JP5943227B2 - Process for producing active energy ray-curable resin composition - Google Patents
Process for producing active energy ray-curable resin composition Download PDFInfo
- Publication number
- JP5943227B2 JP5943227B2 JP2015511191A JP2015511191A JP5943227B2 JP 5943227 B2 JP5943227 B2 JP 5943227B2 JP 2015511191 A JP2015511191 A JP 2015511191A JP 2015511191 A JP2015511191 A JP 2015511191A JP 5943227 B2 JP5943227 B2 JP 5943227B2
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- Prior art keywords
- meth
- acrylate
- polymer
- active energy
- energy ray
- 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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- 239000011342 resin composition Substances 0.000 title claims description 28
- 238000000034 method Methods 0.000 title claims description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 156
- 229920000642 polymer Polymers 0.000 claims description 90
- 238000004519 manufacturing process Methods 0.000 claims description 53
- 239000000178 monomer Substances 0.000 claims description 44
- 150000001875 compounds Chemical class 0.000 claims description 39
- 229920002554 vinyl polymer Polymers 0.000 claims description 33
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000000203 mixture Substances 0.000 description 65
- -1 methacryloyl Chemical group 0.000 description 51
- 238000006116 polymerization reaction Methods 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 16
- 239000001257 hydrogen Substances 0.000 description 16
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- 238000005259 measurement Methods 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 14
- 230000009477 glass transition Effects 0.000 description 14
- 238000005984 hydrogenation reaction Methods 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 13
- 239000012295 chemical reaction liquid Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 239000003960 organic solvent Substances 0.000 description 13
- 239000002994 raw material Substances 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 239000010408 film Substances 0.000 description 12
- 238000005227 gel permeation chromatography Methods 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 239000004793 Polystyrene Substances 0.000 description 10
- 229920002223 polystyrene Polymers 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 239000003999 initiator Substances 0.000 description 8
- 239000003505 polymerization initiator Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 7
- 238000013008 moisture curing Methods 0.000 description 7
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 6
- 125000005370 alkoxysilyl group Chemical group 0.000 description 6
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 6
- 239000004014 plasticizer Substances 0.000 description 6
- 229920000058 polyacrylate Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 229920000193 polymethacrylate Polymers 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000003926 acrylamides Chemical class 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000002638 heterogeneous catalyst Substances 0.000 description 4
- 239000004611 light stabiliser Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- FZEYVTFCMJSGMP-UHFFFAOYSA-N acridone Chemical class C1=CC=C2C(=O)C3=CC=CC=C3NC2=C1 FZEYVTFCMJSGMP-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 150000008366 benzophenones Chemical class 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 2
- HDPNBNXLBDFELL-UHFFFAOYSA-N 1,1,1-trimethoxyethane Chemical compound COC(C)(OC)OC HDPNBNXLBDFELL-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- 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 2
- 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 2
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 208000034189 Sclerosis Diseases 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 150000001251 acridines Chemical class 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000002585 base Substances 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
- 239000012965 benzophenone Substances 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-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
- 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 2
- 230000000740 bleeding effect Effects 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 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
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- UONLDZHKYCFZRW-UHFFFAOYSA-N n-[6-[formyl-(2,2,6,6-tetramethylpiperidin-4-yl)amino]hexyl]-n-(2,2,6,6-tetramethylpiperidin-4-yl)formamide Chemical compound C1C(C)(C)NC(C)(C)CC1N(C=O)CCCCCCN(C=O)C1CC(C)(C)NC(C)(C)C1 UONLDZHKYCFZRW-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229940116351 sebacate Drugs 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 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
- UQQYIAVMUUJWGX-UHFFFAOYSA-N (2,4-dihydroxyphenyl)-(3,4-dihydroxyphenyl)methanone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=C(O)C(O)=C1 UQQYIAVMUUJWGX-UHFFFAOYSA-N 0.000 description 1
- OKJFKPFBSPZTAH-UHFFFAOYSA-N (2,4-dihydroxyphenyl)-(4-hydroxyphenyl)methanone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1O OKJFKPFBSPZTAH-UHFFFAOYSA-N 0.000 description 1
- MAOBFOXLCJIFLV-UHFFFAOYSA-N (2-aminophenyl)-phenylmethanone Chemical compound NC1=CC=CC=C1C(=O)C1=CC=CC=C1 MAOBFOXLCJIFLV-UHFFFAOYSA-N 0.000 description 1
- CKGKXGQVRVAKEA-UHFFFAOYSA-N (2-methylphenyl)-phenylmethanone Chemical compound CC1=CC=CC=C1C(=O)C1=CC=CC=C1 CKGKXGQVRVAKEA-UHFFFAOYSA-N 0.000 description 1
- URBLVRAVOIVZFJ-UHFFFAOYSA-N (3-methylphenyl)-phenylmethanone Chemical compound CC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1 URBLVRAVOIVZFJ-UHFFFAOYSA-N 0.000 description 1
- ZRDYULMDEGRWRC-UHFFFAOYSA-N (4-hydroxyphenyl)-(2,3,4-trihydroxyphenyl)methanone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C(O)=C1O ZRDYULMDEGRWRC-UHFFFAOYSA-N 0.000 description 1
- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 description 1
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 1
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- TYKCBTYOMAUNLH-MTOQALJVSA-J (z)-4-oxopent-2-en-2-olate;titanium(4+) Chemical compound [Ti+4].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O TYKCBTYOMAUNLH-MTOQALJVSA-J 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- MJYFYGVCLHNRKB-UHFFFAOYSA-N 1,1,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)CF MJYFYGVCLHNRKB-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
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- JZKPKNSYAHAKJY-UHFFFAOYSA-N 1-[4-(4-benzoylphenyl)sulfanylphenyl]-2-methyl-2-(4-methylphenyl)sulfonylpropan-1-one Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C)(C)C(=O)C(C=C1)=CC=C1SC1=CC=C(C(=O)C=2C=CC=CC=2)C=C1 JZKPKNSYAHAKJY-UHFFFAOYSA-N 0.000 description 1
- WQQZMYRVHZZOEW-UHFFFAOYSA-N 1-benzyl-4-(2-methylphenyl)sulfanylbenzene Chemical compound CC1=CC=CC=C1SC(C=C1)=CC=C1CC1=CC=CC=C1 WQQZMYRVHZZOEW-UHFFFAOYSA-N 0.000 description 1
- PPHOVLUFQLXZRB-UHFFFAOYSA-N 1-chloro-4-propylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(CCC)=CC=C2Cl PPHOVLUFQLXZRB-UHFFFAOYSA-N 0.000 description 1
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- HSKPJQYAHCKJQC-UHFFFAOYSA-N 1-ethylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CC HSKPJQYAHCKJQC-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
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- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- MJVGBKJNTFCUJM-UHFFFAOYSA-N mexenone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=C(C)C=C1 MJVGBKJNTFCUJM-UHFFFAOYSA-N 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- HPAFOABSQZMTHE-UHFFFAOYSA-N phenyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)C1=CC=CC=C1 HPAFOABSQZMTHE-UHFFFAOYSA-N 0.000 description 1
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- XAFJSPPHVXDRIE-UHFFFAOYSA-L platinum(2+);triphenylphosphane;dichloride Chemical class [Cl-].[Cl-].[Pt+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 XAFJSPPHVXDRIE-UHFFFAOYSA-L 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- GHJOIQFPDMIKHT-UHFFFAOYSA-N propane-1,2,3-triol;prop-2-enoic acid Chemical compound OC(=O)C=C.OCC(O)CO GHJOIQFPDMIKHT-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- VIHDTGHDWPVSMM-UHFFFAOYSA-N ruthenium;triphenylphosphane Chemical compound [Ru].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 VIHDTGHDWPVSMM-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- QLNOVKKVHFRGMA-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical group [CH2]CC[Si](OC)(OC)OC QLNOVKKVHFRGMA-UHFFFAOYSA-N 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Description
本発明は、活性エネルギー線硬化型樹脂組成物、及びこれより得られる硬化物に関するものである。
The present invention relates to an active energy ray-curable resin composition and a cured product obtained therefrom.
アクリル系樹脂硬化物を与える活性エネルギー線硬化型樹脂組成物は、硬化性に優れるため生産性が高い、ほとんど溶剤を使用しないため環境に対する負荷が少ない等の理由により、コーティング剤、接着剤、インク、空隙充填剤等の種々の分野で使用されている。
しかしながら、活性エネルギー線硬化型組成物は、硬化時の収縮が大きく、樹脂中に大きな残留応力が生じるため、基材に対する密着性が悪い、あるいは、塗膜が硬くなりすぎて脆く割れやすい等の問題を有していた。このような問題を解決するため、可塑剤や粘着付与樹脂等を配合した組成物が検討されている。The active energy ray-curable resin composition that gives an acrylic resin cured product is excellent in curability and high productivity, and because it uses almost no solvent, it has little impact on the environment. It is used in various fields such as void fillers.
However, the active energy ray-curable composition has a large shrinkage at the time of curing, and a large residual stress is generated in the resin. Therefore, the adhesiveness to the base material is poor, or the coating film becomes too hard and fragile and easily breaks. Had a problem. In order to solve such problems, a composition containing a plasticizer, a tackifier resin, or the like has been studied.
一般に、可塑剤としてはジオクチルフタレート（ＤＯＰ）のようなフタル酸エステル化合物が広く用いられているが、硬化後のアクリル系樹脂層からブリードアウトする問題があった。また、石油系樹脂及びロジン系樹脂といった粘着付与樹脂を配合する場合は、疎水性が高くアクリル系樹脂との相溶性が低いため、適用可能なアクリル系樹脂及び粘着付与樹脂の組成が制限されるものであった。
上記相溶性の問題を解決する手段として、アクリル系高分子を配合した組成物も提案されている。特許文献１には、アクリル系高分子を可塑剤として含む活性放射線硬化型インク組成物が開示されている。In general, phthalate compounds such as dioctyl phthalate (DOP) are widely used as plasticizers, but there is a problem of bleeding out from the cured acrylic resin layer. In addition, when blending a tackifier resin such as a petroleum resin and a rosin resin, the composition of the applicable acrylic resin and tackifier resin is limited because of high hydrophobicity and low compatibility with the acrylic resin. It was a thing.
As a means for solving the compatibility problem, a composition containing an acrylic polymer has also been proposed. Patent Document 1 discloses an actinic radiation curable ink composition containing an acrylic polymer as a plasticizer.
一方、特許文献２には、無溶剤で効率よくアクリル系高分子可塑剤を製造する方法として、（メタ）アクリロイル基含有単量体を、１５０〜３５０℃で重合する方法が開示されている。更に、出願人は、このアクリル系高分子可塑剤を含む活性エネルギー線硬化型樹脂組成物を提案している（特許文献３）。
On the other hand, Patent Document 2 discloses a method of polymerizing a (meth) acryloyl group-containing monomer at 150 to 350 ° C. as a method for efficiently producing an acrylic polymer plasticizer without solvent. Furthermore, the applicant has proposed an active energy ray-curable resin composition containing this acrylic polymer plasticizer (Patent Document 3).
ところが、特許文献２に記載の方法で合成されたアクリル系高分子は、分子末端に二重結合を有している。このため、このアクリル系高分子を添加した、特許文献３の組成物では、活性エネルギー線による硬化において十分な硬化性が得られないことがあった。
本発明の目的は、硬化性が良好であり、柔軟性に優れた硬化物を与える活性エネルギー線硬化型樹脂組成物の製造方法を提供することである。
However, the acrylic polymer synthesized by the method described in Patent Document 2 has a double bond at the molecular end. For this reason, in the composition of patent document 3 which added this acrylic polymer, sufficient sclerosis | hardenability might not be obtained in hardening by an active energy ray.
An object of the present invention is to provide a method for producing an active energy ray-curable resin composition that provides a cured product having good curability and excellent flexibility.
本発明者は、上記課題を解決するために鋭意検討した結果、ビニル系単量体を１５０〜３５０℃で重合した後に水素を付加して分子末端の二重結合を消失させた重合体とし、これを含む活性エネルギー線硬化性樹脂組成物より得られる硬化物が、柔軟性及び硬化性に優れることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventor made a polymer in which a vinyl-based monomer was polymerized at 150 to 350 ° C. and then hydrogen was added to eliminate the double bond at the molecular end, It discovered that the hardened | cured material obtained from the active energy ray-curable resin composition containing this was excellent in a softness | flexibility and sclerosis | hardenability, and came to complete this invention.
本発明は以下の通りである。
〔１〕ビニル系単量体を１５０〜３５０℃の温度で重合して前駆重合体を得る工程、
前記前駆重合体に水素付加を行うことにより二重結合濃度が０．３０ｍｅｑ／ｇ以下である重合体（Ｂ）を得る工程、及び、
前記重合体（Ｂ）、エチレン性不飽和基含有化合物（Ａ）及び光重合開始剤（Ｃ）を混合する工程を含む活性エネルギー線硬化性樹脂組成物の製造方法。
〔２〕上記化合物（Ａ）及び上記重合体（Ｂ）の合計に対し、上記化合物（Ａ）を１０〜９０質量％、上記重合体（Ｂ）を９０〜１０質量％含む上記〔１〕に記載の活性エネルギー線硬化性樹脂組成物の製造方法。
〔３〕上記重合体（Ｂ）の重量平均分子量が１，０００〜５０，０００である上記〔１〕又は〔２〕に記載の活性エネルギー線硬化性樹脂組成物の製造方法。
〔４〕上記重合体（Ｂ）が、炭素数４以上のアルキル基を有するアルキル（メタ）アクリレートに由来する構造単位を含む上記〔１〕〜〔３〕のいずれかに記載の活性エネルギー線硬化性樹脂組成物の製造方法。
〔５〕上記化合物（Ａ）が多官能（メタ）アクリレートを含む上記〔１〕〜〔４〕のいずれかに記載の活性エネルギー線硬化性樹脂組成物の製造方法。
〔６〕上記化合物（Ａ）の全体に対し、上記多官能（メタ）アクリレートが２０〜１００質量％含まれる上記〔５〕に記載の活性エネルギー線硬化性樹脂組成物の製造方法。
The present invention is as follows.
[1] A step of polymerizing a vinyl monomer at a temperature of 150 to 350 ° C. to obtain a precursor polymer,
A step of obtaining a polymer (B) having a double bond concentration of 0.30 meq / g or less by hydrogenating the precursor polymer; and
The manufacturing method of the active energy ray-curable resin composition including the process of mixing the said polymer (B), an ethylenically unsaturated group containing compound (A), and a photoinitiator (C).
[2] The above [1] containing 10 to 90% by mass of the compound (A) and 90 to 10% by mass of the polymer (B) with respect to the total of the compound (A) and the polymer (B). The manufacturing method of active energy ray curable resin composition of description.
[3] The method for producing an active energy ray-curable resin composition according to the above [1] or [2], wherein the polymer (B) has a weight average molecular weight of 1,000 to 50,000.
[4] The active energy ray curing according to any one of [1] to [3], wherein the polymer (B) includes a structural unit derived from an alkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms. For producing a conductive resin composition.
[5] The method for producing an active energy ray-curable resin composition according to any one of [1] to [4] , wherein the compound (A) contains a polyfunctional (meth) acrylate.
[6] The method for producing an active energy ray-curable resin composition according to the above [5], wherein the polyfunctional (meth) acrylate is contained in an amount of 20 to 100% by mass with respect to the whole of the compound (A).
本発明の製造方法により得られる活性エネルギー線硬化型組成物は、硬化性が良好であり、柔軟性に優れた硬化物、又は、基材に対する密着性が優れた硬化物を与えることができる。
The active energy ray-curable composition obtained by the production method of the present invention has good curability and can give a cured product with excellent flexibility or a cured product with excellent adhesion to a substrate.
本発明の活性エネルギー線硬化型組成物は、液状組成物であり、後述するように、有機溶剤を含む組成物、及び、有機溶剤を含まない組成物のいずれの態様も可能である。
以下、本発明について詳しく説明する。尚、本願明細書において、「（メタ）アクリレート」は、アクリレート及び／又はメタクリレートを表し、また、「（メタ）アクリロイル」は、アクリロイル及び／又はメタクリロイルを表す。The active energy ray-curable composition of the present invention is a liquid composition, and can be any of a composition containing an organic solvent and a composition containing no organic solvent, as will be described later.
The present invention will be described in detail below. In the present specification, “(meth) acrylate” represents acrylate and / or methacrylate, and “(meth) acryloyl” represents acryloyl and / or methacryloyl.
１．エチレン性不飽和基含有化合物（Ａ）
本発明における化合物（Ａ）は、分子内にエチレン性不飽和基を有する化合物である。エチレン性不飽和基としては、ビニル基、ビニルエーテル基、（メタ）アクリロイル基及び（メタ）アクリルアミド基が挙げられる。上記化合物（Ａ）に含まれるエチレン性不飽和基の数は、特に限定されず、１つでも、２つでも、あるいは、３つ以上でもよい。また、２つ以上のエチレン性不飽和基を含む場合、これらのエチレン性不飽和基は、互いに同一であっても異なってもよい。
上記化合物（Ａ）としては、種々の化合物が使用可能である。具体的には、（メタ）アクリレート（以下、「（メタ）アクリレート（ａ１）」という）；（メタ）アクリルアミド類；スチレン、α−メチルスチレン及びビニルトルエン等の芳香族ビニル化合物；酢酸ビニル等のビニルエステル化合物；Ｎ−ビニルピロリドン、Ｎ−ビニルホルムアミド並びにＮ−ビニルカプロラクタム等が挙げられる。本発明の活性エネルギー線硬化型組成物は、化合物（Ａ）を１種のみ含んでよいし、２種以上を含んでもよい。1. Ethylenically unsaturated group-containing compound (A)
The compound (A) in the present invention is a compound having an ethylenically unsaturated group in the molecule. Examples of the ethylenically unsaturated group include a vinyl group, a vinyl ether group, a (meth) acryloyl group, and a (meth) acrylamide group. The number of ethylenically unsaturated groups contained in the compound (A) is not particularly limited, and may be one, two, or three or more. When two or more ethylenically unsaturated groups are contained, these ethylenically unsaturated groups may be the same as or different from each other.
Various compounds can be used as the compound (A). Specifically, (meth) acrylate (hereinafter referred to as “(meth) acrylate (a1)”); (meth) acrylamides; aromatic vinyl compounds such as styrene, α-methylstyrene and vinyltoluene; vinyl acetate and the like Vinyl ester compounds; N-vinyl pyrrolidone, N-vinyl formamide, N-vinyl caprolactam and the like can be mentioned. The active energy ray-curable composition of the present invention may contain only one type of compound (A) or two or more types.
本発明に係る化合物（Ａ）としては、（メタ）アクリレート（ａ１）が好ましい。
（メタ）アクリレート（ａ１）としては、分子内に１個の（メタ）アクリロイル基を有する化合物（以下、「単官能（メタ）アクリレート」という）及び分子内に２個以上の（メタ）アクリロイル基を有する化合物（以下、「多官能（メタ）アクリレート」という）が挙げられる。As the compound (A) according to the present invention, (meth) acrylate (a1) is preferable.
The (meth) acrylate (a1) includes a compound having one (meth) acryloyl group in the molecule (hereinafter referred to as “monofunctional (meth) acrylate”) and two or more (meth) acryloyl groups in the molecule. (Hereinafter, referred to as “polyfunctional (meth) acrylate”).
単官能（メタ）アクリレートとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、イソオクチル（メタ）アクリレート、及びステアリル（メタ）アクリレート等のアルキル（メタ）アクリレート；シクロヘキシル（メタ）アクリレート、トリシクロデカン（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、ジシクロペンタニルオキシエチル（メタ）アクリレート、イソボルニル（メタ）アクリレート及びアダマンチル（メタ）アクリレート等の脂環式（メタ）アクリレート；２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート等の水酸基含有（メタ）アクリレート；２−メトキシエチル（メタ）アクリレート、メトキシトリエチレングリコール（メタ）アクリレート、２−エチルヘキシルカルビトール（メタ）アクリレート、エトキシエトキシエチル（メタ）アクリレート等のアルコキシアルキル（メタ）アクリレート；フェニル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、ｏ−フェニルフェノキシエチル（メタ）アクリレート、p−クミルフェノキシエチル（メタ）アクリレート、ノニルフェノキシエチル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノール誘導体のアルキレンオキサイド変性物の（メタ）アクリレート及び２−ヒドロキシ−３−フェノキシプロピル（メタ）アクリレート等の芳香族（メタ）アクリレート；テトラヒドロフルフリル（メタ）アクリレート；Ｎ−（メタ）アクリロイルオキシエチルテトラヒドロフタルイミド及びＮ−（メタ）アクリロイルオキシエチルヘキサヒドロフタルイミド等のマレイミド（メタ）アクリレート；グリシジル（メタ）アクリレート、（メタ）アクリル酸のポリカプロラクトン変性物、２−ヒドロキシエチル（メタ）アクリレートのポリカプロラクトン変性物、３−（トリメトキシシリル）プロピル（メタ）アクリレート、３−（トリエトキシシリル）プロピル（メタ）アクリレート、３−（メチルジメトキシシリル）プロピル（メタ）アクリレート、３−（メチルジエトキシシリル）プロピル（メタ）アクリレート並びにオキサゾリジノンエチル（メタ）アクリレート等が挙げられる。
これらの単官能（メタ）アクリレートは、単独で用いても、２種類以上を併用してもよい。Examples of monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, and Alkyl (meth) acrylates such as stearyl (meth) acrylate; cyclohexyl (meth) acrylate, tricyclodecane (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl ( Alicyclic (meth) acrylates such as (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate and adamantyl (meth) acrylate; 2-hydride Hydroxyl-containing (meth) acrylates such as xylethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, Alkoxyalkyl (meth) acrylates such as 2-ethylhexyl carbitol (meth) acrylate and ethoxyethoxyethyl (meth) acrylate; phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, o-phenylphenoxyethyl (meth) acrylate, p -Cumylphenoxyethyl (meth) acrylate, nonylphenoxyethyl (meth) acrylate, benzyl (meth) acrylate, modified phenol oxide with alkylene oxide Aromatic (meth) acrylates such as (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate; tetrahydrofurfuryl (meth) acrylate; N- (meth) acryloyloxyethyl tetrahydrophthalimide and N- (meth) Maleimide (meth) acrylate such as acryloyloxyethyl hexahydrophthalimide; glycidyl (meth) acrylate, polycaprolactone modified product of (meth) acrylic acid, polycaprolactone modified product of 2-hydroxyethyl (meth) acrylate, 3- (trimethoxy Silyl) propyl (meth) acrylate, 3- (triethoxysilyl) propyl (meth) acrylate, 3- (methyldimethoxysilyl) propyl (meth) acrylate, 3- (methyldiethoxysilyl) Propyl (meth) acrylate and oxazolidinone ethyl (meth) acrylate.
These monofunctional (meth) acrylates may be used alone or in combination of two or more.
多官能（メタ）アクリレートとしては、例えば、１，４−ブタンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、１，９−ノナンジオールジ（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジ（メタ）アクリレート、３−メチル−１，５−ペンタンジオールジ（メタ）アクリレート、２−ブチル−２−エチル−１，３−ノナンジオールジアクリレート、２−メチル−１，８−オクタンジオールジ（メタ）アクリレート、２−ヒドロキシ−１，３−ジ（メタ）アクリロイルオキシプロパン、２−ヒドロキシ−３−（メタ）アクリロイルオキシプロピル（メタ）アクリレート、グリセリンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート等のポリオールポリ（メタ）アクリレート；これらポリ（メタ）アクリレートの原料アルコールのアルキレンオキサイド〔エチレンオキサイド及びプロピレンオキサイド等〕付加物のポリ（メタ）アクリレート；これらポリ（メタ）アクリレートの原料アルコールのカプロラクトン変性物のポリ（メタ）アクリレート；エチレンオキサイド変性イソシアヌル酸のジ（メタ）アクリレート及びエチレンオキサイド変性イソシアヌル酸のトリ（メタ）アクリレート等のアルキレンオキサイド変性イソシアヌル酸のポリ（メタ）アクリレート；アリル（メタ）アクリレート等が挙げられる。
多官能（メタ）アクリレートとしては、オリゴマーも使用することができ、具体的にはウレタン（メタ）アクリレート、ポリエステル（メタ）アクリレート及びエポキシ（メタ）アクリレート等が挙げられる。
また、多官能（メタ）アクリレートとしては、下記の重合体を用いることもできる。
（ｉ）グリシジル基を有するビニル単量体を単独で重合した後、得られたビニル重合体のグリシジル基に、カルボキシル基を有する（メタ）アクリレートを反応させて得られた、側鎖に（メタ）アクリレート基を有するビニル重合体
（ｉｉ）グリシジル基含有ビニル単量体を、共重合可能な他のビニル単量体とともに重合した後、得られたビニル共重合体のグリシジル基に、カルボキシル基を有する（メタ）アクリレートを反応させて得られた、側鎖に（メタ）アクリレート基を有するビニル重合体Examples of the polyfunctional (meth) acrylate include 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol. Di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 2-butyl-2 -Ethyl-1,3-nonanediol diacrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 2-hydroxy-1,3-di (meth) acryloyloxypropane, 2-hydroxy-3- (Meth) acryloyloxypropyl (meth) acrylate Glycerin di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Poly (meth) acrylates such as ditrimethylolpropane tetra (meth) acrylate; Poly (meth) acrylates of adducts of these poly (meth) acrylates starting from alcohols (ethylene oxide and propylene oxide, etc.); ) Poly (meth) acrylate of caprolactone modified product of acrylate raw material alcohol; Di (meth) acrylate of ethylene oxide modified isocyanuric acid Rate and poly (meth) acrylates of alkylene oxide-modified isocyanuric acid tri (meth) acrylate, ethylene oxide-modified isocyanuric acid; allyl (meth) acrylate.
As polyfunctional (meth) acrylate, an oligomer can also be used, and specifically, urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate and the like can be mentioned.
Moreover, as a polyfunctional (meth) acrylate, the following polymer can also be used.
(I) After polymerizing a vinyl monomer having a glycidyl group alone, the side chain obtained by reacting the glycidyl group of the obtained vinyl polymer with a (meth) acrylate having a carboxyl group ( ) Vinyl polymer having an acrylate group (ii) After polymerizing a glycidyl group-containing vinyl monomer together with another copolymerizable vinyl monomer, a carboxyl group is added to the glycidyl group of the obtained vinyl copolymer. A vinyl polymer having a (meth) acrylate group in the side chain, obtained by reacting (meth) acrylate with
多官能（メタ）アクリレートは単独で用いても、２種類以上を併用してもよい。
（メタ）アクリレート（ａ１）としては、単官能（メタ）アクリレート及び多官能（メタ）アクリレートのいずれか一方を用いてよいし、両方を組み合わせて用いてもよい。本発明においては、多官能（メタ）アクリレートを含む（メタ）アクリレート（ａ１）を用いることが好ましく、その使用量は、（メタ）アクリレート（ａ１）の全体に対して、好ましくは２０〜１００質量％、より好ましくは５０〜１００質量％である。Polyfunctional (meth) acrylate may be used independently or may use 2 or more types together.
As (meth) acrylate (a1), any one of monofunctional (meth) acrylate and polyfunctional (meth) acrylate may be used, or both may be used in combination. In this invention, it is preferable to use the (meth) acrylate (a1) containing polyfunctional (meth) acrylate, and the usage-amount is preferably 20-100 mass with respect to the whole (meth) acrylate (a1). %, More preferably 50 to 100% by mass.
（メタ）アクリルアミド類としては、（メタ）アクリルアミド；Ｎ−メチル（メタ）アクリルアミド、Ｎ−エチル（メタ）アクリルアミド、Ｎ−イソプロピル（メタ）アクリルアミド等のＮ−アルキル（メタ）アクリルアミド；Ｎ，Ｎ−ジメチル（メタ）アクリルアミド及びＮ，Ｎ−ジエチル（メタ）アクリルアミド等のＮ，Ｎ−ジアルキル（メタ）アクリルアミド；並びに（メタ）アクリルロイルモルホリン等が挙げられる。 Examples of (meth) acrylamides include (meth) acrylamide; N-alkyl (meth) acrylamides such as N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, and N-isopropyl (meth) acrylamide; N, N- N, N-dialkyl (meth) acrylamides such as dimethyl (meth) acrylamide and N, N-diethyl (meth) acrylamide; and (meth) acryloylmorpholine.
化合物（Ａ）としては、硬化物の耐衝撃性及び耐薬品性に優れる点、並びに、組成物を適切な粘度とすることができる点で、多官能（メタ）アクリレートが好ましい。本発明では、後述する重合体（Ｂ）が可塑剤として作用することにより、化合物（Ａ）として多官能（メタ）アクリレートのみを使用しても、硬化物の柔軟性、及び、基材に対する密着性を良好なものとすることができる。
化合物（Ａ）が多官能（メタ）アクリレートを含む場合、その割合は、化合物（Ａ）の全体に２０〜１００質量％含まれることが好ましく、より好ましくは５０〜１００質量％である。As the compound (A), a polyfunctional (meth) acrylate is preferable in that the cured product has excellent impact resistance and chemical resistance, and the composition can have an appropriate viscosity. In the present invention, since the polymer (B) described later acts as a plasticizer, even if only the polyfunctional (meth) acrylate is used as the compound (A), the flexibility of the cured product and the adhesion to the base material The property can be improved.
When compound (A) contains polyfunctional (meth) acrylate, it is preferable that the ratio is 20-100 mass% in the whole compound (A), More preferably, it is 50-100 mass%.
２．重合体（Ｂ）
本発明における重合体（Ｂ）は、ビニル単量体を、１５０〜３５０℃の温度で重合する工程及び得られた重合体（以下、「前駆重合体」という）に水素を付加する工程によって得られた重合体である。本発明の活性エネルギー線硬化型組成物は、重合体（Ｂ）を１種のみ含んでよいし、２種以上を含んでもよい。2. Polymer (B)
The polymer (B) in the present invention is obtained by a step of polymerizing a vinyl monomer at a temperature of 150 to 350 ° C. and a step of adding hydrogen to the obtained polymer (hereinafter referred to as “precursor polymer”). Polymer. The active energy ray-curable composition of the present invention may contain only one type of polymer (B), or may contain two or more types.
ビニル単量体は、ビニル結合を有するものであれば、特に制限はなく、例えば、（メタ）アクリレート（以下、「（メタ）アクリレート（ｂ１）」という）；（メタ）アクリル酸等の不飽和酸；スチレン、α−メチルスチレン等の芳香族ビニル化合物；アクリロニトリル等のシアン化ビニル化合物；酢酸ビニル等のビニルエステル化合物等が挙げられる。これらのビニル単量体は、１種のみを用いてよいし、２種以上を用いてもよい。本発明においては、重合工程における共重合性、硬化物の機械的特性、耐候性、耐水性等が優れることから、（メタ）アクリレート（ｂ１）が好ましい。 The vinyl monomer is not particularly limited as long as it has a vinyl bond. For example, (meth) acrylate (hereinafter referred to as “(meth) acrylate (b1)”); unsaturated (meth) acrylic acid, etc. Acids; aromatic vinyl compounds such as styrene and α-methylstyrene; vinyl cyanide compounds such as acrylonitrile; vinyl ester compounds such as vinyl acetate; These vinyl monomers may use only 1 type and may use 2 or more types. In the present invention, (meth) acrylate (b1) is preferred because of excellent copolymerization in the polymerization step, mechanical properties of the cured product, weather resistance, water resistance, and the like.
（メタ）アクリレート（ｂ１）としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｓｅｃ−ブチル（メタ）アクリレート、ｔｅｒｔ−ブチル（メタ）アクリレート、ｎ−ペンチル（メタ）アクリレート、ネオペンチル（メタ）アクリレート、ｎ−ヘキシル（メタ）アクリレート、ｎ−ヘプチル（メタ）アクリレート、ｎ−オクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、トリシクロデカニル（メタ）アクリレート、ノニル（メタ）アクリレート、イソノニル（メタ）アクリレート、ラウリル（メタ）アクリレート、トリデシル（メタ）アクリレート、ステアリル（メタ）アクリレート等の（メタ）アクリル酸脂肪族アルキルエステル（アルキル基を有するアルキル（メタ）アクリレート）；２−メトキシエチル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、トリフルオロエチル（メタ）アクリレート等のヘテロ原子含有（メタ）アクリレート；２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレートのε−カプロラクトン付加物等のヒドロキシアルキル（メタ）アクリレート；グリシジル（メタ）アクリレート等のエポキシ基含有（メタ）アクリレート；３−トリメトキシシリルプロピル（メタ）アクリレート、３−トリエトキシシリルプロピル（メタ）アクリレート、３−トリイソプロポキシシリルプロピル（メタ）アクリレート、３−メチルジメトキシシリルプロピル（メタ）アクリレート、３−メチルジエトキシシリルプロピル（メタ）アクリレート、−メチルジイソプロポキシシリルプロピル（メタ）アクリレート、３−ジメチルメトキシシリルプロピル（メタ）アクリレート、３−ジメチルエトキシシリルプロピル（メタ）アクリレート、３−ジメチルイソプロポキシシリルプロピル（メタ）アクリレート、８−トリメトキシシリルオクチル（メタ）アクリレート等のアルコキシシリル基含有（メタ）アクリレート；フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート等が挙げられる。
これらの（メタ）アクリレート（ｂ１）は、単独で用いても、２種類以上を併用してもよい。Examples of (meth) acrylate (b1) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth). Acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, neopentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n- Octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, nonyl (meth) acrylate, isononyl (Meth) acrylate aliphatic alkyl esters (alkyl (meth) acrylates having an alkyl group) such as (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate; 2-methoxyethyl (meta) ) Acrylate, dimethylaminoethyl (meth) acrylate, heteroatom-containing (meth) acrylate such as trifluoroethyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl Hydroxyalkyl (meth) acrylates such as (meth) acrylate and ε-caprolactone adducts of 2-hydroxyethyl (meth) acrylate; epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate Relate; 3-trimethoxysilylpropyl (meth) acrylate, 3-triethoxysilylpropyl (meth) acrylate, 3-triisopropoxysilylpropyl (meth) acrylate, 3-methyldimethoxysilylpropyl (meth) acrylate, 3-methyl Diethoxysilylpropyl (meth) acrylate, -methyldiisopropoxysilylpropyl (meth) acrylate, 3-dimethylmethoxysilylpropyl (meth) acrylate, 3-dimethylethoxysilylpropyl (meth) acrylate, 3-dimethylisopropoxysilylpropyl Alkoxysilyl group-containing (meth) acrylates such as (meth) acrylate and 8-trimethoxysilyloctyl (meth) acrylate; phenyl (meth) acrylate, benzyl (meth) acrylate Rate, and the like.
These (meth) acrylates (b1) may be used alone or in combination of two or more.
（メタ）アクリレート（ｂ１）は、アルキル基を有するアルキル（メタ）アクリレートを含むことが好ましく、その使用量の割合の下限は、（メタ）アクリレート（ｂ１）の全体に対して、好ましくは４０質量％、より好ましくは６０質量％である。尚、アルキル基を有するアルキル（メタ）アクリレートの中でも、炭素数４以上のアルキル基を有するアルキル（メタ）アクリレートに由来する構造単位を含む重合体（Ｂ）は、硬化物に柔軟性を付与し、耐水性、耐候性にも優れるために好ましい。ビニル単量体に含まれる、炭素数４以上のアルキル基を有するアルキル（メタ）アクリレートの割合は、前駆重合体の製造に用いるビニル単量体の全体に対して、４０質量％以上であることが好ましく、６０質量％以上であることがより好ましい。４０質量％未満では、水素付加後の重合体（Ｂ）のガラス転移温度が高くなり、硬化物の柔軟性が不足する場合がある。 The (meth) acrylate (b1) preferably contains an alkyl (meth) acrylate having an alkyl group, and the lower limit of the amount used is preferably 40 mass with respect to the entire (meth) acrylate (b1). %, More preferably 60% by mass. Among the alkyl (meth) acrylates having an alkyl group, the polymer (B) containing a structural unit derived from an alkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms imparts flexibility to the cured product. It is preferable because it is excellent in water resistance and weather resistance. The ratio of the alkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms contained in the vinyl monomer is 40% by mass or more based on the whole vinyl monomer used for the production of the precursor polymer. Is preferable, and it is more preferable that it is 60 mass% or more. If it is less than 40 mass%, the glass transition temperature of the polymer (B) after hydrogenation will become high, and the softness | flexibility of hardened | cured material may be insufficient.
前駆重合体は、溶液重合、塊状重合、分散重合等の重合方法により得ることができるが、１５０〜３５０℃の範囲の高い温度で重合する必要がある。重合温度を１５０℃以上とすることにより、重合開始剤の使用量を少量化し、かつ連鎖移動剤を用いなくても、前駆重合体の分子量の制御が容易となる。そして、水素付加後の重合体（Ｂ）を含む硬化物とした場合の耐候性が優れたものとなる。また、重合温度を３５０℃以下とすることにより、単量体から重合体への転化率を上げることができる。更に、分解生成物に起因する着色の問題を回避することができる。好ましい重合温度は１７０〜３００℃の範囲であり、１８０〜２５０℃の範囲がより好ましい。反応プロセスとしては、バッチ式、セミバッチ式及び連続重合のいずれでもよいが、組成の均一性の点で、連続重合が好ましい。 The precursor polymer can be obtained by a polymerization method such as solution polymerization, bulk polymerization, or dispersion polymerization, but must be polymerized at a high temperature in the range of 150 to 350 ° C. By setting the polymerization temperature to 150 ° C. or higher, the amount of the polymerization initiator used is reduced, and the molecular weight of the precursor polymer can be easily controlled without using a chain transfer agent. And it becomes what was excellent in the weather resistance at the time of setting it as the hardened | cured material containing the polymer (B) after hydrogenation. Moreover, the conversion rate from a monomer to a polymer can be raised by setting the polymerization temperature to 350 ° C. or lower. Furthermore, the problem of coloring due to decomposition products can be avoided. The preferable polymerization temperature is in the range of 170 to 300 ° C, and more preferably in the range of 180 to 250 ° C. The reaction process may be any of batch, semi-batch and continuous polymerization, but continuous polymerization is preferred from the viewpoint of the uniformity of composition.
高温連続重合法としては、特開昭５７−５０２１７１号公報、特開昭５９−６２０７号公報及び特開昭６０−２１５００７号公報等に開示された公知の方法に従えば良い。
例えば、加圧可能な反応器を、加圧下で所定温度に設定した後、ビニル単量体又はビニル単量体と必要に応じて併用される重合溶媒等とを含む単量体混合物からなる原料を、一定の供給速度で反応器へ供給しつつ重合を行い、原料の供給量に見合う量の反応液を抜き出す方法が挙げられる。原料は、必要に応じて、重合開始剤を含有することもできる。
反応器内の圧力は、反応温度と使用する原料の沸点に依存するもので、重合反応に影響を及ぼさないが、反応温度（１５０〜３５０℃）を維持できる圧力であればよい。
反応器内の原料の滞留時間は、１〜６０分であることが好ましい。滞留時間が１分に満たない場合は単量体が充分に反応しない恐れがあり、未反応単量体が６０分を越える場合は、生産性が悪くなってしまうことがある。好ましい滞留時間は２〜４０分である。As the high-temperature continuous polymerization method, known methods disclosed in JP-A-57-502171, JP-A-59-6207, JP-A-60-215007 and the like may be used.
For example, after setting a reactor capable of pressurization to a predetermined temperature under pressure, a raw material comprising a vinyl monomer or a monomer mixture containing a vinyl monomer and a polymerization solvent or the like used in combination as necessary Can be polymerized while being supplied to the reactor at a constant supply rate, and a reaction liquid in an amount commensurate with the amount of raw material supplied can be extracted. The raw material can also contain a polymerization initiator as needed.
The pressure in the reactor depends on the reaction temperature and the boiling point of the raw material to be used, and does not affect the polymerization reaction, but may be any pressure that can maintain the reaction temperature (150 to 350 ° C.).
The residence time of the raw material in the reactor is preferably 1 to 60 minutes. If the residence time is less than 1 minute, the monomer may not sufficiently react, and if the unreacted monomer exceeds 60 minutes, the productivity may deteriorate. The preferred residence time is 2 to 40 minutes.
反応器から抜き出された前駆重合体を含有する反応液は、そのまま、次の水素付加工程において用いることができる。また、この反応液を、蒸留等に供することにより、未反応のビニル単量体、低分子量オリゴマー、重合溶媒等の揮発性成分を留去した後、単離された前駆重合体を用いて、水素付加工程に供することができる。尚、反応液から留去させた揮発性成分を、原料を収容するタンク又は反応器に戻し、重合反応に再利用することもできる。
このように、未反応単量体及び重合溶媒をリサイクルする方法は経済性の面から好ましい方法である。リサイクルする場合には、反応器内で望ましい構成のビニル単量体と望ましい重合溶媒の量を維持するように、新たに供給するビニル単量体等の混合比を決定する必要がある。The reaction liquid containing the precursor polymer extracted from the reactor can be used as it is in the next hydrogenation step. In addition, by subjecting this reaction solution to distillation, etc., after distilling off volatile components such as unreacted vinyl monomer, low molecular weight oligomer, polymerization solvent, etc., using the isolated precursor polymer, It can use for a hydrogenation process. In addition, the volatile component distilled off from the reaction liquid can be returned to the tank or reactor containing the raw material and reused in the polymerization reaction.
Thus, the method of recycling the unreacted monomer and the polymerization solvent is a preferable method from the viewpoint of economy. In the case of recycling, it is necessary to determine the mixing ratio of the newly supplied vinyl monomer and the like so as to maintain the desired amount of vinyl monomer and the desired polymerization solvent in the reactor.
前駆重合体の製造に、重合溶媒を用いる場合は、テトラヒドロフラン及びジオキサン等の環状エーテル類；ベンゼン、トルエン及びキシレン等の芳香族炭化水素化合物；酢酸エチル及び酢酸ブチル等のエステル類；アセトン、メチルエチルケトン及びシクロヘキサノン等のケトン類；メタノール、エタノール、イソプロパノール等のアルコール類等の有機溶剤を用いることができる。これらの重合溶媒は、１種又は２種以上を用いることができる。尚、（メタ）アクリル酸エステル共重合体をよく溶解しない有機溶剤を用いた場合には、反応器の内壁にスケールが成長しやすく、洗浄工程等で生産上の問題がおきやすい。
重合溶媒の使用量は、ビニル単量体の全量１００質量部に対して、８０質量部以下とすることが好ましい。８０質量部以下とすることにより、短時間で高い転化率が得られる。より好ましくは１〜５０質量部である。また、重合溶媒を用いる場合には、オルト酢酸トリメチル、オルト蟻酸トリメチル等の脱水剤を添加することもできる。When a polymerization solvent is used for the production of the precursor polymer, cyclic ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbon compounds such as benzene, toluene and xylene; esters such as ethyl acetate and butyl acetate; acetone, methyl ethyl ketone and Organic solvents such as ketones such as cyclohexanone; alcohols such as methanol, ethanol and isopropanol can be used. These polymerization solvents can be used alone or in combination of two or more. In addition, when an organic solvent that does not dissolve the (meth) acrylic acid ester copolymer well is used, scales are likely to grow on the inner wall of the reactor, and production problems are likely to occur in the cleaning process.
The amount of the polymerization solvent used is preferably 80 parts by mass or less with respect to 100 parts by mass of the total amount of vinyl monomers. By setting it to 80 parts by mass or less, a high conversion rate can be obtained in a short time. More preferably, it is 1-50 mass parts. When a polymerization solvent is used, a dehydrating agent such as trimethyl orthoacetate or trimethyl orthoformate can be added.
前駆重合体を得るために用いる重合開始剤は、所定の反応温度でラジカルを発生する開始剤であれば、特に限定されない。具体的には、ジ−ｔｅｒｔ−ブチルパーオキシド、ジ−ｔｅｒｔ−ヘキシルパーオキシド等の有機過酸化物；アゾビスイソブチロニトリル、アゾビスシクロヘキサカルボニトリル、アゾビス（２−メチルブチロニトリル）、アゾビス（２，４−ジメチルバレロニトリル）、２，２′−アゾビス（２−アミジノプロパン）ジヒドロクロリド、４，４′−アゾビス（４−シアノバレリックアシッド）等のアゾ系化合物が挙げられる。重合開始剤の使用量は、ビニル単量体１００質量部に対して、好ましくは０．００１〜３質量部である。 The polymerization initiator used for obtaining the precursor polymer is not particularly limited as long as it is an initiator that generates radicals at a predetermined reaction temperature. Specifically, organic peroxides such as di-tert-butyl peroxide and di-tert-hexyl peroxide; azobisisobutyronitrile, azobiscyclohexacarbonitrile, azobis (2-methylbutyronitrile) Azo compounds such as azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-amidinopropane) dihydrochloride, 4,4'-azobis (4-cyanovaleric acid). The amount of the polymerization initiator used is preferably 0.001 to 3 parts by mass with respect to 100 parts by mass of the vinyl monomer.
上記の方法により得られた前駆重合体に水素付加を行うことにより、重合体（Ｂ）が得られる。水素付加は、従来公知の方法により行われる。
例えば、前駆重合体を含む反応液に均一系触媒又は不均一系触媒を添加した後、系内を水素雰囲気にし、圧力を常圧〜１０ＭＰa、温度を２０〜１８０℃程度に加熱し、２〜２０時間ほど反応させることにより、水素付加を行うことができる。均一系触媒としては、例えば、クロロトリス（トリフェニルホスフィン）ロジウム等のロジウム錯体；ジクロロトリス（トリフェニルホスフィン）ルテニウム、クロロヒドロカルボニルトリス（トリフェニルホスフィン）ルテニウム等のルテニウム錯体；ジクロロビス（トリフェニルホスフィン）白金等の白金錯体；カルボニルビス（トリフェニルホスフィン）イリジウム等のイリジウム錯体等が挙げられる。また、不均一系触媒としては、例えば、ニッケル、ロジウム、ルテニウム、パラジウム、白金等の遷移金属を、カーボン、シリカ、アルミナ、繊維、有機ゲル状物等に担持させた固体触媒が挙げられる。不均一系触媒を用いる場合、水素付加工程の後、ろ過等により容易に触媒を除去することができ、高価な触媒が再利用できるといった点で好ましい。また、末端二重結合の濃度を十分に低下させた重合体（Ｂ）を高品質で得ることができる。尚、触媒の使用量としては、均一系触媒の場合、前駆重合体に対して、好ましくは１０〜１，０００ｐｐｍ程度である。不均一系触媒の場合、前駆重合体に対して、好ましくは１，０００〜１０，０００ｐｐｍ程度である。A polymer (B) is obtained by hydrogenating the precursor polymer obtained by said method. Hydrogenation is performed by a conventionally known method.
For example, after adding a homogeneous catalyst or a heterogeneous catalyst to a reaction solution containing a precursor polymer, the inside of the system is made a hydrogen atmosphere, the pressure is heated to normal pressure to 10 MPa, and the temperature is heated to about 20 to 180 ° C. Hydrogenation can be performed by reacting for about 20 hours. Examples of homogeneous catalysts include rhodium complexes such as chlorotris (triphenylphosphine) rhodium; ruthenium complexes such as dichlorotris (triphenylphosphine) ruthenium and chlorohydrocarbonyltris (triphenylphosphine) ruthenium; dichlorobis (triphenylphosphine) Platinum complexes such as platinum; iridium complexes such as carbonylbis (triphenylphosphine) iridium and the like. Examples of the heterogeneous catalyst include solid catalysts in which transition metals such as nickel, rhodium, ruthenium, palladium, and platinum are supported on carbon, silica, alumina, fibers, organic gels, and the like. When a heterogeneous catalyst is used, it is preferable in that the catalyst can be easily removed by filtration or the like after the hydrogenation step, and an expensive catalyst can be reused. Moreover, the polymer (B) which fully reduced the density | concentration of the terminal double bond can be obtained with high quality. The amount of catalyst used is preferably about 10 to 1,000 ppm with respect to the precursor polymer in the case of a homogeneous catalyst. In the case of a heterogeneous catalyst, it is preferably about 1,000 to 10,000 ppm with respect to the precursor polymer.
水素付加工程により、前駆重合体中の二重結合濃度を、好ましくは０．３０ｍｅｑ／ｇ以下、更に好ましくは０．２０ｍｅｑ／ｇ以下まで減少させる。０．２０ｍｅｑ／ｇ以下の重合体（Ｂ）を用いると、組成物の硬化性をより向上させることができる。二重結合濃度は、より好ましくは０．１０ｍｅｑ／ｇ以下、更に好ましくは０．０５ｍｅｑ／ｇ以下である。重合体（Ｂ）中の二重結合濃度は、1Ｈ−ＮＭＲの測定により、ＮＭＲスペクトルにおける、５〜６．５ｐｐｍに認められる二重結合のシグナルと、３〜４．５ｐｐｍに認められるエステルに隣接するメチレン、メチル基のシグナルの積分値の比から算出することができる。By the hydrogenation step, the double bond concentration in the precursor polymer is preferably reduced to 0.30 meq / g or less, more preferably 0.20 meq / g or less. When the polymer (B) of 0.20 meq / g or less is used, the curability of the composition can be further improved. The double bond concentration is more preferably 0.10 meq / g or less, still more preferably 0.05 meq / g or less. The double bond concentration in the polymer (B) is determined by the measurement of 1 H-NMR to the double bond signal observed at 5 to 6.5 ppm and the ester recognized at 3 to 4.5 ppm in the NMR spectrum. It can be calculated from the ratio of the integral values of signals of adjacent methylene and methyl groups.
本発明における重合体（Ｂ）の重量平均分子量（以下、「Ｍｗ」ともいう）は、好ましくは１，０００〜５０，０００、より好ましくは、１，５００〜２０，０００である。Ｍｗが１，０００以上であることにより硬化物において、長期に渡ってブリードせずに安定に系中の存在し、５０，０００以下であることにより、組成物とした時に適正な粘度となり、優れた作業性が確保される。尚、重量平均分子量（Ｍｗ）は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）によって測定された、ポリスチレン換算の値である。
また、本発明における重合体（Ｂ）のガラス転移温度は、好ましくは−８０℃〜２０℃、より好ましくは、−８０℃〜−１０℃である。ガラス転移温度が２０℃以下になることにより、柔軟性が付与される。尚、ガラス転移温度は、示差走査熱量計（ＤＳＣ）において検出される吸熱ピークの中間点により決定される。The weight average molecular weight (hereinafter also referred to as “Mw”) of the polymer (B) in the present invention is preferably 1,000 to 50,000, more preferably 1,500 to 20,000. When the Mw is 1,000 or more, the cured product is stably present in the system without bleeding for a long period of time, and when it is 50,000 or less, the composition has an appropriate viscosity and is excellent. Workability is ensured. The weight average molecular weight (Mw) is a value in terms of polystyrene measured by gel permeation chromatography (GPC).
Moreover, the glass transition temperature of the polymer (B) in this invention becomes like this. Preferably it is -80 degreeC-20 degreeC, More preferably, it is -80 degreeC--10 degreeC. Flexibility is imparted when the glass transition temperature is 20 ° C. or lower. The glass transition temperature is determined by the midpoint of the endothermic peak detected by a differential scanning calorimeter (DSC).
本発明の活性エネルギー線硬化性樹脂組成物において、化合物（Ａ）及び重合体（Ｂ）の質量比は、特に制限されない。重合体（Ｂ）の含有量は、化合物（Ａ）及び重合体（Ｂ）の合計に対し、好ましくは１０〜９０質量％、より好ましくは２０〜７０質量％である。１０質量％以上になることにより柔軟性が付与され、９０質量％以下であることにより、硬化物の強度が発現される。 In the active energy ray-curable resin composition of the present invention, the mass ratio of the compound (A) and the polymer (B) is not particularly limited. Content of a polymer (B) becomes like this. Preferably it is 10-90 mass% with respect to the sum total of a compound (A) and a polymer (B), More preferably, it is 20-70 mass%. By being 10 mass% or more, a softness | flexibility is provided, and the intensity | strength of hardened | cured material is expressed by being 90 mass% or less.
３．光重合開始剤（Ｃ）
本発明の活性エネルギー線硬化性樹脂組成物は、紫外線、可視光等の活性エネルギー線により硬化させる目的で、光重合開始剤（Ｃ）含有する。
光重合開始剤（Ｃ）としては、芳香族ケトン化合物、ベンゾフェノン系化合物、アシルホスフィンオキサイド化合物、チオキサントン系化合物、アクリドン系化合物、オキシムエステル類、２，４，５−トリアリールイミダゾール二量体、アクリジン誘導体等が挙げられる。光重合開始剤は、単独で用いてよいし、２つ以上を組み合わせて用いてもよい。3. Photopolymerization initiator (C)
The active energy ray-curable resin composition of the present invention contains a photopolymerization initiator (C) for the purpose of curing with active energy rays such as ultraviolet rays and visible light.
Photopolymerization initiators (C) include aromatic ketone compounds, benzophenone compounds, acylphosphine oxide compounds, thioxanthone compounds, acridone compounds, oxime esters, 2,4,5-triarylimidazole dimers, acridines Derivatives and the like. A photoinitiator may be used independently and may be used in combination of 2 or more.
芳香族ケトン化合物としては、ベンジルジメチルケタール、ベンジル、ベンゾイン、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、１−ヒドロキシシクロヘキシルフェニルケトン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、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、オリゴ［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、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、２−メチル−１−［４−（メチルチオ）］フェニル］−２−モルホリノプロパン−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）ブタン−１−オン、２−ジメチルアミノ−２−（４−メチルベンジル）−１−（４−モルホリン−４−イル−フェニル）−ブタン−１−オン、３，６−ビス（２−メチル−２−モルホリノプロピオニル）−９−ｎ−オクチルカルバゾール、フェニルグリオキシリックアシッドメチルエステル、エチルアントラキノン、フェナントレンキノン等が挙げられる。
ベンゾフェノン系化合物としては、ベンゾフェノン、２−メチルベンゾフェノン、３−メチルベンゾフェノン、４−メチルベンゾフェノン、２，４，６−トリメチルベンゾフェノン、４−フェニルベンゾフェノン、４−（メチルフェニルチオ）フェニルフェニルメタン、メチル−２−ベンゾフェノン、１−［４−（４−ベンゾイルフェニルスルファニル）フェニル］−２−メチル−２−（４−メチルフェニルスルフォニル）プロパン−１−オン、４，４′−ビス（ジメチルアミノ）ベンゾフェノン、４，４′−ビス（ジエチルアミノ）ベンゾフェノン、Ｎ，Ｎ′−テトラメチル−４，４′−ジアミノベンゾフェノン、Ｎ，Ｎ′−テトラエチル−４，４′−ジアミノベンゾフェノン及び４−メトキシ−４′−ジメチルアミノベンゾフェノン等が挙げられる。
アシルホスフィンオキサイド化合物としては、ビス（２，４，６−トリメチルベンゾイル）−フェニルホスフィンオキサイド、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、エチル−（２，４，６−トリメチルベンゾイル）フェニルフォスフィネート及びビス（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等が挙げられる。
チオキサントン系化合物としては、チオキサントン、２−クロロチオキサントン、２，４−ジエチルチオキサントン、イソプロピルチオキサントン、１−クロロ−４−プロピルチオキサントン、３−［３，４−ジメチル−９−オキソ−９Ｈ−チオキサントン−２−イルオキシ］−２−ヒドロキシプロピル−Ｎ，Ｎ，Ｎ―トリメチルアンモニウムクロライド及びフロロチオキサントン等が挙げられる。
アクリドン系化合物としては、アクリドン、１０−ブチル−２−クロロアクリドン等が挙げられる。
オキシムエステル類としては、１，２−オクタンジオン１−［４−（フェニルチオ）−２−（Ｏ―ベンゾイルオキシム）］及びエタノン１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−１−（Ｏ―アセチルオキシム）等が挙げられる。
２，４，５−トリアリールイミダゾール二量体としては、２−（ｏ−クロロフェニル）−４，５−ジフェニルイミダゾール二量体、２−（ｏ−クロロフェニル）−４，５−ジ（ｍ−メトキシフェニル）イミダゾール二量体、２−（ｏ−フルオロフェニル）−４，５−フェニルイミダゾール二量体、２−（ｏ−メトキシフェニル）−４，５−ジフェニルイミダゾール二量体、２−（ｐ−メトキシフェニル）−４，５−ジフェニルイミダゾール二量体、２，４−ジ（ｐ−メトキシフェニル）−５−フェニルイミダゾール二量体及び２−（２，４−ジメトキシフェニル）−４，５−ジフェニルイミダゾール二量体等が挙げられる。
アクリジン誘導体としては、９−フェニルアクリジン及び１，７−ビス（９，９′−アクリジニル）ヘプタン等が挙げられる。Aromatic ketone compounds include benzyl dimethyl ketal, benzyl, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, oligo [2-hydroxy-2-methyl-1- [4-1- ( Methylvinyl) phenyl] propanone, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methylpropan-1-one, 2-methyl- 1- [4- (Methylthio)] phenyl] -2-morpholinopropane-1 ON, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl- Phenyl) -butan-1-one, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-octylcarbazole, phenylglyoxylic acid methyl ester, ethyl anthraquinone, phenanthrenequinone and the like.
Examples of benzophenone compounds include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4- (methylphenylthio) phenylphenylmethane, methyl- 2-benzophenone, 1- [4- (4-benzoylphenylsulfanyl) phenyl] -2-methyl-2- (4-methylphenylsulfonyl) propan-1-one, 4,4′-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone and 4-methoxy-4'-dimethyl Such as aminobenzophenone It is below.
Examples of the acylphosphine oxide compound include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and ethyl- (2,4,6-trimethylbenzoyl) phenylphosphine. Examples include finate and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide.
Examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3- [3,4-dimethyl-9-oxo-9H-thioxanthone-2. -Yloxy] -2-hydroxypropyl-N, N, N-trimethylammonium chloride, fluorothioxanthone and the like.
Examples of the acridone compounds include acridone, 10-butyl-2-chloroacridone and the like.
Examples of oxime esters include 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)] and ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H- Carbazol-3-yl] -1- (O-acetyloxime) and the like.
Examples of 2,4,5-triarylimidazole dimer include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxy). Phenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-phenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p- Methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer and 2- (2,4-dimethoxyphenyl) -4,5-diphenyl An imidazole dimer etc. are mentioned.
Examples of acridine derivatives include 9-phenylacridine and 1,7-bis (9,9′-acridinyl) heptane.
本発明の活性エネルギー線硬化性樹脂組成物において、光重合開始剤（Ｃ）の含有割合は、硬化性の観点から、化合物（Ａ）及び重合体（Ｂ）の合計量１００質量部に対して、好ましくは０．０１〜１０質量部、より好ましくは０．１〜８質量部である。光重合開始剤（Ｃ）の含有割合を０．０１質量部以上とすることにより、適量な紫外線又は可視光線で組成物を硬化させることができ生産性を向上させることができる。また、１０質量部以下とすることで、硬化物の耐候性や透明性に優れたものとすることができる。 In the active energy ray-curable resin composition of the present invention, the content ratio of the photopolymerization initiator (C) is based on 100 parts by mass of the total amount of the compound (A) and the polymer (B) from the viewpoint of curability. Preferably, it is 0.01-10 mass parts, More preferably, it is 0.1-8 mass parts. By setting the content ratio of the photopolymerization initiator (C) to 0.01 parts by mass or more, the composition can be cured with an appropriate amount of ultraviolet light or visible light, and productivity can be improved. Moreover, it can be made the thing excellent in the weather resistance and transparency of hardened | cured material by setting it as 10 mass parts or less.
４．他の成分
本発明の活性エネルギー線硬化性樹脂組成物は、上記した成分（Ａ）、（Ｂ）及び（Ｃ）を必須とするものであるが、必要に応じて、有機溶剤、湿気硬化用触媒、重合禁止剤、酸化防止剤、紫外線吸収剤、光安定剤、レベリング剤、消泡剤、表面調整剤、密着性付与剤、レオロジーコントロール剤、ワックス、無機フィラー、有機フィラー等の他の成分を含有してもよい。以下、他の成分について説明する。4). Other components The active energy ray-curable resin composition of the present invention essentially comprises the components (A), (B), and (C) described above, and, if necessary, an organic solvent, for moisture curing. Other components such as catalysts, polymerization inhibitors, antioxidants, UV absorbers, light stabilizers, leveling agents, antifoaming agents, surface conditioners, adhesion promoters, rheology control agents, waxes, inorganic fillers, organic fillers, etc. It may contain. Hereinafter, other components will be described.
４−１．有機溶剤
本発明の組成物が有機溶剤を含む場合、塗工性等を改善することができる。有機溶剤としては、例えば、前駆重合体の製造に用いることができる、上記した重合溶媒を使用できる。
本発明の活性エネルギー線硬化性樹脂組成物が有機溶剤を含有する場合、有機溶剤の含有割合は、目的、用途等に応じて、適宜、設定すれば良いが、組成物中における含有割合は、好ましくは１０〜９０質量％、より好ましくは３０〜８０質量％である。4-1. Organic solvent When the composition of this invention contains the organic solvent, coating property etc. can be improved. As an organic solvent, the above-mentioned polymerization solvent which can be used for manufacture of a precursor polymer can be used, for example.
When the active energy ray-curable resin composition of the present invention contains an organic solvent, the content ratio of the organic solvent may be appropriately set according to the purpose, use, etc., but the content ratio in the composition is: Preferably it is 10-90 mass%, More preferably, it is 30-80 mass%.
４−２．湿気硬化用触媒
本発明の組成物は、湿気硬化型組成物として使用することもできる。この場合、湿気硬化用触媒を使用することが好ましい。
湿気硬化用触媒としては、従来の湿気硬化型組成物で使用されているものを用いることができる。また、湿気によりアルコキシシリル基含有共重合体や、アルコキシシリル基含有（メタ）アクリレートのアルコキシシリル基を縮合させることができるものであれば、種々の化合物が使用可能である。4-2. Moisture Curing Catalyst The composition of the present invention can also be used as a moisture curable composition. In this case, it is preferable to use a moisture curing catalyst.
As the moisture curing catalyst, those used in conventional moisture curable compositions can be used. Various compounds can be used as long as they can condense an alkoxysilyl group-containing copolymer or an alkoxysilyl group of an alkoxysilyl group-containing (meth) acrylate by moisture.
具体的な湿気硬化用触媒としては、ジブチル錫ラウレート、ジブチル錫ジアセテート及びジブチル錫ジアセトアセトナート等の錫系触媒、テトラブチルチタネート及びテトラプロピルチタネート等のチタン酸エステル類；アルミニウムトリスアセチルアセトナート、アルミニウムトリスエチルアセトアセテート及びジイソプロポキシアルミニウムエチルアセトアセテート等の有機アルミニウム化合物；ジルコニウムテトラアセチルアセトナート、チタンテトラアセチルアセトナート等のキレート化合物；オクチル酸鉛；ブチルアミン、オクチルアミン、ジブチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、ジエチレントリアミン、トリエチレンテトラミン、オレイルアミン、シクロヘキシルアミン、ベンジルアミン、ジエチルアミノプロピルアミン、キシリレンジアミン、トリエチレンジアミン、グアニジン、ジフェニルグアニジン、２，４，６−トリス（ジメチルアミノメチル）フェノール、モルホリン、Ｎ−メチルモルホリン、２−エチル−４−メチルイミダゾール及び１，８−ジアザビシクロ（５，４，０）ウンデセン−７（ＤＢＵ）等のアミン系化合物；これらのアミン系化合物のカルボン酸等との塩；カルボン酸；カルボン酸金属塩；有機スルホン酸；酸性リン酸エステル；３Ｂ族又は４Ａ族金属を含有する有機金属化合物；その他酸性触媒並びに塩基性触媒等のシラノール縮合触媒が挙げられる。
本発明の活性エネルギー線硬化性樹脂組成物が湿気硬化用触媒を含有する場合、湿気硬化用触媒の含有割合は、目的、用途等や、アルキシシリル基を有する共重合体及びアルコキシシリル基を有する（メタ）アクリレート等の、化合物（Ａ）又は重合体（Ｂ）の種類及びその割合等に応じて、適宜、設定すれば良いが、組成物中における含有割合は、好ましくは０．１〜１０質量％、より好ましくは０．５〜５質量％である。Specific moisture curing catalysts include tin-based catalysts such as dibutyltin laurate, dibutyltin diacetate and dibutyltin diacetoacetonate, titanates such as tetrabutyl titanate and tetrapropyl titanate; aluminum trisacetylacetonate , Organoaluminum compounds such as aluminum trisethyl acetoacetate and diisopropoxyaluminum ethyl acetoacetate; chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; lead octylate; butylamine, octylamine, dibutylamine, monoethanol Amine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzine Amines, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole and 1, Amine-based compounds such as 8-diazabicyclo (5,4,0) undecene-7 (DBU); salts of these amine-based compounds with carboxylic acids and the like; carboxylic acids; carboxylic acid metal salts; organic sulfonic acids; Examples include esters; organometallic compounds containing Group 3B or Group 4A metals; and other silanol condensation catalysts such as acidic catalysts and basic catalysts.
When the active energy ray-curable resin composition of the present invention contains a moisture curing catalyst, the content ratio of the moisture curing catalyst has a purpose, application, etc., a copolymer having an alkoxysilyl group, and an alkoxysilyl group ( What is necessary is just to set suitably according to the kind and ratio, etc. of a compound (A) or a polymer (B), such as (meth) acrylate, However, Preferably the content rate in a composition is 0.1-10 mass. %, More preferably 0.5 to 5% by mass.
４−３．重合禁止剤
重合禁止剤は、ハイドロキノン、ハイドロキノンモノメチルエーテル、２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノール等のフェノール系酸化防止剤が好ましい。また、イオウ系二次酸化防止剤、リン系二次酸化防止剤等を添加することもできる。4-3. Polymerization inhibitor The polymerization inhibitor is preferably a phenolic antioxidant such as hydroquinone, hydroquinone monomethyl ether, or 2,6-di-tert-butyl-4-methylphenol. Moreover, a sulfur type secondary antioxidant, a phosphorus type secondary antioxidant, etc. can also be added.
４−４．紫外線吸収剤
紫外線吸収剤としては、２−（２′−ヒドロキシ−５−メチルフェニル）ベンゾトリアゾール、２−（２′−ヒドロキシ−３′，５′−ジ−ｔｅｒｔ−ブチルフェニル）ベンゾトリアゾール、２−（２′−ヒドロキシ−３′−ｔｅｒｔ−ブチル−５′−メチルフェニル）ベンゾトリアゾール等のベンゾトリアゾール化合物；２，４−ビス（２，４−ジメチルフェニル）−６−（２−ヒドロキシ−４−イソ−オクチルオキシフェニル）−ｓ−トリアジン等のトリアジン化合物；２，４−ジヒドロキシ−ベンゾフェノン、２−ヒドロキシ−４−メトキシ−ベンゾフェノン、２−ヒドロキシ−４−メトキシ−４′−メチルベンゾフェノン、２，２′−ジヒドロキシ−４−メトキシベンゾフェノン、２，４，４′−トリヒドロキシベンゾフェノン、２，２′，４，４′−テトラヒドロキシベンゾフェノン、２，３，４，４′−テトラヒドロキシベンゾフェノン、２，３′，４，４′−テトラヒドロキシベンゾフェノン、２，２′−ジヒドロキシ−４，４′−ジメトキシベンゾフェノン等のベンゾフェノン化合物等が挙げられる。4-4. Ultraviolet absorber As the ultraviolet absorber, 2- (2'-hydroxy-5-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2 Benzotriazole compounds such as-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole; 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4 Triazine compounds such as -iso-octyloxyphenyl) -s-triazine; 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2, 2'-dihydroxy-4-methoxybenzophenone, 2,4,4'-trihydroxybenzo Phenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy- And benzophenone compounds such as 4,4'-dimethoxybenzophenone.
４−５．光安定剤
光安定剤としては、Ｎ，Ｎ′−ビス（２，２，６，６−テトラメチル−４−ピペリジル）−Ｎ，Ｎ′−ジホルミルヘキサメチレンジアミン、ビス（１，２，６，６−）ペンタメチル−４−ピペリジル）−２−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル）−２−ｎ−ブチルマロネート、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジニル）セバケート等の低分子量ヒンダードアミン化合物；Ｎ，Ｎ′−ビス（２，２，６，６−テトラメチル−４−ピペリジル）−Ｎ，Ｎ′−ジホルミルヘキサメチレンジアミン、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジニル）セバケート等の高分子量ヒンダードアミン化合物等のヒンダードアミン系光安定剤等が挙げられる。4-5. Light Stabilizer As the light stabilizer, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) -N, N′-diformylhexamethylenediamine, bis (1,2,6 , 6-) pentamethyl-4-piperidyl) -2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2-n-butylmalonate, bis (1,2,2,6,6- Low molecular weight hindered amine compounds such as pentamethyl-4-piperidinyl) sebacate; N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) -N, N′-diformylhexamethylenediamine, bis ( And hindered amine light stabilizers such as high molecular weight hindered amine compounds such as 1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate.
５．活性エネルギー線硬化性組成物
上記のように、本発明の活性エネルギー線硬化性組成物は、化合物（Ａ）と、特定の製造方法により得られた重合体（Ｂ）と、光重合開始剤（Ｃ）とを含有し、必要に応じて、他の成分を含有する。組成物の粘度は、特に限定されないが、Ｅ型粘度計を用いて測定される２５℃における粘度は、２００〜２０，０００ｍＰａ・ｓであることが好ましい。粘度がこの範囲にあることにより、塗工作業性に優れ、平滑な塗工が容易になる。5). Active energy ray-curable composition As described above, the active energy ray-curable composition of the present invention comprises a compound (A), a polymer (B) obtained by a specific production method, a photopolymerization initiator ( C) and, if necessary, other components. The viscosity of the composition is not particularly limited, but the viscosity at 25 ° C. measured using an E-type viscometer is preferably 200 to 20,000 mPa · s. When the viscosity is in this range, the coating workability is excellent, and smooth coating becomes easy.
６．活性エネルギー線硬化性組成物の製造方法
本発明の組成物は、前述の原料成分を、常温又は加熱下で、従来公知の装置等を用いて混合することにより製造することができる。加熱を行いながら組成物を製造する場合、各原料成分の揮発性等を考慮して温度を設定する。6). Production method of active energy ray-curable composition The composition of the present invention can be produced by mixing the above-described raw material components at room temperature or under heating using a conventionally known apparatus or the like. When producing a composition while heating, the temperature is set in consideration of the volatility of each raw material component.
７．硬化物の形成方法
本発明の活性エネルギー線硬化性組成物を用いて、硬化物を形成する場合には、組成物の構成等により、その方法が、適宜、選択される。例えば、組成物が有機溶剤を含有しない場合、塗膜等を形成した後、直接、活性エネルギー線を照射することにより、硬化膜（硬化物）を形成することができる。しかしながら、組成物が有機溶剤を含有する場合には、塗膜等を形成した後、乾燥等を行って、有機溶剤の含有量を低減させた状態で、活性エネルギー線を照射することが好ましい。尚、硬化物を被着体に密着させつつ形成する場合、被着体の構成材料は、特に限定されず、有機材料及び無機材料のいずれでもよいし、両方でもよい。7). Forming method of hardened | cured material When forming hardened | cured material using the active energy ray curable composition of this invention, the method is suitably selected by the structure of a composition, etc. For example, when the composition does not contain an organic solvent, a cured film (cured product) can be formed by directly irradiating active energy rays after forming a coating film or the like. However, when the composition contains an organic solvent, it is preferable to irradiate active energy rays in a state where the content of the organic solvent is reduced by drying or the like after forming a coating film or the like. In addition, when forming hardened | cured material closely_contact | adhering to a to-be-adhered body, the constituent material of a to-be-adhered body is not specifically limited, Either an organic material and an inorganic material may be sufficient.
活性エネルギー線の具体例としては、紫外線、電子線、可視光等が挙げられるが、紫外線が特に好ましい。紫外線照射装置としては、高圧水銀ランプ、メタルハライドランプ、ＵＶ無電極ランプ、ＬＥＤ等が挙げられる。照射エネルギーは、組成物の構成、活性エネルギー線の種類等に応じて、適宜、設定される。紫外線を照射する場合の光量は、好ましくは５００〜５，０００ｍＪ／ｃｍ2である。
本発明の活性エネルギー線硬化性組成物は、硬化性に優れるため、従来の組成物に比べて、活性エネルギー線の照射量を低減することができ、低コストで硬化物を形成することができる。
Specific examples of the active energy rays include ultraviolet rays, electron beams, and visible light, and ultraviolet rays are particularly preferable. Examples of the ultraviolet irradiation device include a high-pressure mercury lamp, a metal halide lamp, a UV electrodeless lamp, and an LED. The irradiation energy is appropriately set according to the composition of the composition, the type of active energy ray, and the like. The amount of light when irradiating with ultraviolet rays is preferably 500 to 5,000 mJ / cm 2 .
Since the active energy ray-curable composition of the present invention is excellent in curability, the amount of active energy ray irradiation can be reduced compared to conventional compositions, and a cured product can be formed at low cost. .
以下に、本発明を、例を挙げて具体的に説明する。尚、下記において「部」とは、質量部を意味する。 Hereinafter, the present invention will be specifically described by way of examples. In the following, “part” means part by mass.
１．重合体（Ｂ）の製造
以下の製造例１〜１０により、活性エネルギー線硬化型樹脂組成物の製造及び評価に用いるビニル重合体（Ｂ）を製造した（表１参照）。1. Manufacture of polymer (B) By the following manufacture examples 1-10, the vinyl polymer (B) used for manufacture and evaluation of an active energy ray hardening-type resin composition was manufactured (refer Table 1).
製造例１（ビニル重合体Ｂ１の製造）
オイルジャケットを備えた容量１，０００ｍＬの加圧式攪拌槽型反応器のジャケット温度を２４８℃に保った。次いで、反応器の圧力を一定に保ちながら、単量体として、ｎ−ブチルアクリレート（１００部）、重合溶媒として、イソプロピルアルコール（４．２部）及びメチルエチルケトン（１２．２部）、重合開始剤として、ジ−ｔｅｒｔ−ブチルパーオキサイド（１．０部）からなる単量体混合物を、一定の供給速度（４８ｇ／分、滞留時間：１２分）で原料タンクから反応器に連続供給を開始し、単量体混合物の供給量に相当する反応液を出口から連続的に抜き出した。反応開始直後に、一旦反応温度が低下した後、重合熱による温度上昇が認められたが、オイルジャケット温度を制御することにより、反応器の内温を２３９〜２４１℃に保持した。反応器内温が安定してから３６分後の時点を、反応液の採取開始点とし、これから２５分間反応を継続した。この製造では、結果として、１．２ｋｇの単量体混合物を供給し、１．２ｋｇの反応液を回収した。その後、反応液を薄膜蒸発器に導入して、未反応モノマー等の揮発成分の分離及び除去を行い、重合体Ｂ１を得た。重合体Ｂ１のＧＰＣ測定を行った結果、ポリスチレン換算の数平均分子量（以下、「Ｍｎ」という）が１，６００、重量平均分子量（Ｍｗ）が３，０００であり、Ｅ型粘度計による２５℃における粘度が、１，０００ｍＰａ・ｓであった。また、ＤＳＣによるガラス転移温度は−７７℃であり、1Ｈ−ＮＭＲ測定による二重結合濃度は０．３６ｍｅｑ／ｇであった。Production Example 1 (Production of vinyl polymer B1)
The jacket temperature of a 1,000 mL capacity pressurized stirred tank reactor equipped with an oil jacket was kept at 248 ° C. Next, while maintaining the reactor pressure constant, n-butyl acrylate (100 parts) as a monomer, isopropyl alcohol (4.2 parts) and methyl ethyl ketone (12.2 parts) as a polymerization solvent, a polymerization initiator The monomer mixture consisting of di-tert-butyl peroxide (1.0 part) was continuously fed from the raw material tank to the reactor at a constant feed rate (48 g / min, residence time: 12 minutes). The reaction solution corresponding to the amount of monomer mixture supplied was continuously withdrawn from the outlet. Immediately after the start of the reaction, once the reaction temperature decreased, a temperature increase due to the heat of polymerization was observed, but the internal temperature of the reactor was maintained at 239 to 241 ° C. by controlling the oil jacket temperature. The time point after 36 minutes from the stabilization of the reactor internal temperature was taken as the reaction liquid collection start point, and the reaction was continued for 25 minutes thereafter. In this production, as a result, 1.2 kg of the monomer mixture was supplied and 1.2 kg of the reaction liquid was recovered. Thereafter, the reaction solution was introduced into a thin film evaporator, and volatile components such as unreacted monomers were separated and removed to obtain a polymer B1. As a result of GPC measurement of the polymer B1, the number average molecular weight (hereinafter referred to as “Mn”) in terms of polystyrene was 1,600, the weight average molecular weight (Mw) was 3,000, and 25 ° C. measured by an E-type viscometer. The viscosity at 1,000 mPa · s was 1,000 mPa · s. The glass transition temperature by DSC is -77 ° C., the double bond concentration by the 1 H-NMR measurement was 0.36meq / g.
製造例２（ビニル重合体Ｂ２の製造）
オイルジャケットを備えた容量１，０００ｍＬの加圧式攪拌槽型反応器のジャケット温度を２４５℃に保った。次いで、反応器の圧力を一定に保ちながら、単量体として、２−エチルヘキシルアクリレート（７５部）及びメチルメタクリレート（２５部）、重合溶媒として、メチルエチルケトン（４．６部）、重合開始剤として、ジ−ｔｅｒｔ−ブチルパーオキサイド（０．７７部）からなる単量体混合物を、一定の供給速度（４８ｇ／分、滞留時間：１２分）で原料タンクから反応器に連続供給を開始し、単量体混合物の供給量に相当する反応液を出口から連続的に抜き出した。反応開始直後に、一旦反応温度が低下した後、重合熱による温度上昇が認められたが、オイルジャケット温度を制御することにより、反応器の内温を２４０〜２４２℃に保持した。反応器内温が安定してから３６分後の時点を、反応液の採取開始点とし、これから２５分間反応を継続した。この製造では、結果として、１．２ｋｇの単量体混合物を供給し、１．２ｋｇの反応液を回収した。その後、反応液を薄膜蒸発器に導入して、未反応モノマー等の揮発成分の分離及び除去を行い、重合体Ｂ２を得た。重合体Ｂ２のＧＰＣ測定を行った結果、ポリスチレン換算のＭｎが１，５００、Ｍｗが２，４００であり、Ｅ型粘度計による２５℃における粘度が、３，６００ｍＰａ・ｓであった。また、ＤＳＣによるガラス転移温度は−６４℃であり、1Ｈ−ＮＭＲ測定による二重結合濃度は０．６３ｍｅｑ／ｇであった。Production Example 2 (Production of vinyl polymer B2)
The jacket temperature of a 1,000 ml capacity pressurized stirred tank reactor equipped with an oil jacket was kept at 245 ° C. Next, while maintaining the reactor pressure constant, as monomers, 2-ethylhexyl acrylate (75 parts) and methyl methacrylate (25 parts), as a polymerization solvent, methyl ethyl ketone (4.6 parts), as a polymerization initiator, A monomer mixture consisting of di-tert-butyl peroxide (0.77 parts) was continuously fed from the raw material tank to the reactor at a constant feed rate (48 g / min, residence time: 12 minutes). A reaction solution corresponding to the supply amount of the monomer mixture was continuously withdrawn from the outlet. Immediately after the start of the reaction, once the reaction temperature decreased, a temperature increase due to the heat of polymerization was observed. By controlling the oil jacket temperature, the internal temperature of the reactor was maintained at 240 to 242 ° C. The time point after 36 minutes from the stabilization of the reactor internal temperature was taken as the reaction liquid collection start point, and the reaction was continued for 25 minutes thereafter. In this production, as a result, 1.2 kg of the monomer mixture was supplied and 1.2 kg of the reaction liquid was recovered. Thereafter, the reaction solution was introduced into a thin film evaporator, and volatile components such as unreacted monomers were separated and removed to obtain a polymer B2. As a result of GPC measurement of the polymer B2, the polystyrene-converted Mn was 1,500, the Mw was 2,400, and the viscosity at 25 ° C. by an E-type viscometer was 3,600 mPa · s. The glass transition temperature by DSC is -64 ° C., the double bond concentration by the 1 H-NMR measurement was 0.63meq / g.
製造例３（ビニル重合体Ｂ３の製造）
オイルジャケットを備えた容量１，０００ｍＬの加圧式攪拌槽型反応器のジャケット温度を１８１℃に保った。次いで、反応器の圧力を一定に保ちながら、単量体として、ｎ−ブチルアクリレート（４５部）、２−エチルヘキシルアクリレート（４５部）及びメチルメタクリレート（１０部）、重合溶媒として、イソプロピルアルコール（９部）及びメチルエチルケトン（９部）、重合開始剤として、ジ−ｔｅｒｔ−ブチルパーオキサイド（０．２５部）からなる単量体混合物を、一定の供給速度（４８ｇ／分、滞留時間：１２分）で原料タンクから反応器に連続供給を開始し、単量体混合物の供給量に相当する反応液を出口から連続的に抜き出した。反応開始直後に、一旦反応温度が低下した後、重合熱による温度上昇が認められたが、オイルジャケット温度を制御することにより、反応器の内温を１８３〜１８５℃に保持した。反応器内温が安定してから３６分後の時点を、反応液の採取開始点とし、これから２５分間反応を継続した。この製造では、結果として、１．２ｋｇの単量体混合物を供給し、１．２ｋｇの反応液を回収した。その後、反応液を薄膜蒸発器に導入して、未反応モノマー等の揮発成分の分離及び除去を行い、重合体Ｂ３を得た。重合体Ｂ３のＧＰＣ測定を行った結果、ポリスチレン換算のＭｎが２，５００、Ｍｗが７，５００であり、Ｅ型粘度計による２５℃における粘度が、２０，０００ｍＰａ・ｓであった。また、ＤＳＣによるガラス転移温度は−５７℃であり、1Ｈ−ＮＭＲ測定による二重結合濃度は０．３４ｍｅｑ／ｇであった。Production Example 3 (Production of vinyl polymer B3)
The jacket temperature of a 1,000 mL capacity pressurized stirred tank reactor equipped with an oil jacket was kept at 181 ° C. Next, while maintaining the reactor pressure constant, n-butyl acrylate (45 parts), 2-ethylhexyl acrylate (45 parts) and methyl methacrylate (10 parts) were used as monomers, and isopropyl alcohol (9 Part) and methyl ethyl ketone (9 parts), and a monomer mixture consisting of di-tert-butyl peroxide (0.25 part) as a polymerization initiator, a constant feed rate (48 g / min, residence time: 12 minutes) Then, continuous supply from the raw material tank to the reactor was started, and a reaction liquid corresponding to the supply amount of the monomer mixture was continuously extracted from the outlet. Immediately after the start of the reaction, once the reaction temperature decreased, an increase in temperature due to the heat of polymerization was observed, but the internal temperature of the reactor was maintained at 183 to 185 ° C. by controlling the oil jacket temperature. The time point after 36 minutes from the stabilization of the reactor internal temperature was taken as the reaction liquid collection start point, and the reaction was continued for 25 minutes thereafter. In this production, as a result, 1.2 kg of the monomer mixture was supplied and 1.2 kg of the reaction liquid was recovered. Thereafter, the reaction solution was introduced into a thin film evaporator, and volatile components such as unreacted monomers were separated and removed to obtain a polymer B3. As a result of GPC measurement of the polymer B3, the Mn in terms of polystyrene was 2,500, the Mw was 7,500, and the viscosity at 25 ° C. by an E-type viscometer was 20,000 mPa · s. The glass transition temperature by DSC is -57 ° C., the double bond concentration by the 1 H-NMR measurement was 0.34meq / g.
製造例４（ビニル重合体Ｂ４の製造）
オイルジャケットを備えた容量１，０００ｍＬの加圧式攪拌槽型反応器のジャケット温度を２４４℃に保った。次いで、反応器の圧力を一定に保ちながら、単量体として、２−エチルヘキシルアクリレート（７７部）、メチルメタクリレート（２０部）及び３−メタクリロキシトリメトキシシラン（３部）、重合溶媒として、メチルエチルケトン（１３．１部）及びオルト酢酸メチル（３．８部）、重合開始剤としてジ−ｔｅｒｔ−ブチルパーオキサイド（１．０部）からなる単量体混合物を、一定の供給速度（４８ｇ／分、滞留時間：１２分）で原料タンクから反応器に連続供給を開始し、単量体混合物の供給量に相当する反応液を出口から連続的に抜き出した。反応開始直後に、一旦反応温度が低下した後、重合熱による温度上昇が認められたが、オイルジャケット温度を制御することにより、反応器の内温を２３１〜２３３℃に保持した。反応器内温が安定してから３６分後の時点を、反応液の採取開始点とし、これから２５分間反応を継続した。この製造では、結果として、１．２ｋｇの単量体混合物を供給し、１．２ｋｇの反応液を回収した。その後、反応液を薄膜蒸発器に導入して、未反応モノマー等の揮発成分の分離及び除去を行い、重合体Ｂ４を得た。重合体Ｂ４のＧＰＣ測定を行った結果、ポリスチレン換算のＭｎが１，４００、Ｍｗが２，４００であり、Ｅ型粘度計による２５℃における粘度が、２，２００ｍＰａ・ｓであった。また、ＤＳＣによるガラス転移温度は−６５℃であり、1Ｈ−ＮＭＲ測定による二重結合濃度は０．５６ｍｅｑ／ｇであった。Production Example 4 (Production of vinyl polymer B4)
The jacket temperature of a 1,000 mL capacity pressurized stirred tank reactor equipped with an oil jacket was kept at 244 ° C. Next, while maintaining the reactor pressure constant, 2-ethylhexyl acrylate (77 parts), methyl methacrylate (20 parts) and 3-methacryloxytrimethoxysilane (3 parts) as monomers, and methyl ethyl ketone as the polymerization solvent (13.1 parts) and methyl orthoacetate (3.8 parts), a monomer mixture consisting of di-tert-butyl peroxide (1.0 part) as a polymerization initiator, a constant feed rate (48 g / min) , Residence time: 12 minutes), continuous supply from the raw material tank to the reactor was started, and the reaction liquid corresponding to the supply amount of the monomer mixture was continuously withdrawn from the outlet. Immediately after the start of the reaction, once the reaction temperature decreased, a temperature increase due to the heat of polymerization was observed, but the internal temperature of the reactor was maintained at 231 to 233 ° C. by controlling the oil jacket temperature. The time point after 36 minutes from the stabilization of the reactor internal temperature was taken as the reaction liquid collection start point, and the reaction was continued for 25 minutes thereafter. In this production, as a result, 1.2 kg of the monomer mixture was supplied and 1.2 kg of the reaction liquid was recovered. Thereafter, the reaction solution was introduced into a thin film evaporator, and volatile components such as unreacted monomers were separated and removed to obtain a polymer B4. As a result of GPC measurement of the polymer B4, Mn in terms of polystyrene was 1,400, Mw was 2,400, and the viscosity at 25 ° C. by an E-type viscometer was 2,200 mPa · s. The glass transition temperature by DSC is -65 ° C., the double bond concentration by the 1 H-NMR measurement was 0.56meq / g.
製造例５（ビニル重合体Ｂ１への水素付加）
オイルジャケットを備えた容量１，０００ｍＬの加圧式撹拌槽型反応器に、製造例１で得た重合体Ｂ１（７００ｇ）及び乾燥した５％パラジウムカーボン（３．５ｇ）を入れ、反応器内の雰囲気を真空にした。その後、内温を１３０℃に加温し、水素で約１．５ＭＰａまで加圧した。この状態で、８時間撹拌し、水素付加反応を行った。圧力をパージした後、ろ過助剤として、昭和化学工業社製珪藻土「ラジオライト＃１００」を用いて、ろ過し、重合体Ｂ５を得た。重合体Ｂ５のＧＰＣ測定を行った結果、ポリスチレン換算のＭｎが１，６００、Ｍｗが３，０００であり、Ｅ型粘度計による２５℃における粘度が、１，０００ｍＰａ・ｓであった。また、ＤＳＣによるガラス転移温度は−７７℃であり、1Ｈ−ＮＭＲによる二重結合濃度は、検出下限（０．０１ｍｅｑ／ｇ）以下であった。Production Example 5 (Hydrogen addition to vinyl polymer B1)
In a pressure-stirred tank reactor having a capacity of 1,000 mL equipped with an oil jacket, the polymer B1 (700 g) obtained in Production Example 1 and dried 5% palladium carbon (3.5 g) were placed. The atmosphere was evacuated. Thereafter, the internal temperature was heated to 130 ° C. and pressurized to about 1.5 MPa with hydrogen. In this state, the mixture was stirred for 8 hours to perform a hydrogenation reaction. After purging the pressure, filtration was performed using diatomaceous earth “Radiolite # 100” manufactured by Showa Chemical Industry Co., Ltd. as a filter aid to obtain a polymer B5. As a result of GPC measurement of polymer B5, Mn in terms of polystyrene was 1,600, Mw was 3,000, and the viscosity at 25 ° C. by an E-type viscometer was 1,000 mPa · s. Moreover, the glass transition temperature by DSC was -77 degreeC, and the double bond density | concentration by < 1 > H-NMR was below the lower limit of detection (0.01 meq / g).
製造例６（ビニル重合体Ｂ２への水素付加）
重合体Ｂ１に代えて、製造例２で得た重合体Ｂ２を用い、内温を６０℃、水素の圧力を約０．３ＭＰａにして、４時間撹拌し、水素付加反応を行った以外は、製造例５と同じ操作を行い、重合体Ｂ６を得た。重合体Ｂ６のＧＰＣ測定を行った結果、ポリスチレン換算のＭｎが１，５００、Ｍｗが２，４００であり、Ｅ型粘度計による２５℃における粘度が、３，６００ｍＰａ・ｓであった。また、ＤＳＣによるガラス転移温度は−６４℃であり、1Ｈ−ＮＭＲによる二重結合濃度は、０．２２ｍｅｑ／ｇであった。Production Example 6 (Hydrogen addition to vinyl polymer B2)
The polymer B2 obtained in Production Example 2 was used in place of the polymer B1, the internal temperature was 60 ° C., the hydrogen pressure was about 0.3 MPa, the mixture was stirred for 4 hours, and the hydrogenation reaction was performed. The same operation as in Production Example 5 was performed to obtain a polymer B6. As a result of GPC measurement of the polymer B6, Mn in terms of polystyrene was 1,500, Mw was 2,400, and the viscosity at 25 ° C. by an E-type viscometer was 3,600 mPa · s. The glass transition temperature by DSC is -64 ° C., the double bond concentration by 1 H-NMR were was 0.22 meq / g.
製造例７（ビニル重合体Ｂ２への水素付加）
重合体Ｂ１に代えて、製造例２で得た重合体Ｂ２を用い、内温を１００℃、水素の圧力を約０．３ＭＰａにして、４時間撹拌し、水素付加反応を行った以外は、製造例５と同じ操作を行い、重合体Ｂ７を得た。重合体Ｂ７のＧＰＣ測定を行った結果、ポリスチレン換算のＭｎが１，５００、Ｍｗが２，４００であり、Ｅ型粘度計による２５℃における粘度が、３，６００ｍＰａ・ｓであった。また、ＤＳＣによるガラス転移温度は−６４℃であり、1Ｈ−ＮＭＲによる二重結合濃度は、０．１３ｍｅｑ／ｇであった。Production Example 7 (hydrogen addition to vinyl polymer B2)
The polymer B2 obtained in Production Example 2 was used in place of the polymer B1, the internal temperature was 100 ° C., the hydrogen pressure was about 0.3 MPa, the mixture was stirred for 4 hours, and the hydrogenation reaction was performed. The same operation as in Production Example 5 was performed to obtain a polymer B7. As a result of GPC measurement of the polymer B7, Mn in terms of polystyrene was 1,500, Mw was 2,400, and the viscosity at 25 ° C. by an E-type viscometer was 3,600 mPa · s. The glass transition temperature by DSC is -64 ° C., the double bond concentration by 1 H-NMR were a 0.13meq / g.
製造例８（ビニル重合体Ｂ２への水素付加）
重合体Ｂ１に代えて、製造例２で得た重合体Ｂ２を用い、内温を１３０℃、水素の圧力を約１．５ＭＰａにして、８時間撹拌し、水素付加反応を行った以外は、製造例５と同じ操作を行い、重合体Ｂ８を得た。重合体Ｂ８のＧＰＣ測定を行った結果、ポリスチレン換算のＭｎが１，５００、Ｍｗが２，４００であり、Ｅ型粘度計による２５℃における粘度が、３，６００ｍＰａ・ｓであった。また、ＤＳＣによるガラス転移温度は−６４℃であり、1Ｈ−ＮＭＲによる二重結合濃度は、検出下限以下であった。Production Example 8 (Hydrogen addition to vinyl polymer B2)
The polymer B2 obtained in Production Example 2 was used in place of the polymer B1, the internal temperature was 130 ° C., the hydrogen pressure was about 1.5 MPa, the mixture was stirred for 8 hours, and the hydrogenation reaction was performed. The same operation as in Production Example 5 was performed to obtain a polymer B8. As a result of GPC measurement of the polymer B8, Mn in terms of polystyrene was 1,500, Mw was 2,400, and the viscosity at 25 ° C. by an E-type viscometer was 3,600 mPa · s. Moreover, the glass transition temperature by DSC was -64 degreeC, and the double bond density | concentration by < 1 > H-NMR was below the detection minimum.
製造例９（ビニル重合体Ｂ３への水素付加）
重合体Ｂ１に代えて、製造例３で得た重合体Ｂ３を用い、内温を１３０℃、水素の圧力を約１．５ＭＰａにして、８時間撹拌し、水素付加反応を行った以外は、製造例５と同じ操作を行い、重合体Ｂ９を得た。重合体Ｂ９のＧＰＣ測定を行った結果、ポリスチレン換算のＭｎが２，５００、Ｍｗが７，５００であり、Ｅ型粘度計による２５℃における粘度が、２０，０００ｍＰａ・ｓであった。また、ＤＳＣによるガラス転移温度は−５７℃であり、1Ｈ−ＮＭＲによる二重結合濃度は、検出下限以下であった。Production Example 9 (hydrogen addition to vinyl polymer B3)
The polymer B3 obtained in Production Example 3 was used in place of the polymer B1, the internal temperature was 130 ° C., the hydrogen pressure was about 1.5 MPa, the mixture was stirred for 8 hours, and the hydrogenation reaction was performed. The same operation as in Production Example 5 was performed to obtain polymer B9. As a result of GPC measurement of the polymer B9, Mn in terms of polystyrene was 2,500, Mw was 7,500, and the viscosity at 25 ° C. by an E-type viscometer was 20,000 mPa · s. Moreover, the glass transition temperature by DSC was -57 degreeC, and the double bond density | concentration by < 1 > H-NMR was below the detection minimum.
製造例１０（ビニル重合体Ｂ４への水素付加）
重合体Ｂ１に代えて、製造例４で得た重合体Ｂ４を用い、内温を１３０℃、水素の圧力を約１．５ＭＰａにして、８時間撹拌し、水素付加反応を行った以外は、製造例５と同じ操作を行い、重合体Ｂ１０を得た。重合体Ｂ１０のＧＰＣ測定を行った結果、ポリスチレン換算のＭｎが１，４００、Ｍｗが２，４００であり、Ｅ型粘度計による２５℃における粘度が、２，２００ｍＰａ・ｓであった。また、ＤＳＣによるガラス転移温度は−６５℃であり、1Ｈ−ＮＭＲによる二重結合濃度は、検出下限以下であった。Production Example 10 (Hydrogen addition to vinyl polymer B4)
The polymer B4 obtained in Production Example 4 was used in place of the polymer B1, the internal temperature was 130 ° C., the hydrogen pressure was about 1.5 MPa, the mixture was stirred for 8 hours, and the hydrogenation reaction was performed. The same operation as in Production Example 5 was performed to obtain a polymer B10. As a result of GPC measurement of the polymer B10, Mn in terms of polystyrene was 1,400, Mw was 2,400, and the viscosity at 25 ° C. by an E-type viscometer was 2,200 mPa · s. Moreover, the glass transition temperature by DSC was -65 degreeC, and the double bond density | concentration by < 1 > H-NMR was below the detection minimum.
２．活性エネルギー線硬化型樹脂組成物の製造及び評価
実施例１〜１１、比較例１〜１０
製造例１〜１０で得た重合体（Ｂ）と、以下に示す、化合物（Ａ）及び光開始剤（Ｃ）とを用いて、表２及び表３に示す割合で配合し、均一に混合することにより、活性エネルギー線硬化型樹脂組成物を得た。
・化合物（Ａ）
（ａ１）Ｍ−２１１Ｂ：ビスフェノールＡのエチレンオキシド変性ジアクリレート（東亞合成社製、商品名「アロニックス Ｍ−２１１Ｂ」）
（ａ２）Ｍ−４０２：ジペンタエリスリトールヘキサアクリレート（東亞合成社製、商品名「アロニックス Ｍ−４０２」）
（ａ３）ＦＡ−５１３ＡＳ：ジシクロペンタニルアクリレート（日立化成社製、商品名「ファンクリル ＦＡ−５１３ＡＳ」）
・光重合開始剤（Ｃ）
（ｃ１）Ｉｒｇ１８４：１−ヒドロキシ−シクロヘキシルフェニルケトン（ＢＡＳＦ社製、商品名「Ｉｒｇａｃｕｒｅ１８４」）2. Production and evaluation of active energy ray-curable resin composition Examples 1 to 11 and Comparative Examples 1 to 10
Using the polymer (B) obtained in Production Examples 1 to 10 and the compound (A) and photoinitiator (C) shown below, they are blended in the proportions shown in Table 2 and Table 3, and mixed uniformly. By doing this, an active energy ray-curable resin composition was obtained.
Compound (A)
(A1) M-211B: Ethylene oxide-modified diacrylate of bisphenol A (trade name “Aronix M-211B” manufactured by Toagosei Co., Ltd.)
(A2) M-402: Dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd., trade name “Aronix M-402”)
(A3) FA-513AS: dicyclopentanyl acrylate (manufactured by Hitachi Chemical Co., Ltd., trade name “Fancryl FA-513AS”)
・ Photopolymerization initiator (C)
(C1) Irg184: 1-hydroxy-cyclohexylphenylketone (manufactured by BASF, trade name “Irgacure184”)
その後、得られた各組成物について、以下に記載する評価方法に供した。その結果を表２及び表３に併記した。
（１）硬化性
アプリケーターを用いて、組成物をガラス板に膜厚が５０μｍになるように塗布した。その後、アイグラフィックス社製紫外線照射装置「ＥＣＳ−４０１ＧＸ」を用いて、以下の条件により塗膜に紫外線を照射した。紫外線を１回照射するごとに指触を行って塗膜表面を観察し、指に液状物が付着しなくなった照射回数（パス回数）により、硬化性を評価した。
＜紫外線照射条件＞
光源：８０Ｗ／ｃｍ集光型高圧水銀灯
ランプ高さ（光源と塗膜との距離）：１０ｃｍ
コンベアスピードは、１パス当たりの照射量が１００ｍＪ／ｃｍ2になるように調節。Then, each composition obtained was subjected to the evaluation method described below. The results are shown in Tables 2 and 3.
(1) Curability Using an applicator, the composition was applied to a glass plate so that the film thickness was 50 μm. Thereafter, the coating film was irradiated with ultraviolet rays under the following conditions using an ultraviolet irradiation device “ECS-401GX” manufactured by Eye Graphics. Each time an ultraviolet ray was irradiated, the finger was touched to observe the surface of the coating film, and the curability was evaluated based on the number of times of irradiation (number of passes) at which the liquid material no longer adhered to the finger.
<Ultraviolet irradiation conditions>
Light source: 80 W / cm condensing type high pressure mercury lamp Lamp height (distance between light source and coating film): 10 cm
The conveyor speed is adjusted so that the irradiation amount per pass is 100 mJ / cm 2 .
（２）硬化物の破断強度
アプリケーターを用いて、組成物を、幅３００ｍｍ×長さ３００ｍｍ×厚さ５０μｍの東レ社製表面未処理ポリエチレンテレフタレートフィルム「ルミラー５０−Ｔ６０」（以下、「ルミラー」という）に、膜厚が５０μｍになるように塗布した。
次いで、上記紫外線照射装置を用いて、積算光量が３０００ｍＪ／ｃｍ2となるように塗膜に紫外線を照射した。その後、ルミラーから硬化物を剥がし、１５ｍｍ×１５０ｍｍ×５０μｍのサンプルを切り出した。このサンプルを、島津製作所社製引張試験機「オートグラフＡＧＳ−Ｊ」を用いて、引張速度５０ｍｍ／分の条件で引張試験を行い、破断強度を求めた。(2) Breaking strength of cured product Using an applicator, the composition was made into a surface untreated polyethylene terephthalate film “Lumirror 50-T60” (hereinafter referred to as “Lumirror”) having a width of 300 mm × a length of 300 mm × a thickness of 50 μm ) To a film thickness of 50 μm.
Subsequently, the coating film was irradiated with ultraviolet rays so that the integrated light amount was 3000 mJ / cm 2 using the ultraviolet irradiation device. Thereafter, the cured product was peeled off from the Lumirror and a sample of 15 mm × 150 mm × 50 μm was cut out. This sample was subjected to a tensile test using a tensile tester “Autograph AGS-J” manufactured by Shimadzu Corporation under the condition of a tensile speed of 50 mm / min to obtain a breaking strength.
（３）硬化物の柔軟性
バーコーターを用いて、組成物を東洋紡社製易接着ＰＥＴフィルム「コスモシャインＡ４３００」（厚さ１００μｍ）に、膜厚が１０μｍになるように塗布した。
次いで、上記紫外線照射装置を用いて、積算光量が３０００ｍＪ／ｃｍ2となるように塗膜に紫外線を照射した。その後、１００ｍｍ×５０ｍｍの大きさに切り出し、ＪＩＳ Ｋ５６００−５−１に従って、耐屈曲性試験を実施した。屈曲させたときに、割れ又は剥がれが生じたときの円筒の直径により柔軟性を評価した。(3) Flexibility of cured product Using a bar coater, the composition was applied to an easily adhesive PET film “Cosmo Shine A4300” (thickness: 100 μm) manufactured by Toyobo Co., Ltd. so as to have a thickness of 10 μm.
Subsequently, the coating film was irradiated with ultraviolet rays so that the integrated light amount was 3000 mJ / cm 2 using the ultraviolet irradiation device. Then, it cut out to the magnitude | size of 100 mm x 50 mm, and the bending resistance test was implemented according to JISK5600-5-1. Flexibility was evaluated by the diameter of the cylinder when cracking or peeling occurred when bent.
実施例１〜１１の組成物は、硬化に必要なパス回数が少なく、良好な硬化性を示した。実施例２以外の実施例は、二重結合濃度が０．２０ｍｅｑ／ｇ以下の重合体（Ｂ）を用いた組成物の例であるが、パス回数４回以下の低照射条件でも硬化可能であった。
また、その硬化物は、十分な強度を有しながら柔軟性にも優れるものであることが確認できた。In the compositions of Examples 1 to 11, the number of passes required for curing was small and good curability was exhibited. Examples other than Example 2 are examples of compositions using a polymer (B) having a double bond concentration of 0.20 meq / g or less, but can be cured even under low irradiation conditions with 4 passes or less. there were.
Moreover, it has confirmed that the hardened | cured material was excellent also in a softness | flexibility, while having sufficient intensity | strength.
これに対し、水素を付加する処理を行っておらず、二重結合濃度の高い重合体を含有する組成物を用いた比較例１〜９は、硬化に必要なパス回数が多く、硬化性に劣るものであった。また、比較例１０は、重合体（Ｂ）を用いない組成物の例であり、得られる硬化物の柔軟性が不十分なものであることが確認できた。
On the other hand, Comparative Examples 1 to 9 using a composition containing a polymer having a high double bond concentration without performing the process of adding hydrogen have a large number of passes required for curing, and are curable. It was inferior. Moreover, the comparative example 10 is an example of the composition which does not use a polymer (B), and has confirmed that the softness | flexibility of the hardened | cured material obtained was inadequate.
本発明の活性エネルギー線硬化型樹脂組成物は、活性エネルギー線による硬化性が良好であり、柔軟性に優れる硬化物が得られるため、コーティング剤、接着剤、インク、空隙充填剤等の種々の用途に有用である。 Since the active energy ray-curable resin composition of the present invention has good curability by active energy rays and a cured product having excellent flexibility can be obtained, various kinds of coating agents, adhesives, inks, void fillers and the like can be obtained. Useful for applications.
Claims (6)
前記前駆重合体に水素付加を行うことにより二重結合濃度が０．３０ｍｅｑ／ｇ以下である重合体（Ｂ）を得る工程、及び、A step of obtaining a polymer (B) having a double bond concentration of 0.30 meq / g or less by hydrogenating the precursor polymer; and
前記重合体（Ｂ）、エチレン性不飽和基含有化合物（Ａ）及び光重合開始剤（Ｃ）を混合する工程を含む活性エネルギー線硬化性樹脂組成物の製造方法。The manufacturing method of the active energy ray-curable resin composition including the process of mixing the said polymer (B), an ethylenically unsaturated group containing compound (A), and a photoinitiator (C).
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