 2 to 4 hydroxyl groups in the molecule (E) in the present invention include the following. As those having two hydroxyl groups, PCL-205, PCL-212, PCL-240, PCL-L208AL, PCL-L220AL, PCL-220EC, PCL-CD220PL, PCL-CD210HL (all from Daicel Chemical Industries, Ltd.) Commercially available). PCL-303, PCL-308, and PCL-L320AL (all are commercially available from Daicel Chemical Industries) as those having 3 hydroxyl groups, and PCL-410, PCL as those having 4 hydroxyl groups. -420D (all are commercially available from Daicel Chemical Industries, Ltd.).
<配合比>
本発明に使用する(A)脂環式エポキシ2個を有しエステル結合を有していない脂環式エポキシ化合物と、(B)上記(A)と異なるエポキシ化合物は、両者の合計量が100重量部となる割合において、(A)成分は、10〜99重量部、好ましくは20〜70重量部さらに好ましくは30〜60重量部であり、(B)成分は、90〜1重量部、好ましくは80〜30重量部さらに好ましくは70〜40重量部の範囲で使用することができる。(A)成分の量が99重量部を超えると、低照射量の紫外線照射において、接着剤の硬化性が劣る。また、(B)成分の量が1重量部未満となると、得られる接着体の硬度、密着性が劣る。A成分を上記割合で配合することにより、3次元の架橋効果が生じ良好な接着効果が得られる。
<Combination ratio>
The total amount of the (A) alicyclic epoxy compound having two alicyclic epoxies used in the present invention and having no ester bond, and (B) an epoxy compound different from the above (A) is 100. In the ratio of parts by weight, the component (A) is 10 to 99 parts by weight, preferably 20 to 70 parts by weight, more preferably 30 to 60 parts by weight, and the component (B) is 90 to 1 part by weight, preferably Can be used in the range of 80 to 30 parts by weight, more preferably 70 to 40 parts by weight. When the amount of the component (A) exceeds 99 parts by weight, the curability of the adhesive is inferior in irradiation with a low amount of ultraviolet light. Moreover, when the amount of the component (B) is less than 1 part by weight, the hardness and adhesion of the obtained bonded body are inferior. By blending the component A in the above proportion, a three-dimensional crosslinking effect is produced and a good adhesive effect is obtained.
紫外線照射によりカチオンを発生するカチオン重合開始剤(C)の使用量は、(A)脂環式エポキシ2個を有しエステル結合を有していない脂環式エポキシ化合物と、(B)上記(A)と異なるエポキシ化合物はの合計量が100重量部に対して、0.01〜20重量部、好ましくは0.5〜15重量部さらに好ましくは1〜10重量部の範囲とすることができる。 The amount of the cationic polymerization initiator (C) that generates a cation upon irradiation with ultraviolet rays is as follows: (A) an alicyclic epoxy compound having two alicyclic epoxies and no ester bond; and (B) the above ( The total amount of the epoxy compound different from A) is 0.01 to 20 parts by weight, preferably 0.5 to 15 parts by weight, and more preferably 1 to 10 parts by weight with respect to 100 parts by weight. .
本発明の第3の実施形態において、さらに(D)分子中にエポキシ基またはエポキシ基と水酸基を有するアクリル樹脂を使用する。(D)成分の使用量は、(A)成分と(B)成分の合計100重量部に対して1〜85重量部、好ましくは3〜70重量部さらに好ましくは5〜60重量部である。(D)成分の使用量が、1重量部未満では、(D)成分の使用効果がなく、一方(D)成分の使用量が85重量部を超えると得られる硬化物の接着力が低下する。 In the third embodiment of the present invention, (D) an acrylic resin having an epoxy group or an epoxy group and a hydroxyl group in the molecule is used. (D) The usage-amount of a component is 1-85 weight part with respect to a total of 100 weight part of (A) component and (B) component, Preferably it is 3-70 weight part, More preferably, it is 5-60 weight part. When the amount of component (D) used is less than 1 part by weight, there is no effect of using component (D), while when the amount of component (D) used exceeds 85 parts by weight, the adhesive strength of the resulting cured product is reduced. .
カチオン重合開始剤(C)の使用量は、(A)成分と(B)成分の合計100重量部に対して(D)を1〜85重量部加えた組成物100重量部に対して、0.1〜20重量部好ましくは0.5〜15重量部さらに好ましくは1〜10重量部の範囲とすることができる。 The amount of the cationic polymerization initiator (C) used is 0 with respect to 100 parts by weight of the composition obtained by adding 1 to 85 parts by weight of (D) to 100 parts by weight of the total of components (A) and (B). 0.1 to 20 parts by weight, preferably 0.5 to 15 parts by weight, more preferably 1 to 10 parts by weight.
本発明の第4の実施形態において、(E)水酸基を分子中に2〜4個持つカプロラクトン変性ポリオール化合物を使用する。(E)成分の使用量は、(A)成分と(B)成分の合計100重量部に対して1〜50重量部、好ましくは3〜45重量部さらに好ましくは5〜40重量部である。(E)成分の使用量が、1重量部未満では、(E)成分の使用効果がなく、一方(E)成分の使用量が50重量部を超えると得られる硬化物の接着力が低下する。 In the fourth embodiment of the present invention, (E) a caprolactone-modified polyol compound having 2 to 4 hydroxyl groups in the molecule is used. (E) The usage-amount of a component is 1-50 weight part with respect to a total of 100 weight part of (A) component and (B) component, Preferably it is 3-45 weight part, More preferably, it is 5-40 weight part. When the amount of component (E) used is less than 1 part by weight, there is no effect of using component (E). On the other hand, when the amount of component (E) used exceeds 50 parts by weight, the adhesive strength of the resulting cured product decreases. .
カチオン重合開始剤(C)の使用量は、(A)成分と(B)成分の合計100重量部に対して(E)を1〜50重量部加えた樹脂組成物100重量部に対して、0.1〜20重量部好ましくは0.5〜15重量部さらに好ましくは1〜10重量部の範囲とすることができる
接着剤全体としての配合割合として、本発明の第2の実施形態において、(A)成分40〜99重量部、(B)成分1〜60重量部、(C)成分0.3〜10重量部、好ましくは、(A)成分50〜98重量部、(B)成分2〜50重量部、(C)成分0.5〜8重量部、さらに好ましくは、(A)成分60〜95重量部、(B)成分5〜40重量部、(C)成分1〜5重量部の範囲とすることができる。
The amount of the cationic polymerization initiator (C) used is based on 100 parts by weight of the resin composition obtained by adding 1 to 50 parts by weight of (E) to 100 parts by weight of the total of the components (A) and (B). 0.1 to 20 parts by weight, preferably 0.5 to 15 parts by weight, and more preferably 1 to 10 parts by weight. In the second embodiment of the present invention, as a blending ratio as the whole adhesive, (A) Component 40-99 parts by weight, (B) Component 1-60 parts by weight, (C) Component 0.3-10 parts by weight, preferably (A) Component 50-98 parts by weight, (B) Component 2 -50 parts by weight, (C) component 0.5-8 parts by weight, more preferably (A) component 60-95 parts by weight, (B) component 5-40 parts by weight, (C) component 1-5 parts by weight Range.
本発明第3の実施形態において、(A)成分5〜95重量部、(B)成分5〜85重量部、(C)成分0.3〜10重量部、(D)成分1〜85重量部、好ましくは、(A)成分10〜90重量部、(B)成分10〜75重量部、(C)成分0.5〜8重量部、(D)成分が1〜75重量部、さらに好ましくは、(A)成分20〜80重量部、(B)成分17〜60重量部、(C)成分1〜5重量部、(D)成分が3〜60重量部の範囲とすることができる。 In the third embodiment of the present invention, (A) component 5 to 95 parts by weight, (B) component 5 to 85 parts by weight, (C) component 0.3 to 10 parts by weight, and (D) component 1 to 85 parts by weight. The component (A) is preferably 10 to 90 parts by weight, the component (B) is 10 to 75 parts by weight, the component (C) is 0.5 to 8 parts by weight, and the component (D) is 1 to 75 parts by weight, more preferably. , (A) 20-80 parts by weight, (B) 17-17 parts by weight, (C) 1-5 parts by weight, and (D) components 3-60 parts by weight.
本発明第4の実施形態において、(A)成分5〜95重量部、(B)成分3〜85重量部、(C)成分0.3〜10重量部、(E)成分1〜50重量部、好ましくは、(A)成分10〜95重量部、(B)成分5〜80重量部、(C)成分0.5〜8重量部、(E)成分が3〜25重量部、さらに好ましくは、(A)成分20〜90重量部、(B)成分10〜70重量部、(C)成分1〜5重量部、(E)成分が5〜20重量部の範囲とすることができる。 In the fourth embodiment of the present invention, (A) component 5 to 95 parts by weight, (B) component 3 to 85 parts by weight, (C) component 0.3 to 10 parts by weight, and (E) component 1 to 50 parts by weight. The component (A) is 10 to 95 parts by weight, the component (B) is 5 to 80 parts by weight, the component (C) is 0.5 to 8 parts by weight, and the component (E) is 3 to 25 parts by weight, more preferably. , (A) 20-90 parts by weight, (B) 10-70 parts by weight, (C) 1-5 parts by weight, and (E) 5-20 parts by weight.
本発明の接着剤には、上記(A)、(B)、(C)及び(D)、(E)成分以外に、必要に応じて、増感剤;硬化を著しく阻害しない量の着色顔料、体質顔料などの顔料類、染料;ポリオール樹脂、フェノール樹脂、アクリル樹脂、ポリエステル樹脂、ポリオレフィン樹脂、エポキシ樹脂、エポキシ化ポリブタジエン樹脂などの改質樹脂;有機樹脂微粒子;溶剤などを配合することができる。 In the adhesive of the present invention, in addition to the components (A), (B), (C) and (D), (E), if necessary, a sensitizer; an amount of coloring pigment that does not significantly inhibit curing Pigments such as extender pigments, dyes; polyol resins, phenol resins, acrylic resins, polyester resins, polyolefin resins, epoxy resins, epoxidized polybutadiene resins and other modified resins; organic resin fine particles; solvents and the like can be blended .
前記増感剤は、紫外線による硬化性をさらに向上させる目的で配合されるものであり、例えば、ピレン、ペリレン、アクリジンオレンジ、チオキサントン、2−クロロチオキサントン、ベンゾフラビンなどを挙げることができる。この増感剤の配合量は、(A)成分と(B)成分との合計量100重量部に対して通常10重量部以下、好ましくは3重量部以下の範囲内で使用される。 The sensitizer is blended for the purpose of further improving curability by ultraviolet rays, and examples thereof include pyrene, perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, and benzoflavin. The blending amount of the sensitizer is usually 10 parts by weight or less, preferably 3 parts by weight or less with respect to 100 parts by weight of the total amount of the components (A) and (B).
また、改質樹脂を配合する場合には、該改質樹脂は、(A)成分と(B)成分の合計量100重量部に対して通常0.1〜50重量部、特に5〜20重量部の範囲内で使用することが好ましい。 Moreover, when mix | blending a modified resin, this modified resin is 0.1-50 weight part normally with respect to the total amount of 100 weight part of (A) component and (B) component, Especially 5-20 weight part. It is preferable to use within the range of parts.
レべリングを防止し、塗布性能を向上させるために、各種界面活性剤を添加することができる。界面活性剤としてシリコン系化合物、フッ素系化合物が使用できる。 Various surfactants can be added to prevent leveling and improve coating performance. Silicon-based compounds and fluorine-based compounds can be used as the surfactant.
有機樹脂微粒子を使用することも可能である。これらは、粒子径が50〜500nmの範囲内の有機樹脂微粒子が好ましく、例えば内部が3次元架橋したアクリル樹脂微粒子などを挙げることができる。有機樹脂微粒子としては、有機重合体を粉砕して微粒子化したもの;乳化剤の存在下に水中でエマルジョン重合して得られる重合体微粒子を乾燥、粉砕したもの;高分子安定剤の存在下に有機溶剤中でディスパージョン重合して得られる重合体微粒子を乾燥、粉砕したものなどを挙げることができる。本発明の接着剤に有機樹脂微粒子を配合することによって塗膜の密着性及び加工性を改良することができる。有機樹脂微粒子を配合する場合には、該有機樹脂微粒子の配合量は、(A)成分と(B)成分の合計量100重量部に対して通常0.1〜50重量部、特に1〜10重量部の範囲内であることが好ましい。 It is also possible to use organic resin fine particles. These are preferably organic resin fine particles having a particle diameter in the range of 50 to 500 nm, and examples thereof include acrylic resin fine particles whose inside is three-dimensionally cross-linked. Organic resin fine particles are obtained by pulverizing an organic polymer into fine particles; polymer fine particles obtained by emulsion polymerization in water in the presence of an emulsifier; dried and pulverized; organic in the presence of a polymer stabilizer. Examples thereof include those obtained by drying and pulverizing polymer fine particles obtained by dispersion polymerization in a solvent. By blending organic resin fine particles with the adhesive of the present invention, the adhesion and workability of the coating film can be improved. When organic resin fine particles are blended, the amount of the organic resin fine particles is usually 0.1 to 50 parts by weight, particularly 1 to 10 parts per 100 parts by weight of the total amount of the component (A) and the component (B). It is preferably within the range of parts by weight.
本発明の紫外線硬化型接着剤は、以上に述べた各成分を混合し、均一な接着剤となるように撹拌することにより調製することができる。例えば、各成分を混合し、必要に応じて加温、例えば50℃程度で加温し、ディソルバーなどの撹拌機にて均一になるまで、例えば10分間程度撹拌することにより調製することができる。 The ultraviolet curable adhesive of the present invention can be prepared by mixing the components described above and stirring the mixture so as to form a uniform adhesive. For example, each component can be mixed, heated as necessary, for example, at about 50 ° C., and stirred for about 10 minutes until uniform with a stirrer such as a dissolver. .
本発明の紫外線硬化型接着剤は、例えば、ロールコート塗装、スプレー塗装、ハケ塗り、バーコート塗装、ローラー塗り、シルクスクリーン印刷などの方法によって塗布することができる。接着剤が溶剤を含有する場合には、塗布後、加熱などにより溶剤を除去した後、紫外線照射によって硬化されるが、照射条件は塗布された接着剤の種類や膜厚等に応じて適宜変えることができる。照射する紫外線の波長としては、通常、200〜600nmの範囲内が適当であり、カチオン重合開始剤の種類等に応じて、感度の高い波長を有する照射源を適宜選択して使用することができる。 The ultraviolet curable adhesive of the present invention can be applied by a method such as roll coating, spray coating, brush coating, bar coating, roller coating or silk screen printing. When the adhesive contains a solvent, after application, the solvent is removed by heating or the like, and then cured by ultraviolet irradiation, but the irradiation conditions are appropriately changed according to the type of adhesive applied, film thickness, etc. be able to. The wavelength of the ultraviolet rays to be irradiated is usually within the range of 200 to 600 nm, and an irradiation source having a high sensitivity wavelength can be appropriately selected and used depending on the type of the cationic polymerization initiator. .
紫外線の照射源としては、例えば、高圧水銀ランプ、超高圧水銀ランプ、キセノンランプ、カーボンアーク、メタルハライドランプ、太陽光などを挙げることができる。塗膜への照射条件は、通常、線量が10〜1,000mJ/cm2、特に50〜500mJ/cm2となる範囲内が適している。 Examples of the ultraviolet irradiation source include a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, and sunlight. Irradiation condition to the coating film is usually within the range dose is 10~1,000mJ / cm 2, in particular 50 to 500 mJ / cm 2 is suitable.
また、紫外線照射後、必要に応じて接着剤を加熱してもよい。加熱によって接着剤中の未反応物の低減および紫外線照射による塗膜の硬化性や成型加工によって発生した歪みの緩和を行なうことができる。この加熱によって接着剤の硬度や密着性の向上を行なうことができる場合がある。上記加熱は、通常、150〜200℃の雰囲気温度で1〜30分間の条件で行なうことができる。 Moreover, you may heat an adhesive agent as needed after ultraviolet irradiation. Unreacted substances in the adhesive can be reduced by heating, and the curability of the coating film by ultraviolet irradiation and the distortion generated by the molding process can be reduced. In some cases, the heating can improve the hardness and adhesion of the adhesive. The said heating can be normally performed on the conditions for 1 to 30 minutes at 150-200 degreeC atmospheric temperature.
以下、実施例により本発明を具体的に説明するが、本発明はこれらに限定されるものではない。尚、「%」及び「部」は、特に示す場合を除くほか「重量%」及び「重量部」を示す。なお、実施例2、8は、参考例として記載するものである。
[合成例1]
前記式(2)の化合物であるビシクロヘキシル−3,3'−ジエン406gと、酢酸エチル1217gを反応器に仕込み、窒素を気相部に流しながら、且つ、反応器内の温度を37.5℃に保ちながら約3時間かけて30重量%過酢酸の酢酸エチル溶液(水分率0.41重量%)457gを滴下した。過酢酸の酢酸エチル溶液滴下終了後、40℃で1時間攪拌を行い反応を終了した。続いて反応器を30℃まで冷却し、反応粗液を水洗した。その後70℃/20mmHgで反応粗液から低沸成分を除去し、エポキシ化合物415gを得た。得られたエポキシ化合物のオキシラン酸素濃度は14.7重量%で、収率は85%であった。
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. “%” And “part” indicate “% by weight” and “part by weight”, unless otherwise specified. Examples 2 and 8 are described as reference examples.
[Synthesis Example 1]
406 g of bicyclohexyl-3,3′-diene, which is the compound of the formula (2), and 1217 g of ethyl acetate are charged into the reactor, and the temperature in the reactor is adjusted to 37.5 while flowing nitrogen into the gas phase portion. While maintaining the temperature, 457 g of a 30 wt% peracetic acid ethyl acetate solution (water content 0.41 wt%) was added dropwise over about 3 hours. After completion of the dropwise addition of peracetic acid in ethyl acetate, the mixture was stirred at 40 ° C. for 1 hour to complete the reaction. Subsequently, the reactor was cooled to 30 ° C., and the reaction crude liquid was washed with water. Thereafter, low boiling components were removed from the reaction crude liquid at 70 ° C./20 mmHg to obtain 415 g of an epoxy compound. The obtained epoxy compound had an oxirane oxygen concentration of 14.7% by weight and a yield of 85%.
得られたエポキシ化合物の1HNMRを用いて分析したところ、δ4.5〜5ppm付近の内部二重結合に由来するピークが消失し、δ2.9〜3.1ppm付近にエポキシ基に由来するプロトンのピークの生成が確認された。よって、エポキシ化合物が、前記式(1)の構造の非エステル型脂環式エポキシ化合物であることが確認された。
[合成例2]
前記式(4)の化合物であるシクロオクタジエン108gと、酢酸エチル108gを反応器に仕込み、窒素を気相部に流しながら、且つ、反応器内の温度を30℃になるように保ちながら約3時間かけて30重量%過酢酸の酢酸エチル溶液532gを滴下した。過酢酸の酢酸エチル溶液滴下終了後、30℃で5時間攪拌を行い反応を終了した。続いて反応器を20℃まで冷却し、攪拌状態の反応粗液に86.9gの炭酸ソーダを加えた後、更に10%NaOH水溶液219gを加え、攪拌を止めて静置し、反応粗液が2相に分離したら、下相の水相を抜き出した。この操作を3回繰り返した後に、残った有機相に対して250gの脱イオン水を加えて、残存する中和塩の洗浄を二回行った。その後、60℃/20mmHgで反応粗液から低沸成分を除去し、ジエポキシ化合物112.3gを得た。得られたジエポキシ化合物の収率は80.2%であった。
[合成例3]
前記式(6)の化合物であるテトラヒドロインデン240gと、酢酸エチル480gを反応器に仕込み、窒素を気相部に流しながら、且つ、反応器内の温度を30℃になるように保ちながら約3時間かけて30重量%過酢酸の酢酸エチル溶液1220gを滴下した。過酢酸の酢酸エチル溶液滴下終了後、30℃で6時間攪拌を行い反応を終了した。続いて反応器を20℃まで冷却し、攪拌状態の反応粗液に398gの炭酸ソーダを加えた後、更に10%NaOH水溶液1500gを加え、攪拌を止めて静置し、反応粗液が2相に分離したら、下相の水相を抜き出した。続いて、残った有機相に対して1000gの脱イオン水を加えて、残存する中和塩の洗浄を行った。その後、40℃/10mmHgで反応粗液から低沸成分を除去し、ジエポキシ化合物243gを得た。得られたジエポキシ化合物の収率は80%であった。
[合成例4〜5] (D)の合成
撹拌器、還流冷却管、滴下ろうと、温度計を備えたフラスコに表1に示される3,4−エポキシシクロヘキシルメチル−3,4−エポキシシクロヘキサンカルボキシレート(商品名CEL−2021P:ダイセル化学工業(株)製)を233g仕込む。そして空気を吹き込みながら105〜110℃に昇温し、表1に示されるモノマーと開始剤を3時間かけて滴下した。滴下終了後、1時間攪拌を行い反応を終了した。合成例4で得られたエポキシ基と水酸基も有するアクリル樹脂の水酸基価とオキシラン酸素濃度、合成例5で得られたエポキシ基と水酸基も有するアクリル樹脂の水酸基価とオキシラン酸素濃度をそれぞれ表1に示した。
When the obtained epoxy compound was analyzed using 1 HNMR, a peak derived from an internal double bond in the vicinity of δ4.5 to 5 ppm disappeared, and a proton derived from an epoxy group in the vicinity of δ2.9 to 3.1 ppm disappeared. Peak generation was confirmed. Therefore, it was confirmed that the epoxy compound is a non-ester type alicyclic epoxy compound having the structure of the formula (1).
[Synthesis Example 2]
About 108 g of cyclooctadiene, which is the compound of the above formula (4), and 108 g of ethyl acetate were charged into a reactor, and nitrogen was passed through the gas phase portion, and the temperature in the reactor was kept at 30 ° C. Over a period of 3 hours, 532 g of a 30 wt% ethyl acetate solution of peracetic acid was added dropwise. After completion of the dropwise addition of peracetic acid in ethyl acetate, the reaction was terminated by stirring at 30 ° C. for 5 hours. Subsequently, the reactor was cooled to 20 ° C., 86.9 g of sodium carbonate was added to the stirred reaction crude liquid, 219 g of 10% NaOH aqueous solution was further added, the stirring was stopped, and the reaction crude liquid was allowed to stand. After separation into two phases, the lower aqueous phase was extracted. After repeating this operation three times, 250 g of deionized water was added to the remaining organic phase, and the remaining neutralized salt was washed twice. Thereafter, low boiling components were removed from the reaction crude liquid at 60 ° C./20 mmHg to obtain 112.3 g of a diepoxy compound. The yield of the obtained diepoxy compound was 80.2%.
[Synthesis Example 3]
The reactor was charged with 240 g of tetrahydroindene, which is a compound of formula (6), and 480 g of ethyl acetate, and while flowing nitrogen into the gas phase part and maintaining the temperature in the reactor at 30 ° C., about 3 Over a period of time, 1220 g of a 30 wt% peracetic acid ethyl acetate solution was added dropwise. After completion of the dropwise addition of peracetic acid in ethyl acetate, the mixture was stirred at 30 ° C. for 6 hours to complete the reaction. Subsequently, the reactor was cooled to 20 ° C., 398 g of sodium carbonate was added to the stirred reaction crude liquid, and then 1500 g of 10% NaOH aqueous solution was added, stirring was stopped and the reaction crude liquid was separated into two phases. Was separated, the lower aqueous phase was extracted. Subsequently, 1000 g of deionized water was added to the remaining organic phase to wash the remaining neutralized salt. Thereafter, the low boiling component was removed from the reaction crude liquid at 40 ° C./10 mmHg to obtain 243 g of a diepoxy compound. The yield of the obtained diepoxy compound was 80%.
[Synthesis Examples 4 to 5] Synthesis of (D) 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate shown in Table 1 in a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. (Trade name CEL-2021P: manufactured by Daicel Chemical Industries, Ltd.) is charged with 233 g. And it heated up to 105-110 degreeC, blowing air, and the monomer and initiator which are shown in Table 1 were dripped over 3 hours. After completion of the dropwise addition, the reaction was completed by stirring for 1 hour. Table 1 shows the hydroxyl value and oxirane oxygen concentration of the acrylic resin having an epoxy group and a hydroxyl group obtained in Synthesis Example 4, and the hydroxyl value and oxirane oxygen concentration of the acrylic resin having an epoxy group and a hydroxyl group obtained in Synthesis Example 5 respectively. Indicated.
攪拌機、温度計を備えた500mlのフラスコに表2及び表3に示した各成分を加え30℃で20分攪拌して、紫外線硬化型接着剤を得た。このようにして得た各接着剤を、厚さ0.50mmのPET、及び厚さ0.50mmのガラス板に20μmになるように塗布した。
紫外線照射を高圧水銀灯(120W/cm)を用い、塗装板との距離15cmから、エネルギー線量が500mJ/cm2となるように行ない塗膜を硬化させて試験塗板とした。 得られた各試験塗板について下記の試験方法に基づいて試験を行なった。なお、試験はすべて23℃において行なった。
Each component shown in Table 2 and Table 3 was added to a 500 ml flask equipped with a stirrer and a thermometer, and stirred at 30 ° C. for 20 minutes to obtain an ultraviolet curable adhesive. Each of the adhesives thus obtained was applied to PET having a thickness of 0.50 mm and a glass plate having a thickness of 0.50 mm so as to be 20 μm.
Ultraviolet irradiation was performed using a high-pressure mercury lamp (120 W / cm) from a distance of 15 cm to the coating plate so that the energy dose was 500 mJ / cm 2, and the coating film was cured to obtain a test coating plate. Each of the obtained test coated plates was tested based on the following test method. All tests were performed at 23 ° C.
接着力は、以下の手順で測定した。
ガラスの場合は1mm厚、Al板(アルミ板)は0.5mm厚、PET(ポリエステルフィルム)は200μm厚、Acセル(アセチルセルローズフィルム)は200μm厚で、各15mm幅の試験片を用意し、重ね合わせ長さを5mmとし、重ね合わせ部分に接着剤を塗布し、泡を抜きながら貼り合わせて固定し、高圧水銀灯120w×10m×4パス照射した後(照射量1200mJ)引っ張り試験機で接着力(kg/15mm)を測定した。
結果を表4及び表5に示した。
The adhesive force was measured by the following procedure.
In the case of glass, 1 mm thickness, Al plate (aluminum plate) 0.5 mm thickness, PET (polyester film) 200 μm thickness, Ac cell (acetylcellulose film) 200 μm thickness, and prepare 15 mm wide test pieces, Overlap length is 5mm, adhesive is applied to the overlapped part, bonded and fixed while removing bubbles, irradiated with high pressure mercury lamp 120w x 10m x 4 passes (irradiation amount 1200mJ), adhesive strength with tensile tester (Kg / 15 mm) was measured.
The results are shown in Tables 4 and 5.
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JP5143449B2 (en) * | 2007-03-02 | 2013-02-13 | 株式会社ダイセル | Thermal or active energy ray curable adhesive |
JP4973876B2 (en) | 2007-08-22 | 2012-07-11 | 信越化学工業株式会社 | Pattern forming method and pattern surface coating material used therefor |
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