JP6554313B2 - Coating agent and method for producing cured film thereof - Google Patents
Coating agent and method for producing cured film thereof Download PDFInfo
- Publication number
- JP6554313B2 JP6554313B2 JP2015096298A JP2015096298A JP6554313B2 JP 6554313 B2 JP6554313 B2 JP 6554313B2 JP 2015096298 A JP2015096298 A JP 2015096298A JP 2015096298 A JP2015096298 A JP 2015096298A JP 6554313 B2 JP6554313 B2 JP 6554313B2
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- JP
- Japan
- Prior art keywords
- compound
- coating
- active energy
- cyclocarbonate
- photobase generator
- 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.)
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- 239000011248 coating agent Substances 0.000 title claims description 99
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 75
- 238000000576 coating method Methods 0.000 claims description 71
- 239000000203 mixture Substances 0.000 claims description 64
- 239000010408 film Substances 0.000 claims description 62
- 239000003795 chemical substances by application Substances 0.000 claims description 33
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 23
- 230000002062 proliferating effect Effects 0.000 claims description 22
- 150000007514 bases Chemical class 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 9
- 239000010409 thin film Substances 0.000 claims description 8
- 238000009501 film coating Methods 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 description 28
- -1 diamine compound Chemical class 0.000 description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 16
- 239000002904 solvent Substances 0.000 description 15
- 239000000178 monomer Substances 0.000 description 13
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 11
- 239000011521 glass Substances 0.000 description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 238000003860 storage Methods 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 239000003999 initiator Substances 0.000 description 9
- 230000001588 bifunctional effect Effects 0.000 description 8
- 239000005056 polyisocyanate Substances 0.000 description 8
- 229920001228 polyisocyanate Polymers 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 6
- DKYWVDODHFEZIM-UHFFFAOYSA-N ketoprofen Chemical compound OC(=O)C(C)C1=CC=CC(C(=O)C=2C=CC=CC=2)=C1 DKYWVDODHFEZIM-UHFFFAOYSA-N 0.000 description 6
- 229960000991 ketoprofen Drugs 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229920006255 plastic film Polymers 0.000 description 6
- 239000002985 plastic film Substances 0.000 description 6
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 5
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical class OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 5
- 229960001701 chloroform Drugs 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- IRXSLJNXXZKURP-UHFFFAOYSA-N fluorenylmethyloxycarbonyl chloride Chemical compound C1=CC=C2C(COC(=O)Cl)C3=CC=CC=C3C2=C1 IRXSLJNXXZKURP-UHFFFAOYSA-N 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000007142 ring opening reaction Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- IMQFZQVZKBIPCQ-UHFFFAOYSA-N 2,2-bis(3-sulfanylpropanoyloxymethyl)butyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(CC)(COC(=O)CCS)COC(=O)CCS IMQFZQVZKBIPCQ-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- JUCCZCZDAPBGIV-UHFFFAOYSA-N 2-(9-oxoxanthen-2-yl)propanoic acid Chemical compound C1=CC=C2C(=O)C3=CC(C(C(O)=O)C)=CC=C3OC2=C1 JUCCZCZDAPBGIV-UHFFFAOYSA-N 0.000 description 2
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 2
- BYPFICORERPGJY-UHFFFAOYSA-N 3,4-diisocyanatobicyclo[2.2.1]hept-2-ene Chemical compound C1CC2(N=C=O)C(N=C=O)=CC1C2 BYPFICORERPGJY-UHFFFAOYSA-N 0.000 description 2
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 2
- JFMGYULNQJPJCY-UHFFFAOYSA-N 4-(hydroxymethyl)-1,3-dioxolan-2-one Chemical compound OCC1COC(=O)O1 JFMGYULNQJPJCY-UHFFFAOYSA-N 0.000 description 2
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000005587 carbonate group Chemical group 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 229920006264 polyurethane film Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 125000006239 protecting group Chemical group 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- VKQJCUYEEABXNK-UHFFFAOYSA-N 1-chloro-4-propoxythioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(OCCC)=CC=C2Cl VKQJCUYEEABXNK-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- QURLTYPDDOGVKH-UHFFFAOYSA-N 2,3,4,6,7,8,9,9a-octahydro-1h-pyrimido[1,2-a]pyrimidine Chemical compound N1CCCN2CCCNC21 QURLTYPDDOGVKH-UHFFFAOYSA-N 0.000 description 1
- UXCIJKOCUAQMKD-UHFFFAOYSA-N 2,4-dichlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC(Cl)=C3SC2=C1 UXCIJKOCUAQMKD-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- LZHUBCULTHIFNO-UHFFFAOYSA-N 2,4-dihydroxy-1,5-bis[4-(2-hydroxyethoxy)phenyl]-2,4-dimethylpentan-3-one Chemical compound C=1C=C(OCCO)C=CC=1CC(C)(O)C(=O)C(O)(C)CC1=CC=C(OCCO)C=C1 LZHUBCULTHIFNO-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical group CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- BXYWKXBAMJYTKP-UHFFFAOYSA-N 2-[2-[2-[2-(3-sulfanylpropanoyloxy)ethoxy]ethoxy]ethoxy]ethyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCOCCOCCOCCOC(=O)CCS BXYWKXBAMJYTKP-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 PCKZAVNWRLEHIP-UHFFFAOYSA-N 0.000 description 1
- GNDOBZLRZOCGAS-JTQLQIEISA-N 2-isocyanatoethyl (2s)-2,6-diisocyanatohexanoate Chemical compound O=C=NCCCC[C@H](N=C=O)C(=O)OCCN=C=O GNDOBZLRZOCGAS-JTQLQIEISA-N 0.000 description 1
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical class CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- QOUUOKMIAABDOX-UHFFFAOYSA-N 4-(1-hydroxyprop-2-enyl)-1,3-dioxolan-2-one Chemical compound C=CC(O)C1COC(=O)O1 QOUUOKMIAABDOX-UHFFFAOYSA-N 0.000 description 1
- IKVYHNPVKUNCJM-UHFFFAOYSA-N 4-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(C(C)C)=CC=C2 IKVYHNPVKUNCJM-UHFFFAOYSA-N 0.000 description 1
- 125000004864 4-thiomethylphenyl group Chemical group 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Polyesters Or Polycarbonates (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Paints Or Removers (AREA)
Description
本発明は、活性エネルギー線硬化性組成物からなるコーティング剤及びその硬化被膜の製造方法に関し、更に詳しくは、薄膜のコーティング層が求められる用途に有用な活性エネルギー線硬化性組成物からなるコーティング剤と、その硬化被膜の製造方法に関するものである。 The present invention relates to a coating agent comprising an active energy ray-curable composition and a method for producing the cured film, and more particularly, a coating agent comprising an active energy ray-curable composition useful for applications where a thin coating layer is required. And a method for producing the cured coating.
活性エネルギー線硬化性組成物は、硬化速度が速く生産性が向上するなどの理由から、プラスチックや金属の表面コーティングや粘着剤組成物、接着剤組成物、レジスト材料等の用途において、幅広く使用されている。 Active energy ray-curable compositions are widely used in applications such as plastic and metal surface coatings, pressure-sensitive adhesive compositions, adhesive compositions, resist materials, etc., because the curing speed is fast and productivity is improved. ing.
従来より、このような活性エネルギー線硬化性組成物としては、ウレタンアクリレート、エポキシアクリレート、アクリルアクリレート等のアクリレート系化合物が広く使用されていた。中でも、液晶ディスプレイなどの光学部材用途として用いられるプラスチックフィルムのハードコート剤としては、プラスチックフィルムへの密着性に優れていることや、硬化被膜の硬度や耐靭性に優れる点で、分子凝集力の高いウレタン結合を有するウレタン（メタ）アクリレート系のコーティング剤が、好適に用いられていた（特許文献１を参照）。 Heretofore, acrylate compounds such as urethane acrylate, epoxy acrylate and acrylic acrylate have been widely used as such active energy ray curable compositions. Among them, as a hard coating agent for plastic films used for optical member applications such as liquid crystal displays, it has excellent molecular cohesion because it has excellent adhesion to plastic films and excellent hardness and toughness of cured coatings. A urethane (meth) acrylate-based coating agent having a high urethane bond has been suitably used (see Patent Document 1).
ところで、近年、液晶ディスプレイが使用されるデバイスでは、年々薄型化や小型化の要望が強まっており、それに用いられるハードコート剤についても薄膜化が求められるようになっている。しかしながら、特許文献１に示されるようなウレタン（メタ）アクリレート系コーティング剤は、一般的に電子線照射により硬化させたり、光ラジカル開始剤と組み合わせて紫外線照射により硬化させたりして用いられることが多いため、ラジカル反応による硬化反応が、空気中の酸素による重合阻害の影響を受ける場合があった。 By the way, in recent years, there is an increasing demand for thinning and miniaturization of devices in which a liquid crystal display is used, and the hard coating agent used therefor is also required to be thin. However, the urethane (meth) acrylate-based coating agent as disclosed in Patent Document 1 is generally used by being cured by electron beam irradiation or by being cured by ultraviolet irradiation in combination with a photo radical initiator. In many cases, the curing reaction due to the radical reaction may be affected by polymerization inhibition due to oxygen in the air.
そのため、ウレタン（メタ）アクリレート系コーティング剤では、アクリレート基が残留しやすかったり、塗膜表面の硬化が不充分になったりするという問題が生じる。特に、ラジカル重合は、塗膜表面近く（大気の近く）の方がより酸素阻害を大きく受けるため、薄膜状に塗布して硬化させる際には、充分に硬化したコーティング層（硬化体からなる被膜。以下、硬化被膜。）が得られにくい。そこで、このような問題が発生せず、薄膜でのコーティングが可能な系として、多官能アミンとシクロカーボネート化合物を反応させてなるポリウレタン系のコーティング剤が提案されている。 Therefore, in the case of the urethane (meth) acrylate-based coating agent, there arises a problem that the acrylate group tends to remain or the curing of the coating surface becomes insufficient. In particular, since radical polymerization is more susceptible to oxygen inhibition closer to the coating surface (closer to the atmosphere), a sufficiently cured coating layer (a coating consisting of a cured product) when applied in a thin film state and cured It is difficult to obtain a cured film). Therefore, a polyurethane-based coating agent obtained by reacting a polyfunctional amine and a cyclocarbonate compound has been proposed as a system that does not cause such a problem and can be coated with a thin film.
上記ポリウレタン系のコーティング剤の例として、特許文献２には、ジアミン化合物と二官能の５員環カーボナート化合物を反応して得られるポリヒドロキシウレタンが開示されている。また、特許文献３には、特定の五員環カーボネート基を有する化合物と、その分子内に第１級アミノ基及び架橋可能な反応性珪素基を有するアミノシラン化合物とからなる硬化性樹脂組成物が記載されている。 As an example of the polyurethane-based coating agent, Patent Document 2 discloses polyhydroxyurethane obtained by reacting a diamine compound with a bifunctional 5-membered carbonate compound. Patent Document 3 discloses a curable resin composition comprising a compound having a specific five-membered ring carbonate group and an aminosilane compound having a primary amino group and a crosslinkable reactive silicon group in the molecule. Have been described.
しかしながら、上記特許文献２，３に記載のポリウレタン系コーティング剤は、二液型（二液混合型）の硬化塗料として設計されているため、混合後の貯蔵安定性は考慮されておらず、塗布可能時間が短く使用時の作業性にも劣るという欠点があった。また、先にも述べたように、上記特許文献１に記載のウレタン（メタ）アクリレート系のコーティング剤は、使用直前に混合等の作業の必要のない一液型塗工液ではあるものの、塗膜表面の硬化不足により、硬化後の硬化被膜が充分な硬度や耐靭性を得られないという問題を抱えていた。 However, since the polyurethane-based coating agents described in Patent Documents 2 and 3 above are designed as a two-component (two-component mixed) curing paint, storage stability after mixing is not taken into consideration, and the coating is applied. There is a drawback that the available time is short and the workability at the time of use is inferior. Further, as described above, the urethane (meth) acrylate-based coating agent described in Patent Document 1 is a one-component coating liquid which does not require any work such as mixing immediately before use. Due to insufficient curing of the film surface, there has been a problem that the cured film after curing cannot obtain sufficient hardness and toughness.
そこで、本発明は、このような背景下において、塗膜の厚みが薄い場合でも実用的な硬化被膜強度を発現することができ、使用の容易な一液型の塗工液として利用可能な活性エネルギー線硬化性組成物からなるコーティング剤及びその硬化被膜の製造方法を提供することを目的とするものである。 Therefore, the present invention is capable of expressing a practical cured film strength even in the case where the thickness of the coating film is thin, and an activity that can be used as an easy-to-use one-component coating liquid. An object of the present invention is to provide a coating agent comprising an energy ray-curable composition and a method for producing a cured film thereof.
本発明者等は、上記課題を解決するために、鋭意研究を重ねた結果、従来のシクロ（環状）カーボネートとジアミンを反応させてなるポリウレタンの製法に代えて、シクロカーボネートと、ジアミンの発生源である光塩基発生剤とを含む活性エネルギー線硬化性組成物を、活性エネルギー線の照射により重合・硬化させると、塗膜の厚みが薄い場合でも、表面にべたつきのない、充分な硬化被膜強度を有する薄膜コーティング層が得られることを見い出した。また同時に、上記活性エネルギー線硬化性組成物が、保管（貯蔵）安定性に優れるため、一液型の塗工液として設計が可能なことも見い出し、本発明を完成した。 In order to solve the above-mentioned problems, the present inventors have conducted intensive research. As a result, instead of the conventional process for producing a polyurethane obtained by reacting cyclo (cyclic) carbonate and diamine, cyclocarbonate and diamine generation source. When the active energy ray-curable composition containing the photobase generator is polymerized and cured by irradiation with active energy rays, even if the coating thickness is thin, the surface is not sticky and sufficient cured coating strength It has been found that a thin film coating layer is obtained. At the same time, the active energy ray-curable composition is excellent in storage (storage) stability, so that it can be designed as a one-component coating liquid, and the present invention has been completed.
すなわち、本発明の要旨は、シクロカーボネート構造を２つ以上含有する化合物（Ａ）及び特定の光塩基発生剤（Ｂ）を所定の割合で含有する活性エネルギー線硬化性組成物からなるコーティング剤に関するものである。 That is, the gist of the present invention relates to a coating agent comprising an active energy ray-curable composition containing a compound (A) containing two or more cyclocarbonate structures and a specific photobase generator (B) in a predetermined ratio. Is.
また、本発明は、上記活性エネルギー線硬化性組成物からなるコーティング剤を硬化させる硬化被膜の製造方法も提供するものであり、とりわけ、プラスチックフィルム及び金属表面のハードコート剤として有用な、シクロカーボネート構造を２つ以上含有する化合物及び光塩基発生剤を含むコーティング剤である一液型の塗工液を用いて得られるポリウレタン被膜の製造方法を提供するものである。 The present invention also provides a method for producing a cured film that cures a coating agent comprising the above-mentioned active energy ray curable composition, and in particular, a cyclocarbonate useful as a hard coating agent for plastic films and metal surfaces. there is provided a method for producing a polyurethane coating obtained by using the one-component coating solution Ru coating der comprising a compound containing a structure of two or more and photobase generators.
本発明の活性エネルギー線硬化性組成物からなるコーティング剤（以下「活性エネルギー線硬化性組成物」又は単に「組成物」とすることがある）は、硬化被膜の厚みが薄い場合でも、表面にべたつきのない、実用的な被膜強度を有する硬化被膜（ハードコート層）を形成することができる。とりわけ、プラスチックフィルム及び金属表面のハードコート剤として有用である。 The coating agent comprising the active energy ray-curable composition of the present invention (hereinafter sometimes referred to as “active energy ray-curable composition” or simply “composition”) can be applied to the surface even when the thickness of the cured film is thin. A cured coating (hard coat layer) having a practical coating strength without stickiness can be formed. In particular, it is useful as a hard coating agent for plastic films and metal surfaces.
更に、上記本発明の活性エネルギー線硬化性組成物の中でも、塩基増殖剤（Ｃ）を含有しているものは、活性エネルギー線の照射により、多くの塩基が発生し、重合・硬化反応がより促進される。しかも、上記塩基増殖剤（Ｃ）から発生する塩基の連鎖反応により、活性エネルギー線照射後に組成物中に残存する未反応の光塩基発生剤（Ｂ）の量が、大幅に減少する。これにより、活性エネルギー線硬化性組成物の硬化被膜の保存安定性（被膜の経時安定性）がより向上する。 Furthermore, among the active energy ray-curable compositions of the present invention described above, those containing a base proliferating agent (C) generate a large number of bases upon irradiation with active energy rays, resulting in more polymerization / curing reaction. Promoted. Moreover, the amount of unreacted photobase generator (B) remaining in the composition after irradiation with active energy rays is greatly reduced by the chain reaction of the base generated from the base proliferating agent (C). Thereby, the storage stability of the cured coating of the active energy ray-curable composition (the stability over time of the coating) is further improved.
また、本発明において、活性エネルギー線硬化性組成物からなる一液型の塗工液が貯蔵安定性に優れ、しかも、薄膜の塗布においても、空気中の酸素による重合阻害の影響を受けにくいため、本発明の硬化被膜の製造方法は、一液型による塗工作業性の向上と相俟って、充分な被膜強度を有する硬化被膜を、素早く効率的に連続して生産することができる。とりわけ、プラスチックフィルム及び金属表面のハードコート用ポリウレタン被膜の製造に、特に有用である。 Further, in the present invention, a one-part coating liquid composed of an active energy ray-curable composition is excellent in storage stability, and is not easily affected by polymerization inhibition due to oxygen in the air even in the application of a thin film. The method for producing a cured film of the present invention can produce a cured film having sufficient film strength quickly and efficiently in combination with the improvement of the coating workability by a one-component type. It is particularly useful for the production of polyurethane films for hard coatings on plastic films and metal surfaces.
以下に本発明を詳細に説明する。
本発明のコーティング剤は、シクロカーボネート構造を２つ以上含有する化合物（Ａ）及び光塩基発生剤（Ｂ）を含有してなる活性エネルギー線硬化性組成物からなるものである。
The present invention is described in detail below.
The coating agent of the present invention comprises an active energy ray-curable composition comprising a compound (A) containing two or more cyclocarbonate structures and a photobase generator (B).
なお、本発明におけるシクロ（環状）カーボネート構造とは、保護基によりブロックされたエポキシ基を含む構造（以下、シクロカーボネート基）であり、本発明の化合物（Ａ）は、下記一般式（１）又は下記一般式（２）で示されるシクロカーボネート基を、単量体の構造中に２つ以上有する、好ましくは３つ以上含有することを特徴とするものである。 The cyclo (cyclic) carbonate structure in the present invention is a structure containing an epoxy group blocked by a protective group (hereinafter, cyclocarbonate group), and the compound (A) of the present invention is a compound represented by the following general formula (1) Alternatively, it is characterized in that the cyclocarbonate group represented by the following general formula (2) is contained in the structure of the monomer in two or more, preferably three or more.
以下、本発明の活性エネルギー線硬化性組成物に用いる化合物を個別に説明する。 Hereinafter, the compound used for the active energy ray curable composition of this invention is demonstrated separately.
〔シクロカーボネート構造を含有する化合物（Ａ）〕
本発明で用いるシクロカーボネート構造を含有する化合物（Ａ）としては、（ｉ）多価イソシアネート化合物とグリセリンカーボネート〔下記式（１−１）〕とを反応させて得られる、下記式（Ａ−１）のシクロカーボネート構造を２つ含有する化合物〔シクロカーボネート基含有ウレタンプレポリマー〕、（ｉｉ）ビニルグリセリンカーボネート〔下記式（１−２）〕とβ−メルカプトプロピオン酸類の混合物に、アルキルフェノン系光重合開始剤を添加して光照射することにより得られる、下記式（Ａ−２）のシクロカーボネート構造を３つ含有する化合物、（ｉｉｉ）ビニルエーテルシクロヘキシルカーボネート〔下記式（２−１）〕とβ−メルカプトプロピオン酸類の混合物に、アルキルフェノン系光重合開始剤を添加して光照射することにより得られる、下記式（Ａ−３）、（Ａ−４）のシクロカーボネート構造を３つ含有する化合物や、下記式（Ａ−５）のシクロカーボネート構造を４つ含有する化合物等が挙げられる。
[Compound (A) containing cyclocarbonate structure]
As the compound (A) containing a cyclocarbonate structure used in the present invention, (i) a polyvalent isocyanate compound and glycerin carbonate [the following formula (1-1)] are reacted to obtain a compound represented by the following formula (A-1) Compounds having two cyclocarbonate structures (cyclocarbonate group-containing urethane prepolymer), (ii) a mixture of vinylglycerin carbonate (the following formula (1-2)) and β-mercaptopropionic acids, alkylphenone-based light A compound containing three cyclocarbonate structures of the following formula (A-2) obtained by adding a polymerization initiator and irradiating light, (iii) vinyl ether cyclohexyl carbonate [the following formula (2-1)] and β -Irradiating light with the addition of an alkylphenone photopolymerization initiator to a mixture of mercaptopropionic acids And compounds having three cyclocarbonate structures of the following formulas (A-3) and (A-4), compounds having four cyclocarbonate structures of the following formula (A-5), etc. It is done.
また、他の例として、（ｉｖ）多官能エポキシ化合物中のエポキシ基の一部あるいは全部をシクロカーボネート化させた化合物、（ｖ）１分子中に少なくとも１個のエチレン性不飽和二重結合と１個以上のシクロカーボネート基とを有する単量体と他の重合性不飽和単量体との共重合反応によって得られる化合物、（ｖｉ）イソシアネートエチル（メタ）アクリレート共重合体等のイソシアネート基含有重合体にカーボネートモノアルコールを付加反応させた化合物、及び、（ｖｉｉ）酸クロライド基含有重合体にカーボネートモノアルコールを付加反応させた化合物等の中で、シクロカーボネート構造を２つ以上含有するものを、化合物（Ａ）として用いても良い。なお、上記（ｉ）〜（ｖｉｉ）の化合物は、１種類のみを単独で用いても良いし、必要に応じて複数種を組み合わせて用いても良い。 Further, as another example, (iv) a compound obtained by cyclocarbonate a part or all of epoxy groups in a polyfunctional epoxy compound, (v) at least one ethylenically unsaturated double bond in one molecule Compound obtained by copolymerization reaction of monomer having one or more cyclocarbonate groups and other polymerizable unsaturated monomer, (vi) isocyanate group content such as isocyanate ethyl (meth) acrylate copolymer Among compounds obtained by addition reaction of carbonate monoalcohol to a polymer and (vii) compounds obtained by addition reaction of carbonate monoalcohol to an acid chloride group-containing polymer, those containing two or more cyclocarbonate structures And the compound (A). In addition, the compound of said (i)-(vii) may be used individually by 1 type, and may be used in combination of multiple types as needed.
ここで、上記シクロカーボネート構造を２つ以上含有する化合物（Ａ）の中でも、得られる硬化被膜の強度及び硬度の観点から、シクロカーボネート構造を３つ以上含有することが好ましい。なお、使用に適する化合物（Ａ）は、目的とする硬化被膜の諸物性付与を考慮して適宜選択される。 Here, among the compounds (A) containing two or more cyclocarbonate structures, it is preferable to contain three or more cyclocarbonate structures from the viewpoint of the strength and hardness of the resulting cured film. In addition, the compound (A) suitable for use is appropriately selected in consideration of imparting various physical properties of the target cured film.
また、本発明で用いられるシクロカーボネート構造を２以上含有する化合物（Ａ）の分子量は、３００〜５０，０００であることが好ましく、より好ましくは１，０００〜３０，０００、更に好ましくは１，０００〜１０，０００である。かかる分子量が小さすぎると硬化被膜が脆くなる傾向がみられ、大きすぎると高粘度となり取り扱いにくくなる傾向がある。なお、上記の分子量は、分子構造から計算される理論分子量である。 The molecular weight of the compound (A) containing two or more cyclocarbonate structures used in the present invention is preferably 300 to 50,000, more preferably 1,000 to 30,000, and still more preferably 1, 000 to 10,000. If the molecular weight is too small, the cured film tends to be brittle, while if too large, the viscosity tends to be high and difficult to handle. The above molecular weight is the theoretical molecular weight calculated from the molecular structure.
上記（ｉ）の反応で用いられる多価イソシアネート系化合物としては、例えば、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、ポリフェニルメタンポリイソシアネート、変性ジフェニルメタンジイソシアネート、キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート、フェニレンジイソシアネート、ナフタレンジイソシアネート等の芳香族系ポリイソシアネート、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、リジンジイソシアネート、リジントリイソシアネート等の脂肪族系ポリイソシアネート、水添化ジフェニルメタンジイソシアネート、水添化キシリレンジイソシアネート、イソホロンジイソシアネート、ノルボルネンジイソシアネート、１，３−ビス（イソシアナトメチル）シクロヘキサン等の脂環式系ポリイソシアネート、あるいは、これらポリイソシアネートの３量体化合物又は多量体化合物、アロファネート型ポリイソシアネート、ビュレット型ポリイソシアネート、水分散型ポリイソシアネート（例えば、日本ポリウレタン工業社製の「アクアネート１００」、「アクアネート１１０」、「アクアネート２００」「アクアネート２１０」、旭化成ケミカルズ社製の「デュラネートＷＢ４０−１００」「デュラネートＷＴ２０−１００」「デュラネートＷＥ５０−１００」、ＤＩＣ社製の「バーノックＤＮＷ−５５００」「バーノックＤＮＷ−６０００」）等が挙げられる。また、上記の多価イソシアネート系化合物をあらかじめポリオールと反応させて得られるイソシアネート基含有ウレタンプレポリマー等も用いることができる。 Examples of the polyvalent isocyanate compound used in the reaction (i) include tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, and naphthalene. Aromatic polyisocyanates such as diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate and other aliphatic polyisocyanates, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate 1,3-bis (iso Aliphatic polyisocyanates such as anatomethyl) cyclohexane, or trimer compounds or multimer compounds of these polyisocyanates, allophanate type polyisocyanates, burette type polyisocyanates, water dispersion type polyisocyanates (for example, manufactured by Nippon Polyurethane Industry Co., Ltd.) “Aquanate 100”, “Aquanate 110”, “Aquanate 200”, “Aquanate 210”, “Duranate WB 40-100” “Duranate WT 20-100” “Duranate WE 50-100” manufactured by Asahi Kasei Chemicals Corporation, DIC Corporation “Burnock DNW-5500” “Burnock DNW-6000”) and the like. Moreover, the isocyanate group containing urethane prepolymer etc. which are obtained by making said polyvalent isocyanate type compound react with a polyol beforehand can also be used.
これらの中でも、黄変が少ない点から、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、リジンジイソシアネート等の脂肪族系ジイソシアネート、水添化ジフェニルメタンジイソシアネート、水添化キシリレンジイソシアネート、イソホロンジイソシアネート、ノルボルネンジイソシアネート、１，３−ビス（イソシアナトメチル）シクロヘキサン等の脂環式系ジイソシアネート、が好ましく用いられ、特に好ましくは硬化収縮が小さい点でイソホロンジイソシアネート、水添化ジフェニルメタンジイソシアネート、水添化キシリレンジイソシアネートが用いられ、更に好ましくは、反応性及び汎用性に優れる点で、下記式（３−１）で示されるイソホロンジイソシアネートが用いられる。 Among these, from the point of little yellowing, aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1, An alicyclic diisocyanate such as 3-bis (isocyanatomethyl) cyclohexane is preferably used, and particularly preferably isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate from the viewpoint of small curing shrinkage. More preferably, isophorone diisocyanate represented by the following formula (3-1) is used in terms of excellent reactivity and versatility.
また、上記（ｉｉ）の反応で用いられるβ−メルカプトプロピオン酸類としては、β−メルカプトプロピオン酸、トリメチロールプロパントリス（３−メルカプトプロピオネート）〔下記式（４−１）〕、トリス−［（３−メルカプトプロピオニルオキシ）−エチル］−イソシアヌレート〔下記式（４−２）〕、ペンタエリスリトールテトラキス（３−メルカプトプロピオネート）〔下記式（４−３）〕、テトラエチレングリコールビス（３−メルカプトプロピオネート）、ジペンタエリスリトールヘキサキス（３−メルカプトプロピオネート）等が挙げられる。 Examples of β-mercaptopropionic acids used in the reaction (ii) include β-mercaptopropionic acid, trimethylolpropane tris (3-mercaptopropionate) [formula (4-1) below], tris- [ (3-mercaptopropionyloxy) -ethyl] -isocyanurate [following formula (4-2)], pentaerythritol tetrakis (3-mercaptopropionate) [following formula (4-3)], tetraethylene glycol bis (3 -Mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate) and the like.
また更に、上記（ｉｉ）の反応で用いられる光重合開始剤の代表的な例としては、ジエトキシアセトフェノン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン〔下記式（５−１）〕、ベンジルジメチルケタール、４−（２−ヒドロキシエトキシ）フェニル−（２−ヒドロキシ−２−プロピル）ケトン、１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オン、２−ヒドロキシ−１−｛４−［４−（２−ヒドロキシ−２−メチル−プロピオニル）−ベンジル］−フェニル｝−２−メチル−プロパン−１−オン、１−ヒドロキシシクロヘキシルフェニルケトン、２−メチル−２−モルホリノ（４−チオメチルフェニル）プロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）ブタノン、２−ヒドロキシ−２−メチル−１−［４−（１−メチルビニル）フェニル］プロパノンオリゴマー等のアセトフェノン類が挙げられる。 Furthermore, representative examples of the photopolymerization initiator used in the reaction (ii) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one [the following formula (5- 1), benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2- Methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethyla Roh-1- (4-morpholinophenyl) butanone, acetophenone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer and the like.
上記アセトフェノン類（系）の他にも、光重合開始剤（光ラジカル重合開始剤）としては、例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル等のベンゾイン類；ベンゾフェノン、ｏ−ベンゾイル安息香酸メチル、４−フェニルベンゾフェノン、４−ベンゾイル−４’−メチル−ジフェニルサルファイド、３，３’，４，４’−テトラ（ｔ−ブチルパーオキシカルボニル）ベンゾフェノン、２，４，６−トリメチルベンゾフェノン、４−ベンゾイル−Ｎ，Ｎ−ジメチル−Ｎ−［２−（１−オキソ−２−プロペニルオキシ）エチル］ベンゼンメタナミニウムブロミド、（４−ベンゾイルベンジル）トリメチルアンモニウムクロリド等のベンゾフェノン類；２−イソプロピルチオキサントン、４−イソプロピルチオキサントン、２，４−ジエチルチオキサントン、２，４−ジクロロチオキサントン、１−クロロ−４−プロポキシチオキサントン、２−（３−ジメチルアミノ−２−ヒドロキシ）−３，４−ジメチル−９Ｈ−チオキサントン−９−オンメソクロリド等のチオキサントン類；２，４，６−トリメチルベンゾイル−ジフェニルフォスフィンオキサイド、ビス（２，６−ジメトキシベンゾイル）−２，４，４−トリメチル−ペンチルフォスフィンオキサイド、ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイド等のアシルフォスフォンオキサイド類；等を使用することができる。なお、これら光重合開始剤は、１種類のみを単独で用いても良いし、必要に応じて複数種を組み合わせて用いても良い。 Besides the above acetophenones (systems), examples of photopolymerization initiators (photoradical polymerization initiators) include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone , Methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 2,4, Benzopheno such as 6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-benzoylbenzyl) trimethylammonium chloride 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3, Thioxanthones such as 4-dimethyl-9H-thioxanthone-9-one mesochloride; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl- Acyl phosphine oxides such as pentyl phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenyl phosphine oxide; and the like can be used. In addition, these photoinitiators may be used individually by 1 type, and may be used in combination of multiple types as needed.
また、上記他の例の中で、例えば、（ｖ）エチレン性不飽和二重結合とシクロカーボネート基を有する単量体（以下、シクロカーボネート単量体）と、他の重合性不飽和単量体との共重合反応（ビニル重合体）に用いられる「シクロカーボネート単量体」としては、下記一般式（１−３）や一般式（２−２）で示されるようなビニルエーテル系シクロヘキシルカーボネート化合物が挙げられる。 Among the other examples, for example, (v) a monomer having an ethylenically unsaturated double bond and a cyclocarbonate group (hereinafter referred to as a cyclocarbonate monomer), and other polymerizable unsaturated monomers. As a “cyclocarbonate monomer” used in a copolymerization reaction (vinyl polymer) with a polymer, a vinyl ether cyclohexyl carbonate compound represented by the following general formula (1-3) or general formula (2-2) Is mentioned.
上記一般式（１−３）の化合物の具体例としては、２，３−カーボネートプロピル（メタ）アクリレート、２−メチル−２，３−カーボネートプロピル（メタ）アクリレート、３，４−カーボネートブチル（メタ）アクリレート、３−メチル−３，４−カーボネートブチル（メタ）アクリレート、４−メチル−３，４−カーボネートブチル（メタ）アクリレート、３−メチル−３，４−カーボネートブチル（メタ）アクリレート、６，７−カーボネートヘキシル（メタ）アクリレート、５−エチル−５，６−カーボネートヘキシル（メタ）アクリレート、７，８−カーボネートオクチル（メタ）アクリレート等の（メタ）アクリレート類；２，３−カーボネートプロピルビニルエーテル、メチル−２，３−カーボネートプロピルマレート、又は、メチル−２，３−カーボネートプロピルクロトネート等の化合物が挙げられる。 Specific examples of the compound of the general formula (1-3) include 2,3-carbonate propyl (meth) acrylate, 2-methyl-2,3-carbonate propyl (meth) acrylate, 3,4-carbonate butyl (meth) ) Acrylate, 3-methyl-3,4-carbonate butyl (meth) acrylate, 4-methyl-3,4-carbonate butyl (meth) acrylate, 3-methyl-3,4-carbonate butyl (meth) acrylate, 6, (Meth) acrylates such as 7-carbonate hexyl (meth) acrylate, 5-ethyl-5,6-carbonate hexyl (meth) acrylate, and 7,8-carbonate octyl (meth) acrylate; 2,3-carbonate propyl vinyl ether; Methyl-2,3-carbonate propyl malate, or Include compounds such as methyl-2,3-carbonate-propyl crotonate.
上記一般式（２−２）の化合物の具体例としては、５−〔Ｎ−（メタ）アクリロイルカルバモイルオキシメチル〕−５−エチル−１，３−ジオキサン−２−オン、５−〔Ｎ−｛２−（メタ）アクリロイルオキシ｝エチルカルバモイルオキシメチル〕−５−エチル−１，３−ジオキサン−２−オン、５−（アリルオキシメチル）−５−エチル−１，３−ジオキサン−２−オン等の化合物が挙げられる。 Specific examples of the compound of the general formula (2-2) include 5- [N- (meth) acryloylcarbamoyloxymethyl] -5-ethyl-1,3-dioxan-2-one, 5- [N- { 2- (Meth) acryloyloxy} ethylcarbamoyloxymethyl] -5-ethyl-1,3-dioxane-2-one, 5- (allyloxymethyl) -5-ethyl-1,3-dioxane-2-one and the like The compound of this is mentioned.
上記シクロカーボネート単量体は、１種類のみを単独で用いても良いし、必要に応じて複数種を組み合わせて用いても良い。 The said cyclocarbonate monomer may be used individually by 1 type, and may be used combining multiple types as needed.
また、上記共重合反応に用いられる「他の重合性不飽和単量体」としては、例えば、（１）アクリル酸エステル又はメタクリル酸エステル〔脂環式のアルキル基を有するもの、芳香環を有するもの、ヒドロキシアルキル基を有するもの、ポリアルキレングリコール基を有するもの等を含む〕、（２）グリシジル基含有エチレン性不飽和単量体、（３）不飽和ジカルボン酸エステル、（４）スチレン誘導体、（５）ジエン系化合物、（６）ハロゲン化ビニルやハロゲン化ビニリデン、（７）不飽和ケトン、（８）ビニルエステル、（９）ビニルエーテル、（１０）シアン化ビニル、（１１）アクリルアミドやそのアルキド置換アミド、（１２）Ｎ−置換マレイミド、（１３）フッ素含有α−オレフィン類又は（パー）フルオロアルキル・パーフルオロビニルエーテル類、（パー）フルオロアルキル（メタ）アクリレート類等のフッ素含有エチレン性不飽和単量体、（１４）シリル基含有（メタ）アクリレート、Ｎ，Ｎ−ジアルキルアミノアルキル（メタ）アクリレート、等が挙げられる。 Examples of the “other polymerizable unsaturated monomer” used in the copolymerization reaction include (1) acrylic acid ester or methacrylic acid ester [having an alicyclic alkyl group, having an aromatic ring. Including, those having a hydroxyalkyl group, those having a polyalkylene glycol group, etc., (2) glycidyl group-containing ethylenically unsaturated monomer, (3) unsaturated dicarboxylic acid ester, (4) styrene derivative, (5) Diene compounds, (6) vinyl halides and vinylidene halides, (7) unsaturated ketones, (8) vinyl esters, (9) vinyl ethers, (10) vinyl cyanide, (11) acrylamide and alkyds thereof Substituted amide, (12) N-substituted maleimide, (13) fluorine-containing α-olefins or (per) fluoroalkyl perf Fluorine-containing ethylenically unsaturated monomers such as olovinyl ethers, (per) fluoroalkyl (meth) acrylates, (14) silyl group-containing (meth) acrylates, N, N-dialkylaminoalkyl (meth) acrylates, etc. Is mentioned.
なお、上記シクロカーボネート基を開環し架橋反応を促進させるために、開環触媒を使用しても良い。開環触媒の例としては、シクロカーボネート基の開環触媒やエポキシ基の開環触媒などが挙げられる。 A ring-opening catalyst may be used to open the cyclocarbonate group and promote the crosslinking reaction. Examples of the ring-opening catalyst include a cyclocarbonate group ring-opening catalyst and an epoxy group ring-opening catalyst.
更に、エポキシ基をブロック化することにより形成パターンの安定性を高めることができる点で、上記シクロカーボネート単量体と他の重合性不飽和単量体との共重合反応により得られる化合物（ビニル重合体）には、カルボキシル基を導入することが好ましい。これにより、活性エネルギー線照射過程において保護基が解離し、エポキシ基とカルボキシル基とが反応して、最終的に不要なカルボン酸が消費されると共に、この反応により生じる架橋構造により、硬化被膜の耐溶剤性や耐熱性等が向上する。 Furthermore, the compound (vinyl) obtained by the copolymerization reaction of the above-mentioned cyclocarbonate monomer and other polymerizable unsaturated monomer in that the formation stability of the formation pattern can be improved by blocking the epoxy group. It is preferable to introduce a carboxyl group into the polymer). As a result, the protective group is dissociated in the active energy ray irradiation process, the epoxy group reacts with the carboxyl group, and finally the unnecessary carboxylic acid is consumed. Solvent resistance and heat resistance are improved.
〔光塩基発生剤（Ｂ）〕
本発明で用いる光塩基発生剤（Ｂ）としては、活性エネルギー線照射により塩基を２つ以上含有する化合物を生成する光塩基発生剤が好適に用いられ、中でも、安定性及び活性エネルギー線に対する感度が良い点で、塩基性化合物とカルボン酸との塩である光塩基発生剤を用いることが必要である。
[Photobase generator (B)]
As the photobase generator (B) used in the present invention, a photobase generator that generates a compound containing two or more bases by irradiation with active energy rays is preferably used. Among them, stability and sensitivity to active energy rays are particularly preferable. It is necessary to use a photobase generator which is a salt of a basic compound and a carboxylic acid.
上記光塩基発生剤（Ｂ）について詳しく説明すると、この光塩基発生剤（Ｂ）は、例えば、「カルボン酸のカルボキシル基」と「塩基性化合物の塩基性の官能基」との比が１：１となるようにカルボン酸と塩基性化合物とを混合して得られた塩を用いる。 The photobase generator (B) will be described in detail. In the photobase generator (B), for example, the ratio of “carboxyl group of carboxylic acid” to “basic functional group of basic compound” is 1: A salt obtained by mixing a carboxylic acid and a basic compound so as to be 1 is used.
上記カルボン酸には、下記一般式（６），（７）で代表される、光又は熱により酸の機能を失う酸（カルボン酸）が、好適に用いられる。 As the above-mentioned carboxylic acid, an acid (carboxylic acid) which loses the function of the acid by light or heat, which is represented by the following general formulas (6) and (7), is suitably used.
また、上記カルボン酸は、光又は熱により酸の機能を失う酸であれば、従来公知のものを用いることができるが、特に、活性光線又は熱により脱炭酸して酸の機能を失うものが好ましい。熱により酸の機能を失うカルボン酸としては、例えば、２００℃以上の温度範囲で酸の機能を失うものを好ましく用いることができる。 In addition, as the carboxylic acid, a conventionally known acid can be used as long as it loses the acid function by light or heat. In particular, the carboxylic acid loses the acid function by decarboxylation by active light or heat. preferable. As the carboxylic acid that loses the acid function due to heat, for example, one that loses the acid function in a temperature range of 200 ° C. or higher can be preferably used.
更に、上記一般式（６），（７）で表される化合物の中でも、特に、紫外線領域に感光波長を持ち、前記塩基性化合物と塩を形成した場合に光塩基発生剤としての反応開始効率が良い、上記式（６）の構造を有する化合物が好ましく、より好ましくは、下記一般式（６−１），（６−２）で表される化合物が好ましい。 Furthermore, among the compounds represented by the above general formulas (6) and (7), in particular, when the photosensitive wavelength is in the ultraviolet region and a salt is formed with the basic compound, the reaction initiation efficiency as a photobase generator A compound having a structure of the above formula (6) is preferable, and compounds represented by the following general formulas (6-1) and (6-2) are more preferable.
なお、本発明で使用する光塩基発生剤（Ｂ：塩基性化合物とカルボン酸との塩である光
塩基発生剤）に用いられる、他のカルボン酸の具体例としては、下記式（７−１）〜式（７−１６）で表される化合物等が挙げられる。
In addition, as a specific example of the other carboxylic acid used for the photobase generator (B: photobase generator which is a salt of a basic compound and a carboxylic acid) used by this invention, following formula (7-1 Compounds to the formulas (7-16) and the like.
なお、上記各光又は熱により酸の機能を失うカルボン酸は、１種類のみを単独で用いても良いし、必要に応じて複数種類を組み合わせて用いても良い。 In addition, the carboxylic acid which loses the function of an acid by each said light or heat may be used individually by 1 type, and may be used combining multiple types as needed.
次に、本発明の光塩基発生剤（Ｂ）を得るために前記カルボン酸と反応させる塩基性化合物は、特に限定されるものではなく、例えば、アミン誘導体、アミジン誘導体、グアニジン誘導体、ホスファゼン誘導体等を用いることが好ましい。具体例としては、下記の式（８−１）〜式（８−２２）等が挙げられる。なお、これらの塩基性化合物は、１種類のみを単独で用いても良いし、必要に応じて複数種類を組み合わせて用いても良い。 Next, the basic compound to be reacted with the carboxylic acid to obtain the photobase generator (B) of the present invention is not particularly limited, and examples thereof include amine derivatives, amidine derivatives, guanidine derivatives, phosphazene derivatives, and the like. Is preferably used. As a specific example, following formula (8-1)-formula (8-22) etc. are mentioned. In addition, these basic compounds may be used individually by 1 type, and may be used combining multiple types as needed.
上記光塩基発生剤（Ｂ）を作製する方法としては、例えば、（ｉ）溶媒に分散させたカルボン酸に、塩基性化合物を滴下しながら室温下で１時間撹拌して反応させ、反応終了後に溶媒を減圧除去して、カルボン酸と塩基性化合物との塩からなる光塩基発生剤を得る方法や、（ｉｉ）溶媒にカルボン酸と塩基性化合物とを分散させ、加熱しながら２時間撹拌して反応させた後、反応終了後に溶媒を減圧除去して再沈殿させ、カルボン酸と塩基性化合物との塩からなる光塩基発生剤を得る方法等が挙げられる。これらの製法により、活性エネルギー線照射により塩基を２つ以上生成する光塩基発生剤を、効率的に得ることができる。 As a method of producing the said photobase generator (B), for example, it is made to react by stirring at room temperature for 1 hour, dripping a basic compound to carboxylic acid disperse | distributed to the solvent, and after reaction completion Removing the solvent under reduced pressure to obtain a photobase generator comprising a salt of a carboxylic acid and a basic compound, or (ii) dispersing the carboxylic acid and the basic compound in a solvent and stirring for 2 hours while heating. The reaction is carried out, and after completion of the reaction, the solvent is removed under reduced pressure and reprecipitation is carried out to obtain a photobase generator comprising a salt of a carboxylic acid and a basic compound. By these production methods, a photobase generator that generates two or more bases by irradiation with active energy rays can be efficiently obtained.
また、これにより、カルボン酸と塩基性化合物との塩を、光塩基発生剤（Ｂ）として利用することが可能になると共に、硬化被膜（活性エネルギー線照射後）の保存安定性が向上する。すなわち、これら各光塩基発生剤（Ｂ）が、比較的熱により酸の機能を失い易い（熱化学的に分解され易い）光塩基発生剤であることから、活性エネルギー線照射後に組成物（樹脂）中に残存する未反応（未分解）の光塩基発生剤は、加熱により二次的に分解され失活する。これにより、本発明の活性エネルギー線硬化性組成物は、フォトリソグラフィ等の活性エネルギー線を用いたパターニング（パターン成形）に使用された場合でも、成形後の硬化被膜中の残存光塩基発生剤量が少なく、硬化被膜の保存安定性（経時の形状安定性）が大幅に向上する。 This also makes it possible to use a salt of a carboxylic acid and a basic compound as the photobase generator (B) and improve the storage stability of the cured coating (after irradiation with active energy rays). That is, since each of these photobase generators (B) is a photobase generator which is relatively easy to lose the function of an acid by heat (thermochemically decomposed), the composition (resin) after irradiation with active energy rays ) The unreacted (undecomposed) photobase generator remaining therein is secondarily decomposed and deactivated by heating. Thereby, even when the active energy ray-curable composition of the present invention is used for patterning (pattern forming) using active energy rays such as photolithography, the amount of residual photobase generator in the cured film after forming And the storage stability (shape stability over time) of the cured film is significantly improved.
本発明で使用する光塩基発生剤（Ｂ）としては、例えば、下記式（Ｂ−１）〜式（Ｂ−４）で表される化合物等が挙げられる。 As a photobase generator (B) used by this invention, the compound etc. which are represented by following formula (B-1)-formula (B-4) are mentioned, for example.
なお、光塩基発生剤（Ｂ）の含有量は、前記シクロカーボネート構造を２つ以上含有する化合物（Ａ）１００重量部に対して、１〜３００重量部であり、より好ましくは５〜２００重量部、更に好ましくは５〜１５０重量部である。光塩基発生剤（Ｂ）の含有量が少なすぎると硬化不良となる傾向がみられ、多すぎると、溶液安定性（貯蔵安定性）が低下する傾向がみられ、硬化被膜の脆化や着色の問題が起こりやすい傾向にある。 The content of the photobase generator (B), relative to the compound cyclocarbonate structure containing two or more (A) 100 parts by weight of, Ri 1-300 parts by der, more preferably 5 to 200 It is a part by weight, more preferably 5 to 150 parts by weight. If the content of the photo base generator (B) is too small, curing failure tends to be observed. If the content is too large, solution stability (storage stability) tends to decrease, and embrittlement or coloring of the cured film is observed. The problem tends to occur.
次に、本発明の活性エネルギー線硬化性組成物は、前記シクロカーボネート構造を２つ以上含有する化合物（Ａ）及び光塩基発生剤（Ｂ）と共に、塩基増殖剤（Ｃ）を含有する構成を、好適に採用する。 Next, the active energy ray-curable composition of the present invention has a configuration containing a base proliferating agent (C) together with a compound (A) and a photobase generator (B) containing two or more of the above-mentioned cyclocarbonate structures. , Preferably adopted.
〔塩基増殖剤（Ｃ）〕
この塩基増殖剤（Ｃ）は、活性エネルギー線照射によりアミン（塩基）を発生すると共に、この発生した塩基により、塩基増殖剤自身と前記光塩基発生剤とが自己触媒的に分解され、新たに多量の塩基が増殖的に生成される。また、塩基増殖剤は、上記発生した多量の塩基により、シクロカーボネート構造を２つ以上含有する化合物（樹脂組成物）の重合・硬化反応を、より促進する効果を奏する。
[Base proliferating agent (C)]
The base proliferating agent (C) generates an amine (base) by irradiation with active energy rays, and the generated base causes the base proliferating agent itself and the photobase generating agent to be autocatalytically decomposed, and newly A large amount of base is produced proliferatively. Further, the base proliferating agent has an effect of further promoting the polymerization and curing reaction of the compound (resin composition) containing two or more cyclocarbonate structures by the large amount of the generated bases.
本発明で用いる塩基増殖剤（Ｃ）としては、活性エネルギー線照射及び／又は加熱によりアミンを増殖的に発生する化合物を使用する。以下に、代表的な塩基増殖剤として、フルオレニル系化合物〔下記の式（Ｃ−１），（Ｃ−２）及び（Ｃ−３）〜（Ｃ−９）〕、スルホン系化合物〔下記の式（Ｃ−１０）〜（Ｃ−１９）〕、３−ニトロペンタン−２−イル系化合物〔下記の式（Ｃ−２０）〜（Ｃ−２４）〕等を挙げることができる。 As the base proliferating agent (C) used in the present invention, a compound that proliferates an amine by irradiation with active energy rays and / or heating is used. In the following, as representative base multiplication agents, fluorenyl compounds [the following formulas (C-1), (C-2) and (C-3) to (C-9)], sulfone compounds [the following formulas (C-10) to (C-19)], 3-nitropentan-2-yl compounds [the following formulas (C-20) to (C-24)] and the like can be mentioned.
これら塩基増殖剤（Ｃ）の添加により、本発明の活性エネルギー線硬化性組成物は、活性エネルギー線の照射及び加熱により、多くのアミン（塩基）が発生し、重合・硬化反応がより促進される。しかも、上記塩基増殖剤（Ｃ）から発生する塩基の連鎖反応により、活性エネルギー線照射後に組成物（樹脂）中に残存する未反応（未分解）の光塩基発生剤（Ｂ）の量が、大幅に減少する。これにより、活性エネルギー線硬化性組成物の硬化被膜の保存安定性（経時の形状安定性）がより向上する。 By adding these base proliferating agents (C), the active energy ray-curable composition of the present invention generates many amines (bases) by irradiation and heating of the active energy rays, and the polymerization / curing reaction is further accelerated. The Moreover, the amount of the unreacted (undecomposed) photobase generator (B) remaining in the composition (resin) after irradiation with the active energy ray by the chain reaction of the base generated from the base proliferating agent (C), Decrease significantly. Thereby, the storage stability (the shape stability over time) of the cured film of the active energy ray-curable composition is further improved.
なお、上記塩基増殖剤（Ｃ）の含有量は、前記光塩基発生剤（Ｂ）１００重量部に対して、１０〜２，０００重量部であることが好ましく、より好ましくは５０〜１，５００重量部、更に好ましくは１００〜１，０００重量部である。塩基増殖剤（Ｃ）の含有量が少なすぎると硬化不足となる傾向がみられ、多すぎると、溶液安定性（貯蔵安定性）が低下する傾向がみられ、硬化被膜の脆化や着色の問題が起こりやすい傾向にある。 The content of the base proliferating agent (C) is preferably 10 to 2,000 parts by weight, and more preferably 50 to 1,500, based on 100 parts by weight of the photobase generator (B). It is a part by weight, more preferably 100 to 1,000 parts by weight. When the content of the base proliferating agent (C) is too low, curing tends to be insufficient, and when it is too high, solution stability (storage stability) tends to decrease, and embrittlement or coloring of the cured film is caused. Problems tend to occur.
かくして本発明のシクロカーボネート構造を２つ以上含有する化合物（Ａ）及び光塩基発生剤（Ｂ）、好ましくは更に塩基増殖剤（Ｃ）を含有する活性エネルギー線硬化性組成物が得られるが、必要に応じて更に、本発明の効果を阻害しない範囲で、表面調整剤、レベリング剤や、油、酸化防止剤、難燃剤、帯電防止剤、充填剤、安定剤、補強剤、艶消し剤、研削剤、有機微粒子、無機微粒子等を適宜配合することも可能である。 Thus, an active energy ray-curable composition comprising a compound (A) containing two or more cyclocarbonate structures of the present invention and a photobase generator (B), preferably further a base multiplication agent (C) is obtained, If necessary, as long as the effect of the present invention is not impaired, the surface conditioner, leveling agent, oil, antioxidant, flame retardant, antistatic agent, filler, stabilizer, reinforcing agent, matting agent, It is also possible to appropriately blend grinding agents, organic fine particles, inorganic fine particles and the like.
また、本発明の活性エネルギー線硬化性組成物は、必要に応じて、有機溶剤を配合し、粘度を調整して使用することも可能である。かかる有機溶剤としては、例えば、メタノール、エタノール、プロパノール、ｎ−ブタノール、ｉ−ブタノール等のアルコール類、アセトン、メチルイソブチルケトン、メチルエチルケトン、シクロヘキサノン等のケトン類、エチルセロソルブ等のセロソルブ類、トルエン、キシレン等の芳香族類、プロピレングリコールモノメチルエーテル等のグリコールエーテル類、酢酸メチル、酢酸エチル、酢酸ブチル等の酢酸エステル類、ジアセトンアルコール等が挙げられる。これら上記の有機溶剤は、単独で用いても良いし、必要に応じて複数種を組み合わせて用いても良い。 Moreover, the active energy ray-curable composition of the present invention can be used by blending an organic solvent and adjusting the viscosity as necessary. Such organic solvents include, for example, alcohols such as methanol, ethanol, propanol, n-butanol and i-butanol, ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone, cellosolves such as ethyl cellosolve, toluene and xylene And aromatic ethers such as, glycol ethers such as propylene glycol monomethyl ether, acetates such as methyl acetate, ethyl acetate and butyl acetate, and diacetone alcohol. These organic solvents may be used alone or in combination of a plurality of types as necessary.
なお、本発明の活性エネルギー線硬化性組成物を製造するにあたり、シクロカーボネート構造を２つ以上含有する化合物（Ａ）及び光塩基発生剤（Ｂ）、好ましくは更に塩基増殖剤（Ｃ）を含有する組成物の混合方法については、特に限定されるものではなく、例えば、３成分を一括で混合する方法、２成分を混合した後に残る１成分を混合する方法等、種々の方法により混合することができる。また、このようにして得られる本発明の活性エネルギー線硬化性組成物は、先にも述べたように、一液型の塗工液として用いられる。 In addition, in manufacturing the active energy ray curable composition of the present invention, a compound (A) containing two or more cyclocarbonate structures and a photo base generator (B), preferably further containing a base multiplying agent (C) The mixing method of the composition to be mixed is not particularly limited, and for example, mixing may be performed by various methods such as a method of mixing three components at once, a method of mixing one component remaining after mixing the two components, Can do. Moreover, the active energy ray-curable composition of the present invention obtained in this way is used as a one-component coating solution as described above.
更に、本発明の活性エネルギー線硬化性組成物は、各種基材へのトップコート剤やアンカーコート剤など、塗膜形成用の硬化性樹脂組成物として有効に用いられるものであり、活性エネルギー線硬化性組成物を基材に塗工した後（有機溶剤で希釈した組成物を塗工した場合には、更に乾燥させた後）、活性エネルギー線を照射することにより硬化される。塗工方法としては、特に限定されるものではなく、例えば、スプレー、シャワー、ディッピング、ロール、スピン、スクリーン印刷、インクジェット印刷、ディスペンサー等のようなウェットコーティング法が挙げられる。 Furthermore, the active energy ray-curable composition of the present invention is effectively used as a curable resin composition for coating film formation, such as a topcoat agent and an anchor coat agent on various substrates. After the curable composition is applied to the substrate (when the composition diluted with an organic solvent is applied, it is further dried) and then cured by irradiation with active energy rays. The coating method is not particularly limited, and examples thereof include wet coating methods such as spraying, showering, dipping, roll, spinning, screen printing, ink jet printing, and dispenser.
また、かかる活性エネルギー線としては、遠紫外線、紫外線、近紫外線、赤外線等の光線、Ｘ線、γ線等の電磁波の他、電子線、プロトン線、中性子線等が利用できるが、硬化速度、照射装置の入手のし易さ、価格面等から紫外線照射による硬化が有利である。 Further, as such active energy rays, rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, electromagnetic waves such as X-rays and γ rays, electron beams, proton rays, neutron rays, etc. can be used. Curing by ultraviolet irradiation is advantageous from the viewpoint of availability and cost of the irradiation apparatus.
更に、紫外線照射により硬化させる方法としては、１５０〜４５０ｎｍ波長域の光を発する高圧水銀ランプ、超高圧水銀灯、カーボンアーク灯、メタルハライドランプ、キセノンランプ、ケミカルランプ、無電極放電ランプ、ＬＥＤ等を用いて、１０〜５０００ｍＪ／ｃｍ２程度照射すればよい。 Furthermore, as a method of curing by ultraviolet irradiation, a high pressure mercury lamp, an ultra high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrode discharge lamp, an LED, etc. emitting light in the 150-450 nm wavelength region The irradiation may be performed at about 10 to 5000 mJ / cm 2 .
また、紫外線照射後は、必要に応じて加熱を行って硬化の完全を図ることが好ましい。加熱条件としては、５０〜２００℃で５〜１２０分程度の硬化加熱を行うことができる。 Moreover, after ultraviolet irradiation, it is preferable to heat as needed and to aim at completion of hardening. As heating conditions, curing heating can be performed at 50 to 200 ° C. for about 5 to 120 minutes.
塗工膜厚（硬化後の膜厚）としては、薄塗りの場合は、通常０．１〜１５μｍであることが好ましく、厚塗りの場合は、１５〜１００μｍであることが好ましい。本発明においては、薄塗りで用いた場合に特に顕著な効果を発揮するものである。 The coating film thickness (film thickness after curing) is usually preferably 0.1 to 15 μm in the case of thin coating, and preferably 15 to 100 μm in the case of thick coating. In the present invention, a particularly remarkable effect is exhibited when used in a thin coating.
また、本発明の活性エネルギー線硬化性組成物を塗工する対象である基材としては、ポリオレフィン系樹脂、ポリエステル系樹脂、ポリカーボネート系樹脂、アクリロニトリルブタジエンスチレン共重合体（ＡＢＳ）、ポリスチレン系樹脂等やそれらの成型品（フィルム、シート、カップ、等）、金属基材（アルミニウム、銅、鉄、ＳＵＳ，亜鉛、マグネシウム、これらの合金等）、金属蒸着膜、ガラス等が挙げられる。 Examples of the base material to which the active energy ray-curable composition of the present invention is applied include polyolefin resins, polyester resins, polycarbonate resins, acrylonitrile butadiene styrene copolymers (ABS), polystyrene resins, and the like. And moldings thereof (films, sheets, cups, etc.), metal substrates (aluminum, copper, iron, SUS, zinc, magnesium, alloys thereof, etc.), metal vapor deposition films, glass and the like.
以下、実施例を挙げて本発明を更に具体的に説明するが、本発明はその要旨を超えない限り以下の実施例に限定されるものではない。なお、例中、「部」、「％」は、重量基準を意味する。また、以下の実施例は、硬化性組成物がウレタン系樹脂組成物であり、予め混合して準備した、シクロカーボネート構造を２つ以上含有する化合物（Ａ）及び光塩基発生剤（Ｂ）を含む一液型のウレタン系活性エネルギー線硬化性樹脂組成物塗工液を、薄膜状に塗布した後、活性エネルギー線を照射して重合を開始させ、更に加熱によりこの重合反応を完了させることを特徴とするポリウレタン被膜の製造方法である。 EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In the examples, "parts" and "%" mean weight basis. In the following examples, the curable composition is a urethane resin composition, and a compound (A) containing two or more cyclocarbonate structures and a photobase generator (B) prepared by mixing in advance are used. After applying a coating solution of a one-part type urethane-based active energy ray curable resin composition into a thin film, the active energy ray is irradiated to initiate polymerization, and further, the polymerization reaction is completed by heating. It is a manufacturing method of the polyurethane film characterized by the above.
＜シクロカーボネート構造を含有する化合物（Ａ）＞
シクロカーボネート構造を２つ以上含有する化合物（Ａ）として以下のものを調製した。
<Compound (A) containing cyclocarbonate structure>
The following were prepared as a compound (A) containing two or more cyclocarbonate structures.
＜シクロカーボネート構造を２つ以上含有する化合物（Ａ−１）の製造＞
温度計、撹拌機、水冷コンデンサー備えたフラスコに、多価イソシアネート化合物としてイソホロンジイソシアネート〔前記式（３−１）〕３２６ｇ（１．５ｍｏｌ）と、４−（ヒドロキシメチル）−１，３−ジオキソラン−２−オン〔前記式（１−１）〕３５１．４ｇ（３．０ｍｏｌ）と、溶媒としてメチルエチルケトン３３３ｇと、反応触媒としてジブチルスズジラウレート０．０５ｇを仕込み、６０℃で反応させ、残存イソシアネート基が０．３％以下となった時点で反応を終了し、シクロカーボネート構造を２つ有する化合物〔下記式（Ａ−１）、分子量４５８〕を得た。
<Production of Compound (A-1) Having Two or More Cyclocarbonate Structures>
In a flask equipped with a thermometer, a stirrer, and a water-cooled condenser, 326 g (1.5 mol) of isophorone diisocyanate [the above formula (3-1)] as a polyvalent isocyanate compound, 4- (hydroxymethyl) -1,3-dioxolane- 2-One [said formula (1-1)] 351.4g (3.0mol), methyl ethyl ketone 333g as a solvent, 0.05g of dibutyltin dilaurate as a reaction catalyst are charged, reacted at 60 ° C, residual isocyanate group is 0 The reaction was terminated when it became 3% or less, and a compound having the two cyclocarbonate structures [the following formula (A-1), molecular weight 458] was obtained.
＜シクロカーボネート構造を２つ以上含有する化合物（Ａ−２）の製造＞
温度計、撹拌機、水冷コンデンサー、窒素吹込み口を備えたフラスコに、４−ビニル−１，３−ジオキソラン−２−オン〔前記式（１−２）〕１．８ｇ（１．６ｍｍｏｌ）と、β−メルカプトプロピオン酸類としてトリメチロールプロパントリス（３−メルカプトプロピオネート）〔前記式（４−１）〕１．８ｇ（４．４ｍｍｏｌ）と、光重合開始剤として２−ヒドロキシ−２−メチル−１−フェニル−プロパン−１−オン〔前記式（５−１）〕０．０２ｇ（０．１２ｍｍｏｌ）を仕込み、撹拌しながら、２５４ｎｍの波長の紫外線を２時間かけて照射（全照射量１０ｍＷ／ｃｍ２）して、シクロカーボネート構造を３つ有する化合物〔下記式（Ａ−２）、分子量７５７〕を得た。
<Production of Compound (A-2) Having Two or More Cyclocarbonate Structures>
In a flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen inlet, 1.8 g (1.6 mmol) of 4-vinyl-1,3-dioxolan-2-one [Formula (1-2)] 1.8 g (4.4 mmol) of trimethylolpropane tris (3-mercaptopropionate) [the above formula (4-1)] as a β-mercaptopropionic acid, and 2-hydroxy-2-methyl as a photopolymerization initiator 1-phenyl-propan-1-one [said Formula (5-1)] 0.02 g (0.12 mmol) was charged, and it irradiated, over 2 hours, the ultraviolet-ray of the wavelength of 254 nm while stirring (total irradiation amount 10 mW / Cm 2 ) to obtain a compound having three cyclocarbonate structures (the following formula (A-2), molecular weight 757).
＜シクロカーボネート構造を２つ以上含有する化合物（Ａ−３）の製造＞
温度計、撹拌機、水冷コンデンサー、窒素吹込み口を備えたフラスコに、５−（アリルオキシメチル）−５−エチル−１，３−ジオキサン−２−オン〔前記式（２−１）〕３．５ｇ（１８ｍｍｏｌ）と、β−メルカプトプロピオン酸類としてトリメチロールプロパントリス（３−メルカプトプロピオネート）〔前記式（４−１）〕２．３ｇ（５．７ｍｍｏｌ）と、光重合開始剤として２−ヒドロキシ−２−メチル−１−フェニル−プロパン−１−オン〔前記式（５−１）〕０．０６３ｇ（０．３８ｍｍｏｌ）を仕込み、撹拌しながら、２５４ｎｍの波長の紫外線を２時間かけて照射（全照射量１０ｍＷ／ｃｍ２）して、シクロカーボネート構造を３つ有する化合物〔下記式（Ａ−３）、分子量１０１４〕を得た。
<Production of Compound (A-3) Having Two or More Cyclocarbonate Structures>
In a flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen inlet, 5- (allyloxymethyl) -5-ethyl-1,3-dioxan-2-one [formula (2-1)] 3 .5 g (18 mmol), 2.3 g (5.7 mmol) of trimethylolpropane tris (3-mercapto propionate) [the formula (4-1)] as .beta.-mercaptopropionic acids, and 2 as a photopolymerization initiator -Hydroxy-2-methyl-1-phenyl-propan-1-one [formula (5-1)] 0.063 g (0.38 mmol) was charged, and ultraviolet light having a wavelength of 254 nm was applied over 2 hours while stirring. Irradiation (total irradiation amount: 10 mW / cm 2 ) gave a compound having three cyclocarbonate structures (the following formula (A-3), molecular weight 1014).
＜シクロカーボネート構造を２つ以上含有する化合物（Ａ−４）の製造＞
温度計、撹拌機、水冷コンデンサー、窒素吹込み口を備えたフラスコに、５−（アリルオキシメチル）−５−エチル−１，３−ジオキサン−２−オン〔前記式（２−１）〕３．５ｇ（１７ｍｍｏｌ）と、β−メルカプトプロピオン酸類としてトリス−［（３−メルカプトプロピオニルオキシ）−エチル］−イソシアヌレート〔前記式（４−２）〕３．０ｇ（５．８ｍｍｏｌ）と、光重合開始剤として２−ヒドロキシ−２−メチル−１−フェニル−プロパン−１−オン〔前記式（５−１）〕０．０５ｇ（０．３ｍｍｏｌ）を仕込み、撹拌しながら、２５４ｎｍの波長の紫外線を２時間かけて照射（全照射量１０ｍＷ／ｃｍ２）して、シクロカーボネート構造を３つ有する化合物〔下記式（Ａ−４）、分子量１１２５〕を得た。
<Production of Compound (A-4) Having Two or More Cyclocarbonate Structures>
In a flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen inlet, 5- (allyloxymethyl) -5-ethyl-1,3-dioxan-2-one [formula (2-1)] 3 And .5 g (17 mmol), and 3.0 g (5.8 mmol) of tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate [the formula (4-2)] as the β-mercaptopropionic acids, and photopolymerization As an initiator, 0.05 g (0.3 mmol) of 2-hydroxy-2-methyl-1-phenyl-propan-1-one [formula (5-1)] was charged, and UV light having a wavelength of 254 nm was stirred. Irradiation (total irradiation amount 10 mW / cm 2 ) was performed for 2 hours to obtain a compound having the three cyclocarbonate structure [formula (A-4) below, molecular weight 1125].
＜シクロカーボネート構造を２つ以上含有する化合物（Ａ−５）の製造＞
温度計、撹拌機、水冷コンデンサー、窒素吹込み口を備えたフラスコに、５−（アリルオキシメチル）−５−エチル−１，３−ジオキサン−２−オン〔前記式（２−１）〕５．０ｇ（２５ｍｍｏｌ）と、ペンタエリスリトールテトラキス（メルカプトプロピオネート）〔前記式（４−３）〕３．０ｇ（６．２ｍｍｏｌ）と、光重合開始剤として２−ヒドロキシ−２−メチル−１−フェニル−プロパン−１−オン〔前記式（５−１）〕０．１１ｇ（０．６８ｍｍｏｌ）を仕込み、撹拌しながら、２５４ｎｍの波長の紫外線を２時間かけて照射（全照射量１０ｍＷ／ｃｍ２）して、シクロカーボネート構造を４つ有する化合物〔下記式（Ａ−５）、分子量１３０４〕を得た。
<Production of Compound (A-5) Having Two or More Cyclocarbonate Structures>
In a flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen inlet, 5- (allyloxymethyl) -5-ethyl-1,3-dioxan-2-one [formula (2-1)] 5 .0 g (25 mmol), 3.0 g (6.2 mmol) of pentaerythritol tetrakis (mercaptopropionate) [said formula (4-3)] and 2-hydroxy-2-methyl-1-l as a photopolymerization initiator 0.11 g (0.68 mmol) of phenyl-propan-1-one [said formula (5-1)] was charged, and it was irradiated for 2 hours with ultraviolet light of a wavelength of 254 nm while stirring (total irradiation amount 10 mW / cm 2 Thus, a compound having the four cyclocarbonate structures [the following formula (A-5), molecular weight 1304] was obtained.
＜光塩基発生剤（Ｂ）＞
光塩基発生剤（Ｂ）として以下のものを調製した。
<Photobase generator (B)>
The following were prepared as a photobase generator (B).
＜光塩基発生剤（Ｂ−１）の製造＞
バイアル瓶に、カルボン酸としてケトプロフェン〔前記式（７−７）〕１．０２ｇ（４ｍｍｏｌ）と、ジエチルエーテルを仕込み、塩基性化合物としてイソホロンジアミン〔前記式（８−６）〕０．３４ｇ（２ｍｍｏｌ）を滴下して、その後室温で１時間撹拌して反応させた。反応終了後に溶媒を除去して減圧乾燥し、ケトプロフェンとイソホロンジアミンの塩からなる光塩基発生剤〔下記式（Ｂ−１）、分子量６７９〕を得た。
<Production of photobase generator (B-1)>
In a vial, ketoprofen [the above formula (7-7)] 1.02 g (4 mmol) as a carboxylic acid and diethyl ether are charged, and as a basic compound, isophorone diamine [the above formula (8-6)] 0.34 g (2 mmol) ) Was added dropwise and then reacted at room temperature with stirring for 1 hour. After completion of the reaction, the solvent was removed and the residue was dried under reduced pressure to obtain a photobase generator (the following formula (B-1), molecular weight 679) consisting of a salt of ketoprofen and isophorone diamine.
＜光塩基発生剤（Ｂ−２）の製造＞
温度計、撹拌機、水冷コンデンサーを備えたフラスコに、カルボン酸としてケトプロフェン〔前記式（７−７）〕２．０４ｇ（８．０２ｍｍｏｌ）と、塩基性化合物としてトリス（２−アミノエチル）アミン〔前記式（８−５）〕０．３９ｇ（２．６７ｍｍｏｌ）と溶媒としてアセトンを加え、４０℃で２時間撹拌して反応させた。その後溶媒を除去し、アセトンとジエチルエーテルで再沈殿し、ケトプロフェンとトリス（２−アミノエチル）アミンの塩からなる光塩基発生剤〔下記式（Ｂ−２）、分子量９０９〕を得た。
<Production of photobase generator (B-2)>
In a flask equipped with a thermometer, a stirrer, and a water-cooled condenser, 2.04 g (8.02 mmol) of ketoprofen [said formula (7-7)] as a carboxylic acid and tris (2-aminoethyl) amine [a basic compound] [Formula (8-5)] 0.39 g (2.67 mmol) and acetone as a solvent were added, and the mixture was stirred at 40 ° C. for 2 hours to be reacted. Thereafter, the solvent was removed, and reprecipitation was carried out with acetone and diethyl ether to obtain a photobase generator (the following formula (B-2), molecular weight 909) consisting of ketoprofen and a salt of tris (2-aminoethyl) amine.
＜光塩基発生剤（Ｂ−３）の製造＞
温度計、撹拌機、水冷コンデンサーを備えたフラスコに、カルボン酸としてケトプロフェン〔前記式（７−７）〕３．０ｇを含有したエーテル溶液３０ｍＬを仕込み、塩基性化合物としてジアザビシクロウンデセン〔前記式（８−１５）〕１．８ｇを滴下後、室温で１時間撹拌して反応させた。その後溶媒を除去し、ケトプロフェンとジアザビシクロウンデセンの塩からなる光塩基発生剤〔下記式（Ｂ−３）、分子量４０７〕を得た。
<Production of photobase generator (B-3)>
In a flask equipped with a thermometer, a stirrer, and a water-cooled condenser, 30 mL of an ether solution containing 3.0 g of ketoprofen [said formula (7-7)] is charged as a carboxylic acid, and diazabicycloundecene [said as a basic compound] After dropwise addition of 1.8 g of the formula (8-15), the mixture was reacted by stirring at room temperature for 1 hour. Thereafter, the solvent was removed to obtain a photobase generator (the following formula (B-3), molecular weight 407) consisting of a salt of ketoprofen and diazabicycloundecene.
＜光塩基発生剤（Ｂ−４）の製造＞
温度計、撹拌機、水冷コンデンサーを備えたフラスコに、カルボン酸として２−（９−オキソ−９Ｈ−キサンテン−２−イル）プロパン酸〔前記式（７−１１）〕３．０ｇを含有したエーテル溶液３０ｍＬを仕込み、塩基性化合物として２，３，４，６，７，８，９，９ａ−オクタヒドロ−１Ｈ−ピリミド［１，２−ａ］ピリミジン〔前記式（８−１８）〕１．６ｇを滴下後、室温で１時間撹拌して反応させた。その後溶媒を除去し、２−（９−オキソ−９Ｈ−キサンテン−２−イル）プロパン酸と２，３，４，６，７，８，９，９ａ−オクタヒドロ−１Ｈ−ピリミド［１，２−ａ］ピリミジンの塩からなる光塩基発生剤〔下記式（Ｂ−４）、分子量４１０〕を得た。
<Production of photobase generator (B-4)>
Ether having 3.0 g of 2- (9-oxo-9H-xanthen-2-yl) propanoic acid [the above formula (7-11)] as a carboxylic acid in a flask equipped with a thermometer, a stirrer, and a water-cooled condenser 30 mL of the solution is charged, and 1.6 g of 2,3,4,6,7,8,9,9a-octahydro-1H-pyrimido [1,2-a] pyrimidine [said formula (8-18)] as a basic compound The reaction mixture was reacted by stirring at room temperature for 1 hour. The solvent is then removed and 2- (9-oxo-9H-xanthen-2-yl) propanoic acid and 2,3,4,6,7,8,9,9,9a-octahydro-1H-pyrimido [1,2- a) A photobase generator consisting of a salt of pyrimidine (the following formula (B-4), molecular weight 410) was obtained.
＜塩基増殖剤（Ｃ）＞
塩基増殖剤（Ｃ）として以下のものを調製した。
<Base proliferating agent (C)>
The following were prepared as base proliferating agents (C).
＜塩基増殖剤（Ｃ−１）の製造＞
温度計、撹拌機、水冷コンデンサーを備えたフラスコに、９−フルオレニルメチルオキシカルボン酸クロライド２．０７ｇ（８．０ｍｍｏｌ）と溶媒としてテトラヒドロフラン（ＴＨＦ）５０ｍＬを仕込み、そこにイソホロンジアミン〔前記式（８−６）〕０．６８ｇ（４．０ｍｍｏｌ）とトリエチルアミン〔前記式（８−９）〕０．８２ｇ（８．１ｍｍｏｌ）をＴＨＦ １０ｍＬに溶解させた溶液を滴下し、室温で１時間反応させた。その後クロロホルムで抽出し、乾燥して、９−フルオレニルメチルオキシカルボン酸クロライドとイソホロンジアミンの塩からなる二官能の塩基増殖剤〔下記式（Ｃ−１）、分子量６１５〕を得た。
<Production of base proliferating agent (C-1)>
In a flask equipped with a thermometer, a stirrer, and a water-cooled condenser, 2.07 g (8.0 mmol) of 9-fluorenylmethyl oxycarboxylic acid chloride and 50 mL of tetrahydrofuran (THF) as a solvent are charged, and there is isophorone diamine [said formula (8-6)] A solution of 0.68 g (4.0 mmol) and 0.82 g (8.1 mmol) of triethylamine [the above formula (8-9)] dissolved in 10 mL of THF is added dropwise, and reacted at room temperature for 1 hour I let you. Thereafter, extraction with chloroform and drying were carried out to obtain a difunctional base proliferating agent consisting of a salt of 9-fluorenylmethyl oxycarboxylic acid chloride and isophorone diamine [the following formula (C-1), molecular weight 615].
＜塩基増殖剤（Ｃ−２）の製造＞
温度計、撹拌機、水冷コンデンサーを備えたフラスコに、９−フルオレニルメチルオキシカルボン酸クロライド２．０２ｇ（７．８ｍｍｏｌ）と溶媒としてＴＨＦ ３０ｍＬを仕込み、そこに２，２，２−トリアミノエチルトリアミン０．３１ｇ（２．１ｍｍｏｌ）とトリエチルアミン０．９０ｇ（９．０ｍｍｏｌ）をＴＨＦ ２０ｍＬに溶解させた溶液を滴下し、室温で１．５時間反応させた。その後溶媒を除去してクロロホルムを加え、５％塩酸水溶液、炭酸水素ナトリウム飽和水溶液、塩酸ナトリウム飽和水溶液で順次抽出し、減圧乾燥して、９−フルオレニルメチルオキシカルボン酸クロライドとトリアミノエチルトリアミンの塩からなる三官能の塩基増殖剤〔下記式（Ｃ−２）、分子量８１３〕を得た。
<Production of base proliferating agent (C-2)>
In a flask equipped with a thermometer, a stirrer, and a water-cooled condenser, 2.02 g (7.8 mmol) of 9-fluorenylmethyl oxycarboxylic acid chloride and 30 mL of THF as a solvent are charged, and 2,2,2-triamino is added thereto. A solution of 0.31 g (2.1 mmol) of ethyltriamine and 0.90 g (9.0 mmol) of triethylamine in 20 mL of THF was added dropwise and allowed to react at room temperature for 1.5 hours. Thereafter, the solvent is removed, chloroform is added, and the mixture is sequentially extracted with a 5% aqueous hydrochloric acid solution, a saturated aqueous sodium hydrogencarbonate solution and a saturated aqueous sodium chloride solution, and dried under reduced pressure to obtain 9-fluorenylmethyl oxycarboxylic acid chloride and triaminoethyltriamine. The trifunctional base growth agent [following Formula (C-2), molecular weight 813] which consists of a salt of is obtained.
＜実施例１〜８の評価用硬化被膜の形成＞
上記のシクロカーボネート構造を２つ以上含有する化合物（Ａ）、光塩基発生剤（Ｂ）、塩基増殖剤（Ｃ）を、表１に示す割合で配合して塗工液を調整した後、バーコーターで薄膜状に塗布して、紫外線を照射することにより、本発明の実施例の組成物からなる硬化被膜を作製した。
<Formation of a cured film for evaluation of Examples 1 to 8>
A compound (A) containing two or more of the above cyclocarbonate structures, a photo base generator (B), and a base growth agent (C) are blended in the proportions shown in Table 1 to prepare a coating solution, and then a bar is prepared. A cured film made of the composition of the example of the present invention was prepared by coating the film with a coater and irradiating with ultraviolet rays.
〔実施例１〕
上記で得られた二官能のシクロカーボネート化合物（Ａ−１）０．０８ｇと、三官能の光塩基発生剤（Ｂ−２）０．１０ｇとを、テトラヒドロフラン（ＴＨＦ）０．４ｇに溶解して活性エネルギー線硬化性組成物の塗工液を得た。得られた塗工液をガラス板上にバーコーターで塗布し、８０℃で１分間予備乾燥した。その後、３１３ｎｍの波長の紫外線を５０００ｍＪ／ｃｍ２照射し、更に１００℃で６０分間加熱して、実施例１の硬化被膜（膜厚１μｍ）を得た。
Example 1
In 0.4 g of tetrahydrofuran (THF), 0.08 g of the bifunctional cyclocarbonate compound (A-1) obtained above and 0.10 g of the trifunctional photobase generator (B-2) are dissolved. The coating liquid of the active energy ray curable composition was obtained. The obtained coating liquid was coated on a glass plate with a bar coater, and predried at 80 ° C. for 1 minute. Thereafter, ultraviolet rays having a wavelength of 313 nm were irradiated at 5000 mJ / cm 2 and further heated at 100 ° C. for 60 minutes to obtain a cured film of Example 1 (film thickness: 1 μm).
〔実施例２〕
上記で得られた二官能のシクロカーボネート化合物（Ａ−１）０．０８ｇと、二官能の光塩基発生剤（Ｂ−１）０．００８ｇと、二官能の塩基増殖剤（Ｃ−１）０．０６ｇとを、ＴＨＦ ０．４ｇに溶解して活性エネルギー線硬化性組成物の塗工液を得た。得られた塗工液をガラス板上にバーコーターで塗布し、８０℃で１分間予備乾燥した。その後、３１３ｎｍの波長の紫外線を５０００ｍＪ／ｃｍ２照射し、更に１００℃で６０分間加熱して、実施例２の硬化被膜（膜厚１μｍ）を得た。
Example 2
0.08 g of the bifunctional cyclocarbonate compound (A-1) obtained above, 0.008 g of the bifunctional photobase generator (B-1), and bifunctional base proliferating agent (C-1) 0 .06 g was dissolved in 0.4 g of THF to obtain a coating liquid of an active energy ray-curable composition. The obtained coating liquid was coated on a glass plate with a bar coater, and predried at 80 ° C. for 1 minute. Thereafter, ultraviolet rays with a wavelength of 313 nm were irradiated at 5000 mJ / cm 2 and further heated at 100 ° C. for 60 minutes to obtain a cured coating of Example 2 (film thickness 1 μm).
〔実施例３〕
上記で得られた二官能のシクロカーボネート化合物（Ａ−１）０．０８ｇと、二官能の光塩基発生剤（Ｂ−１）０．００８ｇと、三官能の塩基増殖剤（Ｃ−２）０．０１４ｇとを、ＴＨＦ １ｇに溶解して活性エネルギー線硬化性組成物の塗工液を得た。得られた塗工液をガラス板上にバーコーターで塗布し、８０℃で１分間予備乾燥した。その後、３１３ｎｍの波長の紫外線を５０００ｍＪ／ｃｍ２照射し、更に８０℃で６０分間加熱して、実施例３の硬化被膜（膜厚１μｍ）を得た。
[Example 3]
0.08 g of the bifunctional cyclocarbonate compound (A-1) obtained above, 0.008 g of the bifunctional photobase generator (B-1), and trifunctional base proliferating agent (C-2) 0 .014 g was dissolved in 1 g of THF to obtain a coating liquid of an active energy ray-curable composition. The obtained coating liquid was coated on a glass plate with a bar coater, and predried at 80 ° C. for 1 minute. Thereafter, the film was irradiated with 5,000 mJ / cm 2 of ultraviolet light of a wavelength of 313 nm, and further heated at 80 ° C. for 60 minutes to obtain a cured film (film thickness 1 μm) of Example 3.
〔実施例４〕
上記で得られた三官能のシクロカーボネート化合物（Ａ−２）０．０５ｇと、単官能の光塩基発生剤（Ｂ−３）０．００２８ｇと、三官能の塩基増殖剤（Ｃ−２）０．０２７ｇとを、ＴＨＦ １ｇに溶解して活性エネルギー線硬化性組成物の塗工液を得た。得られた塗工液をガラス板上にバーコーターで塗布し、８０℃で１分間予備乾燥した。その後、３１３ｎｍの波長の紫外線を１０００ｍＪ／ｃｍ２照射し、更に８０℃で６０分間加熱して、実施例４の硬化被膜を得た。
Example 4
0.05 g of the trifunctional cyclocarbonate compound (A-2) obtained above, 0.0028 g of a monofunctional photobase generator (B-3), and a trifunctional base growth agent (C-2) .27 g were dissolved in 1 g of THF to obtain a coating liquid of an active energy ray-curable composition. The obtained coating liquid was coated on a glass plate with a bar coater, and predried at 80 ° C. for 1 minute. Thereafter, ultraviolet rays having a wavelength of 313 nm were irradiated at 1000 mJ / cm 2 and further heated at 80 ° C. for 60 minutes to obtain a cured coating film of Example 4.
〔実施例５〕
上記で得られた三官能のシクロカーボネート化合物（Ａ−３）０．０５ｇと、単官能の光塩基発生剤（Ｂ−４）０．００２ｇを、トリクロロメタン０．１５ｇに溶解して活性エネルギー線硬化性組成物の塗工液を得た。得られた塗工液をガラス板上にバーコーターで塗布し、６０℃で３０秒間予備乾燥した。その後、３６５ｎｍの波長の紫外線を１０００ｍＪ／ｃｍ２照射し、更に８０℃で６０分間加熱して、実施例５の硬化被膜を得た。
[Example 5]
0.05 g of the trifunctional cyclocarbonate compound (A-3) obtained above and 0.002 g of a monofunctional photobase generator (B-4) are dissolved in 0.15 g of trichloromethane to obtain an active energy ray A coating liquid of a curable composition was obtained. The obtained coating liquid was coated on a glass plate by a bar coater, and predried at 60 ° C. for 30 seconds. Thereafter, ultraviolet light having a wavelength of 365 nm was irradiated at 1000 mJ / cm 2 and further heated at 80 ° C. for 60 minutes to obtain a cured film of Example 5.
〔実施例６〕
上記で得られた三官能のシクロカーボネート化合物（Ａ−３）０．０５ｇと、単官能の光塩基発生剤（Ｂ−４）０．００２ｇと、三官能の塩基増殖剤（Ｃ−２）０．０４ｇとを、ヘキサフルオロイソプロパノール０．５ｇに溶解して活性エネルギー線硬化性組成物の塗工液を得た。得られた塗工液をガラス板上にバーコーターで塗布し、６０℃で３０秒間予備乾燥した。その後、３６５ｎｍの波長の紫外線を１０００ｍＪ／ｃｍ２照射し、更に８０℃で６０分間加熱して、実施例６の硬化被膜を得た。
[Example 6]
0.05 g of the trifunctional cyclocarbonate compound (A-3) obtained above, 0.002 g of a monofunctional photobase generator (B-4), and trifunctional base proliferating agent (C-2) 0 0.04 g was dissolved in 0.5 g of hexafluoroisopropanol to obtain a coating liquid of the active energy ray-curable composition. The obtained coating liquid was coated on a glass plate by a bar coater, and predried at 60 ° C. for 30 seconds. Thereafter, ultraviolet light having a wavelength of 365 nm was irradiated at 1000 mJ / cm 2 and further heated at 80 ° C. for 60 minutes to obtain a cured film of Example 6.
〔実施例７〕
上記で得られた三官能のシクロカーボネート化合物（Ａ−４）０．０５ｇと、単官能の光塩基発生剤（Ｂ−４）０．００２ｇを、トリクロロメタン０．１５ｇに溶解して活性エネルギー線硬化性組成物の塗工液を得た。得られた塗工液をガラス板上にバーコーターで塗布し、６０℃で３０秒間予備乾燥した。その後、３６５ｎｍの波長の紫外線を１００００ｍＪ／ｃｍ２照射し、更に８０℃で１０分間加熱して、実施例７の硬化被膜を得た。
[Example 7]
0.05 g of the trifunctional cyclocarbonate compound (A-4) obtained above and 0.002 g of a monofunctional photobase generator (B-4) are dissolved in 0.15 g of trichloromethane to obtain an active energy ray A coating liquid of a curable composition was obtained. The obtained coating liquid was coated on a glass plate by a bar coater, and predried at 60 ° C. for 30 seconds. Thereafter, ultraviolet rays having a wavelength of 365 nm were irradiated at 10,000 mJ / cm 2 and further heated at 80 ° C. for 10 minutes to obtain a cured film of Example 7.
〔実施例８〕
上記で得られた四官能のシクロカーボネート化合物（Ａ−５）０．０５ｇと、単官能の光塩基発生剤（Ｂ−４）０．００２ｇを、トリクロロメタン０．１５ｇに溶解して活性エネルギー線硬化性組成物の塗工液を得た。得られた塗工液をガラス板上にバーコーターで塗布し、６０℃で３０秒間予備乾燥した。その後、３６５ｎｍの波長の紫外線を１００００ｍＪ／ｃｍ２照射し、更に８０℃で１０分間加熱して、実施例８の硬化被膜を得た。
Example 8
0.05 g of the tetrafunctional cyclocarbonate compound (A-5) obtained above and 0.002 g of a monofunctional photobase generator (B-4) are dissolved in 0.15 g of trichloromethane to obtain an active energy ray A coating liquid of a curable composition was obtained. The obtained coating liquid was coated on a glass plate by a bar coater, and predried at 60 ° C. for 30 seconds. Thereafter, ultraviolet light having a wavelength of 365 nm was irradiated at 10,000 mJ / cm 2 and further heated at 80 ° C. for 10 minutes to obtain a cured film of Example 8.
次に、比較例の組成物からなる硬化被膜を作製した。 Next, the cured film which consists of a composition of a comparative example was produced.
〔比較例１〕
上記で得られた二官能のシクロカーボネート化合物（Ａ−１）１０．８ｇと、二官能のアミンであるイソホロンジアミン〔単体、Ｂ’、前記式（８−６）を参照〕２．８ｇとを混合して、活性エネルギー線硬化性組成物の塗工液を得た。得られた塗工液を室温で３日放置したところ、塗工液はゲル化して、塗布（コーティング）不能となった。
Comparative Example 1
10.8 g of the difunctional cyclocarbonate compound (A-1) obtained above, and 2.8 g of a difunctional amine isophorone diamine [refer to simple substance, B ', formula (8-6)]. It mixed, and obtained the coating liquid of the active energy ray curable composition. When the obtained coating liquid was allowed to stand at room temperature for 3 days, the coating liquid gelled and became unable to be applied (coated).
〔比較例２〕
単官能のシクロカーボネート化合物〔グリセリンカーボネート（単体、Ａ’、前記式（１−１）を参照）０．０２４ｇと、上記で得られた二官能の光塩基発生剤（Ｂ−１）０．０６８ｇとを、ＴＨＦ ０．２ｇに溶解して活性エネルギー線硬化性組成物の塗工液を得た。得られた塗工液をガラス板上にバーコーターで塗布し、８０℃で１分間予備乾燥した。その後、３１３ｎｍの波長の紫外線を１０００ｍＪ／ｃｍ２照射し、更に８０℃で６０分間加熱して、比較例２の硬化被膜（膜厚１μｍ）を得た。
Comparative Example 2
Monofunctional cyclocarbonate compound [glycerine carbonate (alone, A ′, see the above formula (1-1)) 0.024 g, and the bifunctional photobase generator (B-1) 0.068 g obtained above] Were dissolved in 0.2 g of THF to obtain a coating liquid of an active energy ray-curable composition. The obtained coating liquid was coated on a glass plate with a bar coater, and predried at 80 ° C. for 1 minute. Thereafter, ultraviolet rays having a wavelength of 313 nm were irradiated at 1000 mJ / cm 2 , and further heated at 80 ° C. for 60 minutes to obtain a cured film (film thickness 1 μm) of Comparative Example 2.
〔比較例３〕
比較例用に、ウレタン（メタ）アクリレート系化合物を作製した。
＜ウレタン（メタ）アクリレート系化合物（Ｄ）の製造＞
温度計、撹拌機、水冷コンデンサー、窒素ガス吹き込み口を備えた４つ口フラスコに、イソホロンジイソシアネート６．６ｇ（０．０３ｍｏｌ）、ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物（水酸基価４８ｍｇＫＯＨ／ｇ）９３．４ｇ、重合禁止剤として２，６−ジ−ｔｅｒｔ−ブチルクレゾール０．０６ｇ、反応触媒としてジブチルスズジラウレート０．０２ｇを仕込み、６０℃で反応させ、残存イソシアネート基が０．３％以下となった時点で反応を終了し、ウレタン（メタ）アクリレート系化合物（Ｄ）（エチレン性不飽和基濃度７．９ｍｍｏｌ／ｇ；重量平均分子量は２，０００）５６ｇ、ジペンタエリスリトールペンタアクリレート８．６ｇ、ジペンタエリスリトールヘキサアクリレート４７．４ｇの混合物を得た。
Comparative Example 3
The urethane (meth) acrylate type compound was produced for comparative examples.
<Production of Urethane (Meth) Acrylate Compound (D)>
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port, 6.6 g (0.03 mol) of isophorone diisocyanate, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value 48 mg KOH) / G) 93.4 g, 0.06 g of 2,6-di-tert-butylcresol as a polymerization inhibitor, 0.02 g of dibutyltin dilaurate as a reaction catalyst are charged, reacted at 60 ° C., residual isocyanate group is 0.3% The reaction is terminated when the following results are obtained, and 56 g of urethane (meth) acrylate compound (D) (ethylenically unsaturated group concentration: 7.9 mmol / g; weight average molecular weight is 2,000), dipentaerythritol pentaacrylate 8 .6 g, dipentaerythritol hex To give a mixture of acrylate 47.4 g.
次に、上記で得られたウレタン（メタ）アクリレート系化合物（Ｄ）１００部、光重合開始剤として１−ヒドロキシ−シクロヘキシル−フェニル−ケトン（ＢＡＳＦジャパン社製；「イルガキュア１８４」）を４部、希釈溶剤として酢酸エチル１００部を均一に混合し、活性エネルギー線硬化性組成物の塗工液を得た。得られた塗工液をガラス板上にバーコーターで塗布し、８０℃で１分間予備乾燥した。その後、３６５ｎｍの波長の紫外線を５００ｍＪ／ｃｍ２照射して、比較例３の硬化被膜（膜厚１μｍ）を得た。 Next, 100 parts of the urethane (meth) acrylate compound (D) obtained above, 4 parts of 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF Japan; “IRGACURE 184”) as a photopolymerization initiator, 100 parts of ethyl acetate was uniformly mixed as a dilution solvent to obtain a coating liquid of an active energy ray-curable composition. The obtained coating liquid was coated on a glass plate with a bar coater, and predried at 80 ° C. for 1 minute. Thereafter, ultraviolet light having a wavelength of 365 nm was irradiated at 500 mJ / cm 2 to obtain a cured film of Comparative Example 3 (film thickness: 1 μm).
得られた活性エネルギー線硬化性組成物の塗工液、及びその硬化被膜について、以下の評価を行った。評価結果は表１に示す。 The following evaluation was performed about the coating liquid of the obtained active energy ray curable composition, and its cured film. The evaluation results are shown in Table 1.
＜溶液（一液）安定性＞
上記で得られた各塗工液を室温で１週間放置し、１週間後に塗工液の外観を目視により確認した。評価基準は以下の通りである。
［評価基準］
○：外観変化なし
×：増粘又はゲル化
<Solution (one solution) stability>
Each coating solution obtained above was allowed to stand at room temperature for 1 week, and after 1 week, the appearance of the coating solution was visually confirmed. Evaluation criteria are as follows.
[Evaluation criteria]
○: No change in appearance ×: Thickening or gelation
＜硬化性＞
１．鉛筆硬度
上記各硬化被膜について、ＪＩＳ Ｋ ５６００−５−４に準じて鉛筆硬度を測定した。評価基準は以下の通りである。
［評価基準］
○：硬度Ｂ以上
×：硬度２Ｂ以下
<Curing property>
1. Pencil hardness About each said hardened film, pencil hardness was measured according to JISK5600-5-4. Evaluation criteria are as follows.
[Evaluation criteria]
○: Hardness B or more ×: Hardness 2B or less
２．硬化被膜のべたつき性
また、上記硬化被膜について、表面のべたつき性を指で触って判断した。評価基準は以下の通りである。
［評価基準］
○：べたつきなし
×：べたつきあり
2. Stickiness of Cured Film Further, the stickiness of the surface of the cured film was judged by touching with a finger. Evaluation criteria are as follows.
[Evaluation criteria]
○: No stickiness ×: Stickiness
上記評価結果より、シクロカーボネート構造を２つ以上含有する化合物（Ａ）及び光塩基発生剤（Ｂ）を含有してなる活性エネルギー線硬化性組成物から得られる実施例１〜８の硬化被膜は、膜厚１μｍという薄膜であるのにも関わらず、実用上充分な硬化被膜強度を有する薄膜コーティング層が得られることが分かる。 From the above evaluation results, the cured films of Examples 1 to 8 obtained from the active energy ray-curable composition containing the compound (A) containing two or more cyclocarbonate structures and the photobase generator (B) are as follows. It can be seen that a thin film coating layer having a practically sufficient cured film strength can be obtained in spite of being a thin film having a thickness of 1 μm.
一方、本発明の光塩基発生剤（Ｂ）ではない光塩基発生剤（Ｂ’）を含有する、比較例１の活性エネルギー線硬化性組成物は、経時でゲル化して、塗布（コーティング）不能となった。また、シクロカーボネート構造が１つのみの化合物（Ａ’）を含有する活性エネルギー線硬化性組成物から得られる比較例２の硬化被膜は、被膜の硬化不足（未硬化）による被膜表面のべたつきが見られ、充分な硬化被膜強度が得られなかった。更に、従来技術であるウレタンアクリレート系化合物（Ｄ）から得られる比較例３の硬化被膜は、酸素阻害による硬化不足（未硬化）による被膜表面のべたつきが見られ、充分な硬化被膜強度が得られなかった。 On the other hand, the active energy ray-curable composition of Comparative Example 1 containing the photobase generator (B ′) that is not the photobase generator (B) of the present invention gels with time and cannot be applied (coated). It became. Moreover, the cured coating film of Comparative Example 2 obtained from the active energy ray-curable composition containing the compound (A ′) having only one cyclocarbonate structure has a stickiness of the coating surface due to insufficient curing (uncured) of the coating film. As a result, sufficient cured film strength was not obtained. Furthermore, the cured film of Comparative Example 3 obtained from the urethane acrylate compound (D), which is a conventional technique, shows stickiness of the film surface due to insufficient curing due to oxygen inhibition (uncured), and sufficient cured film strength is obtained. There wasn't.
本発明のシクロカーボネート構造を２つ以上含有する化合物（Ａ）及び光塩基発生剤（Ｂ）を含む活性エネルギー線硬化性組成物からなるコーティング剤は、硬化被膜の厚みが薄い場合でも、実用的な硬化物被膜強度を発現することができる。しかも、塗工液として使用の容易な、一液型のコーティング剤として用いることができる。そして、本発明の活性エネルギー線硬化性組成物からなるコーティング剤は、保護コーティング剤、アンカーコーティング剤、磁性粉コーティングバインダー、サンドブラスト用被膜、版材など、各種の被膜形成材料として有用である。中でも、液晶ディスプレイなどの光学部材用途として用いられるプラスチックフィルムのハードコート用コーティング剤として、非常に有用である。 A coating agent comprising an active energy ray-curable composition comprising a compound (A) containing two or more cyclocarbonate structures according to the present invention and a photobase generator (B) is practical even when the thickness of the cured film is thin. It is possible to express a cured product film strength. Moreover, it can be used as a one-component coating agent that is easy to use as a coating solution. Then, a coating agent composed of the active energy ray curable composition of the present invention, protection coatings, anchor coating agents, magnetic powder coating binders, sandblasting film, plate material, etc., is useful as various film-forming material. Above all, it is very useful as a coating agent for a hard coat of a plastic film used for an optical member application such as a liquid crystal display.
Claims (7)
光塩基発生剤（Ｂ）が、塩基性化合物とカルボン酸との塩であり、
光塩基発生剤（Ｂ）の含有量が、化合物（Ａ）１００重量部に対して１〜３００重量部である活性エネルギー線硬化性組成物からなることを特徴とするコーティング剤。 A compound (A) containing two or more cyclocarbonate structures and a photobase generator (B) ,
The photo base generator (B) is a salt of a basic compound and a carboxylic acid,
A coating agent comprising an active energy ray-curable composition wherein the content of the photobase generator (B) is 1 to 300 parts by weight with respect to 100 parts by weight of the compound (A) .
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