JP2016104859A - Active energy ray-curable resin composition and coating agent - Google Patents
Active energy ray-curable resin composition and coating agent Download PDFInfo
- Publication number
- JP2016104859A JP2016104859A JP2015227895A JP2015227895A JP2016104859A JP 2016104859 A JP2016104859 A JP 2016104859A JP 2015227895 A JP2015227895 A JP 2015227895A JP 2015227895 A JP2015227895 A JP 2015227895A JP 2016104859 A JP2016104859 A JP 2016104859A
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- JP
- Japan
- Prior art keywords
- meth
- acrylate
- curable resin
- 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.)
- Pending
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- 239000011248 coating agent Substances 0.000 title claims abstract description 75
- 239000011342 resin composition Substances 0.000 title claims abstract description 46
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 131
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000203 mixture Substances 0.000 claims abstract description 48
- 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 claims abstract description 33
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 23
- 239000012948 isocyanate Substances 0.000 claims abstract description 19
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 13
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012788 optical film Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 abstract description 52
- 238000010586 diagram Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 58
- -1 acryl Chemical group 0.000 description 45
- 239000000178 monomer Substances 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000005056 polyisocyanate Substances 0.000 description 11
- 229920001228 polyisocyanate Polymers 0.000 description 11
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- 229920005862 polyol Polymers 0.000 description 9
- 150000003077 polyols Chemical class 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 229920002799 BoPET Polymers 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 229910052797 bismuth Inorganic materials 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000007809 chemical reaction catalyst Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000013638 trimer Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 3
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 2
- LZHUBCULTHIFNO-UHFFFAOYSA-N 2,4-dihydroxy-1,5-bis[4-(2-hydroxyethoxy)phenyl]-2,4-dimethylpentan-3-one Chemical compound C=1C=C(OCCO)C=CC=1CC(C)(O)C(=O)C(O)(C)CC1=CC=C(OCCO)C=C1 LZHUBCULTHIFNO-UHFFFAOYSA-N 0.000 description 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
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000001588 bifunctional effect Effects 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
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- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 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 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
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- 230000001678 irradiating effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
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- 229920001223 polyethylene glycol Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
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- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 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 1
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
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- SSUJUUNLZQVZMO-UHFFFAOYSA-N 1,2,3,4,8,9,10,10a-octahydropyrimido[1,2-a]azepine Chemical compound C1CCC=CN2CCCNC21 SSUJUUNLZQVZMO-UHFFFAOYSA-N 0.000 description 1
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
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- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-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
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
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- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 description 1
- NQUXRXBRYDZZDL-UHFFFAOYSA-N 1-(2-prop-2-enoyloxyethyl)cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1(CCOC(=O)C=C)C(O)=O NQUXRXBRYDZZDL-UHFFFAOYSA-N 0.000 description 1
- YUTHQCGFZNYPIG-UHFFFAOYSA-N 1-[2-(2-methylprop-2-enoyloxy)ethyl]cyclohexane-1,2-dicarboxylic acid Chemical compound CC(=C)C(=O)OCCC1(C(O)=O)CCCCC1C(O)=O YUTHQCGFZNYPIG-UHFFFAOYSA-N 0.000 description 1
- VKQJCUYEEABXNK-UHFFFAOYSA-N 1-chloro-4-propoxythioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(OCCC)=CC=C2Cl VKQJCUYEEABXNK-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- AXFVIWBTKYFOCY-UHFFFAOYSA-N 1-n,1-n,3-n,3-n-tetramethylbutane-1,3-diamine Chemical compound CN(C)C(C)CCN(C)C AXFVIWBTKYFOCY-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
【課題】 硬化収縮が小さくカールしにくく、かつ、屈曲性にも優れた硬化塗膜を形成することができるウレタン（メタ）アクリレート系組成物を含有する活性エネルギー線硬化性樹脂組成物、及びそれを用いたコーティング剤を提供すること。【解決手段】 水酸基価が６０ｍｇＫＯＨ／ｇ以上であるジペンタエリスリトールの（メタ）アクリル酸付加物（Ａ）中の水酸基と、多価イソシアネート（Ｂ）のイソシアネート基とを反応させて得られるウレタン（メタ）アクリレート系組成物（Ｃ）を含有してなることを特徴とする活性エネルギー線硬化性樹脂組成物。【選択図】なしPROBLEM TO BE SOLVED: To provide an active energy ray-curable resin composition containing a urethane (meth) acrylate-based composition capable of forming a cured coating film having small curing shrinkage, being hard to curl, and having excellent flexibility, and an active energy ray-curable resin composition thereof. To provide a coating agent using. A urethane obtained by reacting a hydroxyl group in a (meth) acrylic acid adduct (A) of dipentaerythritol having a hydroxyl value of 60 mgKOH / g or more with an isocyanate group of a polyhydric isocyanate (B). A active energy ray-curable resin composition comprising the meta) acrylate-based composition (C). [Selection diagram] None
Description
本発明は、ウレタン（メタ）アクリレート系組成物を含有してなる活性エネルギー線硬化性樹脂組成物及びコーティング剤に関し、更に詳しくは、硬化塗膜を形成した際に、硬化収縮が小さくカールがしにくく、更に屈曲性にも優れた塗膜を形成することができる活性エネルギー線硬化性樹脂組成物、及びこれを用いてなるコーティング剤に関するものである。 The present invention relates to an active energy ray-curable resin composition containing a urethane (meth) acrylate composition and a coating agent. More specifically, when a cured coating film is formed, the curing shrinkage is small and curling occurs. The present invention relates to an active energy ray-curable resin composition that can form a coating film that is difficult and has excellent flexibility, and a coating agent using the same.
従来、活性エネルギー線硬化性樹脂組成物は、ごく短時間の放射線や紫外線等の活性エネルギー線の照射により硬化が完了するため、各種基材へのコーティング剤や接着剤、又はアンカーコート剤等として幅広く用いられており、その中の硬化成分としては、ウレタン（メタ）アクリレート系化合物や多官能モノマーが使用されている。ところが、活性エネルギー線硬化性樹脂組成物を、特にコーティング剤、とりわけハードコート用コーティング剤として用いる際に、塗膜の硬化収縮が起こり、硬化塗膜がカールし易いという問題点があり、カールしにくいものが求められている。 Conventionally, active energy ray-curable resin compositions are cured by irradiation with active energy rays such as radiation and ultraviolet rays for a very short time. Widely used, urethane (meth) acrylate compounds and polyfunctional monomers are used as the curing component. However, when the active energy ray-curable resin composition is used as a coating agent, particularly as a coating agent for a hard coat, there is a problem that the shrinkage of the coating film occurs and the cured coating film tends to curl. Difficult things are needed.
また、ハードコート用コーティング剤は保護フィルムとして成型品やディスプレイ等の屈曲部にも使用されるため、硬化塗膜を形成したプラスチックフィルムを曲げてもクラック等が生じ難いといった屈曲性が求められている。 In addition, since the coating agent for hard coat is also used as a protective film in bent parts of molded products, displays, etc., flexibility is required such that cracks are not easily generated even when a plastic film with a cured coating film is bent. Yes.
上記のカールしにくいことについては、硬化収縮を抑えるために、硬化性樹脂に無機微粒子を添加した硬化性樹脂組成物（例えば、特許文献１参照。）や、硬化成分として高分子量化されたウレタン（メタ）アクリレートを含有させた硬化性樹脂組成物（例えば、特許文献２参照。）が提案されている。また、耐擦傷性を向上させるためにハードコート層をより高硬度化する手法として、例えばペンタエリスリトールヘキサアクリレート及びトリペンタエリスリトールオクタアクリレートを含有してなる樹脂組成物を、厚さ８０μｍのトリアセチルセルロースフィルム上に膜厚１２μｍで塗布して硬化させて得られるフィルムが、鉛筆硬度５Ｈ程度の硬度を発現する技術が知られている（例えば、特許文献３参照。）。 Regarding the above-mentioned difficulty in curling, a curable resin composition in which inorganic fine particles are added to a curable resin (for example, refer to Patent Document 1) or a high molecular weight urethane as a curing component in order to suppress curing shrinkage. A curable resin composition containing (meth) acrylate has been proposed (for example, see Patent Document 2). In addition, as a technique for increasing the hardness of the hard coat layer in order to improve the scratch resistance, for example, a resin composition containing pentaerythritol hexaacrylate and tripentaerythritol octaacrylate is used as a triacetyl cellulose having a thickness of 80 μm. There is known a technique in which a film obtained by applying and curing on a film with a film thickness of 12 μm exhibits a hardness of about 5H pencil hardness (see, for example, Patent Document 3).
しかしながら、上記特許文献１の開示技術では、無機微粒子と硬化性樹脂との相溶性を考慮すると使用できる有機溶剤が限られたり、塗膜の表面異常が起こる可能性が高くなるという問題があったり、更に一般的に無機微粒子は高価なため、それを配合した樹脂や塗料も高価となり、現実的には硬化性樹脂の使用用途が特殊な用途に限られてしまうものであった。 However, the disclosed technique of Patent Document 1 has a problem that the organic solvent that can be used is limited in consideration of the compatibility between the inorganic fine particles and the curable resin, and the possibility that the surface abnormality of the coating film increases. Furthermore, since inorganic fine particles are generally expensive, resins and paints containing them are also expensive, and practically, the use of the curable resin is limited to special applications.
また、上記特許文献２の開示技術では、硬化成分として使用するウレタン（メタ）アクリレートを高分子量化させるための製造法が多段反応となるため、反応に時間がかかったり、塗膜の耐擦傷性が低下してしまうものであった。 Moreover, in the disclosed technique of Patent Document 2, since the production method for increasing the molecular weight of urethane (meth) acrylate used as a curing component is a multistage reaction, the reaction takes time, and the scratch resistance of the coating film Would be reduced.
一方、特許文献３の開示技術では、硬化塗膜の表面硬度は高いものの、硬化時に生じるカールが大きく、また硬く脆いものであるために、塗膜を屈曲させた際に割れが生じてしまうものであった。 On the other hand, in the disclosed technique of Patent Document 3, although the surface hardness of the cured coating film is high, the curl generated at the time of curing is large, and because the coating film is hard and brittle, cracking occurs when the coating film is bent. Met.
そこで、本発明では、このような背景下において、硬化塗膜を形成した際に、硬化収縮が小さくカールがしにくく、かつ屈曲性にも優れた塗膜を形成することができるウレタン（メタ）アクリレート系組成物を含有する活性エネルギー線硬化性樹脂組成物、及びそれを用いたコーティング剤を提供することを目的とするものである。 Therefore, in the present invention, under such a background, when a cured coating film is formed, urethane (meta) that can form a coating film having small curing shrinkage and being difficult to curl and having excellent flexibility. An object of the present invention is to provide an active energy ray-curable resin composition containing an acrylate composition and a coating agent using the same.
しかるに本発明者等は、かかる事情に鑑み鋭意研究を重ねた結果、硬化成分としてジペンタエリスリトールの（メタ）アクリル酸付加物と多価イソシアネートとを反応させて得られるウレタン（メタ）アクリレート系組成物を含有するものであり、更に、ジペンタエリスリトールの（メタ）アクリル酸付加物の水酸基価が通常よりも高い付加物を用いることにより、硬化収縮が小さくカールしにくく、かつ屈曲性にも優れた硬化塗膜が得られることを見出し、本発明を完成した。 However, the present inventors have made extensive studies in view of such circumstances, and as a result, urethane (meth) acrylate-based compositions obtained by reacting a (meth) acrylic acid adduct of dipentaerythritol with a polyvalent isocyanate as a curing component. In addition, by using an adduct with a higher hydroxyl value than usual for the (meth) acrylic acid adduct of dipentaerythritol, the shrinkage of curing is small, curling is difficult, and the flexibility is excellent. The present invention was completed by finding that a cured coating film could be obtained.
即ち、本発明の要旨は、水酸基価が６０ｍｇＫＯＨ／ｇ以上であるジペンタエリスリトールの（メタ）アクリル酸付加物（Ａ）中の水酸基と、多価イソシアネート（Ｂ）のイソシアネート基とを反応させてなるウレタン（メタ）アクリレート系組成物（Ｃ）を含有してなる活性エネルギー線硬化性樹脂組成物に関するものである。
また、本発明においては、前記活性エネルギー線硬化性樹脂組成物を含有してなるコーティング剤も提供するものである。
That is, the gist of the present invention is to react the hydroxyl group in the (meth) acrylic acid adduct (A) of dipentaerythritol having a hydroxyl value of 60 mgKOH / g or more with the isocyanate group of the polyvalent isocyanate (B). It is related with the active energy ray-curable resin composition containing the urethane (meth) acrylate type composition (C) which becomes.
Moreover, in this invention, the coating agent formed by containing the said active energy ray curable resin composition is also provided.
本発明の活性エネルギー線硬化性樹脂組成物は、硬化収縮が小さくカールしにくく、更に屈曲性にも優れた硬化塗膜を形成することができ、更には、硬化塗膜とした際の耐擦傷性にも優れるものである。 The active energy ray-curable resin composition of the present invention is capable of forming a cured coating film that has small curing shrinkage and is less likely to curl, and has excellent flexibility, and is further resistant to scratches when used as a cured coating film. It is also excellent in properties.
以下に本発明を詳細に説明する。
なお、本発明において、（メタ）アクリルとはアクリルあるいはメタクリルを、（メタ）アクリロイルとはアクリロイルあるいはメタクリロイルを、（メタ）アクリレートとはアクリレートあるいはメタクリレートをそれぞれ意味するものである。
The present invention is described in detail below.
In the present invention, (meth) acryl means acryl or methacryl, (meth) acryloyl means acryloyl or methacryloyl, and (meth) acrylate means acrylate or methacrylate.
本発明の活性エネルギー線硬化性樹脂組成物は、水酸基価が６０ｍｇＫＯＨ／ｇ以上であるジペンタエリスリトールの（メタ）アクリル酸付加物（Ａ）中の水酸基と、多価イソシアネート（Ｂ）のイソシアネート基とを反応させて得られるウレタン（メタ）アクリレート系組成物（Ｃ）を含むものである。 The active energy ray-curable resin composition of the present invention comprises a hydroxyl group in a (meth) acrylic acid adduct (A) of dipentaerythritol having a hydroxyl value of 60 mgKOH / g or more, and an isocyanate group of a polyvalent isocyanate (B). And a urethane (meth) acrylate composition (C) obtained by reacting with.
かかるウレタン（メタ）アクリレート系組成物（Ｃ）は、水酸基価が６０ｍｇＫＯＨ／ｇ以上であるジペンタエリスリトールの（メタ）アクリル酸付加物（Ａ）中の水酸基と、多価イソシアネート（Ｂ）のイソシアネート基を反応させることにより、ウレタン結合が形成され、得られるものである。 Such urethane (meth) acrylate-based composition (C) includes a hydroxyl group in a (meth) acrylic acid adduct (A) of dipentaerythritol having a hydroxyl value of 60 mgKOH / g or more, and an isocyanate of polyvalent isocyanate (B). By reacting the group, a urethane bond is formed and obtained.
上記ジペンタエリスリトールの（メタ）アクリル酸付加物（Ａ）の水酸基価としては、６０ｍｇＫＯＨ／ｇ以上であることが必要であり、好ましくは６３〜１２０ｍｇＫＯＨ／ｇ、特に好ましくは６５〜１００ｍｇＫＯＨ／ｇである。
かかる水酸基価が小さすぎると、低分子量でエチレン性不飽和基数が多く、イソシアネートと反応しないジペンタエリスリトールヘキサ（メタ）アクリレートの含有量が多くなるため、硬化時の硬化収縮が大きくなり、カールしやすくなり、更には屈曲性が低下し好ましくない。なお、通常、上記水酸基価が大きくなりすぎると分子量の増加に伴い、粘度が向上するため、取り扱いにくくなる傾向がある。
The hydroxyl value of the (meth) acrylic acid adduct (A) of dipentaerythritol needs to be 60 mgKOH / g or more, preferably 63 to 120 mgKOH / g, particularly preferably 65 to 100 mgKOH / g. is there.
If the hydroxyl value is too small, the content of dipentaerythritol hexa (meth) acrylate, which has a low molecular weight and a large number of ethylenically unsaturated groups and does not react with isocyanate, increases, resulting in increased curing shrinkage during curing and curling. This is not preferable because it becomes easier and the flexibility is lowered. In general, when the hydroxyl value is too large, the viscosity increases with increasing molecular weight, which tends to be difficult to handle.
かかるジペンタエリスリトールの（メタ）アクリル酸付加物（Ａ）は、ジペンタエリスリトールと（メタ）アクリル酸を公知一般の方法で反応させたものであればよい。
ジペンタエリスリトールの（メタ）アクリル酸付加物（Ａ）としては、その成分中に、ジペンタエリスリトールに対して（メタ）アクリル酸が一つ付加したもの、二つ付加したもの、三つ付加したもの、四つ付加したもの、五つ付加したもの、六つ付加したものが含まれ、全体として上記の水酸基価を満足するものである。
水酸基価の調整に際しては、例えば、（メタ）アクリル酸が一つから六つ付加したものまでの付加物の混合比率を調整することにより行われる。
The (meth) acrylic acid adduct (A) of dipentaerythritol may be any one obtained by reacting dipentaerythritol and (meth) acrylic acid by a known general method.
As the (meth) acrylic acid adduct (A) of dipentaerythritol, one of (meth) acrylic acid added to dipentaerythritol, one added two, three added And those with four additions, those with five additions, and those with six additions, and satisfy the above hydroxyl values as a whole.
In adjusting the hydroxyl value, for example, the mixing ratio of adducts from one to six (meth) acrylic acids is adjusted.
上記多価イソシアネート（Ｂ）としては、例えば、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、ポリフェニルメタンポリイソシアネート、変性ジフェニルメタンジイソシアネート、キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート、フェニレンジイソシアネート、ナフタレンジイソシアネート等の芳香族系ポリイソシアネート；ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、リジンジイソシアネート、リジントリイソシアネート等の脂肪族系ポリイソシアネート；水添化ジフェニルメタンジイソシアネート、水添化キシリレンジイソシアネート、イソホロンジイソシアネート、ノルボルネンジイソシアネート、１，４−ビス（イソシアナトメチル）シクロヘキサン等の脂環式系ポリイソシアネート；或いはこれらポリイソシアネートの３量体化合物又は多量体化合物、アロファネート型ポリイソシアネート、ビュレット型ポリイソシアネート、水分散型ポリイソシアネート（例えば、東ソー（株）製の「アクアネート１００」、「アクアネート１０５」、「アクアネート１２０」、「アクアネート２１０」等）、等が挙げられる。これらは１種または２種以上組み合わせて使用することができる。 Examples of the polyvalent isocyanate (B) include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate. Isocyanates; aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate; hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,4-bis ( Isocyanatomethyl) cyclohex Alicyclic polyisocyanates such as styrene; or trimer compounds or multimeric compounds of these polyisocyanates, allophanate type polyisocyanates, burette type polyisocyanates, water-dispersed polyisocyanates (for example, "Aqua" manufactured by Tosoh Corporation) Nate 100 "," Aquanate 105 "," Aquanate 120 "," Aquanate 210 ", etc.). These can be used alone or in combination of two or more.
また、上記ポリイソシアネートと、各種ポリオール、例えば、低分子量のポリオールや高分子量のポリオール、中でもポリエーテル系ポリオール、ポリエステル系ポリオール、ポリカーボネート系ポリオール、ポリオレフィン系ポリオール、ポリブタジエン系ポリオール、（メタ）アクリル系ポリオール等のポリオールとの反応物であってもよい。 In addition, the above polyisocyanate and various polyols such as low molecular weight polyols and high molecular weight polyols, among them, polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, polybutadiene polyols, (meth) acrylic polyols A reaction product with a polyol such as
これらの中でも、脂肪族ポリイソシアネート、脂環式ポリイソシアネートであることが、耐候性と強度の点で好ましく、特に好ましくはヘキサメチレンジイソシアネートの３量体、水添化ジフェニルメタンジイソシアネート、イソホロンジイソシアネートである。 Among these, aliphatic polyisocyanates and alicyclic polyisocyanates are preferable in terms of weather resistance and strength, and hexamethylene diisocyanate trimer, hydrogenated diphenylmethane diisocyanate, and isophorone diisocyanate are particularly preferable.
本発明で用いられるウレタン（メタ）アクリレート系組成物（Ｃ）は、上記のイソシアネート系化合物（Ｂ）のイソシアネート基とジペンタエリスリトールの（メタ）アクリル酸付加物（Ａ）の水酸基との官能基モル比を調整し、必要に応じてジブチル錫ジラウレートなどの触媒を用いて、イソシアネート系化合物（Ｂ）とジペンタエリスリトールの（メタ）アクリル酸付加物（Ａ）とを反応させて得ることができる。 The urethane (meth) acrylate composition (C) used in the present invention is a functional group of the isocyanate group of the isocyanate compound (B) and the hydroxyl group of the (meth) acrylic acid adduct (A) of dipentaerythritol. It can be obtained by adjusting the molar ratio and reacting the isocyanate compound (B) with the (meth) acrylic acid adduct of dipentaerythritol (A) using a catalyst such as dibutyltin dilaurate as necessary. .
かかるイソシアネート系化合物（Ｂ）とジペンタエリスリトールの（メタ）アクリル酸付加物（Ａ）との仕込みの反応モル比は、イソシアネート系化合物（Ｂ）のイソシアネート基が２個である場合は、イソシアネート系化合物（Ｂ）：ジペンタエリスリトールの（メタ）アクリル酸付加物（Ａ）が１：２〜１：５程度である。 The reaction molar ratio of the preparation of the isocyanate compound (B) and the (meth) acrylic acid adduct (A) of dipentaerythritol is an isocyanate compound when the isocyanate compound (B) has two isocyanate groups. Compound (B): The (meth) acrylic acid adduct (A) of dipentaerythritol is about 1: 2 to 1: 5.
かかるジペンタエリスリトールの（メタ）アクリル酸付加物（Ａ）の割合が多すぎると、低分子量モノマーが多くなり、硬化収縮が大きくなるためカールが大きくなる傾向があり、ジペンタエリスリトールの（メタ）アクリル酸付加物（Ａ）の割合が少なすぎると、未反応のイソシアネートが残存し、硬化塗膜の安定性や安全性が低下する傾向がある。 When the proportion of the (meth) acrylic acid adduct (A) of dipentaerythritol is too large, the amount of low molecular weight monomers increases, and the curling tends to increase due to increased shrinkage of curing. When the ratio of the acrylic acid adduct (A) is too small, unreacted isocyanate remains, and the stability and safety of the cured coating film tend to be lowered.
ジペンタエリスリトールの（メタ）アクリル酸付加物（Ａ）と多価イソシアネート系化合物（Ｂ）の反応は、通常、上記ジペンタエリスリトールの（メタ）アクリル酸付加物（Ａ）、多価イソシアネート（Ｂ）を、反応器に一括又は別々に仕込み反応させればよい。 The reaction between the (meth) acrylic acid adduct (A) of dipentaerythritol and the polyvalent isocyanate compound (B) is usually performed by the above (meth) acrylic acid adduct (A) of dipentaerythritol, polyvalent isocyanate (B ) May be charged into the reactor or reacted separately.
上記反応においては、反応を促進する目的で触媒を用いることも好ましく、かかる触媒としては、例えばジブチル錫ジラウレート、ジブチル錫ジアセテート、トリメチル錫ヒドロキシド、テトラ−ｎ−ブチル錫、ビスアセチルアセトナート亜鉛、ジルコニウムトリス（アセチルアセトネート）エチルアセトアセテート、ジルコニウムテトラアセチルアセトネート等の有機金属化合物、オクチル酸錫、オクテン酸錫、ヘキサン酸亜鉛、オクテン酸亜鉛、ステアリン酸亜鉛、２−エチルヘキサン酸ジルコニウム、ナフテン酸コバルト、塩化第１錫、塩化第２錫、酢酸カリウム等の金属塩、トリエチルアミン、トリエチレンジアミン、ベンジルジエチルアミン、１，４−ジアザビシクロ［２，２，２］オクタン、１，８−ジアザビシクロ［５，４，０］ウンデセン、Ｎ，Ｎ，Ｎ′，Ｎ′−テトラメチル−１，３−ブタンジアミン、Ｎ−メチルモルホリン、Ｎ−エチルモルホリン等のアミン系触媒、硝酸ビスマス、臭化ビスマス、ヨウ化ビスマス、硫化ビスマス等の他、ジブチルビスマスジラウレート、ジオクチルビスマスジラウレート等の有機ビスマス化合物や、２−エチルヘキサン酸ビスマス塩、ナフテン酸ビスマス塩、イソデカン酸ビスマス塩、ネオデカン酸ビスマス塩、ラウリル酸ビスマス塩、マレイン酸ビスマス塩、ステアリン酸ビスマス塩、オレイン酸ビスマス塩、リノール酸ビスマス塩、酢酸ビスマス塩、ビスマスリビスネオデカノエート、ジサリチル酸ビスマス塩、ジ没食子酸ビスマス塩等の有機酸ビスマス塩等のビスマス系触媒等が挙げられ、中でも、ジブチル錫ジラウレート、１，８−ジアザビシクロ［５，４，０］ウンデセンが好適である。これらを１種単独で用いるか、あるいは２種以上併せて用いることができる。 In the above reaction, it is also preferable to use a catalyst for the purpose of accelerating the reaction, such as dibutyltin dilaurate, dibutyltin diacetate, trimethyltin hydroxide, tetra-n-butyltin, zinc bisacetylacetonate. , Organometallic compounds such as zirconium tris (acetylacetonate) ethyl acetoacetate, zirconium tetraacetylacetonate, tin octylate, tin octenoate, zinc hexanoate, zinc octenoate, zinc stearate, zirconium 2-ethylhexanoate, Metal salts such as cobalt naphthenate, stannous chloride, stannic chloride, potassium acetate, triethylamine, triethylenediamine, benzyldiethylamine, 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5 , 4, ] Amine catalyst such as undecene, N, N, N ', N'-tetramethyl-1,3-butanediamine, N-methylmorpholine, N-ethylmorpholine, bismuth nitrate, bismuth bromide, bismuth iodide, sulfide In addition to bismuth, etc., organic bismuth compounds such as dibutyl bismuth dilaurate and dioctyl bismuth dilaurate, bismuth 2-ethylhexanoate, bismuth naphthenate, bismuth isodecanoate, bismuth neodecanoate, bismuth laurate, bismuth maleate Bismuth catalysts such as organic acid bismuth salts such as salts, bismuth stearate, bismuth oleate, bismuth linoleate, bismuth acetate, bismuth bisneodecanoate, bismuth disalicylate, bismuth digallate, etc. Among them, among them, dibutyltin dilaur Over DOO, 1,8-diazabicyclo [5,4,0] undecene is preferred. These may be used alone or in combination of two or more.
また、イソシアネート基に対して反応する官能基を有しない有機溶剤、例えば、酢酸エチル、酢酸ブチル等のエステル類、メチルエチルケトン、メチルイソブチルケトン等のケトン類、トルエン、キシレン等の芳香族類等の有機溶剤を用いることができる。 Organic solvents that do not have a functional group that reacts with isocyanate groups, for example, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and organics such as aromatics such as toluene and xylene A solvent can be used.
反応温度は、通常３０〜９０℃、好ましくは４０〜８０℃であり、反応時間は、通常２〜１０時間、好ましくは３〜８時間である。 The reaction temperature is usually 30 to 90 ° C., preferably 40 to 80 ° C., and the reaction time is usually 2 to 10 hours, preferably 3 to 8 hours.
かくしてウレタン（メタ）アクリレート系組成物（Ｃ）が得られるが、かかるウレタン（メタ）アクリレート系組成物（Ｃ）の重量平均分子量としては３，０００〜３０，０００であることが好ましく、更に好ましくは３，２００〜２０，０００、特に好ましくは３，５００〜１０，０００である。
かかる重量平均分子量が小さすぎると硬化塗膜が脆くなる傾向があり、大きすぎると高粘度となり取り扱いにくくなる傾向がある。
Thus, a urethane (meth) acrylate-based composition (C) is obtained. The weight-average molecular weight of the urethane (meth) acrylate-based composition (C) is preferably 3,000 to 30,000, more preferably. Is 3,200 to 20,000, particularly preferably 3,500 to 10,000.
If the weight average molecular weight is too small, the cured coating film tends to be brittle, and if it is too large, the viscosity tends to be high and difficult to handle.
尚、上記の重量平均分子量とは、標準ポリスチレン分子量換算による重量平均分子量であり、高速液体クロマトグラフィー（昭和電工社製、「Ｓｈｏｄｅｘ ＧＰＣ ｓｙｓｔｅｍ−１１型」）に、カラム：Ｓｈｏｄｅｘ ＧＰＣ ＫＦ−８０６Ｌ（排除限界分子量：２×１０7、分離範囲：１００〜２×１０7、理論段数：１０，０００段／本、充填剤材質：スチレン−ジビニルベンゼン共重合体、充填剤粒径：１０μｍ）の３本直列を用いることにより測定される。 In addition, said weight average molecular weight is a weight average molecular weight by standard polystyrene molecular weight conversion, a column: Shodex GPC KF-806L (high-performance liquid chromatography (the Showa Denko company make, "Shodex GPC system-11 type | mold")). Exclusion limit molecular weight: 2 × 10 7 , separation range: 100 to 2 × 10 7 , theoretical plate number: 10,000 plate / piece, filler material: styrene-divinylbenzene copolymer, filler particle size: 10 μm) Measured by using this series.
また、ウレタン（メタ）アクリレート系組成物（Ｃ）の６０℃における粘度は、１，０００〜３００，０００ｍＰａ・ｓであることが好ましく、特には３，０００〜２０００，０００ｍＰａ・ｓ、更には５，０００〜１５０，０００ｍＰａ・ｓであることが好ましい。かかる粘度が上記範囲外では塗工性が低下する傾向がある。
尚、粘度の測定法はＥ型粘度計による。
The viscosity of the urethane (meth) acrylate composition (C) at 60 ° C. is preferably 1,000 to 300,000 mPa · s, particularly 3,000 to 2,000,000 mPa · s, and more preferably 5 , And preferably 150,000 to 150,000 mPa · s. When the viscosity is out of the above range, the coatability tends to be lowered.
The viscosity is measured with an E-type viscometer.
かくして、本発明のウレタン（メタ）アクリレート系組成物（Ｃ）が得られる。
本発明のウレタン（メタ）アクリレート系組成物（Ｃ）は、複数種のウレタン（メタ）アクリレートを含有し、更に、ジペンタエリスリトールの（メタ）アクリル酸付加物（Ａ）であるジペンタエリスリトールジ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート、ジ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、上記以外のポリペンタエリスリトールポリ（メタ）アクリレート等を含有することがある。
Thus, the urethane (meth) acrylate composition (C) of the present invention is obtained.
The urethane (meth) acrylate-based composition (C) of the present invention contains a plurality of types of urethane (meth) acrylates, and further dipentaerythritol di (E) is a (meth) acrylic acid adduct (A) of dipentaerythritol. (Meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, other polypentaerythritol poly (meth) ) May contain acrylate or the like.
本発明のウレタン（メタ）アクリレート系組成物（Ｃ）におけるウレタン（メタ）アクリレートの含有量は、好ましくは５０重量％以上、特に好ましくは６０重量％以上、更に好ましくは７０重量％以上、殊に好ましくは８０重量％以上である。 The urethane (meth) acrylate content in the urethane (meth) acrylate-based composition (C) of the present invention is preferably 50% by weight or more, particularly preferably 60% by weight or more, and further preferably 70% by weight or more. Preferably it is 80 weight% or more.
本発明の活性エネルギー線硬化性樹脂組成物は、上記ウレタン（メタ）アクリレート系組成物（Ｃ）を含有してなるものであり、かかる活性エネルギー線硬化性樹脂組成物には、更に光重合開始剤（Ｄ）を含有することが好ましく、また、本発明の硬化を損なわない範囲で、ウレタン（メタ）アクリレート以外のエチレン性不飽和モノマー、アクリル樹脂、表面調整剤、レベリング剤、重合禁止剤等を添加することができ、更にはフィラー、染顔料、油、可塑剤、ワックス類、乾燥剤、分散剤、湿潤剤、ゲル化剤、安定剤、消泡剤、界面活性剤、レベリング剤、チクソトロピー性付与剤、酸化防止剤、難燃剤、帯電防止剤、充填剤、補強剤、艶消し剤、架橋剤、シリカ、水分散または溶剤分散されたシリカ、ジルコニウム化合物、防腐剤等を配合することも可能である。 The active energy ray-curable resin composition of the present invention contains the urethane (meth) acrylate composition (C), and the active energy ray-curable resin composition further includes photopolymerization. It is preferable to contain an agent (D), and, as long as the curing of the present invention is not impaired, an ethylenically unsaturated monomer other than urethane (meth) acrylate, an acrylic resin, a surface conditioner, a leveling agent, a polymerization inhibitor, etc. Furthermore, fillers, dyes and pigments, oils, plasticizers, waxes, desiccants, dispersants, wetting agents, gelling agents, stabilizers, antifoaming agents, surfactants, leveling agents, thixotropy Properties imparting agent, antioxidant, flame retardant, antistatic agent, filler, reinforcing agent, matting agent, cross-linking agent, silica, water-dispersed or solvent-dispersed silica, zirconium compound, preservative, etc. It is also possible to focus.
上記光重合開始剤（Ｄ）としては、例えば、ジエトキシアセトフェノン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、ベンジルジメチルケタール、４−（２−ヒドロキシエトキシ）フェニル−（２−ヒドロキシ−２−プロピル）ケトン、１−ヒドロキシシクロヘキシルフェニルケトン、１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オン、２−ヒドロキシ−１−｛４−［４−（２−ヒドロキシ−２−メチル−プロピオニル）−ベンジル］−フェニル｝−２−メチル−プロパン、２−メチル−２−モルホリノ（４−チオメチルフェニル）プロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）ブタノン、２−ヒドロキシ−２−メチル−１−［４−（１−メチルビニル）フェニル］プロパノンオリゴマー等のアセトフェノン類；ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル等のベンゾイン類；ベンゾフェノン、ｏ−ベンゾイル安息香酸メチル、４−フェニルベンゾフェノン、４−ベンゾイル−４′−メチル−ジフェニルサルファイド、３，３′，４，４′−テトラ（ｔ−ブチルパーオキシカルボニル）ベンゾフェノン、２，４，６−トリメチルベンゾフェノン、４−ベンゾイル−Ｎ，Ｎ−ジメチル−Ｎ−［２−（１−オキソ−２−プロペニルオキシ）エチル］ベンゼンメタナミニウムブロミド、（４−ベンゾイルベンジル）トリメチルアンモニウムクロリド等のベンゾフェノン類；２−イソプロピルチオキサントン、４−イソプロピルチオキサントン、２，４−ジエチルチオキサントン、２，４−ジクロロチオキサントン、１−クロロ−４−プロポキシチオキサントン、２−（３−ジメチルアミノ−２−ヒドロキシ）−３，４−ジメチル−９Ｈ−チオキサントン−９−オンメソクロリド等のチオキサントン類；２，４，６−トリメチルベンゾイル−ジフェニルフォスフィンオキサイド、ビス（２，６−ジメトキシベンゾイル）−２，４，４−トリメチル−ペンチルフォスフィンオキサイド、ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイド等のアシルフォスフォンオキサイド類；等があげられる。なお、これら光重合開始剤（Ｄ）、１種のみが単独で用いられてもよいし、２種以上が併用されてもよい。 Examples of the photopolymerization initiator (D) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2 -Hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy -1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propane, 2-methyl-2-morpholino (4-thiomethylphenyl) propane-1 -One, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2-hydroxy-2 Acetophenones such as methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer; benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, o-benzoyl Methyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone Benzophene such as 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-benzoylbenzyl) trimethylammonium chloride 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3 Thioxanthones such as 2,4-dimethyl-9H-thioxanthone-9-one mesochloride; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl -Acyl phosphine oxides such as pentylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; In addition, only 1 type of these photoinitiators (D) may be used independently, and 2 or more types may be used together.
また、これらの助剤として、トリエタノールアミン、トリイソプロパノールアミン、４，４′−ジメチルアミノベンゾフェノン（ミヒラーケトン）、４，４′−ジエチルアミノベンゾフェノン、２−ジメチルアミノエチル安息香酸、４−ジメチルアミノ安息香酸エチル、４−ジメチルアミノ安息香酸（ｎ−ブトキシ）エチル、４−ジメチルアミノ安息香酸イソアミル、４−ジメチルアミノ安息香酸２−エチルヘキシル、２，４−ジエチルチオキサンソン、２，４−ジイソプロピルチオキサンソン等を併用することも可能である。 These auxiliary agents include triethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone (Michler ketone), 4,4′-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethylaminobenzoic acid. Ethyl, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone Etc. can be used in combination.
これらの中でも、ベンジルジメチルケタール、１−ヒドロキシシクロヘキシルフェニルケトン、ベンゾイルイソプロピルエーテル、４−（２−ヒドロキシエトキシ）−フェニル（２−ヒドロキシ−２−プロピル）ケトン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オンを用いることが好ましい。 Among these, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoyl isopropyl ether, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 2-hydroxy-2-methyl-1- It is preferable to use phenylpropan-1-one.
光重合開始剤（Ｄ）の含有量としては、組成物中に含まれる硬化成分１００重量部に対して、０．１〜２０重量部であることが好ましく、特に好ましくは０．５〜１０重量部、さらに好ましくは１〜１０重量部である。
光重合開始剤（Ｄ）の含有量が少なすぎると、硬化不良となり膜形成がなされにくい傾向があり、多すぎると硬化塗膜の黄変の原因となり、着色の問題が起こりやすい傾向がある。
As content of a photoinitiator (D), it is preferable that it is 0.1-20 weight part with respect to 100 weight part of hardening components contained in a composition, Most preferably, it is 0.5-10 weight. Parts, more preferably 1 to 10 parts by weight.
If the content of the photopolymerization initiator (D) is too small, curing tends to be poor and film formation tends to be difficult, and if too large, yellowing of the cured coating film tends to occur, and coloring problems tend to occur.
ウレタン（メタ）アクリレート以外のエチレン性不飽和モノマーとしては、例えば、単官能モノマー、２官能モノマー、３官能以上の多官能モノマーが挙げられる。
かかる単官能モノマーとしては、例えば、スチレン、ビニルトルエン、クロロスチレン、α−メチルスチレン等のスチレン系モノマー、メチル（メタ）アクリレート、エチル（メタ）アクリレート、アクリロニトリル、２−メトキシエチル（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、２−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、２−フェノキシ−２−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシ−３−フェノキシプロピル（メタ）アクリレート、３−クロロ−２−ヒドロキシプロピル（メタ）アクリレート、グリセリンモノ（メタ）アクリレート、グリシジル（メタ）アクリレート、ラウリル（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、ジシクロペンテニル（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）アクリルレート、ジシクロペンタニル（メタ）アクリレート、（２−メチル−２−エチル−１，３−ジオキソラン−４−イル）−メチル（メタ）アクリレート、シクロヘキサンスピロ−２−（１，３−ジオキソラン−４−イル）−メチル（メタ）アクリレート、３−エチル−３−オキセタニルメチル（メタ）アクリレート、γ−ブチロラクトン（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、オクチル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ドデシル（メタ）アクリレート、ｎ−ステアリル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノールエチレンオキサイド変性（ｎ＝２）（メタ）アクリレート、ノニルフェノールプロピレンオキサイド変性（ｎ＝２．５）（メタ）アクリレート、２−（メタ）アクリロイルオキシエチルアシッドホスフェート、２−（メタ）アクリロイルオキシ−２−ヒドロキシプロピルフタレート等のフタル酸誘導体のハーフ（メタ）アクリレート、フルフリル（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、カルビトール（メタ）アクリレート、ベンジル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、アリル（メタ）アクリレート、（メタ）アクリロイルモルフォリン、ポリオキシエチレン第２級アルキルエーテルアクリレート等の（メタ）アクリレート系モノマー、２−ヒドロキシエチルアクリルアミド、Ｎ−メチロール（メタ）アクリルアミド、Ｎ−ビニルピロリドン、２−ビニルピリジン、酢酸ビニル等が挙げられる。
かかる２官能モノマーとしては、例えば、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ブチレングリコールジ（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、エチレンオキサイド変性ビスフェノールＡ型ジ（メタ）アクリレート、プロピレンオキサイド変性ビスフェノールＡ型ジ（メタ）アクリレート、シクロヘキサンジメタノールジ（メタ）アクリレート、エトキシ化シクロヘキサンジメタノールジ（メタ）アクリレート、ジメチロールジシクロペンタンジ（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、１，６−ヘキサンジオールジ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、エチレングリコールジグリシジルエーテルジ（メタ）アクリレート、ジエチレングリコールジグリシジルエーテルジ（メタ）アクリレート、フタル酸ジグリシジルエステルジ（メタ）アクリレート、ヒドロキシピバリン酸変性ネオペンチルグリコールジ（メタ）アクリレート、イソシアヌル酸エチレンオキサイド変性ジアクリレート等が挙げられる。
かかる３官能以上のモノマーとしては、例えば、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、トリ（メタ）アクリロイルオキシエトキシトリメチロールプロパン、グリセリンポリグリシジルエーテルポリ（メタ）アクリレート、イソシアヌル酸エチレンオキサイド変性トリアクリレート、カプロラクトン変性ジペンタエリスリトールペンタ（メタ）アクリレート、カプロラクトン変性ジペンタエリスリトールヘキサ（メタ）アクリレート、カプロラクトン変性ペンタエリスリトールトリ（メタ）アクリレート、カプロラクトン変性ペンタエリスリトールテトラ（メタ）アクリレート、エチレンオキサイド変性ジペンタエリスリトールペンタ（メタ）アクリレート、エチレンオキサイド変性ジペンタエリスリトールヘキサ（メタ）アクリレート、エチレンオキサイド変性ペンタエリスリトールトリ（メタ）アクリレート、エチレンオキサイド変性ペンタエリスリトールテトラ（メタ）アクリレート、エトキシ化15グリセリントリアクリレート等が挙げられる。
また、アクリル酸のミカエル付加物あるいは２−アクリロイルオキシエチルジカルボン酸モノエステルも併用可能であり、かかるアクリル酸のミカエル付加物としては、アクリル酸ダイマー、メタクリル酸ダイマー、アクリル酸トリマー、メタクリル酸トリマー、アクリル酸テトラマー、メタクリル酸テトラマー等が挙げられる。上記２−アクリロイルオキシエチルジカルボン酸モノエステルとしては、特定の置換基をもつカルボン酸であり、例えば２−アクリロイルオキシエチルコハク酸モノエステル、２−メタクリロイルオキシエチルコハク酸モノエステル、２−アクリロイルオキシエチルフタル酸モノエステル、２−メタクリロイルオキシエチルフタル酸モノエステル、２−アクリロイルオキシエチルヘキサヒドロフタル酸モノエステル、２−メタクリロイルオキシエチルヘキサヒドロフタル酸モノエステル等が挙げられる。更に、その他オリゴエステルアクリレート等を挙げることができる。
ウレタン（メタ）アクリレート以外のエチレン性不飽和モノマーの含有量としては、組成物中に含まれる全硬化成分中、５０重量％以下であることが好ましく、特に好ましくは４０重量％以下、更に好ましくは３０重量％以下である。
Examples of the ethylenically unsaturated monomer other than urethane (meth) acrylate include a monofunctional monomer, a bifunctional monomer, and a trifunctional or higher polyfunctional monomer.
Examples of such monofunctional monomers include styrene monomers such as styrene, vinyl toluene, chlorostyrene, α-methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, acrylonitrile, 2-methoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2-hydroxy -3-phenoxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) acrylate Rate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate (2-methyl-2-ethyl-1,3-dioxolan-4-yl) -methyl (meth) acrylate, cyclohexanespiro-2- (1,3-dioxolan-4-yl) -methyl (meth) acrylate, 3-ethyl-3-oxetanylmethyl (meth) acrylate, γ-butyrolactone (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) Acu Rate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, n-stearyl (meth) acrylate, benzyl (meth) acrylate, phenol ethylene oxide modified (n = 2) (meth) acrylate, nonylphenol propylene Half (meth) acrylates of phthalic acid derivatives such as oxide-modified (n = 2.5) (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, Furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, carbitol (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate, allyl (meth) (Meth) acrylate monomers such as acrylate, (meth) acryloylmorpholine, polyoxyethylene secondary alkyl ether acrylate, 2-hydroxyethylacrylamide, N-methylol (meth) acrylamide, N-vinylpyrrolidone, 2-vinylpyridine And vinyl acetate.
Examples of such bifunctional monomers include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and di Propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified bisphenol A type di (meth) acrylate, propylene oxide modified bisphenol A Type di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, ethoxylated cyclohexanedimethanol di (me ) Acrylate, dimethylol dicyclopentane di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) Acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, hydroxypivalic acid modified neopentyl glycol di (meth) acrylate, ethylene isocyanurate Examples thereof include oxide-modified diacrylate.
Examples of the tri- or higher functional monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly (meth) acrylate, isocyanuric acid ethylene oxide modified triacrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexa (Meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, capro Kuton modified pentaerythritol tetra (meth) acrylate, ethylene oxide modified dipentaerythritol penta (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol Examples include tetra (meth) acrylate and ethoxylated 15 glycerin triacrylate.
Further, a Michael adduct of acrylic acid or 2-acryloyloxyethyldicarboxylic acid monoester can be used in combination, and as such a Michael adduct of acrylic acid, acrylic acid dimer, methacrylic acid dimer, acrylic acid trimer, methacrylic acid trimer, An acrylic acid tetramer, a methacrylic acid tetramer, etc. are mentioned. The 2-acryloyloxyethyl dicarboxylic acid monoester is a carboxylic acid having a specific substituent, such as 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, 2-acryloyloxyethyl. Examples include phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahydrophthalic acid monoester, and 2-methacryloyloxyethyl hexahydrophthalic acid monoester. Furthermore, other oligoester acrylates can be mentioned.
The content of the ethylenically unsaturated monomer other than the urethane (meth) acrylate is preferably 50% by weight or less, particularly preferably 40% by weight or less, and still more preferably, in all the curing components contained in the composition. 30% by weight or less.
表面調整剤としては特に限定されず、例えば、セルロース樹脂やアルキッド樹脂等を挙げることができる。かかる、セルロース樹脂は、塗膜の表面平滑性を向上させる作用が有り、アルキッド樹脂は、塗布時の造膜性を付与する作用を有する。 It does not specifically limit as a surface conditioning agent, For example, a cellulose resin, an alkyd resin, etc. can be mentioned. Such a cellulose resin has an action of improving the surface smoothness of the coating film, and an alkyd resin has an action of imparting a film-forming property at the time of coating.
レベリング剤としては、塗液の基材への濡れ性付与作用、表面張力の低下作用を有するものであれば、公知一般のレベリング剤を用いることができ、例えば、シリコーン変性樹脂、フッ素変性樹脂、アルキル変性の樹脂等を用いることができる。 As the leveling agent, a known general leveling agent can be used as long as it has a wettability imparting action to the base material of the coating liquid and a surface tension reducing action. For example, a silicone-modified resin, a fluorine-modified resin, An alkyl-modified resin or the like can be used.
重合禁止剤としては、例えば、ｐ−ベンゾキノン、ナフトキノン、トルキノン、２，５−ジフェニル−ｐ−ベンゾキノン、ハイドロキノン、２，５−ジ−ｔ−ブチルハイドロキノン、メチルハイドロキノン、ハイドロキノンモノメチルエーテル、モノ−ｔ−ブチルハイドロキノン、ｐ−ｔ−ブチルカテコール等を挙げることができる。 Examples of the polymerization inhibitor include p-benzoquinone, naphthoquinone, tolquinone, 2,5-diphenyl-p-benzoquinone, hydroquinone, 2,5-di-t-butylhydroquinone, methylhydroquinone, hydroquinone monomethyl ether, mono-t- Examples thereof include butyl hydroquinone and pt-butyl catechol.
また、本発明の活性エネルギー線硬化性樹脂組成物は、必要に応じて、塗工時の粘度を適正なものにするために、希釈のための有機溶剤を使用することも好ましい。かかる有機溶剤としては、例えば、メタノール、エタノール、プロパノール、ｎ−ブタノール、ｉ−ブタノール等のアルコール類、アセトン、メチルイソブチルケトン、メチルエチルケトン、シクロヘキサノン等のケトン類、エチルセロソルブ等のセロソルブ類、トルエン、キシレン等の芳香族類、プロピレングリコールモノメチルエーテル等のグリコールエーテル類、酢酸メチル、酢酸エチル、酢酸ブチル等の酢酸エステル類、ジアセトンアルコール等が挙げられる。これら上記の有機溶剤は、単独で用いてもよいし、２種以上を併用してもよい。 Moreover, it is also preferable to use the organic solvent for dilution for the active energy ray curable resin composition of this invention as needed, in order to make the viscosity at the time of coating appropriate. Examples of the organic solvent include alcohols such as methanol, ethanol, propanol, n-butanol and i-butanol, ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone, cellosolves such as ethyl cellosolve, toluene and xylene. And the like, glycol ethers such as propylene glycol monomethyl ether, acetates such as methyl acetate, ethyl acetate and butyl acetate, and diacetone alcohol. These organic solvents may be used alone or in combination of two or more.
２種以上を併用する場合は、プロピレングリコールモノメチルエーテル等のグリコールエーテル類とメチルエチルケトン等のケトン類やメタノール等のアルコール類との組み合わせや、メチルエチルケトン等のケトン類とメタノール等のアルコール類の組み合わせ、メタノール等のアルコール類の中から２種以上を選び併用すること等が、塗膜外観の点で好ましい。 When two or more types are used in combination, a combination of glycol ethers such as propylene glycol monomethyl ether and ketones such as methyl ethyl ketone and alcohols such as methanol, a combination of ketones such as methyl ethyl ketone and alcohols such as methanol, methanol From the viewpoint of the appearance of the coating film, it is preferable to use two or more alcohols such as alcohols in combination.
本発明の活性エネルギー線硬化性樹脂組成物は、各種基材へのトップコート剤やアンカーコート剤など、塗膜形成用の硬化性組成物として有効に用いられるものであり、かかる組成物を基材に塗工した後（有機溶剤で希釈した組成物を塗工した場合には、さらに乾燥させた後）、活性エネルギー線を照射することにより硬化される。 The active energy ray-curable resin composition of the present invention is effectively used as a curable composition for forming a coating film such as a topcoat agent and an anchor coat agent for various substrates, and is based on such a composition. After being applied to the material (when the composition diluted with an organic solvent is applied, it is further dried) and then cured by irradiation with active energy rays.
上記本発明の活性エネルギー線硬化性樹脂組成物を塗工する対象である基材としては、ポリオレフィン系樹脂、ポリエステル系樹脂、ポリカーボネート系樹脂、アクリロニトリルブタジエンスチレン共重合体（ＡＢＳ）、ポリスチレン系樹脂等やそれらの成型品（フィルム、シート、カップ、等）等のプラスチック基材、またポリエチレンテレフタレートフィルム、トリアセチルセルロースフィルム、シクロオレフィンフィルム等の光学フィルム、それらの複合基材、またはガラス繊維や無機物を混合した前記材料の複合基材等、金属（アルミニウム、銅、鉄、ＳＵＳ、亜鉛、マグネシウム、これらの合金等）やガラス、または、これらの基材上にプライマー層を設けた基材等が挙げられる。 Examples of the substrate on which the active energy ray-curable resin composition of the present invention is applied include polyolefin resins, polyester resins, polycarbonate resins, acrylonitrile butadiene styrene copolymers (ABS), polystyrene resins, and the like. And plastic base materials such as molded products (films, sheets, cups, etc.), optical films such as polyethylene terephthalate films, triacetyl cellulose films, cycloolefin films, composite base materials, glass fibers or inorganic materials. Examples include mixed base materials of the above materials, metals (aluminum, copper, iron, SUS, zinc, magnesium, alloys thereof, etc.), glass, or base materials provided with a primer layer on these base materials. It is done.
本発明の活性エネルギー線硬化性樹脂組成物の塗工方法としては、例えば、スプレー、シャワー、グラビア、ディッピング、ロール、スピン、スクリーン印刷等のようなウェットコーティング法が挙げられ、通常は常温の条件化で、基材に塗工すればよい。 Examples of the coating method of the active energy ray-curable resin composition of the present invention include wet coating methods such as spray, shower, gravure, dipping, roll, spin, screen printing, etc. In this case, the base material may be applied.
また、本発明の活性エネルギー線硬化性樹脂組成物は、そのまま塗工してもよいし、有機溶剤で希釈して塗工してもよい。希釈する場合には、上記有機溶剤を用いて、固形分濃度が、通常３〜６０重量％（好ましくは５〜４０重量％）とすることが好ましい。 Moreover, the active energy ray-curable resin composition of the present invention may be applied as it is, or may be applied after diluting with an organic solvent. In the case of dilution, it is preferable that the solid content concentration is usually 3 to 60% by weight (preferably 5 to 40% by weight) using the organic solvent.
上記有機溶剤による希釈を行なった際の乾燥条件としては、温度が、通常４０〜１２０℃（好ましくは５０〜１００℃）で、乾燥時間が、通常１〜２０分（好ましくは２〜１０分）であればよい。 As drying conditions when diluted with the organic solvent, the temperature is usually 40 to 120 ° C. (preferably 50 to 100 ° C.), and the drying time is usually 1 to 20 minutes (preferably 2 to 10 minutes). If it is.
本発明の活性エネルギー線硬化性樹脂組成物の２０℃での粘度は、５〜５０，０００ｍＰａ・ｓであることが好ましく、特に好ましくは１０〜１０，０００ｍＰａ・ｓ、更に好ましくは５０〜５，０００ｍＰａである。かかる粘度が上記範囲外では塗工性が低下する傾向がある。
なお、粘度の測定法はＥ型粘度計による。
The viscosity at 20 ° C. of the active energy ray-curable resin composition of the present invention is preferably 5 to 50,000 mPa · s, particularly preferably 10 to 10,000 mPa · s, and further preferably 50 to 5, 000 mPa. When the viscosity is out of the above range, the coatability tends to be lowered.
In addition, the measuring method of a viscosity is based on an E-type viscometer.
基材上に塗工された活性エネルギー線硬化性樹脂組成物を硬化させる際に使用する活性エネルギー線としては、遠紫外線、紫外線、近紫外線、赤外線等の光線、Ｘ線、γ線等の電磁波の他、電子線、プロトン線、中性子線等が利用できるが、硬化速度、照射装置の入手のし易さ、価格等から紫外線照射による硬化が有利である。尚、電子線照射を行う場合は、光重合開始剤（Ｄ）を用いなくても硬化し得る。 Active energy rays used for curing the active energy ray-curable resin composition coated on the substrate include rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, and infrared rays, and electromagnetic waves such as X-rays and γ rays. In addition, electron beams, proton beams, neutron beams, and the like can be used, but curing by ultraviolet irradiation is advantageous from the viewpoint of curing speed, availability of an irradiation device, price, and the like. In addition, when performing electron beam irradiation, it can harden | cure even if it does not use a photoinitiator (D).
紫外線照射により硬化させる際には、１５０〜４５０ｎｍ波長域の光を発する高圧水銀ランプ、超高圧水銀灯、カーボンアーク灯、メタルハライドランプ、キセノンランプ、ケミカルランプ、無電極放電ランプ、ＬＥＤランプ等を用いて、通常３０〜３０００ｍＪ／ｃｍ2（好ましくは１００〜１５００ｍＪ／ｃｍ2）の紫外線を照射すればよい。
紫外線照射後は、必要に応じて加熱を行って硬化の完全を図ることもできる。
When curing by ultraviolet irradiation, use a high-pressure mercury lamp, ultra-high pressure mercury lamp, carbon arc lamp, metal halide lamp, xenon lamp, chemical lamp, electrodeless discharge lamp, LED lamp, etc. that emits light in the wavelength range of 150 to 450 nm. In general, ultraviolet rays of 30 to 3000 mJ / cm 2 (preferably 100 to 1500 mJ / cm 2 ) may be irradiated.
After the ultraviolet irradiation, heating can be performed as necessary to complete the curing.
塗工膜厚（硬化後の膜厚）としては、通常、活性エネルギー線硬化型の塗膜として光重合開始剤が均一に反応するべく光線透過を鑑みると１〜１０００μｍであればよく、好ましくは２〜５００μｍであり、特に好ましくは３〜２００μｍである。 The coating film thickness (film thickness after curing) is usually 1 to 1000 μm in view of light transmission so that the photopolymerization initiator can react uniformly as an active energy ray curable coating film, preferably It is 2-500 micrometers, Most preferably, it is 3-200 micrometers.
本発明の活性エネルギー線硬化性樹脂組成物は、コーティング剤として用いることが好ましく、特にはハードコート用コーティング剤や光学フィルム用コーティング剤として用いることが好ましい。 The active energy ray-curable resin composition of the present invention is preferably used as a coating agent, and particularly preferably used as a hard coat coating agent or an optical film coating agent.
また、本発明においては、活性エネルギー線硬化性樹脂組成物を、サイズ１５ｃｍ×１５ｃｍで厚み１２５μｍの易接着ポリエチレンテレフタレートフィルムに、１０μｍの厚みで塗工し、温度６０℃で３分間乾燥させた後、高さ１８ｃｍの位置から８０Ｗの高圧水銀灯を用い、５．１ｍ／ｍｉｎの速度で積算照射量が５００ｍＪ／ｃｍ2となるように紫外線を照射することにより、得られる硬化塗膜を５ｃｍ×５ｃｍになるように切り出し、四隅の跳ね上がり高さの平均値が１０ｍｍ以下、更には５ｍｍ以下である硬化塗膜となるコーティング剤とすることが好ましい。 In the present invention, the active energy ray-curable resin composition is applied to an easily-adhesive polyethylene terephthalate film having a size of 15 cm × 15 cm and a thickness of 125 μm with a thickness of 10 μm and dried at a temperature of 60 ° C. for 3 minutes. Using a high pressure mercury lamp of 80 W from a position of 18 cm in height, and irradiating with ultraviolet rays at a speed of 5.1 m / min so that the integrated irradiation amount is 500 mJ / cm 2 , the resulting cured coating film is 5 cm × 5 cm It is preferable to make a coating agent that becomes a cured coating film having an average value of the height of jumping at the four corners of 10 mm or less, and further 5 mm or less.
また、本発明においては、活性エネルギー線硬化性樹脂組成物を、サイズ１５ｃｍ×１５ｃｍで厚み１２５μｍの易接着ポリエチレンテレフタレートフィルムに、１０μｍの厚みで塗工し、温度６０℃で３分間乾燥させた後、高さ１８ｃｍの位置から８０Ｗの高圧水銀灯を用い、５．１ｍ／ｍｉｎの速度で積算照射量が５００ｍＪ／ｃｍ2となるように紫外線を照射することにより、得られる硬化塗膜において、ＪＩＳ Ｋ ５６００−５−１に準じて、円筒形マンドレル屈曲試験機を用いて屈曲性の評価を行い、評価用硬化塗膜を試験棒に巻き付けた際に、割れ又は剥がれが生じる最大の径（整数値、ｍｍ）が２０ｍｍ以下、更には１６ｍｍ以下である硬化塗膜となるコーティング剤とすることが好ましい。 In the present invention, the active energy ray-curable resin composition is applied to an easily-adhesive polyethylene terephthalate film having a size of 15 cm × 15 cm and a thickness of 125 μm with a thickness of 10 μm and dried at a temperature of 60 ° C. for 3 minutes. In a cured coating film obtained by irradiating ultraviolet rays at a speed of 5.1 m / min using an 80 W high-pressure mercury lamp from a position of 18 cm in height so that the integrated irradiation amount becomes 500 mJ / cm 2 , JIS K According to 5600-5-1, the flexibility is evaluated using a cylindrical mandrel bending tester, and the maximum diameter (integer value) at which cracking or peeling occurs when a cured coating film for evaluation is wound around a test rod. Mm) is preferably 20 mm or less, and more preferably 16 mm or less.
本発明においては、水酸基価が６０ｍｇＫＯＨ／ｇ以上であるジペンタエリスリトールの（メタ）アクリル酸付加物（Ａ）中の水酸基と、多価イソシアネート（Ｂ）のイソシアネート基とを反応させてなるウレタン（メタ）アクリレート系組成物（Ｃ）を含有してなる活性エネルギー線硬化性樹脂組成物は、硬化収縮が小さくカールしにくく、更に屈曲性にも優れた硬化塗膜を形成することができ、更には、硬化塗膜とした際の耐擦傷性、基材密着性にも優れるものであり、特にコーティング剤（更にはハードコート用コーティング剤や光学フィルム用コーティング剤）として有用であり、また、塗料、インク等としても有用である。 In the present invention, a urethane obtained by reacting a hydroxyl group in a (meth) acrylic acid adduct (A) of dipentaerythritol having a hydroxyl value of 60 mgKOH / g or more and an isocyanate group of a polyvalent isocyanate (B) ( The active energy ray-curable resin composition containing the (meth) acrylate-based composition (C) can form a cured coating film that has a small curing shrinkage and is difficult to curl, and has excellent flexibility. Is excellent in scratch resistance and substrate adhesion when used as a cured coating film, and is particularly useful as a coating agent (further, a coating agent for hard coats and a coating agent for optical films). It is also useful as an ink.
以下、実施例を挙げて本発明を更に具体的に説明するが、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。なお、例中、「部」、「％」とあるのは、重量基準を意味する。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to a following example, unless the summary is exceeded. In the examples, “parts” and “%” mean weight basis.
ウレタン（メタ）アクリレート系組成物（Ｃ）として、以下のものを調製した（表１参照。）。 The following were prepared as urethane (meth) acrylate composition (C) (see Table 1).
＜実施例１＞
〔ウレタン（メタ）アクリレート系組成物（Ｃ−１）の製造〕
温度計、撹拌機、水冷コンデンサー、窒素ガス吹き込み口を備えた４つ口フラスコに、イソホロンジイソシアネート（Ｂ−１）１１４．６ｇ（０．５２モル）と水酸基価６７ｍｇＫＯＨ／ｇのジペンタエリスリトールのアクリル酸付加物（Ａ−１）８８５．４ｇ（１．０６モル）、重合禁止剤として２，６−ジ−ｔｅｒｔ−ブチルクレゾール０．６ｇ、反応触媒としてジブチルスズジラウレート０．０５ｇを仕込み、６０℃で反応させ、残存イソシアネート基が０．３％となった時点で反応を終了し、ウレタン（メタ）アクリレート系組成物（Ｃ−１）を得た（樹脂分濃度１００％）。
得られたウレタン（メタ）アクリレート系組成物（Ｃ−１）の重量平均分子量は４，３００、６０℃での粘度は１５，５００ｍＰａ・ｓであった。
<Example 1>
[Production of Urethane (meth) acrylate Composition (C-1)]
A four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port was charged with 114.6 g (0.52 mol) of isophorone diisocyanate (B-1) and dipentaerythritol with a hydroxyl value of 67 mgKOH / g. 885.4 g (1.06 mol) of acid adduct (A-1), 0.6 g of 2,6-di-tert-butylcresol as a polymerization inhibitor, and 0.05 g of dibutyltin dilaurate as a reaction catalyst were charged at 60 ° C. The reaction was terminated when the residual isocyanate group reached 0.3%, and a urethane (meth) acrylate composition (C-1) was obtained (resin concentration 100%).
The urethane (meth) acrylate composition (C-1) obtained had a weight average molecular weight of 4,300 and a viscosity at 60 ° C. of 15,500 mPa · s.
〔活性エネルギー線硬化性樹脂組成物の製造〕
上記で得られたウレタン（メタ）アクリレート系組成物（Ｃ−１）４０部に、酢酸エチル６０部と光重合開始剤（Ｄ）として、α−ヒドロキシアルキルフェノン系光重合開始剤（ＢＡＳＦ社製、「イルガキュア１８４」）を１．６部配合し、活性エネルギー線硬化性樹脂組成物を得た。
[Production of active energy ray-curable resin composition]
40 parts of the urethane (meth) acrylate composition (C-1) obtained above, 60 parts of ethyl acetate and a photopolymerization initiator (D), α-hydroxyalkylphenone photopolymerization initiator (manufactured by BASF) 1.6 parts of “Irgacure 184”) was blended to obtain an active energy ray-curable resin composition.
＜実施例２＞
〔ウレタン（メタ）アクリレート系組成物（Ｃ−２）の製造〕
温度計、撹拌機、水冷コンデンサー、窒素ガス吹き込み口を備えた４つ口フラスコに、イソホロンジイソシアネート（Ｂ−１）１５９．２ｇ（０．７２モル）と水酸基価９８ｍｇＫＯＨ／ｇのジペンタエリスリトールのアクリル酸付加物（Ａ−２）８４０．８ｇ（１．４７モル）、重合禁止剤として２，６−ジ−ｔｅｒｔ−ブチルクレゾール０．６ｇ、反応触媒としてジブチルスズジラウレート０．０５ｇを仕込み、６０℃で反応させ、残存イソシアネート基が０．３％となった時点で反応を終了し、ウレタン（メタ）アクリレート系組成物（Ｃ−２）を得た（樹脂分濃度１００％）。
得られたウレタン（メタ）アクリレート系組成物（Ｃ−２）の重量平均分子量は４，７００、６０℃での粘度は６７，０００ｍＰａ・ｓであった。
<Example 2>
[Production of Urethane (meth) acrylate Composition (C-2)]
A four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port was charged with 159.2 g (0.72 mol) of isophorone diisocyanate (B-1) and dipentaerythritol with a hydroxyl value of 98 mgKOH / g. 840.8 g (1.47 mol) of acid adduct (A-2), 0.6 g of 2,6-di-tert-butylcresol as a polymerization inhibitor, and 0.05 g of dibutyltin dilaurate as a reaction catalyst were charged at 60 ° C. The reaction was terminated when the residual isocyanate group reached 0.3%, and a urethane (meth) acrylate composition (C-2) was obtained (resin content concentration 100%).
The urethane (meth) acrylate composition (C-2) obtained had a weight average molecular weight of 4,700 and a viscosity at 60 ° C. of 67,000 mPa · s.
〔活性エネルギー線硬化性樹脂組成物の製造〕
実施例１において、ウレタン（メタ）アクリレート経組成物（Ｃ−１）に代えて上記で得られたウレタンアクリレート系組成物（Ｃ−２）を用いた以外は実施例１と同様にして活性エネルギー線硬化性樹脂組成物を得た。
[Production of active energy ray-curable resin composition]
In Example 1, active energy was obtained in the same manner as in Example 1 except that the urethane acrylate composition (C-2) obtained above was used in place of the urethane (meth) acrylate composition (C-1). A linear curable resin composition was obtained.
＜実施例３＞
〔ウレタン（メタ）アクリレート組成物（Ｃ−３）の製造〕
温度計、撹拌機、水冷コンデンサー、窒素ガス吹き込み口を備えた４つ口フラスコに、イソホロンジイソシアネート（Ｂ−１）１７５．３ｇ（０．７９モル）と水酸基価１１０ｍｇＫＯＨ／ｇのジペンタエリスリトールのアクリル酸付加物（Ａ−３）８２４．７ｇ（１．６２モル）、重合禁止剤として２，６−ジ−ｔｅｒｔ−ブチルクレゾール０．６ｇ、反応触媒としてジブチルスズジラウレート０．０５ｇを仕込み、６０℃で反応させ、残存イソシアネート基が０．３％となった時点で反応を終了し、ウレタンアクリレート系組成物（Ｃ−３）を得た（樹脂分濃度１００％）。
得られたウレタン（メタ）アクリレート系組成物（Ｃ−３）の重量平均分子量は６，６００、６０℃での粘度は１５０，０００ｍＰａ・ｓであった。
<Example 3>
[Production of urethane (meth) acrylate composition (C-3)]
A four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port was mixed with 175.3 g (0.79 mol) of isophorone diisocyanate (B-1) and dipentaerythritol having a hydroxyl value of 110 mgKOH / g. 824.7 g (1.62 mol) of acid adduct (A-3), 0.6 g of 2,6-di-tert-butylcresol as a polymerization inhibitor, and 0.05 g of dibutyltin dilaurate as a reaction catalyst were charged at 60 ° C. The reaction was terminated when the residual isocyanate group reached 0.3%, and a urethane acrylate composition (C-3) was obtained (resin concentration 100%).
The obtained urethane (meth) acrylate-based composition (C-3) had a weight average molecular weight of 6,600 and a viscosity at 60 ° C. of 150,000 mPa · s.
〔活性エネルギー線硬化性樹脂組成物の製造〕
実施例１において、ウレタン（メタ）アクリレート経組成物（Ｃ−１）に代えて上記で得られたウレタン（メタ）アクリレート系組成物（Ｃ−３）を用いた以外は実施例１と同様にして活性エネルギー線硬化性樹脂組成物を得た。
[Production of active energy ray-curable resin composition]
In Example 1, it replaced with the urethane (meth) acrylate mesocomposition (C-1), and it was the same as that of Example 1 except having used the urethane (meth) acrylate type composition (C-3) obtained above. Thus, an active energy ray-curable resin composition was obtained.
＜比較例１＞
〔ウレタンアクリレート系組成物（Ｃ’−１）の製造〕
温度計、撹拌機、水冷コンデンサー、窒素ガス吹き込み口を備えた４つ口フラスコに、イソホロンジイソシアネート（Ｂ−１）８４．９ｇ（０．３８モル）と水酸基価４８ｍｇＫＯＨ／ｇのジペンタエリスリトールのアクリル酸付加物（Ａ’−１）９１５．１ｇ（０．７８モル）、重合禁止剤として２，６−ジ−ｔｅｒｔ−ブチルクレゾール０．６ｇ、反応触媒としてジブチルスズジラウレート０．０５ｇを仕込み、６０℃で反応させ、残存イソシアネート基が０．３％となった時点で反応を終了し、ウレタンアクリレート系組成物（Ｃ’−１）を製造した。
得られたウレタン（メタ）アクリレート系組成物（Ｃ’−１）の重量平均分子量は２，２００、６０℃での粘度は１，５００ｍＰａ・ｓであった。
<Comparative Example 1>
[Production of urethane acrylate composition (C′-1)]
A four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port was charged with 84.9 g (0.38 mol) of isophorone diisocyanate (B-1) and dipentaerythritol with a hydroxyl value of 48 mgKOH / g. 915.1 g (0.78 mol) of acid adduct (A′-1), 0.6 g of 2,6-di-tert-butylcresol as a polymerization inhibitor, and 0.05 g of dibutyltin dilaurate as a reaction catalyst were charged at 60 ° C. The reaction was terminated when the residual isocyanate group became 0.3%, and a urethane acrylate composition (C′-1) was produced.
The obtained urethane (meth) acrylate-based composition (C′-1) had a weight average molecular weight of 2,200 and a viscosity at 60 ° C. of 1,500 mPa · s.
〔活性エネルギー線硬化性樹脂組成物の製造〕
実施例１において、ウレタン（メタ）アクリレート経組成物（Ｃ−１）に代えて上記で得られたウレタン（メタ）アクリレート系組成物（Ｃ’−１）を用いた以外は実施例１と同様にして活性エネルギー線硬化性樹脂組成物を得た。
[Production of active energy ray-curable resin composition]
Example 1 is the same as Example 1 except that the urethane (meth) acrylate composition (C′-1) obtained above is used instead of the urethane (meth) acrylate composition (C-1). Thus, an active energy ray-curable resin composition was obtained.
＜比較例２＞
〔活性エネルギー線硬化性樹脂組成物の製造〕
上記で得られたウレタン（メタ）アクリレート系組成物（Ｃ’−１）２０部に、メチルエチルケトンを分散媒とするシリカゾル〔商品名：ＭＥＫ−ＳＴ−４０、日産化学工業社製（不揮発分４０％、平均粒子径約１０ｎｍのコロイダルシリカ）〕５０部、酢酸エチル３０部と光重合開始剤（Ｄ）として、α−ヒドロキシアルキルフェノン系光重合開始剤（ＢＡＳＦ社製、「イルガキュア１８４」）を１．６部配合し、活性エネルギー線硬化性樹脂組成物を得た。
<Comparative Example 2>
[Production of active energy ray-curable resin composition]
Silica sol (trade name: MEK-ST-40, manufactured by Nissan Chemical Industries, Ltd. (nonvolatile content: 40%) with 20 parts of the urethane (meth) acrylate composition (C′-1) obtained above as a dispersion medium. , Colloidal silica having an average particle diameter of about 10 nm)] 50 parts, 30 parts of ethyl acetate and 1 photopolymerization initiator (D) as an α-hydroxyalkylphenone photopolymerization initiator (“Irgacure 184” manufactured by BASF) .6 parts was blended to obtain an active energy ray-curable resin composition.
上記ウレタン（メタ）アクリレート系組成物（Ｃ−１）、（Ｃ−２）、（Ｃ−３）、（Ｃ’−１）を用いて得られた活性エネルギー線硬化性樹脂組成物について、下記の通り硬化塗膜を形成し、塗膜物性（カール値、屈曲性、耐擦傷性、硬度）を評価した。評価結果は表１の通りである。 About the active energy ray-curable resin composition obtained using the urethane (meth) acrylate-based composition (C-1), (C-2), (C-3), (C′-1), the following A cured coating film was formed as described above, and the coating film properties (curl value, flexibility, scratch resistance, hardness) were evaluated. The evaluation results are shown in Table 1.
〔評価用サンプルの製造方法〕
上記で得られた活性エネルギー線硬化性樹脂組成物を、易接着ＰＥＴフィルム（東洋紡（株）製、「Ａ４３００」、サイズ１５ｃｍ×１５ｃｍ、厚み１２５μｍ）基板上にバーコーターを用いて、乾燥後の膜厚が１０μｍとなるように塗工し、６０℃で３分間乾燥した後、高圧水銀灯ランプ８０Ｗ、１灯を用いて、１８ｃｍの高さから５．１ｍ／ｍｉｎのコンベア速度で２パスの紫外線照射（積算照射量５００ｍＪ／ｃｍ2）を行い、硬化塗膜を形成した。
[Method for producing sample for evaluation]
The active energy ray-curable resin composition obtained above was dried on an easily-adhesive PET film (Toyobo Co., Ltd., “A4300”, size 15 cm × 15 cm, thickness 125 μm) using a bar coater. After coating to a film thickness of 10 μm and drying at 60 ° C. for 3 minutes, two passes of UV light at a conveyor speed of 5.1 m / min from a height of 18 cm using a high pressure mercury lamp lamp 80 W and one lamp. Irradiation (accumulated dose 500 mJ / cm 2 ) was performed to form a cured coating film.
［カール値（四隅の跳ね上がり高さ）］
易接着ＰＥＴフィルム上に塗工した上記硬化塗膜を５ｃｍ×５ｃｍとなるように切り出し、四角の跳ね上がり高さの平均値（ｍｍ）をカール値として測定した。値が小さいほどカールが小さく、カールしにくい塗膜であることを意味する。
[Curl value (heap height of four corners)]
The cured coating film coated on the easy-adhesion PET film was cut out to be 5 cm × 5 cm, and the average value (mm) of the height of the square jump was measured as a curl value. The smaller the value, the smaller the curl and the harder it is to curl.
［屈曲性］
易接着ＰＥＴフィルム上に塗工した上記硬化塗膜について、ＪＩＳ Ｋ ５６００−５−１に準じて、円筒形マンドレル屈曲試験機を用いて屈曲性の評価を行った。評価用硬化塗膜を、塗膜面が外側になるように試験棒に巻き付けた際に、割れ又は剥がれが生じる最大の径（整数値、ｍｍ）を測定した。値が小さいほど屈曲性の高い塗膜であることを意味する。
[Flexibility]
The above-mentioned cured coating film coated on the easy-adhesion PET film was evaluated for flexibility using a cylindrical mandrel bending tester according to JIS K 5600-5-1. The maximum diameter (integer value, mm) at which cracking or peeling occurred was measured when the evaluation cured coating film was wound around a test bar such that the coating film surface was on the outside. It means that it is a coating film with high flexibility, so that a value is small.
［耐擦傷性］
易接着ＰＥＴフィルム上に塗工した上記硬化塗膜について、スチールウール（日本スチールウール社製、ボンスター＃００００）を用い、１ｋｇの荷重をかけながら硬化塗膜表面を１０往復させた後、表面の傷付き度合いを目視により観察した。
（評価）
○・・・傷が見えないもの
△・・・傷が少ないもの
×・・・傷が多いもの
[Abrasion resistance]
About the above-mentioned cured coating film coated on the easy-adhesive PET film, steel wool (manufactured by Nippon Steel Wool Co., Ltd., Bonstar # 0000) was used, and after the surface of the cured coating film was reciprocated 10 times while applying a 1 kg load, The degree of damage was visually observed.
(Evaluation)
○ ・ ・ ・ Scratches are invisible △ ・ ・ ・ Scratches are low × ・ ・ ・ Scratches are high
［鉛筆硬度］
易接着ＰＥＴフィルム上に塗工した上記硬化塗膜について、ＪＩＳＫ５６００に準じて試験を行ない、鉛筆硬度を測定した。
[Pencil hardness]
About the said cured coating film apply | coated on the easily bonding PET film, the test was done according to JISK5600 and the pencil hardness was measured.
上記評価結果より、実施例１〜３のウレタン（メタ）アクリレート系組成物から得られる硬化塗膜は、カール値が小さくカールしにくいものであり、かつ屈曲性に優れ、更に耐擦傷性及び鉛筆硬度にも優れるものであることがわかる。
一方、特定のウレタン（メタ）アクリレート系組成物以外である比較例１のウレタン（メタ）アクリレート系組成物から得られる硬化塗膜は、カール値が大きくカールしやすいものであり、さらに、屈曲性も実施例と比べて非常に劣るものであることがわかる。また、比較例２では活性エネルギー線硬化性樹脂組成物中にシリカ粒子を含有させることで、硬化収縮を抑えることができカール値は低くなっているが、屈曲性には全く改善がみられないものであった。
From the above evaluation results, the cured coating films obtained from the urethane (meth) acrylate-based compositions of Examples 1 to 3 have a small curl value and are difficult to curl, have excellent flexibility, and have scratch resistance and pencil. It turns out that it is excellent also in hardness.
On the other hand, the cured coating film obtained from the urethane (meth) acrylate composition of Comparative Example 1 other than the specific urethane (meth) acrylate composition has a large curl value and is easily curled, and further has flexibility. It can also be seen that this is very inferior to the examples. Further, in Comparative Example 2, by containing silica particles in the active energy ray-curable resin composition, curing shrinkage can be suppressed and the curl value is low, but the flexibility is not improved at all. It was a thing.
本発明の活性エネルギー線硬化性樹脂組成物は、硬化塗膜とした際に、硬化収縮が小さくカールしにくく、かつ屈曲性にも優れた硬化塗膜を形成することができ、更には、硬化塗膜とした際の耐擦傷性にも優れるものであり、コーティング剤、とりわけハードコート用コーティング剤や光学フィルム用コーティング剤として有用である。また、塗料、インク等としても有用である。 When the active energy ray-curable resin composition of the present invention is used as a cured coating film, it can form a cured coating film that has a small curing shrinkage and is less likely to curl and has excellent flexibility, and further, It also has excellent scratch resistance when used as a coating film, and is useful as a coating agent, particularly as a coating agent for hard coats and a coating agent for optical films. It is also useful as a paint or ink.
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