KR20190129848A - Active energy ray curable resin composition and coating agent - Google Patents
Active energy ray curable resin composition and coating agent Download PDFInfo
- Publication number
- KR20190129848A KR20190129848A KR1020197025035A KR20197025035A KR20190129848A KR 20190129848 A KR20190129848 A KR 20190129848A KR 1020197025035 A KR1020197025035 A KR 1020197025035A KR 20197025035 A KR20197025035 A KR 20197025035A KR 20190129848 A KR20190129848 A KR 20190129848A
- Authority
- KR
- South Korea
- Prior art keywords
- meth
- acrylate
- mixture
- pentaerythritol
- urethane
- Prior art date
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- 239000011248 coating agent Substances 0.000 title claims abstract description 163
- 239000011342 resin composition Substances 0.000 title claims abstract description 85
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 525
- 239000000203 mixture Substances 0.000 claims abstract description 332
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 100
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 90
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 89
- 239000012948 isocyanate Substances 0.000 claims abstract description 83
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 79
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 5
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 94
- 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 description 92
- 238000006243 chemical reaction Methods 0.000 claims description 60
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 43
- 229920005989 resin Polymers 0.000 claims description 34
- 239000011347 resin Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 24
- 239000000376 reactant Substances 0.000 claims description 14
- 239000012788 optical film Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 abstract description 129
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 33
- 229940048053 acrylate Drugs 0.000 description 344
- 239000010408 film Substances 0.000 description 124
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 60
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 54
- -1 isocyanate compound Chemical class 0.000 description 49
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 38
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 38
- 229940114077 acrylic acid Drugs 0.000 description 38
- 239000003112 inhibitor Substances 0.000 description 35
- 238000006116 polymerization reaction Methods 0.000 description 32
- 239000007809 chemical reaction catalyst Substances 0.000 description 27
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 26
- 239000012975 dibutyltin dilaurate Substances 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 25
- 229910001873 dinitrogen Inorganic materials 0.000 description 25
- 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 24
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- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 9
- CQHKDHVZYZUZMJ-UHFFFAOYSA-N [2,2-bis(hydroxymethyl)-3-prop-2-enoyloxypropyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(CO)COC(=O)C=C CQHKDHVZYZUZMJ-UHFFFAOYSA-N 0.000 description 9
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 9
- ZCZFEIZSYJAXKS-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COC(=O)C=C ZCZFEIZSYJAXKS-UHFFFAOYSA-N 0.000 description 9
- 239000002585 base Substances 0.000 description 9
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- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
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- 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 6
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- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 5
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- 238000012360 testing method Methods 0.000 description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
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- 238000006845 Michael addition reaction Methods 0.000 description 4
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- IETUUPFUMFSAAO-UHFFFAOYSA-N pent-1-ene prop-2-enoic acid Chemical compound C(C=C)(=O)O.C=CCCC IETUUPFUMFSAAO-UHFFFAOYSA-N 0.000 description 3
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- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- LMVLMXRQTANNQN-UHFFFAOYSA-J hexanoate zirconium(4+) Chemical compound [Zr+4].CCCCCC([O-])=O.CCCCCC([O-])=O.CCCCCC([O-])=O.CCCCCC([O-])=O LMVLMXRQTANNQN-UHFFFAOYSA-J 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
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 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
- 125000005641 methacryl group Chemical group 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 description 1
- ZWRDBWDXRLPESY-UHFFFAOYSA-N n-benzyl-n-ethylethanamine Chemical compound CCN(CC)CC1=CC=CC=C1 ZWRDBWDXRLPESY-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
- 229910052757 nitrogen 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
- 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
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920002601 oligoester Polymers 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000003755 preservative agent 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
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229960000953 salsalate Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- JUYONNFUNDDKBE-UHFFFAOYSA-J tri(oct-2-enoyloxy)stannyl oct-2-enoate Chemical compound [Sn+4].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O JUYONNFUNDDKBE-UHFFFAOYSA-J 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- PKJOUIVGCFHFTK-UHFFFAOYSA-L zinc;hexanoate Chemical compound [Zn+2].CCCCCC([O-])=O.CCCCCC([O-])=O PKJOUIVGCFHFTK-UHFFFAOYSA-L 0.000 description 1
- RVXKJRWBHPHVOV-UHFFFAOYSA-L zinc;oct-2-enoate Chemical compound [Zn+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O RVXKJRWBHPHVOV-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- 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
-
- 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
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
Abstract
경화수축이 작기 때문에 컬되기 어렵고, 또한, 경도 및 굴곡성에도 뛰어난 경화도막을 형성할 수 있는 우레탄(메타)아크릴레이트계 조성물을 함유하는 활성 에너지선 경화성 수지 조성물로서, 펜타에리쓰리톨과 (메타)아크릴산과의 반응물인 (메타)아크릴레이트의 혼합물(A) 중의 (메타)아크릴레이트의 수산기와, 다가 이소시아네이트(CA)의 이소시아네이트기가 반응한 우레탄(메타)아크릴레이트계 조성물［I］를 함유하여 이루어지고, 상기 혼합물(A)의 수산기값이 200mgKOH/g 이상인 활성 에너지선 경화성 수지 조성물을 제공한다.Pentaerythritol and (meth) acrylic acid are active energy ray-curable resin compositions containing a urethane (meth) acrylate-based composition which is hard to curl because of its small shrinkage and can form a cured coating film excellent in hardness and flexibility. It consists of containing the hydroxyl group of (meth) acrylate in the mixture (A) of (meth) acrylate which is a reaction product with, and the urethane (meth) acrylate type composition [I] which the isocyanate group of polyvalent isocyanate (CA) reacted, And the hydroxyl value of the said mixture (A) provides 200 mgKOH / g or more of active energy ray curable resin compositions.
Description
본 발명은 우레탄(메타)아크릴레이트계 조성물을 함유하는 활성 에너지선 경화성 수지 조성물 및 코팅제에 관한 것으로, 더욱 상세하게는 경화도막을 형성했을 때에, 경화 수축이 작기 때문에 컬되기 어렵고, 또한 경도 및 굴곡성이 뛰어난 도막을 형성할 수 있는 활성 에너지선 경화성 수지 조성물, 및 이를 사용한 코팅제에 관한 것이다.The present invention relates to an active energy ray-curable resin composition and a coating agent containing a urethane (meth) acrylate-based composition, and more particularly, when the cured coating film is formed, it is difficult to curl due to small curing shrinkage, and furthermore, hardness and flexibility The present invention relates to an active energy ray curable resin composition capable of forming an excellent coating film, and a coating agent using the same.
종래, 활성 에너지선 경화성 수지 조성물은 극히 단시간의 방사선이나 자외선 등의 활성 에너지선의 조사에 의해 경화가 완료되기 때문에, 각종 기재로의 코팅제나 접착제, 또는 앵커 코트제 등으로서 폭넓게 사용되고 있으며 그 중의 경화 성분으로서는 우레탄(메타)아크릴레이트계 화합물이나 다관능 모노머가 사용되고 있다. 그런데, 활성 에너지선 경화성 수지 조성물을 특히 코팅제, 특히 하드 코트용 코팅제로서 사용할 때에, 도막의 경화 수축이 일어나, 경화 도막이 컬되기 쉽다는 문제점이 있어, 컬되기 어려운 것이 요구되고 있다.Conventionally, since an active energy ray curable resin composition is hardened | cured by irradiation of active energy rays, such as a very short time radiation and an ultraviolet-ray, it is widely used as a coating agent, an adhesive agent, an anchor coat agent, etc. to various base materials, and the hardening component in it As a urethane (meth) acrylate type compound and a polyfunctional monomer are used. By the way, when using an active-energy-ray-curable resin composition especially as a coating agent, especially a coating agent for hard coats, there exists a problem that hardening shrinkage of a coating film occurs, and a cured coating film is easy to curl, and it is difficult to curl.
또, 하드 코트용 코팅제는 보호 필름으로서 성형품이나 디스플레이 등의 굴곡부에도 사용되기 때문에, 경화 도막을 형성한 플라스틱 필름을 구부려도 크랙 등이 생기기 어렵다는 굴곡성이 요구되고 있다.Moreover, since the coating agent for hard coats is used also for bending parts, such as a molded article and a display, as a protective film, the flexibility which hardly produces a crack is calculated | required even if the plastic film in which the hardened coating film was formed was bent.
상기 컬되기 어려운 것에 대해서, 경화 수축을 억제하기 위해서, 경화성 수지에 무기 미립자를 첨가한 경화성 수지 조성물(예를 들면, 특허 문헌 1 참조)이나, 경화 성분으로서 고분자량화된 우레탄(메타)아크릴레이트를 함유시킨 경화성 수지 조성물(예를 들면, 특허 문헌 2 참조), 또한, 수산기값이 130mgKOH/g 이상인 펜타에리쓰리톨의 (메타)아크릴산 부가물 중의 수산기와, 다가 이소시아네이트계 화합물의 이소시아네이트기를 반응시켜 이루어진 우레탄(메타)아크릴레이트를 함유 하여 이루어진 경화성 수지 조성물(예를 들면, 특허 문헌 3 참조)이 제안되어 있다.In order to suppress hardening shrinkage, the curable resin composition (for example, refer patent document 1) which added inorganic fine particles to curable resin, and the urethane (meth) acrylate high molecular weight as a hardening component in order to suppress hardening curling Curable resin composition (for example, refer to Patent Document 2) containing, and further, a hydroxyl group in the (meth) acrylic acid adduct of pentaerythritol having a hydroxyl value of 130 mgKOH / g or more, and an isocyanate group of a polyvalent isocyanate compound The curable resin composition (for example, refer patent document 3) containing the made urethane (meth) acrylate is proposed.
또, 내찰상성을 향상시키기 위해서 하드 코트층을 더욱 고경도화하는 수법으로서, 예를 들면 디펜타에리쓰리톨 헥사아크릴레이트 및 트리펜타에리쓰리톨 옥타아크릴레이트를 함유하는 수지 조성물을, 두께 80㎛의 트리아세틸셀룰로오스필름 상에 막 두께 12㎛로 도포하여 경화 시키는 것으로, 연필 경도 5H 정도의 경도를 갖는 필름을 얻을 수 있다는 기술이 알려져 있다(예를 들면, 특허 문헌 4 참조).Moreover, as a method of further hardening a hard-coat layer in order to improve scratch resistance, the resin composition containing dipentaerythritol hexaacrylate and tripentaerythritol octaacrylate, for example is 80 micrometers in thickness. It is known that a film having a hardness of about 5H of pencil hardness is obtained by applying and curing a triacetyl cellulose film with a film thickness of 12 µm (see Patent Document 4, for example).
그러나, 상기 특허 문헌 1의 개시 기술에서는, 무기 미립자와 경화성 수지와의 상용성을 고려하면 사용할 수 있는 유기용제가 한정되거나 도막의 표면 이상이 일어날 가능성이 높아진다는 문제가 있거나, 또한, 일반적으로 무기 미립자는 고가이기 때문에 이를 배합한 수지나 도료도 고가가 되어, 현실적으로는 경화성 수지의 사용 용도가 특수한 용도로 한정되어 버리는 것이었다.However, in the disclosed technique of Patent Document 1, when the compatibility between inorganic fine particles and the curable resin is taken into consideration, there is a problem that the organic solvent that can be used is limited, or the possibility of surface abnormality of the coating film is increased. Since microparticles | fine-particles are expensive, resin and coating material which mix | blended them became expensive, and the practical use of curable resin was limited to the special use.
또, 상기 특허 문헌 2의 개시 기술에서는, 경화 성분으로서 사용하는 우레탄(메타)아크릴레이트를 고분자량화시키기 위한 제조법이 다단 반응이 되기 때문에, 조작이 번잡하게 되거나 도막의 내찰상성이 저하해 버리는 것이었다.Moreover, since the manufacturing method for making high molecular weight of the urethane (meth) acrylate used as a hardening component becomes a multistage reaction in the starting technique of the said patent document 2, operation became complicated and scratch resistance of a coating film fell. .
한편, 특허 문헌 3의 개시 기술에서는, 경화 수축이 작고 컬이 억제된 경화 도막을 얻을 수 있지만, 경도의 관점에서 불충분했다.On the other hand, in the technique disclosed in Patent Document 3, although a cured shrinkage was small and a cured coating film in which curl was suppressed was obtained, it was insufficient from the viewpoint of hardness.
또한, 특허 문헌 4의 개시 기술에서는, 경화 도막의 표면 경도는 높기는 하지만, 경화 시에 생기는 컬이 크고, 또 딱딱하고 취약한 것이기 때문에, 도막을 굴곡 시켰을 때에 분열이 생겨 버리는 것이었다.In addition, although the surface hardness of the cured coating film is high in the technique disclosed in Patent Document 4, since curls generated during curing are large, hard, and fragile, breakage occurs when the coating film is bent.
따라서, 본 발명에서는, 이러한 배경하에서, 경화 도막을 형성했을 때에, 경화 수축이 작기 때문에 컬되기 어렵고, 한편 경도 및 굴곡성에도 뛰어난 도막을 형성할 수 있는 우레탄(메타)아크릴레이트계 조성물을 함유하는 활성 에너지선 경화성 수지 조성물, 및 이를 사용한 코팅제를 제공한다.Therefore, in the present invention, when the cured coating film is formed under such a background, it is difficult to curl because of the small shrinkage of the cured coating, and the active containing a urethane (meth) acrylate-based composition capable of forming a coating film excellent in hardness and flexibility. An energy ray curable resin composition and a coating agent using the same are provided.
그런데 본 발명자들은 이와 같은 사정을 감안하여 예의 연구를 거듭한 결과, 경화 성분으로서 펜타에리쓰리톨 및 디펜타에리쓰리톨의 적어도 한쪽과 (메타)아크릴산과의 반응물이 특정 범위의 수산기값을 나타내며, 그 반응물 중의 (메타)아크릴레이트의 수산기와 다가 이소시아네이트를 반응시켜 이루어진 우레탄(메타)아크릴레이트계 조성물을 사용하는 것으로, 경화 수축이 작기 때문에 컬되기 어렵고, 또한 경도 및 굴곡성에도 뛰어난 경화 도막을 얻을 수 있다는 것을 발견하였다.However, the present inventors have made intensive studies in view of such circumstances, and as a result, the reaction product of at least one of pentaerythritol and dipentaerythritol with (meth) acrylic acid exhibits a hydroxyl value in a specific range. By using the urethane (meth) acrylate-based composition formed by reacting the hydroxyl group of the (meth) acrylate in the reactant with a polyvalent isocyanate, the cured shrinkage is small, and thus a cured coating film excellent in hardness and flexibility can be obtained. I found it.
즉, 본 발명 제1 요지는 펜타에리쓰리톨과 (메타)아크릴산과의 반응물인 하기 (메타)아크릴레이트(a1)∼(a4)의 혼합물(A) 중의 (메타)아크릴레이트(a1)∼(a3)와, 다가 이소시아네이트(CA)가 반응한 우레탄(메타)아크릴레이트계 조성물［I］를 함유하고, 상기 혼합물(A)의 수산기값이 200mgKOH/g 이상인 활성 에너지선 경화성 수지 조성물에 관한 것이다.That is, the 1st summary of this invention is the (meth) acrylate (a1)-(in the mixture (A) of the following (meth) acrylate (a1)-(a4) which is a reactant of pentaerythritol and (meth) acrylic acid. It contains urethane (meth) acrylate type composition [I] which a3) and polyvalent isocyanate (CA) reacted, and the hydroxyl value of the said mixture (A) are related with the active energy ray curable resin composition which is 200 mgKOH / g or more.
혼합물(A)Mixture (A)
(a1) 펜타에리쓰리톨 모노(메타)아크릴레이트(a1) pentaerythritol mono (meth) acrylate
(a2) 펜타에리쓰리톨 디(메타)아크릴레이트(a2) pentaerythritol di (meth) acrylate
(a3) 펜타에리쓰리톨 트리(메타)아크릴레이트(a3) pentaerythritol tri (meth) acrylate
(a4) 펜타에리쓰리톨 테트라(메타)아크릴레이트(a4) pentaerythritol tetra (meth) acrylate
또, 본 발명의 제2 요지는 상기 우레탄(메타)아크릴레이트계 조성물［I］, 및, 디펜타에리쓰리톨과 (메타)아크릴산과의 반응물인 하기 (메타)아크릴레이트(b1)∼(b6)의 혼합물(B) 중의 (메타)아크릴레이트(b1)∼(b5)와, 다가 이소시아네이트(CB)가 반응한 우레탄(메타)아크릴레이트계 조성물［II］를 함유하고, 상기 혼합물(B)의 수산기값이 40mgKOH/g 이상인 활성 에너지선 경화성 수지 조성물에 관한 것이다.Moreover, the 2nd summary of this invention is the following (meth) acrylate (b1)-(b6) which is a reaction material of the said urethane (meth) acrylate type composition [I], and dipentaerythritol and (meth) acrylic acid. (Meth) acrylate (b1)-(b5) in the mixture (B) of (), and the urethane (meth) acrylate type composition [II] which the polyhydric isocyanate (CB) reacted, and contains the said (B) It is related with active energy ray curable resin composition whose hydroxyl value is 40 mgKOH / g or more.
혼합물(B)Mixture (B)
(b1) 디펜타에리쓰리톨 모노(메타)아크릴레이트(b1) dipentaerythritol mono (meth) acrylate
(b2) 디펜타에리쓰리톨 디(메타)아크릴레이트(b2) dipentaerythritol di (meth) acrylate
(b3) 디펜타에리쓰리톨 트리(메타)아크릴레이트(b3) dipentaerythritol tri (meth) acrylate
(b4) 디펜타에리쓰리톨 테트라(메타)아크릴레이트(b4) dipentaerythritol tetra (meth) acrylate
(b5) 디펜타에리쓰리톨 펜타(메타)아크릴레이트(b5) dipentaerythritol penta (meth) acrylate
(b6) 디펜타에리쓰리톨 헥사(메타)아크릴레이트(b6) dipentaerythritol hexa (meth) acrylate
또한, 본 발명의 제3 요지는, 하기의［α］인 (메타)아크릴레이트(a1)∼(a3), 하기의［β］인 (메타)아크릴레이트(b1)∼(b5), 및, 다가 이소시아네이트(CC)가 반응한 우레탄(메타)아크릴레이트계 조성물［III］를 함유하는 활성 에너지선 경화성 수지 조성물에 관한 것이다.Moreover, the 3rd summary of this invention is (meth) acrylate (a1)-(a3) which is [alpha] below, (meth) acrylate (b1)-(b5) which is [beta] below, and It relates to the active energy ray curable resin composition containing urethane (meth) acrylate type composition [III] which polyvalent isocyanate (CC) reacted.
［α］펜타에리쓰리톨과 (메타)아크릴산과의 반응물인 하기 (메타)아크릴레이트(a1)∼(a4)의 혼합물(A)의 수산기값이 200mgKOH/g 이상이며, 상기 혼합물(A) 중의 (메타)아크릴레이트(a1)∼(a3).The hydroxyl value of the mixture (A) of the following (meth) acrylate (a1)-(a4) which is a reaction of [(alpha)] pentaerythritol and (meth) acrylic acid is 200 mgKOH / g or more, and in the said mixture (A) (Meth) acrylate (a1)-(a3).
(a1) 펜타에리쓰리톨 모노(메타)아크릴레이트(a1) pentaerythritol mono (meth) acrylate
(a2) 펜타에리쓰리톨 디(메타)아크릴레이트(a2) pentaerythritol di (meth) acrylate
(a3) 펜타에리쓰리톨 트리(메타)아크릴레이트(a3) pentaerythritol tri (meth) acrylate
(a4) 펜타에리쓰리톨 테트라(메타)아크릴레이트(a4) pentaerythritol tetra (meth) acrylate
［β］디펜타에리쓰리톨과 (메타)아크릴산과의 반응물인 하기 (메타)아크릴레이트 (b1)∼(b6)의 혼합물(B)의 수산기값이 40mgKOH/g 이상이며, 상기 혼합물(B) 중의 (메타)아크릴레이트(b1)∼(b5).[Beta] The hydroxyl value of the mixture (B) of the following (meth) acrylate (b1)-(b6) which is a reactant of dipentaerythritol and (meth) acrylic acid is 40 mgKOH / g or more, The said mixture (B) (Meth) acrylate (b1)-(b5) in the medium.
(b1) 디펜타에리쓰리톨 모노(메타)아크릴레이트(b1) dipentaerythritol mono (meth) acrylate
(b2) 디펜타에리쓰리톨 디(메타)아크릴레이트(b2) dipentaerythritol di (meth) acrylate
(b3) 디펜타에리쓰리톨 트리(메타)아크릴레이트(b3) dipentaerythritol tri (meth) acrylate
(b4) 디펜타에리쓰리톨 테트라(메타)아크릴레이트(b4) dipentaerythritol tetra (meth) acrylate
(b5) 디펜타에리쓰리톨 펜타(메타)아크릴레이트(b5) dipentaerythritol penta (meth) acrylate
(b6) 디펜타에리쓰리톨 헥사(메타)아크릴레이트(b6) dipentaerythritol hexa (meth) acrylate
또, 본 발명에서는 상기 활성 에너지선 경화성 수지 조성물을 함유하는 코팅제도 제공하는 것이다.Moreover, in this invention, the coating agent containing the said active energy ray curable resin composition is also provided.
본 발명의 제1 요지와 같은 활성 에너지선 경화성 수지 조성물은, 경화 수축이 작기 때문에 컬되기 어렵고, 경도 및 굴곡성이 뛰어난 경화 도막을 형성할 수 있고, 또한 경화 전의 도막에서도 택 프리인 도막 표면을 형성할 수 있는 것이며, 특히 하드 코트용 코팅제 등, 여러 가지의 용도에 유용하다.The active energy ray-curable resin composition like the 1st summary of this invention is hard to curl because hardening shrinkage | contraction is small, and can form the cured coating film excellent in hardness and bendability, and also forms the tack free coating film surface in the coating film before hardening. It is possible to do this, and especially useful for various uses, such as a coating agent for hard coats.
또, 본 발명의 제2 요지와 같은 활성 에너지선 경화성 수지 조성물은, 경화 수축이 작기 때문에 컬되기 어렵고, 또한 경도 및 굴곡성이 뛰어난 경화 도막을 형성할 수 있는 것이며, 특히 하드 코트용 코팅제 등, 여러 가지의 용도에 유용하다.Moreover, since active shrinkage shrinkage | contraction is small, the active energy ray curable resin composition like the 2nd summary of this invention is hard to curl, and can form the cured coating film excellent in hardness and flexibility, especially the coating agent for hard coats, etc. Useful for eggplant use.
또한, 본 발명의 제3 요지와 같은 활성 에너지선 경화성 수지 조성물은, 경화 수축이 작기 때문에 컬되기 어렵고, 또한 경도, 굴곡성 및 내찰상성이 뛰어난 경화 도막을 형성할 수 있는 것이며, 특히 하드 코트용의 코팅제 등, 여러 가지의 용도에 유용하다.In addition, an active energy ray-curable resin composition as in the third aspect of the present invention is capable of forming a cured coating film which is hard to curl because of its small shrinkage, and which is excellent in hardness, flexibility and scratch resistance, and particularly for hard coats. It is useful for various uses, such as a coating agent.
상기 (메타)아크릴레이트(a1)∼(a4)의 혼합물(A) 중의 펜타에리쓰리톨 디(메타)아크릴레이트(a2)의 함유 비율이 10∼50중량%이면, 경도와 굴곡성의 양립의 관점에서 뛰어나게 된다.When the content ratio of pentaerythritol di (meth) acrylate (a2) in the mixture (A) of the above-mentioned (meth) acrylates (a1) to (a4) is 10 to 50% by weight, the viewpoint of compatibility of hardness and flexibility Outstanding in
상기 (메타)아크릴레이트(a1)∼(a3) 합계에 대한 펜타에리쓰리톨 디(메타)아크릴레이트(a2)의 함유 비율이 15∼55중량%이면, 경도와 굴곡성의 양립의 관점에 의해 뛰어나게 된다.When the content ratio of pentaerythritol di (meth) acrylate (a2) to the total of the (meth) acrylates (a1) to (a3) is 15 to 55% by weight, it is excellent from the viewpoint of compatibility of hardness and flexibility. do.
상기 우레탄(메타)아크릴레이트계 조성물［I］의 중량 평균 분자량이 1,000∼20,000이면 활성 에너지선 경화성 수지 조성물의 취급의 용이함이 뛰어나게 된다.When the weight average molecular weight of the said urethane (meth) acrylate type composition [I] is 1,000-20,000, the ease of handling of an active energy ray curable resin composition will become excellent.
상기 (메타)아크릴레이트(b1)∼(b6)의 혼합물(B) 중의 디펜타에리쓰리톨 펜타(메타)아크릴레이트(b5)의 함유 비율이 15∼60중량%이면, 경도와 굴곡성의 양립에 더욱 뛰어나게 된다.When the content ratio of dipentaerythritol penta (meth) acrylate (b5) in the mixture (B) of the above-mentioned (meth) acrylates (b1) to (b6) is 15 to 60% by weight, both hardness and flexibility are compatible. It's even better.
상기 (메타)아크릴레이트(b1)∼(b5) 합계에 대한 디펜타에리쓰리톨 펜타(메타)아크릴레이트(b5)의 함유 비율이 45∼90중량%이면 경도와 굴곡성의 양립에 더욱 뛰어나게 된다.When the content ratio of dipentaerythritol penta (meth) acrylate (b5) to the total of the (meth) acrylates (b1) to (b5) is 45 to 90% by weight, the hardness and flexibility are more excellent.
상기 (메타)아크릴레이트(b1)∼(b6)의 혼합물(B) 중의 디펜타에리쓰리톨 테트라(메타)아크릴레이트(b4)의 함유 비율이 1∼35중량%이면 굴곡성이 뛰어나게 된다.When the content ratio of dipentaerythritol tetra (meth) acrylate (b4) in the mixture (B) of the (meth) acrylates (b1) to (b6) is 1 to 35% by weight, the flexibility is excellent.
상기 (메타)아크릴레이트(b1)∼(b5) 합계에 대한 디펜타에리쓰리톨 테트라(메타)아크릴레이트(b4)의 함유 비율이 2∼40중량%이면 굴곡성이 더욱 뛰어나게 된다.When the content ratio of dipentaerythritol tetra (meth) acrylate (b4) to the total of the (meth) acrylates (b1) to (b5) is 2 to 40% by weight, the flexibility becomes more excellent.
상기 우레탄(메타)아크릴레이트계 조성물［II］의 중량 평균 분자량이 1,000∼20,000이면 활성 에너지선 경화성 수지 조성물의 취급의 용이함이 뛰어나게 된다.When the weight average molecular weight of the said urethane (meth) acrylate type composition [II] is 1,000-20,000, the ease of handling of an active energy ray curable resin composition will become excellent.
상기 우레탄(메타)아크릴레이트계 조성물［III］의 중량 평균 분자량이 1,000∼20,000이면 활성 에너지선 경화성 수지 조성물의 취급의 용이함이 더욱 뛰어나게 된다.When the weight average molecular weight of the said urethane (meth) acrylate type composition [III] is 1,000-20,000, the ease of handling of an active energy ray curable resin composition will become more excellent.
이하에 본 발명을 상세하게 설명한다.The present invention will be described in detail below.
또한, 본 발명에서 (메타)아크릴은 아크릴 또는 메타크릴을, (메타)아크릴로 일은 아크릴로일 또는 메타크리로일을, (메타)아크릴레이트는 아크릴레이트 또는 메타크릴레이트를 각각 의미하는 것이다.In addition, in this invention, (meth) acryl means acryl or methacryl, what is (meth) acryl is acryloyl or methacryloyl, and (meth) acrylate means an acrylate or methacrylate, respectively.
본 발명의 활성 에너지선 경화성 수지 조성물은 하기 우레탄(메타)아크릴레이트계 조성물［I］와, 우레탄(메타)아크릴레이트계 조성물［I］및［II］와 우레탄(메타)아크릴레이트계 조성물［III］로 이루어진 군으로부터 선택되는 어느 하나의 우레탄(메타)아크릴레이트계 조성물을 함유하는 점에 특징이 있고, 3개의 태양이 있다.The active energy ray curable resin composition of this invention is the following urethane (meth) acrylate type composition [I], urethane (meth) acrylate type composition [I] and [II], and urethane (meth) acrylate type composition [III] It is characteristic in containing any urethane (meth) acrylate type composition chosen from the group which consists of], and there are three aspects.
상기 우레탄(메타)아크릴레이트계 조성물［I］이란, 펜타에리쓰리톨과 (메타)아크릴산과의 반응물인 하기 (메타)아크릴레이트(a1)∼(a4)의 혼합물(A) 중의 (메타)아크릴레이트(a1)∼(a3)와, 다가 이소시아네이트(CA)가 반응하여 이루어진 것이며, 상기 혼합물(A)의 수산기값이 200mgKOH/g 이상이다.The said urethane (meth) acrylate type composition [I] is the (meth) acryl in the mixture (A) of the following (meth) acrylate (a1)-(a4) which is a reactant of pentaerythritol and (meth) acrylic acid The rate (a1)-(a3) and polyhydric isocyanate (CA) react, and the hydroxyl value of the said mixture (A) is 200 mgKOH / g or more.
혼합물(A)Mixture (A)
(a1) 펜타에리쓰리톨 모노(메타)아크릴레이트(a1) pentaerythritol mono (meth) acrylate
(a2) 펜타에리쓰리톨 디(메타)아크릴레이트(a2) pentaerythritol di (meth) acrylate
(a3) 펜타에리쓰리톨 트리(메타)아크릴레이트(a3) pentaerythritol tri (meth) acrylate
(a4) 펜타에리쓰리톨 테트라(메타)아크릴레이트(a4) pentaerythritol tetra (meth) acrylate
상기 우레탄(메타)아크릴레이트계 조성물［II］이란, 디펜타에리쓰리톨과 (메타)아크릴산과의 반응물인 하기 (메타)아크릴레이트(b1)∼(b6)의 혼합물(B) 중의 (메타)아크릴레이트(b1)∼(b5)와, 다가 이소시아네이트(CB)가 반응하여 이루어진 것이며, 상기 혼합물(B)의 수산기값이 40mgKOH/g 이상이다.The said urethane (meth) acrylate type composition [II] is the (meth) in the mixture (B) of the following (meth) acrylate (b1)-(b6) which is a reactant of dipentaerythritol and (meth) acrylic acid The acrylates (b1) to (b5) and the polyvalent isocyanate (CB) react to each other, and the hydroxyl value of the mixture (B) is 40 mgKOH / g or more.
혼합물(B)Mixture (B)
(b1) 디펜타에리쓰리톨 모노(메타)아크릴레이트(b1) dipentaerythritol mono (meth) acrylate
(b2) 디펜타에리쓰리톨 디(메타)아크릴레이트(b2) dipentaerythritol di (meth) acrylate
(b3) 디펜타에리쓰리톨 트리(메타)아크릴레이트(b3) dipentaerythritol tri (meth) acrylate
(b4) 디펜타에리쓰리톨 테트라(메타)아크릴레이트(b4) dipentaerythritol tetra (meth) acrylate
(b5) 디펜타에리쓰리톨 펜타(메타)아크릴레이트(b5) dipentaerythritol penta (meth) acrylate
(b6) 디펜타에리쓰리톨 헥사(메타)아크릴레이트(b6) dipentaerythritol hexa (meth) acrylate
상기 우레탄(메타)아크릴레이트계 조성물［III］이란, 하기［α］인 (메타)아크릴레이트(a1)∼(a3), 하기［β］인 (메타)아크릴레이트(b1)∼(b5), 및, 다가 이소시아네이트(CC)가 반응하여 이루어진 것이다.The said urethane (meth) acrylate type composition [III] is (meth) acrylate (a1)-(a3) which is the following [alpha], (meth) acrylate (b1)-(b5) which is the following [beta], And polyhydric isocyanate (CC) is made by reaction.
［α］펜타에리쓰리톨과 (메타)아크릴산과의 반응물인 하기 (메타)아크릴레이트(a1)∼(a4)의 혼합물(A)의 수산기값이 200mgKOH/g 이상이며, 상기 혼합물(A) 중의 (메타)아크릴레이트(a1)∼(a3).The hydroxyl value of the mixture (A) of the following (meth) acrylate (a1)-(a4) which is a reaction of [(alpha)] pentaerythritol and (meth) acrylic acid is 200 mgKOH / g or more, and in the said mixture (A) (Meth) acrylate (a1)-(a3).
(a1) 펜타에리쓰리톨 모노(메타)아크릴레이트(a1) pentaerythritol mono (meth) acrylate
(a2) 펜타에리쓰리톨 디(메타)아크릴레이트(a2) pentaerythritol di (meth) acrylate
(a3) 펜타에리쓰리톨 트리(메타)아크릴레이트(a3) pentaerythritol tri (meth) acrylate
(a4) 펜타에리쓰리톨 테트라(메타)아크릴레이트(a4) pentaerythritol tetra (meth) acrylate
［β］디펜타에리쓰리톨과 (메타)아크릴산과의 반응물인 하기 (메타)아크릴레이트(b1)∼(b6)의 혼합물(B)의 수산기값이 40mgKOH/g 이상이며, 상기 혼합물(B) 중의 (메타)아크릴레이트(b1)∼(b5).[Beta] The hydroxyl value of the mixture (B) of the following (meth) acrylate (b1)-(b6) which is a reactant of dipentaerythritol and (meth) acrylic acid is 40 mgKOH / g or more, The said mixture (B) (Meth) acrylate (b1)-(b5) in the medium.
(b1) 디펜타에리쓰리톨 모노(메타)아크릴레이트(b1) dipentaerythritol mono (meth) acrylate
(b2) 디펜타에리쓰리톨 디(메타)아크릴레이트(b2) dipentaerythritol di (meth) acrylate
(b3) 디펜타에리쓰리톨 트리(메타)아크릴레이트(b3) dipentaerythritol tri (meth) acrylate
(b4) 디펜타에리쓰리톨 테트라(메타)아크릴레이트(b4) dipentaerythritol tetra (meth) acrylate
(b5) 디펜타에리쓰리톨 펜타(메타)아크릴레이트(b5) dipentaerythritol penta (meth) acrylate
(b6) 디펜타에리쓰리톨 헥사(메타)아크릴레이트(b6) dipentaerythritol hexa (meth) acrylate
＜우레탄(메타)아크릴레이트계 조성물［I］＞ <Urethane (meth) acrylate type composition [I]>
우선, 상기 우레탄(메타)아크릴레이트계 조성물［I］에 대해 설명한다. First, the said urethane (meth) acrylate type composition [I] is demonstrated.
본 발명에서, 상기 펜타에리쓰리톨과 (메타)아크릴산이 반응하여 얻어지는 상기 (메타)아크릴레이트(a1)∼(a4)의 혼합물(A)의 수산기값으로서는, 200mgKOH/g 이상인 것이 필요하고, 바람직하게는 210∼380mgKOH/g, 특히 바람직하게는 230∼320 mgKOH/g이다.In the present invention, the hydroxyl value of the mixture (A) of the above-mentioned (meth) acrylates (a1) to (a4) obtained by the reaction of the pentaerythritol and (meth) acrylic acid is required to be 200 mgKOH / g or more, and is preferable. Preferably 210-380 mgKOH / g, particularly preferably 230-320 mgKOH / g.
이와 같은 혼합물(A)의 수산기값이 너무 작으면, 우레탄(메타)아크릴레이트계 조성물［III］의 중량 평균 분자량이 저하되기 때문에, 경화 시의 경화 수축이 커지는 것으로부터, 컬되기 쉬워지는 경향이 있고, 또한, 굴곡성이 저하되는 경향이 있다. 또한, 통상, 상기 수산기값이 너무 커지면 분자량의 증가에 수반하여 점도가 향상되기 때문에, 취급하기 어려워지는 경향이 있다.When the hydroxyl value of such a mixture (A) is too small, since the weight average molecular weight of urethane (meth) acrylate type composition [III] falls, since the cure shrinkage at the time of hardening becomes large, it becomes easy to curl. Moreover, there exists a tendency for flexibility to fall. Moreover, since the viscosity improves with increase of molecular weight normally, when the said hydroxyl value becomes too large, it exists in the tendency to become difficult to handle.
본 발명에 있어서의 수산기값은 JIS K 0070 1992에 준한 방법에 의해 구할 수 있다.The hydroxyl value in this invention can be calculated | required by the method based on JISK07070 1992.
또, 본 발명에서는, 상기 (메타)아크릴레이트(a1)∼(a4)의 혼합물(A) 중의 펜타에리쓰리톨 디(메타)아크릴레이트(a2)의 함유 비율이 10∼50중량%인 것이 경도와 굴곡성의 양립의 관점에서 바람직하고, 특히 바람직하게는 15∼45중량%, 더욱 바람직하게는 20∼40중량%이다. 이와 같은 함유 비율이 너무 작으면 굴곡성이 저하되는 경향이 있고, 너무 크면 경도가 저하되거나 점도가 증대하거나 하는 경향이 있다.Moreover, in this invention, it is hardness that the content rate of pentaerythritol di (meth) acrylate (a2) in the mixture (A) of said (meth) acrylate (a1)-(a4) is 10-50 weight% It is preferable from the viewpoint of compatibility with and flexibility, Especially preferably, it is 15-45 weight%, More preferably, it is 20-40 weight%. If such a content ratio is too small, there exists a tendency for flexibility to fall, and when too large, there exists a tendency for hardness to fall or a viscosity to increase.
또한, 상기 (메타)아크릴레이트(a1)∼(a3) 합계에 대한 펜타에리쓰리톨 디(메타)아크릴레이트(a2)의 함유 비율이 15∼55중량%인 것이 경도와 굴곡성의 양립의 관점에서 바람직하고, 특히 바람직하게는 20∼50중량%, 더욱 바람직하게는 25∼45중량%이다. 이와 같은 함유 비율이 너무 작으면 굴곡성이 저하되는 경향이 있고, 너무 크면 경도가 저하되거나 점도가 증대하거나 하는 경향이 있다.In addition, it is 15-55 weight% of content of the pentaerythritol di (meth) acrylate (a2) with respect to the said (meth) acrylate (a1)-(a3) total from a viewpoint of compatibility of hardness and flexibility. Preferably it is 20-50 weight%, More preferably, it is 25-45 weight%. If such a content ratio is too small, there exists a tendency for flexibility to fall, and when too large, there exists a tendency for hardness to fall or a viscosity to increase.
본 발명에서는 펜타에리쓰리톨과 (메타)아크릴산을 반응시켜 펜타에리쓰리톨의 (메타)아크릴산 부가물을 조제하지만, 펜타에리쓰리톨과 (메타)아크릴산의 반응에 대해서는, 공지 일반의 방법으로 실시할 수 있다. 이와 같은 반응에서 펜타에리쓰리톨에 대해서 (메타)아크릴산이 한개 부가된 펜타에리쓰리톨 모노(메타)아크릴레이트(a1), 두개 부가된 펜타에리쓰리톨 디(메타)아크릴레이트(a2), 세개 부가된 펜타에리쓰리톨 트리(메타)아크릴레이트(a3), 네개 부가된 펜타에리쓰리톨 테트라(메타)아크릴레이트(a4)가 함유된 혼합물(A)가 얻어지며, 전체적으로 상기의 수산기값을 갖는 혼합물(A)을 얻을 수 있다.In the present invention, pentaerythritol and (meth) acrylic acid are reacted to prepare a (meth) acrylic acid adduct of pentaerythritol.However, the reaction of pentaerythritol and (meth) acrylic acid is carried out by a publicly known method. can do. In this reaction, pentaerythritol mono (meth) acrylate (a1) added with one (meth) acrylic acid to pentaerythritol in this reaction, and pentaerythritol di (meth) acrylate (a2) added with two A mixture (A) containing an added pentaerythritol tri (meth) acrylate (a3) and four added pentaerythritol tetra (meth) acrylates (a4) is obtained, having a hydroxyl value as a whole. Mixture A can be obtained.
또한, 상기 혼합물(A) 중에는, 아크릴산의 미카엘 부가물 등의 부반응 생성물이 포함되는 경우가 있다.In addition, in the said mixture (A), side reaction products, such as the Michael addition product of acrylic acid, may be contained.
수산기값의 조정 시에는, 예를 들면, (메타)아크릴레이트(a1)∼(a4)의 함유 비율을 조정함으로써 실시할 수 있다.At the time of adjustment of a hydroxyl value, it can carry out by adjusting the content rate of (meth) acrylate (a1)-(a4), for example.
본 발명에서, 상기 다가 이소시아네이트(CA)는 상기 (메타)아크릴레이트(a1)∼(a3)와 반응하는 것이며, 구체적으로는, 예를 들면, 톨릴렌디이소시아네이트, 디페닐메탄디이소시아네이트, 폴리페닐메탄폴리이소시아네이트, 변성 디페닐메탄디이소시아네이트, 자일렌디이소시아네이트, 테트라메틸자일렌디이소시아네이트, 페닐렌디이소시아네이트, 나프탈렌디이소시아네이트 등의 방향족계 폴리이소시아네이트；헥사메틸렌디이소시아네이트, 트리메틸헥사메틸렌디이소시아네이트, 라이신디이소시아네이트, 라이신트리이소시아네이트 등의 지방족계 폴리이소시아네이트；수첨화 디페닐메탄디이소시아네이트, 수첨화 자일렌 디이소시아네이트, 이소포론디이소시아네이트, 노르보르넨디이소시아네이트 등의 지환식계 폴리이소시아네이트； 또는 이들 폴리이소시아네이트의 3량체 화합물 또는 다량체 화합물, 아로파네이트형 폴리이소시아네이트, 뷰렛형 폴리이소시아네이트, 수분산형 폴리이소시아네이트(예를 들면, 토소사 제조의 「아쿠아네이트 105」, 「아쿠아네이트 120」, 「아쿠아네이트 210」등 ), 등을 들 수 있다. 이들은 단독으로 또는 2종 이상 함께 사용할 수 있다.In the present invention, the polyvalent isocyanate (CA) is reacted with the (meth) acrylates (a1) to (a3), and specifically, for example, tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane Aromatic polyisocyanates such as polyisocyanate, modified diphenylmethane diisocyanate, xylene diisocyanate, tetramethyl xylene diisocyanate, phenylene diisocyanate, naphthalene diisocyanate; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine Aliphatic polyisocyanates such as triisocyanate; alicyclic polyisocyanates such as hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, isophorone diisocyanate and norbornene diisocyanate; or Terpolymer compound or multimer compound of polyisocyanate, arophanate type polyisocyanate, biuret type polyisocyanate, water dispersion type polyisocyanate (for example, "Aquanate 105", "Aquanate 120" made by Tosoh Corporation, "Aqua" Nate 210 "etc.), etc. are mentioned. These may be used alone or in combination of two or more.
이들 중에서도, 지환식계 폴리이소시아네이트, 방향족계 폴리이소시아네이트인 것이 강도의 관점에서 바람직하고, 특히 바람직하게는, 이소포론디이소시아네이트, 수첨화 자일렌 디이소시아네이트, 자일렌디이소시아네이트, 톨릴렌디이소시아네이트이다.Among these, an alicyclic polyisocyanate and an aromatic polyisocyanate are preferable from a viewpoint of strength, Especially preferably, they are isophorone diisocyanate, hydrogenated xylene diisocyanate, xylene diisocyanate, and tolylene diisocyanate.
본 발명에서 우레탄(메타)아크릴레이트계 조성물［I］은 상기 (메타)아크릴레이트(a1)∼(a4)의 혼합물(A) 중의 (메타)아크릴레이트(a1)∼(a3)의 수산기와, 상기 다가 이소시아네이트(CA)의 이소시아네이트기를 반응시켜서 얻어질 수 있다. 이 경우, 우레탄(메타)아크릴레이트계 조성물［I］에는, (메타)아크릴레이트(a1)와 다가 이소시아네이트(CA)가 반응한 것, (메타)아크릴레이트(a2)와 다가 이소시아네이트(CA)가 반응한 것, (메타)아크릴레이트(a3)와 다가 이소시아네이트(CA)가 반응한 것이 함유되게 되고, 또한, 계 중에는 (메타)아크릴레이트(a1)∼(a3)의 미반응물이나 반응에 관여하지 않는 (메타)아크릴레이트(a4) 등도 함유되게 된다.In this invention, urethane (meth) acrylate type composition [I] is a hydroxyl group of (meth) acrylate (a1)-(a3) in the mixture (A) of said (meth) acrylate (a1)-(a4), It can be obtained by reacting the isocyanate group of the polyvalent isocyanate (CA). In this case, the thing which (meth) acrylate (a1) and polyhydric isocyanate (CA) reacted with urethane (meth) acrylate type composition [I], (meth) acrylate (a2) and polyvalent isocyanate (CA) Reaction, the thing which the (meth) acrylate (a3) and polyvalent isocyanate (CA) reacted, are contained, and the system does not participate in the unreacted material and reaction of (meth) acrylate (a1)-(a3). (Meth) acrylate (a4) etc. which do not contain will be contained.
(메타)아크릴레이트(a1)∼(a3)와 다가 이소시아네이트(CA)와의 반응에서는, 수산기와 이소시아네이트기의 관능기 몰비를 조정하고, 필요에 따라서 후술의 반응 촉매를 사용하여 실시할 수 있다.In reaction of (meth) acrylate (a1)-(a3) and polyhydric isocyanate (CA), the functional group molar ratio of a hydroxyl group and an isocyanate group can be adjusted, and it can carry out using the reaction catalyst mentioned later as needed.
이와 같은 다가 이소시아네이트(CA)와 (메타)아크릴레이트(a1)∼(a4)의 혼합물(A)과의 사입 반응 몰비는, 다가 이소시아네이트(CA)의 이소시아네이트기가 2개인 경우는, 다가 이소시아네이트(CA)：(메타)아크릴레이트 혼합물(A)이 1：1∼1：5인 것이 바람직하고, 특히 바람직하게는 1：1∼1：3, 더욱 바람직하게는 1：1∼1：2이다.The insertion reaction molar ratio of such a polyvalent isocyanate (CA) and a mixture (A) of (meth) acrylates (a1) to (a4) is polyvalent isocyanate (CA) when two isocyanate groups of polyvalent isocyanate (CA) are used. : It is preferable that (meth) acrylate mixture (A) is 1: 1-1: 5, Especially preferably, it is 1: 1-1: 3, More preferably, it is 1: 1-1: 1.
이와 같은 혼합물(A)의 비율이 너무 많으면, 저분자량 모노머가 많아져서, 경화 수축이 커지기 때문에 컬이 커지는 경향이 있고, 혼합물(A)의 비율이 너무 적으면, 미반응의 다가 이소시아네이트(CA)가 잔존하여, 경화 도막의 안정성이나 안전성이 저하되는 경향이 있다.If the ratio of such a mixture (A) is too large, the low molecular weight monomer will increase, and the curing shrinkage will increase, so the curl tends to be large, and if the ratio of the mixture (A) is too small, unreacted polyvalent isocyanate (CA) There exists a tendency for residual to remain and the stability and stability of a cured coating film fall.
(메타)아크릴레이트 혼합물(A) 중의 (메타)아크릴레이트(a1)∼(a3)와 다가 이소시아네이트(CA)와의 반응은 통상, 상기 혼합물(A) 및 다가 이소시아네이트(CA)를 반응기에 일괄 또는 따로 따로 넣어 반응시킬 수 있다.The reaction of (meth) acrylates (a1) to (a3) and polyhydric isocyanate (CA) in the (meth) acrylate mixture (A) usually comprises the mixture (A) and polyvalent isocyanate (CA) in a reactor or separately. Can be reacted separately.
상기 반응에서는 반응을 촉진하는 목적으로 촉매를 사용하는 것도 바람직하고, 이와 같은 촉매로서는, 예를 들면, 디부틸주석디라우레이트, 디부틸주석디아세테이트, 트리메틸주석수산화물, 테트라-n-부틸주석, 비스아세틸아세트네이트아연, 지르코늄트리스(아세틸아세트네이트)에틸아세트아세테이트, 지르코늄테트라아세틸아세트네이트 등의 유기 금속 화합물； 옥틸산 주석, 옥텐산 주석, 헥산산 아연, 옥텐산아연, 스테아린산아연, 2-에틸헥산산 지르코늄, 나프텐산 코발트, 염화제1주석, 염화제2주석, 초산 칼륨 등의 금속염；트리에틸아민, 트리에틸렌디아민, 벤질디에틸아민, 1,4-디아자비시클로［2,2,2］옥탄, 1,8-디아자비시클로［5,4,0］운데센, N,N,N´,N´-테트라메틸-1,3-부탄디아민, N-메틸모르폴린, N-에틸모르폴린 등의 아민계 촉매； 질산 비스무스, 브롬화 비스무스, 요오드화 비스무스, 황화 비스무스 등의 외, 디부틸비스무스디라우레이트, 디옥틸비스무스디라우레이트 등의 유기 비스무스 화합물이나, 2-에틸헥산산 비스무스염, 나프텐산 비스무스염, 이소데칸산 비스무스염, 네오데칸산비스무스염, 라우릴산비스무스염, 밀레인산비스무스염, 스테아린산 비스무스염, 올레인산 비스무스염, 리놀산 비스무스염, 초산 비스무스염, 비스무스 리비스네오데카노에이트, 디살리실산 비스무스염, 디몰식자산 비스무스염 등의 유기산 비스무스 염 등의 비스무스계 촉매 등을 들 수 있고, 이 중에서도, 디부틸주석디라우레이트, 1,8-디아자비시클로［5,4,0］운데센이 매우 적합하다. 이들은 단독으로 또는 2종 이상 함께 사용할 수 있다.In the above reaction, a catalyst is also preferably used for the purpose of promoting the reaction. Examples of such a catalyst include dibutyltin dilaurate, dibutyltin diacetate, trimethyltin hydroxide, tetra-n-butyltin, Organometallic compounds such as bisacetylacetate zinc, zirconium tris (acetylacetate) ethyl acetate, zirconium tetraacetylacetate; tin octylate, tin octenate, zinc hexanoate, zinc octenate, zinc stearate, 2-ethyl Metal salts such as zirconium hexanoate, cobalt naphthenate, stannous chloride, stannous chloride, potassium acetate; triethylamine, triethylenediamine, benzyldiethylamine, 1,4-diazabicyclo [2,2,2 ] Octane, 1,8-diazabicyclo [5,4,0] undecene, N, N, N ', N'-tetramethyl-1,3-butanediamine, N-methylmorpholine, N-ethylmor Amine catalysts such as pauline; bismuth nitrate Organic bismuth compounds such as dibutyl bismuth dilaurate, dioctyl bismuth dilaurate, and other 2-ethylhexanoic acid bismuth salts, naphthenic acid bismuth salts, and isodecanoic acid Bismuth salt, bismuth neodecanoic acid salt, bismuth lauryl acid bismuth salt, bismuth stearic acid salt, bismuth stearate salt, bismuth oleic acid salt, bismuth salt bismuth acetate, bismuth acetate bismuth salt, bismuth bismuth bismuth salt, disalicylic acid bismuth salt Bismuth type catalysts, such as organic acid bismuth salts, such as a bismuth salt, etc. are mentioned, Among these, dibutyltin dilaurate and 1,8- diazabicyclo [5,4,0] undecene are very suitable. These may be used alone or in combination of two or more.
또, 상기 반응에서는, 또한 중합 금지제를 사용하는 것이 바람직하다. 상기 중합 금지제로서는, 중합 금지제로서 사용되고 있는 공지 일반의 것을 사용할 수 있고, 예를 들면, p-벤조퀴논, 나프토퀴논, 톨퀴논, 2,5-디페닐-p-벤조퀴논, 하이드로퀴논, 2,5-디-t-부틸하이드로퀴논, 메틸하이드로퀴논, 모노-t-부틸하이드로퀴논 등의 퀴논류, 4-메톡시페놀, 2,6-디-t-부틸크레졸 등의 방향족류, p-t-부틸카테콜 등을 들 수 있다. 그 중에서도, 방향족류가 바람직하고, 4-메톡시페놀, 2,6-디-t-부틸크레졸이 특히 바람직하다. 이들은 단독으로 또는 2종 이상 함께 사용할 수 있다.Moreover, in the said reaction, it is preferable to use a polymerization inhibitor further. As said polymerization inhibitor, the well-known general thing used as a polymerization inhibitor can be used, For example, p-benzoquinone, naphthoquinone, tolquinone, 2, 5- diphenyl- p-benzoquinone, hydroquinone Quinones such as 2,5-di-t-butylhydroquinone, methylhydroquinone and mono-t-butylhydroquinone, aromatics such as 4-methoxyphenol and 2,6-di-t-butylcresol, pt-butyl catechol etc. are mentioned. Especially, aromatics are preferable and 4-methoxy phenol and 2, 6- di- t-butyl cresol are especially preferable. These may be used alone or in combination of two or more.
또, 상기 반응에서는 이소시아네이트기에 대해 반응하는 관능기를 갖지 않는 유기용제, 예를 들면, 초산에틸, 초산부틸 등의 에스테르류, 메틸에틸케톤, 메틸이소부틸케톤 등의 케톤류, 톨루엔, 자일렌 등의 방향족류 등의 유기용제를 사용할 수 있다. 이들은 단독으로 또는 2종 이상 함께 사용할 수 있다.Moreover, in the said reaction, the organic solvent which does not have a functional group reacting with an isocyanate group, For example, esters, such as ethyl acetate and butyl acetate, ketones, such as methyl ethyl ketone and methyl isobutyl ketone, aromatics, such as toluene and xylene Organic solvents, such as these, can be used. These may be used alone or in combination of two or more.
반응 온도는, 통상 30∼90℃, 바람직하게는 40∼80℃이며, 반응 시간은 통상 4∼72시간, 바람직하게는 8∼48시간이다.The reaction temperature is usually 30 to 90 ° C, preferably 40 to 80 ° C, and the reaction time is usually 4 to 72 hours, preferably 8 to 48 hours.
이렇게 하여 본 발명에서 사용되는 우레탄(메타)아크릴레이트계 조성물［I］이 얻어진다.In this way, urethane (meth) acrylate type composition [I] used by this invention is obtained.
이와 같은 우레탄(메타)아크릴레이트계 조성물［I］의 중량 평균 분자량으로서는 1,000∼20,000인 것이 바람직하고, 특히 바람직하게는 2,000∼18,000, 더욱 바람직하게는 3,000∼16,000이다. 이와 같은 중량 평균 분자량이 너무 작으면 경화 도막이 취약해지는 경향이 있고, 너무 크면 고점도가 되어 취급하기 어려워지는 경향이 있다.As a weight average molecular weight of such urethane (meth) acrylate type composition [I], it is preferable that it is 1,000-20,000, Especially preferably, it is 2,000-18,000, More preferably, it is 3,000-16,000. When such a weight average molecular weight is too small, there exists a tendency for a cured coating film to become weak, and when too large, it becomes high viscosity and it becomes difficult to handle.
또한, 상기 중량 평균 분자량은 표준 폴리스티렌 분자량 환산에 의한 중량 평균 분자량이며, 고속 액체 크로마토 그래프(Waters사 제조, 「ACQUITY APC 시스템」)에, 컬럼：ACQUITY APC XT450를 1개, ACQUITY APC XT200를 1개, ACQUITY APC XT45를 2개의 합계 4개를 직렬로 하여 사용하는 것으로 측정된다.In addition, the said weight average molecular weight is a weight average molecular weight by conversion of a standard polystyrene molecular weight, and a column: ACQUITY APC XT450 one, ACQUITY APC XT200 one in a high performance liquid chromatograph ("ACQUITY APC system" made by Waters) It is measured by using two ACQUITY APC XT45s in series.
상기 우레탄(메타)아크릴레이트계 조성물［I］에 있어서의 우레탄(메타)아크릴레이트의 함유량은 바람직하게는 50중량% 이상, 특히 바람직하게는 60중량% 이상, 더욱 바람직하게는 70중량% 이상, 특히 바람직하게는 80중량% 이상이다. 또한,상한은 통상 95중량%이다.Content of the urethane (meth) acrylate in the said urethane (meth) acrylate type composition [I] becomes like this. Preferably it is 50 weight% or more, Especially preferably, it is 60 weight% or more, More preferably, 70 weight% or more, Especially preferably, it is 80 weight% or more. In addition, an upper limit is 95 weight% normally.
＜우레탄(메타)아크릴레이트계 조성물［II］＞ <Urethane (meth) acrylate type composition [II]>
이어서, 우레탄(메타)아크릴레이트계 조성물［II］에 대해 설명한다.Next, urethane (meth) acrylate type composition [II] is demonstrated.
본 발명에서 상기 디펜타에리쓰리톨과 (메타)아크릴산이 반응하여 얻어지는 상기 (메타)아크릴레이트(b1)∼(b6)의 혼합물(B)의 수산기값으로서는, 40mgKOH/g 이상인 것이 필요하고, 바람직하게는 43∼130mgKOH/g, 특히 바람직하게는 45∼125 mgKOH/g, 더욱 바람직하게는 70∼120mgKOH/g이다.The hydroxyl value of the mixture (B) of the (meth) acrylates (b1) to (b6) obtained by the reaction of the dipentaerythritol and (meth) acrylic acid in the present invention is preferably 40 mgKOH / g or more, and is preferable. Preferably it is 43-130 mgKOH / g, Especially preferably, it is 45-125 mgKOH / g, More preferably, it is 70-120 mgKOH / g.
이와 같은 혼합물(B)의 수산기값이 너무 작으면, 저분자량으로 에틸렌성 불포화기수가 많아, 이소시아네이트와 반응하지 않는 디펜타에리쓰리톨 헥사(메타)아크릴레이트(b6)의 함유량이 많아지기 때문에, 경화 시의 경화 수축이 커지는 것으로부터 컬하기 쉬워지는 경향이 있고, 또한, 굴곡성이 저하되는 경향이 있다. 또한, 통상, 상기 수산기값이 너무 커지면 분자량의 증가에 수반하여 점도가 향상하기 때문에, 취급하기 어려워지는 경향이 있다.When the hydroxyl value of such a mixture (B) is too small, since there are many ethylenically unsaturated groups in low molecular weight, and content of dipentaerythritol hexa (meth) acrylate (b6) which does not react with an isocyanate increases, There exists a tendency for it to curl easily from hardening shrinkage at the time of hardening, and also tend to fall of flexibility. In addition, since the viscosity improves with increase of molecular weight normally when the said hydroxyl value becomes too large, it exists in the tendency to become difficult to handle.
본 발명에서는, 상기 (메타)아크릴레이트(b1)∼(b6)의 혼합물(B) 중의 디펜타에리쓰리톨 펜타(메타)아크릴레이트(b5)의 함유 비율이 15∼60중량%인 것이 경도와 굴곡성의 양립의 관점에서 바람직하고, 특히 바람직하게는 20∼55중량%, 더욱 바람직하게는 25∼55중량%이다. 이와 같은 함유 비율이 너무 작으면 굴곡성이 저하되는 경향이 있고, 너무 크면 경도가 저하되거나 점도가 증대하거나 하는 경향이 있다.In this invention, it is hardness and the content rate of dipentaerythritol penta (meth) acrylate (b5) in the mixture (B) of the said (meth) acrylate (b1)-(b6). It is preferable from a viewpoint of compatibility of flexibility, Especially preferably, it is 20 to 55 weight%, More preferably, it is 25 to 55 weight%. If such a content ratio is too small, there exists a tendency for flexibility to fall, and when too large, there exists a tendency for hardness to fall or a viscosity to increase.
상기 (메타)아크릴레이트(b1)∼(b5) 합계에 대한 디펜타에리쓰리톨 펜타(메타)아크릴레이트(b5)의 함유 비율이 45∼90중량%인 것이 경도와 굴곡성의 양립의 관점에서 바람직하고, 특히 바람직하게는 50∼90중량%, 더욱 바람직하게는 55∼90 중량%이다. 이와 같은 함유 비율이 너무 작으면 굴곡성이 저하되는 경향이 있고, 너무 크면 경도가 저하되거나 점도가 증대하거나 하는 경향이 있다.It is preferable from a viewpoint of compatibility with hardness and flexibility that the content rate of dipentaerythritol penta (meth) acrylate (b5) with respect to the said (meth) acrylate (b1) (b5) total is 45-90 weight%. Especially preferably, it is 50 to 90 weight%, More preferably, it is 55 to 90 weight%. If such a content ratio is too small, there exists a tendency for flexibility to fall, and when too large, there exists a tendency for hardness to fall or a viscosity to increase.
상기 (메타)아크릴레이트(b1)∼(b6)의 혼합물(B) 중의 디펜타에리쓰리톨 테트라(메타)아크릴레이트(b4)의 함유 비율이 1∼35중량%인 것이 굴곡성의 관점에서 바람직하고, 특히 바람직하게는 2∼30중량%, 더욱 바람직하게는 3∼25중량%이다. 이와 같은 함유 비율이 너무 작으면 굴곡성이 저하되는 경향이 있고, 너무 크면 경도가 저하되거나 점도가 증대되거나 하는 경향이 있다.It is preferable from a flexible viewpoint that the content rate of dipentaerythritol tetra (meth) acrylate (b4) in the mixture (B) of the said (meth) acrylate (b1)-(b6) is 1 to 35 weight%. Especially preferably, it is 2-30 weight%, More preferably, it is 3-25 weight%. If such a content ratio is too small, there exists a tendency for flexibility to fall, and when too large, there exists a tendency for hardness to fall or a viscosity to increase.
상기 (메타)아크릴레이트(b1)∼(b5) 합계에 대한 디펜타에리쓰리톨 테트라(메타)아크릴레이트(b4)의 함유 비율이 2∼40중량%인 것이 굴곡성의 관점에서 바람직하고, 특히 바람직하게는 3∼35중량%, 더욱 바람직하게는 4∼30중량%이다. 이와 같은 함유 비율이 너무 작으면 굴곡성이 저하되는 경향이 있고, 너무 크면 경도가 저하되거나 점도가 증대하거나 하는 경향이 있다.It is preferable from a viewpoint of flexibility that the content rate of dipentaerythritol tetra (meth) acrylate (b4) with respect to the said (meth) acrylate (b1)-(b5) total is 2-40 weight%, and it is especially preferable. Preferably it is 3 to 35 weight%, More preferably, it is 4 to 30 weight%. If such a content ratio is too small, there exists a tendency for flexibility to fall, and when too large, there exists a tendency for hardness to fall or a viscosity to increase.
본 발명에서는, 디펜타에리쓰리톨과 (메타)아크릴산을 반응시켜서 디펜타에리쓰리톨의 (메타)아크릴산 부가물을 조제하지만, 디펜타에리쓰리톨과 (메타)아크릴산과의 반응에서는, 공지 일반의 방법으로 실시할 수 있다. 이와 같은 반응에서, 디펜타에리쓰리톨에 대해서 (메타)아크릴산이 한개 부가된 디펜타에리쓰리톨 모노(메타)아크릴레이트(b1), 두개 부가된 디펜타에리쓰리톨 디(메타)아크릴레이트(b2), 세개 부가된 디펜타에리쓰리톨 트리(메타)아크릴레이트(b3), 네개 부가된 디펜타에리쓰리톨 테트라(메타)아크릴레이트(b4), 다섯개 부가된 디펜타에리쓰리톨 펜타(메타)아크릴레이트(b5), 여섯개 부가된 디펜타에리쓰리톨 헥사(메타)아크릴레이트(b6)가 함유된 혼합물(B)을 얻을 수 있고, 전체적으로 상기의 수산기값을 만족하는 혼합물(B)을 얻을 수 있다.In the present invention, dipentaerythritol and (meth) acrylic acid are reacted to prepare a (meth) acrylic acid adduct of dipentaerythritol. However, in the reaction between dipentaerythritol and (meth) acrylic acid, it is well known in general. It can be carried out by the method. In this reaction, dipentaerythritol mono (meth) acrylate (b1) having one added (meth) acrylic acid to dipentaerythritol and dipentaerythritol di (meth) acrylate added with two ( b2), three added dipentaerythritol tri (meth) acrylates (b3), four added dipentaerythritol tetra (meth) acrylates (b4), five added dipentaerythritol penta (meth) ) A mixture (B) containing acrylate (b5) and six added dipentaerythritol hexa (meth) acrylates (b6) can be obtained, and a mixture (B) which satisfies the hydroxyl value as a whole is obtained. You can get it.
또한, 상기 혼합물(B) 중에는, 아크릴산의 미카엘 부가물 등의 부반응 생성물이 포함되는 경우가 있다.In addition, the said mixture (B) may contain side reaction products, such as the Michael addition product of acrylic acid.
수산기값의 조정 시에는, 예를 들면, (메타)아크릴레이트(b1)∼(b6)의 함유 비율을 조정함으로써 실시할 수 있다.At the time of adjustment of a hydroxyl value, it can carry out by adjusting the content rate of (meth) acrylate (b1)-(b6), for example.
본 발명에서 상기 다가 이소시아네이트(CB)는 상기 (메타)아크릴레이트(b1)∼(b5)와 반응하는 것이며, 구체적으로는, 상기에서 설명한 다가 이소시아네이트(CA)와 같은 것을 예시할 수 있다. 상기 다가 이소시아네이트(CB)는 상기 다가 이소시아네이트(CA)와 같거나 다를 수 있다.In this invention, the said polyvalent isocyanate (CB) reacts with the said (meth) acrylate (b1)-(b5), Specifically, the thing similar to the polyvalent isocyanate (CA) demonstrated above can be illustrated. The polyvalent isocyanate (CB) may be the same as or different from the polyvalent isocyanate (CA).
또, 다가 이소시아네이트(CB)로서 상기 폴리이소시아네이트와 폴리올과의 반응물일 수 있다. 이러한 폴리올로서는, 예를 들면, 저분자량의 폴리올이나 고분자량의 폴리올, 구체적으로는, 폴리에테르계 폴리올, 폴리에스테르계 폴리올, 폴리카보네이트계 폴리올, 폴리부타디엔계 폴리올, 에틸렌·이소프렌·부타디엔 등을 반응하여 얻어지는 폴리올레핀계 폴리올 또는 그 수첨화물, 상기 이외의 폴리올레핀계 폴리올, (메타)아크릴계 폴리올 등을 들 수 있다.The polyisocyanate (CB) may also be a reactant of the polyisocyanate with the polyol. As such a polyol, for example, a low molecular weight polyol or a high molecular weight polyol, specifically, a polyether polyol, a polyester polyol, a polycarbonate polyol, a polybutadiene polyol, ethylene isoprene, butadiene or the like is reacted. The polyolefin type polyol obtained by the above, or the hydrogenated compound thereof, the polyolefin type polyol of that excepting the above, a (meth) acrylic polyol, etc. are mentioned.
이들 다가 이소시아네이트(CB) 중 에서도, 지환식계 폴리이소시아네이트, 방향족계 폴리이소시아네이트인 것이 내후성과 강도의 관점에서 바람직하고, 특히 바람직하게는, 이소포론 디이소시아네이트, 수첨화 자일렌디이소시아네이트, 자일렌디이소시아네이트, 톨릴렌디이소시아네이트이다.Among these polyvalent isocyanates (CB), alicyclic polyisocyanates and aromatic polyisocyanates are preferred from the viewpoint of weatherability and strength, and particularly preferably isophorone diisocyanate, hydrogenated xylene diisocyanate, xylene diisocyanate, tolyl Rendiisocyanate.
본 발명에서, 우레탄(메타)아크릴레이트계 조성물［II］은 상기 (메타)아크릴레이트(b1)∼(b6)의 혼합물(B) 중의 (메타)아크릴레이트(b1)∼(b5)의 수산기와,상기 다가 이소시아네이트(CB)의 이소시아네이트기를 반응시켜서 얻을 수 있다. 이 경우, 우레탄(메타)아크릴레이트계 조성물［II］에는, (메타)아크릴레이트(b1)와 다가 이소시아네이트(CB)가 반응한 것, (메타)아크릴레이트(b2)와 다가 이소시아네이트(CB)가 반응한 것, (메타)아크릴레이트(b3)와 다가 이소시아네이트(CB)가 반응한 것, (메타)아크릴레이트(b4)와 다가 이소시아네이트(CB)가 반응한 것, (메타)아크릴레이트(b5)와 다가 이소시아네이트(CB)가 반응한 것이 함유되게 되며, 또한, 계 중에는 (메타)아크릴레이트(b1)∼(b5)의 미반응물이나 반응에 관여하지 않는 (메타)아크릴레이트(b6) 등도 함유되게 된다.In this invention, urethane (meth) acrylate type composition [II] is a hydroxyl group of (meth) acrylate (b1)-(b5) in the mixture (B) of said (meth) acrylate (b1)-(b6). It can obtain by making the isocyanate group of the said polyvalent isocyanate (CB) react. In this case, the thing which (meth) acrylate (b1) and polyhydric isocyanate (CB) reacted with urethane (meth) acrylate type composition [II], (meth) acrylate (b2) and polyvalent isocyanate (CB) Reacted, reacted (meth) acrylate (b3) with polyvalent isocyanate (CB), reacted (meth) acrylate (b4) with polyvalent isocyanate (CB), (meth) acrylate (b5) And the polyhydric isocyanate (CB) reacted, and the system also contains unreacted materials of (meth) acrylates (b1) to (b5) and (meth) acrylates (b6) not involved in the reaction. do.
이와 같은 다가 이소시아네이트(CB)와 (메타)아크릴레이트(b1)∼(b6)의 혼합물(B)과의 사입 반응 몰비는, 예를 들면, 다가 이소시아네이트(CB)의 이소시아네이트기가 2개인 경우는, 다가 이소시아네이트(CB)：(메타)아크릴레이트 혼합물(B)이 1：1∼1：5인 것이 바람직하고, 특히 바람직하게는 1：1∼1：4, 더욱 바람직하게는 1：1∼1：3이다.The insertion reaction molar ratio of such a polyvalent isocyanate (CB) and a mixture (B) of (meth) acrylates (b1) to (b6) is, for example, when two isocyanate groups of polyvalent isocyanate (CB) are polyvalent. It is preferable that an isocyanate (CB) :( meth) acrylate mixture (B) is 1: 1-1: 5, Especially preferably, it is 1: 1-1: 4, More preferably, it is 1: 1: 1: 3. to be.
이와 같은 혼합물(B)의 비율이 너무 많으면, 저분자량 모노머가 많아져 경화 수축이 커지기 때문에 컬이 커지는 경향이 있고, 혼합물(B)의 비율이 너무 적으면, 미반응의 다가 이소시아네이트(CB)가 잔존하여 경화 도막의 안정성이나 안전성이 저하되는 경향이 있다.If the ratio of such a mixture (B) is too large, the curling tends to be large because the low molecular weight monomer increases and the curing shrinkage increases, and if the ratio of the mixture (B) is too small, unreacted polyvalent isocyanate (CB) There exists a tendency which remain | survives and the stability and stability of a cured coating film fall.
(메타)아크릴레이트 혼합물(B) 중의 (메타)아크릴레이트(b1)∼(b5)와 다가 이소시아네이트(CB)와의 반응은 통상, 상기 혼합물(B) 및 다가 이소시아네이트(CB)를, 반응기에 일괄 또는 따로 따로 사입하여 반응시킬 수 있다.The reaction of (meth) acrylates (b1) to (b5) and polyhydric isocyanate (CB) in the (meth) acrylate mixture (B) usually includes the mixture (B) and polyvalent isocyanate (CB) in a batch or in a reactor. It can be injected separately and reacted.
상기 반응에서는, 반응을 촉진할 목적으로 촉매를 사용하는 것도 바람직하고, 이와 같은 촉매로서는, 상기 우레탄(메타)아크릴레이트계 조성물［I］에서 설명한 것과 같은 것을 예시할 수 있다.In the said reaction, it is also preferable to use a catalyst for the purpose of promoting reaction, and as such a catalyst, the same thing as what was demonstrated by the said urethane (meth) acrylate type composition [I] can be illustrated.
또, 상기 반응에서는 중합 금지제, 이소시아네이트기에 대해 반응하는 관능기를 갖지 않는 유기용제를 사용하는 경우에 대해서도, 상기 우레탄(메타)아크릴레이트계 조성물［I］에서 설명한 것과 같은 것을 예시할 수 있다.Moreover, in the said reaction, the thing similar to what was demonstrated by the said urethane (meth) acrylate type composition [I] can be illustrated also when using the organic inhibitor which does not have a polymerization inhibitor and the functional group which reacts with an isocyanate group.
또, 우레탄(메타)아크릴레이트계 조성물［II］의 조제에서는, 상기 우레탄(메타)아크릴레이트계 조성물［I］의 조제에 준하여 실시할 수 있다.Moreover, in preparation of urethane (meth) acrylate type composition [II], it can carry out according to preparation of the said urethane (meth) acrylate type composition [I].
이렇게 하여 본 발명에서 사용되는 우레탄(메타)아크릴레이트계 조성물［II］이 얻어진다.In this way, urethane (meth) acrylate type composition [II] used by this invention is obtained.
이와 같은 우레탄(메타)아크릴레이트계 조성물［II］의 중량 평균 분자량으로서는 1,000∼20,000인 것이 바람직하고, 더욱 바람직하게는 1,500∼18,000, 특히 바람직하게는 2,000∼16,000이다. 이와 같은 중량 평균 분자량이 너무 작으면 경화 도막이 취약해지는 경향이 있고, 너무 크면 고점도가 되어 취급하기 어려워지는 경향이 있다. As weight average molecular weight of such urethane (meth) acrylate type composition [II], it is preferable that it is 1,000-20,000, More preferably, it is 1,500-18,000, Especially preferably, it is 2,000-16,000. When such a weight average molecular weight is too small, there exists a tendency for a cured coating film to become weak, and when too large, it becomes high viscosity and it becomes difficult to handle.
또한, 상기의 중량 평균 분자량의 측정법이란, 상기 측정법과 같다.In addition, the measuring method of said weight average molecular weight is the same as the said measuring method.
이와 같은 우레탄(메타)아크릴레이트계 조성물［II］의 60℃에 있어서의 점도는 1,000∼300,000mPa·s인 것이 바람직하고, 특히 바람직하게는 1,500∼200,000 ma·s, 더욱 바람직하게는 2,000∼100,000mPa·s이다. 이와 같은 점도가 상기 범위 외에서는 도공성이 저하되는 경향이 있다. It is preferable that the viscosity at 60 degrees C of such urethane (meth) acrylate type composition [II] is 1,000-300,000 mPa * s, Especially preferably, 1,500-200,000 ma * s, More preferably, 2,000-100,000 mPa · s. There exists a tendency for such viscosity to fall in coating property out of the said range.
또한, 60℃에 있어서의 점도의 측정법은 E형 점도계에 의한다.In addition, the measuring method of the viscosity in 60 degreeC is an E-type viscosity meter.
상기 우레탄(메타)아크릴레이트계 조성물［II］에 있어서의 우레탄(메타)아크릴레이트의 함유량은 바람직하게는 35중량% 이상, 특히 바람직하게는 40중량% 이상, 더욱 바람직하게는 45중량% 이상, 특히 바람직하게는 50중량% 이상, 더욱 바람직하게는 60중량% 이상이다. 또한, 상한은 통상 95중량%이다.Content of the urethane (meth) acrylate in the said urethane (meth) acrylate type composition [II] becomes like this. Preferably it is 35 weight% or more, Especially preferably, it is 40 weight% or more, More preferably, 45 weight% or more, Especially preferably, it is 50 weight% or more, More preferably, it is 60 weight% or more. In addition, an upper limit is 95 weight% normally.
＜우레탄(메타)아크릴레이트계 조성물［III］＞ <Urethane (meth) acrylate type composition [III]>
또한, 우레탄(메타)아크릴레이트계 조성물［III］에 대해 설명한다.Moreover, urethane (meth) acrylate type composition [III] is demonstrated.
〈혼합물(A)〉 <Mixture (A)>
우선, 우레탄(메타)아크릴레이트계 조성물［III］의 구성 재료인 (메타)아크릴레이트(a1)∼(a3)를 포함한, 혼합물(A)에 대해 설명한다.First, the mixture (A) containing (meth) acrylate (a1)-(a3) which is a structural material of urethane (meth) acrylate type composition [III] is demonstrated.
혼합물(A)은 상기 펜타에리쓰리톨과 (메타)아크릴산이 반응하여 얻어지는 상기 (메타)아크릴레이트(a1)∼(a4)의 혼합물이며, 그 수산기값으로서는, 200 mgKOH/g 이상인 것이 필요하고, 바람직하게는 210∼380mgKOH/g, 특히 바람직하게는 230∼320mgKOH/g이다.The mixture (A) is a mixture of the above-mentioned (meth) acrylates (a1) to (a4) obtained by the reaction of the pentaerythritol and (meth) acrylic acid, and the hydroxyl value needs to be 200 mgKOH / g or more, Preferably it is 210-380 mgKOH / g, Especially preferably, it is 230-320 mgKOH / g.
상기 혼합물(A)에 대해서는, 상기 우레탄(메타)아크릴레이트계 조성물［I］로 설명한 것과 같은 것을 예시할 수 있다.About the said mixture (A), the thing similar to what was demonstrated by the said urethane (meth) acrylate type composition [I] can be illustrated.
상기 혼합물(A) 중에서, 수산기를 갖는 (메타)아크릴레이트(a1)∼(a3)가 후술의 다가 이소시아네이트(CC)와 반응하게 된다.In the said mixture (A), (meth) acrylate (a1)-(a3) which has a hydroxyl group will react with the polyhydric isocyanate (CC) mentioned later.
〈혼합물(B)〉 <Mixture (B)>
이어서, 우레탄(메타)아크릴레이트계 조성물［III］의 구성 재료인 (메타)아크릴레이트(b1)∼(b5)를 포함한 혼합물(B)에 대해 설명한다. 혼합물(B)은 상기 디펜타에리쓰리톨과 (메타)아크릴산이 반응하여 얻어지는 상기 (메타)아크릴레이트(b1)∼(b6)의 혼합물이며, 그 수산기값으로서는, 40mgKOH/g 이상인 것이 필요하고, 바람직하게는 43∼130mgKOH/g, 특히 바람직하게는 45∼125mgKOH/g, 더욱 바람직하게는 70∼120mgKOH/g이다.Next, the mixture (B) containing (meth) acrylate (b1)-(b5) which is a structural material of urethane (meth) acrylate type composition [III] is demonstrated. The mixture (B) is a mixture of the above-mentioned (meth) acrylates (b1) to (b6) obtained by reacting the dipentaerythritol with (meth) acrylic acid, and the hydroxyl value needs to be 40 mgKOH / g or more, Preferably it is 43-130 mgKOH / g, Especially preferably, it is 45-125 mgKOH / g, More preferably, it is 70-120 mgKOH / g.
상기 혼합물(B)에 대해서는, 상기 우레탄(메타)아크릴레이트계 조성물［II］에서 설명한 것과 같은 것을 예시할 수 있다.About the said mixture (B), the thing similar to what was demonstrated by the said urethane (meth) acrylate type composition [II] can be illustrated.
상기 혼합물(B) 중에서, 수산기를 갖는 (메타)아크릴레이트(b1)∼(b5)가 하기 다가 이소시아네이트(CC)와 반응하게 된다.In the said mixture (B), the (meth) acrylate (b1)-(b5) which has a hydroxyl group will react with the following polyvalent isocyanate (CC).
〈다가 이소시아네이트(CC)〉 <Polyvalent isocyanate (CC)>
이어서, 우레탄(메타)아크릴레이트계 조성물［III］의 구성 재료인 다가 이소시아네이트(CC)에 대해 설명한다.Next, the polyvalent isocyanate (CC) which is a structural material of urethane (meth) acrylate type composition [III] is demonstrated.
본 발명에서 상기 다가 이소시아네이트(CC)는 수산기 함유의 (메타)아크릴레이트, 즉, 상기 (메타)아크릴레이트(a1)∼(a3) 및 (메타)아크릴레이트(b1)∼(b5)와 반응하는 것이며, 구체적으로는, 상기 우레탄(메타)아크릴레이트계 조성물［I］에서 설명한 다가 이소시아네이트(CA), 및 상기 우레탄(메타)아크릴레이트계 조성물［II］에서 설명한 다가 이소시아네이트(CB)와 같은 것을 예시할 수 있다. 상기 다가 이소시아네이트(CC)는, 상기 다가 이소시아네이트(CA) 또는 다가 이소시아네이트(CB)와 같거나 다를 수 있다.In the present invention, the polyhydric isocyanate (CC) is reacted with a (meth) acrylate containing a hydroxyl group, that is, the (meth) acrylates (a1) to (a3) and (meth) acrylates (b1) to (b5). Specific examples thereof include polyhydric isocyanates (CA) described in the urethane (meth) acrylate-based composition [I] and polyhydric isocyanates (CB) described in the urethane (meth) acrylate-based composition [II]. can do. The polyvalent isocyanate (CC) may be the same as or different from the polyvalent isocyanate (CA) or polyvalent isocyanate (CB).
또한, 상기 다가 이소시아네이트(CC), 상기 다가 이소시아네이트(CA) 및 다가 이소시아네이트(CB)를 정리하여 「다가 이소시아네이트(C)」라고 하기도 한다.In addition, the said polyvalent isocyanate (CC), the said polyvalent isocyanate (CA), and polyvalent isocyanate (CB) are collectively called "polyvalent isocyanate (C)."
본 발명에서는, 상기 (메타)아크릴레이트(a1)∼(a4)의 혼합물(A) 중의 (메타)아크릴레이트(a1)∼(a3)의 수산기와, 상기 (메타)아크릴레이트(b1)∼(b6)의 혼합물(B) 중의 (메타)아크릴레이트(b1)∼(b5)의 수산기와, 상기 다가 이소시아네이트(CC)의 이소시아네이트기를 반응시켜서, 우레탄(메타)아크릴레이트계 조성물［III］를 얻을 수 있다. 이 경우, 우레탄(메타)아크릴레이트계 조성물［III］에는, (메타)아크릴레이트(a1)와 다가 이소시아네이트(CC)가 반응한 것, (메타)아크릴레이트(a2)와 다가 이소시아네이트(CC)가 반응한 것, (메타)아크릴레이트(a3)와 다가 이소시아네이트(CC)가 반응한 것, 또한, (메타)아크릴레이트(b1)와 다가 이소시아네이트(CC)가 반응한 것, (메타)아크릴레이트(b2)와 다가 이소시아네이트(CC)가 반응한 것, (메타)아크릴레이트(b3)와 다가 이소시아네이트(CC)가 반응한 것, (메타)아크릴레이트(b4)와 다가 이소시아네이트(CC)가 반응한 것, (메타)아크릴레이트(b5)와 다가 이소시아네이트(CC)가 반응한 것, (a1)∼(a3) 및 (메타)아크릴레이트(b1)∼(b5)가 혼재하여 다가 이소시아네이트(CC)와 반응한 것 등이 함유되게 되어, 또한, 계 중에는 (메타)아크릴레이트(a1)∼(a3) 및 (b1)∼(b5)의 미반응물이나 반응에 관여하지 않는 (메타)아크릴레이트(a4) 및 (b6) 등도 함유되게 된다.In this invention, the hydroxyl group of (meth) acrylate (a1)-(a3) in the mixture (A) of said (meth) acrylate (a1)-(a4), and the said (meth) acrylate (b1)-( Urethane (meth) acrylate type composition [III] can be obtained by making the hydroxyl group of (meth) acrylate (b1)-(b5) in the mixture (B) of b6) react with the isocyanate group of the said polyvalent isocyanate (CC). have. In this case, the thing which (meth) acrylate (a1) and polyvalent isocyanate (CC) reacted with urethane (meth) acrylate type composition [III], (meth) acrylate (a2) and polyvalent isocyanate (CC) Reacted, reacted (meth) acrylate (a3) with polyvalent isocyanate (CC), reacted (meth) acrylate (b1) with polyvalent isocyanate (CC), (meth) acrylate ( b2) and polyvalent isocyanate (CC) reacted, (meth) acrylate (b3) and polyvalent isocyanate (CC) reacted, (meth) acrylate (b4) and polyvalent isocyanate (CC) reacted , (Meth) acrylate (b5) and polyvalent isocyanate (CC) react, (a1) to (a3) and (meth) acrylate (b1) to (b5) are mixed and react with polyvalent isocyanate (CC) One or the like, and further, in the system, (meth) acrylates (a1) to (a3) and (b1) to (b5) It does not participate in the reaction water and (meth) acrylate be contained also (a4) and (b6).
(메타)아크릴레이트(a1)∼(a3) 및 (메타)아크릴레이트(b1)∼(b5)와 다가 이소시아네이트(CC)와의 반응에 대해서는, 수산기와 이소시아네이트기의 관능기 몰비를 조정하고, 필요에 따라 후술하는 반응 촉매를 사용하여 실시할 수 있다.About reaction of (meth) acrylate (a1)-(a3) and (meth) acrylate (b1)-(b5) and polyhydric isocyanate (CC), the molar ratio of the functional group of a hydroxyl group and an isocyanate group is adjusted, if necessary. It can carry out using the reaction catalyst mentioned later.
이와 같은 (메타)아크릴레이트(a1)∼(a4)의 혼합물(A)과, (메타)아크릴레이트(b1)∼(b6)의 혼합물(B)과 다가 이소시아네이트(CC)와의 사입 반응 몰비는, 다가 이소시아네이트(CC)의 이소시아네이트기가 2개인 경우는, 다가 이소시아네이트(CC)：(메타)아크릴레이트 혼합물(A)과 (메타)아크릴레이트 혼합물(B)의 합계가 1：1∼1：5인 것이 바람직하고, 특히 바람직하게는 1：1∼1：3, 더욱 바람직하게는 1：1∼1：2이다. 또, (메타)아크릴레이트 혼합물(A)：(메타)아크릴레이트 혼합물(B)이중*로, 90：10∼10：90인 것이 바람직하고, 특히 바람직하게는 70：30∼15：85, 더욱 바람직하게는 50：50∼20：80이다.The insertion reaction molar ratio of the mixture (A) of such (meth) acrylate (a1)-(a4), the mixture (B) of (meth) acrylate (b1)-(b6), and polyhydric isocyanate (CC), When there are two isocyanate groups of polyvalent isocyanate (CC), the sum total of polyvalent isocyanate (CC) :( meth) acrylate mixture (A) and (meth) acrylate mixture (B) is 1: 1: 1: 5. It is preferable, particularly preferably 1: 1 to 1: 3, more preferably 1: 1 to 1: 2. Moreover, it is preferable that it is 90: 10-10: 90 in (meth) acrylate mixture (A) :( meth) acrylate mixture (B) double *, Especially preferably, it is 70: 30-15: 85, More Preferably it is 50: 50-20: 80.
다가 이소시아네이트(CC)에 대한, 혼합물(A)과 혼합물(B)의 합계의 비율이 너무 많으면, 저분자량 모노머가 많아져, 경화 수축이 커지기 때문에 컬이 커지는 경향이 있고, 혼합물(A)과 혼합물(B)의 합계의 비율이 너무 적으면, 미반응의 다가 이소시아네이트(CC)가 잔존하여, 경화 도막의 안정성이나 안전성이 저하되는 경향이 있다.When the ratio of the sum total of the mixture (A) and the mixture (B) with respect to a polyisocyanate (CC) is too large, there will be many low molecular weight monomers and it will become large curling because a cure shrinkage becomes large, and the mixture (A) and a mixture When the ratio of the sum total of (B) is too small, unreacted polyvalent isocyanate (CC) will remain and there exists a tendency for the stability and safety of a cured coating film to fall.
혼합물(A)에 대한 혼합물(B)의 비율이 너무 많으면, 저분자량 모노머가 많아져, 경화 수축이 커지기 때문에 컬이 커지는 경향이 있고, 혼합물(B)의 비율이 너무 적으면, 경도 및 찰상성이 저하되는 경향이 있다.If the ratio of the mixture (B) to the mixture (A) is too large, the low molecular weight monomer will increase, and the curing shrinkage will increase, so the curl tends to be large, and if the ratio of the mixture (B) is too small, hardness and scratches This tends to be lowered.
(메타)아크릴레이트 혼합물(A) 중의 (메타)아크릴레이트(a1)∼(a3)와 (메타)아크릴레이트 혼합물(B) 중의 (메타)아크릴레이트(b1)∼(b5)와 다가 이소시아네이트(CC)와의 반응은 통상, 상기 혼합물(A), 혼합물(B) 및 다가 이소시아네이트(CC)를, 반응기에 일괄 또는 따로 따로 넣어 반응시킬 수 있다.(Meth) acrylates (a1) to (a3) in the (meth) acrylate mixture (A) and (meth) acrylates (b1) to (b5) and polyvalent isocyanates (CC) in the (meth) acrylate mixture (B) In the reaction with), the mixture (A), the mixture (B) and the polyvalent isocyanate (CC) can be reacted in a batch or separately.
상기 반응에서는, 반응을 촉진하는 목적으로 촉매를 사용하는 것도 바람직하고, 이와 같은 촉매로서는, 상기 우레탄(메타)아크릴레이트계 조성물［I］에서 설명한 것과 같은 것을 예시할 수 있다.In the said reaction, it is also preferable to use a catalyst for the purpose of promoting reaction, and as such a catalyst, the thing similar to what was demonstrated by the said urethane (meth) acrylate type composition [I] can be illustrated.
또, 상기 반응에서는, 중합 금지제, 이소시아네이트기에 대해 반응하는 관능기를 갖지 않는 유기용제를 사용하는 경우에 대해서도, 상기 우레탄(메타)아크릴레이트계 조성물［I］에서 설명한 것과 같은 것을 예시할 수 있다.Moreover, in the said reaction, also when using the organic inhibitor which does not have a functional inhibitor which reacts with a polymerization inhibitor and an isocyanate group, the thing similar to what was demonstrated by the said urethane (meth) acrylate type composition [I] can be illustrated.
또, 우레탄(메타)아크릴레이트계 조성물［III］의 조제에서는, 상기 우레탄(메타)아크릴레이트계 조성물［I］의 조제에 준하여 실시할 수 있다.Moreover, in preparation of urethane (meth) acrylate type composition [III], it can carry out according to preparation of the said urethane (meth) acrylate type composition [I].
이렇게 하여, 상기［α］의 (메타)아크릴레이트(a1)∼(a3), 상기［β］의 (메타)아크릴레이트(b1)∼(b5), 및, 다가 이소시아네이트(CC)를 반응시켜서 이루어진 우레탄(메타)아크릴레이트계 조성물［III］를 얻을 수 있다.In this way, it is made by making (meth) acrylate (a1)-(a3) of said [(alpha)], (meth) acrylate (b1)-(b5) of said [(beta)], and polyvalent isocyanate (CC) react. Urethane (meth) acrylate type composition [III] can be obtained.
본 발명에서는, 또한, 폴리올도 함유시켜서, 다가 이소시아네이트(CC)와 반응시키고,［α］의 (메타)아크릴레이트(a1)∼(a3),［β］의 (메타)아크릴레이트(b1)∼(b5), 다가 이소시아네이트(CC) 및 폴리올로 이루어진 우레탄(메타)아크릴레이트계 조성물［III］이 얻어진다.In the present invention, the polyol is also contained, reacted with polyvalent isocyanate (CC), and (meth) acrylates (a1) to (a3) of [α], and (meth) acrylates (b1) to [β] to (b5), urethane (meth) acrylate type composition [III] which consists of polyhydric isocyanate (CC) and a polyol is obtained.
상기 폴리올로서는, 예를 들면, 저분자량의 폴리올이나 고분자량의 폴리올, 구체적으로는, 폴리 에테르계 폴리올, 폴리에스테르계 폴리올, 폴리카보네이트계 폴리올, 에틸렌·이소프렌·부타디엔 등을 반응하여 얻어지는 폴리올레핀계 폴리올 또는 그 수첨화물, 상기 이외의 폴리올레핀계 폴리올, (메타)아크릴계 폴리올 등의 폴리올 등을 들 수 있다.As said polyol, for example, a low molecular weight polyol or a high molecular weight polyol, specifically, a polyolefin polyol obtained by reacting a polyether polyol, a polyester polyol, a polycarbonate polyol, ethylene isoprene, butadiene or the like Or polyols, such as the hydrogenated substance, polyolefin polyol of that excepting the above, and a (meth) acrylic polyol, etc. are mentioned.
이와 같은 우레탄(메타)아크릴레이트계 조성물［III］의 중량 평균 분자량으로서는 1,000∼20,000인 것이 바람직하고, 더욱 바람직하게는 2,000∼15,000, 특히 바람직하게는 3,000∼12,000, 특히 바람직하게는 4,000∼10,000이다. 이와 같은 중량 평균 분자량이 너무 작으면 경화 도막이 취약해지는 경향이 있고, 너무 크면 고점도가 되어 취급하기 어려워지는 경향이 있다.As weight average molecular weight of such urethane (meth) acrylate type composition [III], it is preferable that it is 1,000-20,000, More preferably, it is 2,000-15,000, Especially preferably, it is 3,000-12,000, Especially preferably, it is 4,000-10,000. . When such a weight average molecular weight is too small, there exists a tendency for a cured coating film to become weak, and when too large, it becomes high viscosity and it becomes difficult to handle.
또한, 상기 중량 평균 분자량은, 표준 폴리스티렌 분자량 환산에 의한 중량 평균 분자량이며, 고속 액체 크로마토 그래프(Waters사 wph,「ACQUITY APC 시스템」)에, 컬럼：ACQUITY APC XT450를 1개, ACQUITY APC XT200를 1개, ACQUITY APC XT45를 2개의 합계 4개를 직렬로 하여 사용하는 것으로 측정된다.In addition, the said weight average molecular weight is a weight average molecular weight by conversion of a standard polystyrene molecular weight, and a column: ACQUITY APC XT450 1 and ACQUITY APC XT200 1 in a high performance liquid chromatograph (Waters wph, "ACQUITY APC system") It is measured to use ACQUITY APC XT45 in total of two in total.
상기 우레탄(메타)아크릴레이트계 조성물［III］에 있어서의 우레탄(메타)아크릴레이트의 함유량은 바람직하게는 50중량% 이상, 특히 바람직하게는 60중량% 이상, 더욱 바람직하게는 70중량% 이상, 특히 바람직하게는 80중량% 이상이다. 또한, 상한은 통상 95중량%이다.Content of the urethane (meth) acrylate in the said urethane (meth) acrylate type composition [III] becomes like this. Preferably it is 50 weight% or more, Especially preferably, it is 60 weight% or more, More preferably, 70 weight% or more, Especially preferably, it is 80 weight% or more. In addition, an upper limit is 95 weight% normally.
＜활성 에너지선 경화성 수지 조성물＞ <Active energy ray curable resin composition>
본 발명의 활성 에너지선 경화성 수지 조성물은, 상기 우레탄(메타)아크릴레이트계 조성물［I］를 함유하는 제1 태양(제1 요지에 관한 발명)과, 상기 우레탄(메타)아크릴레이트계 조성물［I］및 우레탄(메타)아크릴레이트계 조성물［II］를 함유하는 제2 태양(제2 요지에 관한 발명)과, 상기 우레탄(메타)아크릴레이트계 조성물［III］를 함유하는 제3 태양(제3 요지에 관한 발명)을 갖는다.The active energy ray curable resin composition of this invention is the 1st aspect (invention which concerns on the 1st summary) containing the said urethane (meth) acrylate type composition [I], and the said urethane (meth) acrylate type composition [I] ] 2nd aspect (invention concerning 2nd summary) containing urethane (meth) acrylate type composition [II], and 3rd aspect containing the said urethane (meth) acrylate type composition [III] (third) Invention related to the subject matter).
상기 제 2의 태양인 활성 에너지선 경화성 수지 조성물은, 상기와 같이 우레탄(메타)아크릴레이트계 조성물［I］및 우레탄(메타)아크릴레이트계 조성물［II］를 함유하여 이루어진 것이다. 이와 같은 우레탄(메타)아크릴레이트계 조성물［I］와 우레탄(메타)아크릴레이트계 조성물［II］의 함유 비율(［I］/［II］)에 대해서는, 중량비로 90/10∼10/90인 것이 바람직하고, 특히 바람직하게는 87/13∼20/80, 더욱 바람직하게는 85/15∼30/70, 특히 바람직하게는 80/20∼55/45, 더더욱 바람직하게는 80/20∼65/35이다. 이와 같은 함유 비율이 너무 작으면 굴곡성이 저하되는 경향이 있고, 너무 크면 경도가 불충분해지는 경향이 있다.The active energy ray-curable resin composition which is the said 2nd aspect is a thing containing urethane (meth) acrylate type composition [I] and urethane (meth) acrylate type composition [II] as mentioned above. About the content ratio ([I] / [II]) of such urethane (meth) acrylate type composition [I] and urethane (meth) acrylate type composition [II], it is 90/10-10/90 by weight ratio. It is preferred, especially preferably 87/13 to 20/80, more preferably 85/15 to 30/70, particularly preferably 80/20 to 55/45, even more preferably 80/20 to 65 / 35. If such a content ratio is too small, there exists a tendency for flexibility to fall, and when too large, there exists a tendency for hardness to become inadequate.
상기 제 1∼3 태양의 본 발명의 활성 에너지선 경화성 수지 조성물(이하 「수지 조성물」이라고 생략하기도 함)에는, 광중합 개시제(D)를 더욱 함유하는 것이 바람직하다. 또, 본 발명의 효과를 해치지 않는 범위에서, 그 외의 우레탄(메타)아크릴레이트, 우레탄(메타)아크릴레이트 이외의 에틸렌성 불포화 모노머, 아크릴 수지, 표면 조정제, 라벨링제, 중합 금지제 등을 첨가할 수 있고, 또한 필러, 염료, 안료, 기름, 가소제, 왁스류, 건조제, 분산제, 습윤제, 겔화제, 안정제, 소포제, 계면활성제, 라벨링제, 칙소트로피성 부여제, 산화 방지제, 난연제, 대전 방지제, 충전제, 보강제, 광제거제, 가교제, 실리카, 수분산 또는 용제 분산된 실리카, 지르코늄 화합물, 방부제 등을 배합하는 것도 가능하다.It is preferable to further contain a photoinitiator (D) in the active-energy-ray-curable resin composition (it may abbreviate as "resin composition" hereafter) of this invention of the said 1st-3rd aspect. In addition, ethylenically unsaturated monomers other than urethane (meth) acrylates and urethane (meth) acrylates, acrylic resins, surface conditioners, labeling agents, polymerization inhibitors, and the like may be added within the scope of not impairing the effects of the present invention. Fillers, dyes, pigments, oils, plasticizers, waxes, desiccants, dispersants, wetting agents, gelling agents, stabilizers, antifoaming agents, surfactants, labeling agents, thixotropic agents, antioxidants, flame retardants, antistatic agents, It is also possible to blend fillers, reinforcing agents, light removers, crosslinking agents, silica, water dispersion or solvent dispersed silica, zirconium compounds, preservatives and the like.
상기 광중합 개시제(D)로서는, 예를 들면, 디에톡시아세트페논, 2-히드록시-2-메틸-1-페닐프로판-1-온, 벤질디메틸 케탈, 4-(2-히드록시에톡시) 페닐-(2-히드록시-2-프로필)케톤, 1-히드록시시클로헥실페닐케톤, 1-［4-(2-히드록시에톡시)-페닐］-2-히드록시-2-메틸-1-프로판-1-온, 2-히드록시-1-｛4-［4-(2-히드록시-2-메틸프로피오닐)-벤질］-페닐｝-2-메틸-프로판, 2-메틸-2-모르폴리노(4-티오메틸페닐) 프로판-1-온, 2-벤질-2-디메틸아미노-1-(4-모르폴리노페닐)부타논, 2-히드록시-2-메틸-1-［4-(1-메틸비닐)페닐］프로파논올리고머 등의 아세트페논류；벤조인, 벤조인메틸에테르, 벤조인에틸에테르, 벤조인이소프로필에테르, 벤조인이소부틸에테르 등의 벤조인류； 벤조페논, o-벤조일안식향산 메틸, 4-페닐벤조페논, 4-벤조일-4´-메틸-디페닐설파이드, 3,3´,4,4´-테트라(t-부틸퍼옥시카르보닐)벤조페논, 2,4, 6-트리메틸벤조페논, 4-벤조일-N,N-디메틸-N-［2-(1-옥소-2-프로페닐옥시)에틸］벤젠메타나미늄브로미드, (4-벤조일벤질)트리메틸암모늄 염화물 등의 벤조페논류；2-이소프로필티옥산톤, 4-이소프로필티옥산톤, 2,4-디에틸티옥산톤, 2,4-디클로로티옥산톤, 1-클로로-4-프로폭시티옥산톤, 2-(3-디메틸아미노-2-히드록시)-3,4-디메틸-9H-티옥산톤-9-온메소클로리드 등의 티옥산톤류；2,4,6-트리메틸벤조일-디페닐포스핀옥사이드, 비스(2,6-디메톡시벤조일)-2,4,4-트리메틸-펜틸포스핀옥사이드, 비스사(2,4,6-트리메틸벤조일)-페닐포스핀옥사이드 등의 아실포스핀 옥사이드류；1.2-옥탄디온, 1-［4-(페닐티오)-, 2-(o-벤조일옥심)］등의 옥심 에스테르류 등을 들 수 있다. 또한, 이들 광중합 개시제(D)의 1종만이 단독으로 사용될 수 있고, 2종 이상이 병용될 수도 있다.As said photoinitiator (D), for example, diethoxyacetphenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 4- (2-hydroxyethoxy) phenyl -(2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1- Propane-1-one, 2-hydroxy-1- ｛4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] -phenyl｝ -2-methyl-propane, 2-methyl-2- Morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2-hydroxy-2-methyl-1- [4 Acetphenones such as-(1-methylvinyl) phenyl] propane oligomer; benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, 3,3 ', 4,4'-tetra (t- Tilperoxycarbonyl) benzophenone, 2,4, 6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium Benzophenones such as bromid and (4-benzoylbenzyl) trimethylammonium chloride; 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloroti Tees, such as oxanthone, 1-chloro-4- propoxy city oxanthone, 2- (3-dimethylamino-2-hydroxy) -3, 4-dimethyl-9H- thioxanthone-9-on mesochloride Oxanthones; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bissa (2,4,6 Acylphosphine oxides such as -trimethylbenzoyl) -phenylphosphine oxide; oxime esters such as 1.2-octanedione, 1- [4- (phenylthio)-and 2- (o-benzoyloxime)]; Can be. In addition, only 1 type of these photoinitiators (D) may be used independently, and 2 or more types may be used together.
이들 중에서도, 벤질디메틸케탈, 1-히드록시시클로헥실페닐케톤, 벤조일이소프로필에테르, 4-(2-히드록시에톡시)-페닐(2-히드록시-2-프로필)케톤, 2-히드록시-2-메틸-1-페닐 프로판-1-온을 사용하는 것이 바람직하다.Among these, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoyl isopropyl ether, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 2-hydroxy- Preference is given to using 2-methyl-1-phenyl propane-1-one.
또, 이들 조제로서 예를 들면, 트리에탄올아민, 트리이소프로판올아민, 4,4´-디메틸아미노벤조페논(미히라케톤), 4,4´-디에틸아미노벤조페논, 2-디메틸아미노에틸안식향산, 4-디메틸아미노안식향산에틸, 4-디메틸아미노안식향산(n-부톡시) 에틸, 4-디메틸아미노안식향산 이소아밀, 4-디메틸아미노안식향산 2-에틸헥실, 2, 4-디에틸티옥산톤, 2,4-디이소프로필티옥산톤 등을 병용하는 것도 가능하다. 이들은 단독으로 또는 2종 이상 함께 사용할 수 있다.In addition, as these preparations, for example, triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (mihiraketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethyl benzoic acid, 4 Ethyl dimethylaminobenzoate, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, isoamyl 4-dimethylaminobenzoic acid, 2-ethylhexyl 4-dimethylaminobenzoic acid, 2,4-diethylthioxanthone, 2,4 It is also possible to use diisopropyl thioxanthone together. These may be used alone or in combination of two or more.
광중합 개시제(D)의 함유량으로서는, 수지 조성물 중에 포함되는 경화 성분 100중량부에 대해서, 0.1∼20중량부인 것이 바람직하고, 특히 바람직하게는 0.5∼10중량부, 더욱 바람직하게는 1∼10중량부이다. 광중합 개시제(D)의 함유량이 너무 적으면, 경화 불량이 되어 막형성이 이루어지기 어려운 경향이 있고, 너무 많으면 경화 도막의 황변의 원인이 되어, 착색의 문제가 일어나기 쉬운 경향이 있다.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 resin composition, Especially preferably, it is 0.5-10 weight part, More preferably, it is 1-10 weight part to be. When there is too little content of a photoinitiator (D), it will become a hardening defect and it will become difficult to form a film, too much will cause yellowing of a cured coating film, and there exists a tendency for the problem of coloring to arise easily.
우레탄(메타)아크릴레이트 이외의 에틸렌성 불포화 모노머로서는, 예를 들면, 단관능 모노머, 2관능 모노머, 3관능 이상의 다관능 모노머를 들 수 있다. 이들은 단독으로 또는 2종 이상 함께 사용할 수 있다.As ethylenically unsaturated monomers other than urethane (meth) acrylate, a monofunctional monomer, a bifunctional monomer, and a trifunctional or more than trifunctional monomer are mentioned, for example. These may be used alone or in combination of two or more.
이와 같은 단관능 모노머로서는, 예를 들면, 스티렌, 비닐톨루엔, 클로로스타렌,α-메틸스티렌 등의 스티렌계 모노머, 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 아크릴로니트릴, 2-메톡시에틸(메타)아크릴레이트, 2-히드록시에틸(메타)아크릴레이트, 2-히드록시프로필(메타)아크릴레이트, 2-히드록시부틸(메타)아크릴레이트, 페녹시에틸(메타)아크릴레이트, 2-페녹시-2-히드록시프로필(메타)아크릴레이트, 2-히드록시-3-페녹시프로필(메타)아크릴레이트, 3-클로로-2-히드록시프로필(메타)아크릴레이트, 글리세린모노(메타)아크릴레이트, 글리시딜(메타)아크릴레이트, 라우릴(메타)아크릴레이트, 시클로헥실(메타)아크릴레이트, 이소보닐(메타)아크릴레이트, 트리시클로데카닐(메타)아크릴레이트, 디시클로펜테닐(메타)아크릴레이트, 디시클로펜테닐옥시에틸(메타)아크릴레이트, 디시클로펜타닐(메타)아크릴레이트, (2-메틸-2-에틸-1,3-디옥소런-4-일)-메틸(메타)아크릴레이트, 시클로헥산스피로-2-(1,3-디옥소런-4-일)-메틸(메타)아크릴레이트, 3-에틸-3-옥세타닐메틸(메타)아크릴레이트,γ-부티롤락톤(메타)아크릴레이트, n-부틸(메타)아크릴레이트, 헥실(메타)아크릴레이트, 헵틸(메타)아크릴레이트, 옥틸(메타)아크릴레이트, 노닐(메타)아크릴레이트, 데실(메타)아크릴레이트, 이소데실(메타)아크릴레이트, 도데실(메타)아크릴레이트, n-스테아릴(메타)아크릴레이트, 벤질(메타)아크릴레이트, 페놀에틸렌옥사이드 변성(n=2)(메타)아크릴레이트, 노닐페놀프로필렌옥사이드 변성(n=2.5)(메타)아크릴레이트, 2-(메타)아크릴로일옥시에틸애시드인산염, 2-(메타)아크릴로일옥시-2-히드록시프로필프탈레이트 등의 프탈산 유도체의 하프(메타)아크릴레이트, 푸르푸릴(메타)아크릴레이트, 테트라히드로푸르푸릴(메타)아크릴레이트, 카르비톨(메타)아크릴레이트, 벤질(메타)아크릴레이트, 부톡시에틸(메타)아크릴레이트, 아릴(메타)아크릴레이트, (메타)아크릴로일모르폴린, 폴리옥시에틸렌 제2급 알킬에테르아크릴레이트 등의 (메타)아크릴레이트계 모노머, 2-히드록시에틸아크릴 아미드, N-메틸올(메타)아크릴아미드, N-비닐피롤리돈, 2-비닐피리딘, 초산 비닐 등을 들 수 있다.As such a monofunctional monomer, styrene type monomers, such as styrene, vinyltoluene, chlorostarene, (alpha) -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, cyclohexyl (meth) acrylate, isobonyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dish Clopentenyl (meth) acrylate, dicyclopentenyl Cyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, (2-methyl-2-ethyl-1,3-dioxolon-4-yl) -methyl (meth) acrylate, cyclohexanespiro- 2- (1,3-dioxolon-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) acrylate, decyl (meth) acrylate, isodecyl (meth) acryl Rate, dodecyl (meth) acrylate, n-stearyl (meth) acrylate, benzyl (meth) acrylate, phenolethylene oxide modified (n = 2) (meth) acrylate, nonylphenol propylene oxide modified (n = 2.5) Phthales such as (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, and 2- (meth) acryloyloxy-2-hydroxypropyl phthalate Half (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, carbitol (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate of the derivative (Meth) acrylate monomers such as aryl (meth) acrylate, (meth) acryloyl morpholine, polyoxyethylene secondary alkyl ether acrylate, 2-hydroxyethyl acrylamide, N-methylol ( Meta) acrylamide, N-vinylpyrrolidone, 2-vinylpyridine, vinyl acetate and the like.
이와 같은 2 관능 모노머로서는, 예를 들면, 에틸렌글리콜디(메타)아크릴레이트, 디에틸렌글리콜디(메타)아크릴레이트, 테트라에틸렌글리콜디(메타)아크릴레이트, 폴리에틸렌글리콜디(메타)아크릴레이트, 프로필렌글리콜디(메타)아크릴레이트, 디프로필렌글리콜디(메타)아크릴레이트, 폴리프로필렌글리콜디(메타)아크릴레이트, 부틸렌글리콜디(메타)아크릴레이트, 네오펜틸글리콜디(메타)아크릴레이트, 에틸렌옥사이드 변성 비스페놀 A형 디(메타)아크릴레이트, 프로필렌 옥사이드 변성 비스페놀 A형 디(메타)아크릴레이트, 시클로헥산디메탄올디(메타)아크릴레이트, 에톡시화 시클로헥산디메탄올디(메타)아크릴레이트, 디메틸올디시클로펜탄지(메타)아크릴레이트, 트리시클로데칸디메탄올디(메타)아크릴레이트, 1,6-헥산디올디(메타)아크릴레이트, 글리세린디(메타)아크릴레이트, 펜타에리쓰리톨 디(메타)아크릴레이트, 에틸렌글리콜디글리시딜에테르디(메타)아크릴레이트, 디에틸렌글리콜디글리시딜에테르디(메타)아크릴레이트, 푸탈산디글리시딜에스테르디(메타)아크릴레이트, 히드록시 피바린산 변성 네오펜틸글리콜디(메타)아크릴레이트, 이소시아눌산에틸렌옥사이드 변성 디아크릴레이트 등을 들 수 있다.As such a bifunctional monomer, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and propylene Glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide Modified bisphenol A di (meth) acrylate, propylene oxide modified bisphenol A di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, ethoxylated cyclohexanedimethanol di (meth) acrylate, dimethyloldi Cyclopentane (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, Riserindi (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid Diglycidyl ester di (meth) acrylate, hydroxy pivalinic acid modified neopentylglycol di (meth) acrylate, isocyanuric acid ethylene oxide modified diacrylate, and the like.
이와 같은 3관능 이상의 모노머로서는, 예를 들면, 트리메틸올프로판트리(메타)아크릴레이트, 펜타에리쓰리톨 트리(메타)아크릴레이트, 펜타에리쓰리톨 테트라(메타)아크릴레이트, 디펜타에리쓰리톨 펜타(메타)아크릴레이트, 디펜타에리쓰리톨 헥사(메타)아크릴레이트, 트리(메타)아크릴로일옥시에톡시트리메티올프로판, 글리세린폴리글리시딜에테르폴리(메타)아크릴레이트, 이소시아눌산에틸렌옥사이드 변성 트리아크릴레이트, 카프로락톤 변성 디펜타에리쓰리톨 펜타(메타)아크릴레이트, 카프로락톤 변성 디펜타에리쓰리톨 헥사(메타)아크릴레이트, 카프로락톤 변성 펜타에리쓰리톨 트리(메타)아크릴레이트, 카프로락톤 변성 펜타에리쓰리톨 테트라(메타)아크릴레이트, 에틸렌옥사이드 변성 디펜타에리쓰리톨 펜타(메타)아크릴레이트, 에틸렌옥사이드 변성 디펜타에리쓰리톨 헥사(메타)아크릴레이트, 에틸렌옥사이드 변성 펜타에리쓰리톨 트리(메타)아크릴레이트, 에틸렌옥사이드 변성 펜타에리쓰리톨 테트라(메타)아크릴레이트, 에톡시화 15 글리세린트리아크릴레이트 등을 들 수 있다.As such a trifunctional or more than trifunctional monomer, a trimethylol propane tri (meth) acrylate, a pentaerythritol tri (meth) acrylate, a pentaerythritol tetra (meth) acrylate, dipentaerythritol penta, for example (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (meth) acryloyloxyethoxytrimethol propane, glycerin polyglycidyl ether poly (meth) acrylate, isocyanurate ethylene Oxide modified triacrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate, Caprolactone modified pentaerythritol tetra (meth) acrylate, ethylene oxide modified dipentaerythritol penta (meth) acrylate, ethylene jade Id modified dipentaerythritol hexa (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol tetra (meth) acrylate, ethoxylated 15 glycerine triacrylate, etc. Can be mentioned.
또, 아크릴산의 미카엘 부가물 또는 2-아크릴로일옥시에틸디카르본산모노에스테르도 병용 가능하고, 이와 같은 아크릴산의 미카엘 부가물로서는, (메타)아크릴산다이머, (메타)아크릴산트리머, (메타)아크릴산테트라머 등을 들 수 있다. 상기 2-아크릴로일옥시에틸디카르본산모노 에스테르로서는, 특정 치환기를 갖는 카르본산이며, 예를 들면, 2-아크릴로일옥시에틸호박산 모노에스테르, 2-메타크릴로일옥시에틸호박산 모노에스테르, 2-아크릴로일옥시에틸푸탈산 모노에스테르, 2-메타크릴로일옥시에틸푸탈산 모노에스테르, 2-아크릴로일옥시에틸헥사히드로푸탈산 모노에스테르, 2-메타크릴로일옥시에틸헥사히드로푸탈산 모노에스테르 등을 들 수 있다. 또한, 그 외 올리고 에스테르 아크릴레이트 등을 들 수 있다.Moreover, the Michael addition product of acrylic acid or 2-acryloyloxyethyl dicarboxylic acid monoester can also be used together, As such Michael addition product of acrylic acid, (meth) acrylic-acid dimer, (meth) acrylic acid trimer, (meth) acrylic acid Tetramers; and the like. As said 2-acryloyloxy ethyl dicarboxylic acid mono ester, it is carboxylic acid which has a specific substituent, For example, 2-acryloyloxy ethyl succinic acid monoester, 2-methacryloyl oxyethyl succinic acid monoester, 2-acryloyloxyethyl phthalate monoester, 2-methacryloyloxyethyl phthalate monoester, 2-acryloyloxyethyl hexahydrophthalic acid monoester, 2-methacryloyloxyethyl hexahydrofu Deoxidation monoester, etc. are mentioned. Moreover, other oligo ester acrylate etc. are mentioned.
본 발명의 제1 요지 및 제2 요지에 관한 발명에 있어서의, 우레탄(메타)아크릴레이트 이외의 에틸렌성 불포화 모노머의 함유량으로서는, 활성 에너지선 경화성 수지 조성물 중에 포함되는 전경화 성분 중, 60중량% 이하인 것이 바람직하고, 특히 바람직하게는 55중량% 이하, 더욱 바람직하게는 50중량% 이하이다. 또한, 하한값으로서는 통상 5중량%이다.As content of ethylenically unsaturated monomers other than urethane (meth) acrylate in invention which concerns on the 1st summary and 2nd summary of this invention, it is 60 weight% or less in the foreground component contained in active energy ray curable resin composition. It is preferable, Especially preferably, it is 55 weight% or less, More preferably, it is 50 weight% or less. In addition, as a lower limit, it is 5 weight% normally.
한편, 본 발명의 제3 요지에 관한 발명에 있어서의, 우레탄(메타)아크릴레이트 이외의 에틸렌성 불포화 모노머의 함유량으로서는, 활성 에너지선 경화성 수지 조성물 중에 포함되는 전경화 성분 중, 50중량% 이하인 것이 바람직하고, 특히 바람직하게는 40중량% 이하, 더욱 바람직하게는 30중량% 이하, 특히 바람직하게는 20중량% 이하이다. 또한, 하한값으로서는 통상 5중량%이다.On the other hand, as content of ethylenically unsaturated monomers other than urethane (meth) acrylate in invention which concerns on the 3rd summary of this invention, it is preferable that it is 50 weight% or less in the foreground component contained in active energy ray curable resin composition. And particularly preferably 40% by weight or less, more preferably 30% by weight or less, particularly preferably 20% by weight or less. In addition, as a lower limit, it is 5 weight% normally.
상기 표면 조정제로서는, 예를 들면, 셀룰로오스 수지나 알키드 수지 등을 들 수 있다. 이와 같은 셀룰로오스 수지는, 도막의 표면 평활성을 향상시키는 작용이 있으며, 알키드 수지는 도포 시의 조막성을 부여하는 작용을 갖는 것이다. 이들은 단독으로 또는 2종 이상 함께 사용할 수 있다.As said surface regulator, a cellulose resin, an alkyd resin, etc. are mentioned, for example. Such a cellulose resin has the effect | action which improves the surface smoothness of a coating film, and an alkyd resin has the effect | action which gives the film forming property at the time of application | coating. These may be used alone or in combination of two or more.
상기 라벨링제로서는, 도액의 기재으로의 습윤성 부여 작용, 표면 장력의 저하 작용을 갖는 것이면, 공지 일반의 라벨링제를 사용할 수 있으며, 예를 들면, 실리콘 변성 수지, 불소 변성 수지, 알킬 변성의 수지 등을 사용할 수 있다. 이들은 단독으로 또는 2종 이상 함께 사용할 수 있다.As the labeling agent, a known general labeling agent can be used as long as it has a wettability imparting effect to the base material of the coating liquid and a lowering effect on the surface tension. For example, a silicone modified resin, a fluorine modified resin, an alkyl modified resin, or the like can be used. Can be used. These may be used alone or in combination of two or more.
상기 중합 금지제로서는, 반응 시에 사용한 것과 같은 것을 사용할 수 있으며, 예를 들면, p-벤조퀴논, 나프토퀴논, 톨퀴논, 2,5-디페닐-p-벤조퀴논, 하이드로퀴논, 2,5-디-t-부틸하이드로퀴논, 메틸하이드로퀴논, 하이드로퀴논 모노메틸에테르, 모노-t-부틸하이드로퀴논 등의 퀴논류, 4-메톡시페놀, 2,6-디-t-부틸크레졸 등의 방향족류, p-t-부틸카테콜 등을 들 수 있다. 이들은 단독으로 또는 2종 이상 함께 사용할 수 있다.As said polymerization inhibitor, the same thing as what was used at the time of reaction can be used, For example, p-benzoquinone, naphthoquinone, tolquinone, 2, 5- diphenyl- p-benzoquinone, hydroquinone, 2, Quinones such as 5-di-t-butylhydroquinone, methylhydroquinone, hydroquinone monomethyl ether, mono-t-butylhydroquinone, 4-methoxyphenol, and 2,6-di-t-butylcresol Aromatics, pt-butyl catechol, etc. are mentioned. These may be used alone or in combination of two or more.
또, 본 발명의 활성 에너지선 경화성 수지 조성물은, 필요에 따라 도공시의 점도를 적정한 것으로 하기 위해서, 희석을 위한 유기용제를 사용하는 것도 바람직하다. 이와 같은 유기용제로서는, 예를 들면, 메탄올, 에탄올, 프로판올, n-부탄올, i-부탄올 등의 알코올류, 아세톤, 메틸이소부틸케톤, 메틸에틸케톤, 시클로헥사논 등의 케톤류, 에틸셀로솔브 등의 셀로솔브류, 톨루엔, 자일렌 등의 방향족류, 프로필렌글리콜모노메틸에테르 등의 글리콜에테르류, 초산메틸, 초산에틸, 초산 부틸 등의 초산 에스테르류, 디아세톤알코올 등을 들 수 있다. 이들 상기의 유기용제는 단독으로 사용할 수도 있고, 2종 이상을 병용할 수도 있다.Moreover, in order for the active energy ray curable resin composition of this invention to make an appropriate viscosity at the time of coating as needed, it is also preferable to use the organic solvent for dilution. As such an organic solvent, For example, alcohols, such as methanol, ethanol, a propanol, n-butanol, i-butanol, ketones, such as acetone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, an ethyl cellosolve, for example. And other cellosolves, aromatics such as toluene and xylene, glycol ethers such as propylene glycol monomethyl ether, acetate esters such as methyl acetate, ethyl acetate and butyl acetate, diacetone alcohol, and the like. These said organic solvents may be used independently and may use 2 or more types together.
2종 이상을 병용하는 경우는, 프로필렌글리콜모노메틸에테르 등의 글리콜에테르류와 메틸에틸케톤 등의 케톤류나 메탄올 등의 알코올류와의 조합이나, 메틸 에틸케톤 등의 케톤류와 메탄올 등의 알코올류와의 조합, 메탄올 등의 알코올류 중에서 2종 이상을 선택하여 병용하는 것이 도막 외관의 관점에서 바람직하다.When using 2 or more types together, it is a combination of glycol ethers, such as propylene glycol monomethyl ether, ketones, such as methyl ethyl ketone, alcohol, such as methanol, ketones, such as methyl ethyl ketone, alcohol, such as methanol, It is preferable to select and use 2 or more types together from alcohols, such as a combination and methanol, from a viewpoint of a coating film external appearance.
본 발명의 활성 에너지선 경화성 수지 조성물은 각종 기재로의 오버코트제나 엥커 코트제 등, 도막 형성용 경화성 조성물로서 유효하게 사용되는 것이다. 그리고, 활성 에너지선 경화성 수지 조성물을 기재에 도공한 후(유기용제로 희석한 수지 조성물을 도공한 경우에는, 다시 건조시킨 후), 활성 에너지선을 조사하는 것으로써 경화된다.The active energy ray curable resin composition of this invention is used effectively as curable composition for coating film formation, such as an overcoat agent and anchor coat agent to various base materials. And after apply | coating an active energy ray curable resin composition to a base material (when drying the resin composition diluted with the organic solvent, after drying again), it hardens | cures by irradiating an active energy ray.
상기 본 발명의 활성 에너지선 경화성 수지 조성물을 도공하는 대상인 기재로서는, 예를 들면, 폴리올레핀계 수지, 폴리에스테르계 수지, 폴리카보네이트계 수지, 아크릴로니트릴부타디엔스티렌 공중합체(ABS), 폴리스티렌계 수지 등이나 이들 성형품(필름, 시트, 컵 등) 등의 플라스틱기재, 또 폴리에틸렌테레프탈레이트 필름, 트리아세틸셀룰로오스필름, 시클로올레핀 필름 등의 광학 필름, 이들 복합기재, 또는 유리 섬유나 무기물을 혼합한 상기 재료의 복합기재 등, 금속(알루미늄, 동, 철, SUS, 아연, 마그네슘, 이들 합금 등)이나 유리, 또는, 이들 기재 상에 프라이머층을 설치한 기재 등을 들 수 있다.As a base material which coats the active-energy-ray-curable resin composition of the said invention, For example, polyolefin resin, polyester resin, polycarbonate resin, an acrylonitrile butadiene styrene copolymer (ABS), polystyrene resin, etc. Or plastic films such as molded articles (films, sheets, cups, etc.), optical films such as polyethylene terephthalate films, triacetyl cellulose films, cycloolefin films, these composite materials, or the aforementioned materials obtained by mixing glass fibers or inorganic materials. Examples of the composite base include metals (aluminum, copper, iron, SUS, zinc, magnesium, alloys thereof, etc.), glass, and bases provided with primer layers on these bases.
본 발명의 활성 에너지선 경화성 수지 조성물의 도공 방법으로서는, 예를 들면, 스프레이, 샤워, 그라비아, 디핑, 롤, 스핀, 스크린 인쇄 등과 같은 웨트 코팅법을 들 수 있고, 통상은 상온하에서, 기재에 도공하면 좋다.As a coating method of the active-energy-ray-curable resin composition of this invention, wet coating methods, such as spray, shower, gravure, dipping, roll, spin, screen printing, are mentioned, for example, Usually, it coats a base material at normal temperature. Do it.
또, 본 발명의 활성 에너지선 경화성 수지 조성물은 그대로 도공할 수도 있고, 유기용제로 희석하여 도공할 수도 있다. 희석하는 경우에는, 상기 유기 용제를 사용하여 고형분 농도가 통상 3∼70중량이며, 바람직하게는 5∼60중량%가 되도록 희석한다.The active energy ray-curable resin composition of the present invention may be coated as it is, or may be diluted with an organic solvent and coated. When diluting, the solid content concentration is 3 to 70 weight% using the said organic solvent normally, and it dilutes so that it may become 5 to 60 weight%.
상기 유기용제에 의한 희석을 실시했을 때의 건조 조건으로서는, 온도는 통상 40∼120℃, 바람직하게는 50∼100℃에서, 건조 시간은 통상 1∼20분간, 바람직하게는 2∼10분간이면 좋다.As drying conditions when dilution with the said organic solvent, temperature is 40-120 degreeC normally, Preferably it is 50-100 degreeC, and drying time is 1-20 minutes normally, Preferably it is 2-10 minutes. .
본 발명의 활성 에너지선 경화성 수지 조성물을 도공 시에는, 수지 조성물의 20℃에서의 점도는 5∼50,000mPa·s인 것이 바람직하고, 특히 바람직하게는 10∼10,000mPa·s, 더욱 바람직하게는 50∼5,000mPa·s이다. 이와 같은 점도가 상기 범위 외에서는 도공성이 저하되는 경향이 있다. When coating the active energy ray-curable resin composition of the present invention, the viscosity at 20 ° C. of the resin composition is preferably 5 to 50,000 mPa · s, particularly preferably 10 to 10,000 mPa · s, more preferably 50 It is-5,000 mPa * s. There exists a tendency for such viscosity to fall in coating property out of the said range.
또한, 상기 20℃에서의 점도의 측정법은 B형 점도계에 의하는 것이다. 단, 용제 희석하지 않는 상태에서 고점도이기 때문에 20℃에서의 B형 점도계에 의한 측정을 할 수 없는 경우는, 60℃에서 E형 점도계를 사용하여 측정을 실시한다.In addition, the measuring method of the viscosity in said 20 degreeC is a B type viscometer. However, when it cannot be measured by the Brookfield viscometer at 20 degreeC because it is high viscosity in the state which does not dilute a solvent, it measures at 60 degreeC using an E-type viscosity meter.
기재 상에 도공된 활성 에너지선 경화성 수지 조성물을 경화 시킬 때에 사용하는 활성 에너지선으로서는, 예를 들면, 원자외선, 자외선, 근자외선, 적외선 등의 광선, X선, γ선 등의 전자파의 외, 전자선, 플로톤선, 중성자선 등을 사용할 수 있지만, 경화 속도, 조사 장치의 입수의 용이함, 가격 등으로부터 자외선 조사에 의한 경화가 유리하다. 또한, 전자선 조사를 실시하는 경우는, 광중합 개시제(D)를 사용하지 않아도 경화할 수 있다.As an active energy ray used when hardening the active energy ray curable resin composition coated on the base material, For example, in addition to the electromagnetic waves, such as rays, such as far ultraviolet rays, an ultraviolet-ray, a near-ultraviolet, infrared rays, X-rays, (gamma) rays, Although an electron beam, a floton ray, a neutron beam, etc. can be used, hardening by ultraviolet irradiation is advantageous from a curing rate, the availability of an irradiation apparatus, a price, etc. In addition, when performing electron beam irradiation, it can harden | cure without using a photoinitiator (D).
자외선 조사에 의해 경화 시킬 때, 150∼450nm 파장역의 광을 발하는 고압 수은 등, 초고압 수은 등, 카본 아크 등, 메탈할라이드캠프, 크세논램프, 케미컬 램프, 무전극 방전 램프, LED 램프 등을 사용하여 통상 30∼3,000mJ/㎠, 바람직하게는 100∼1,500mJ/㎠의 자외선을 조사할 수 있다. When curing by ultraviolet irradiation, using a high-pressure mercury lamp, ultra-high pressure mercury lamp, carbon arc lamp, metal halide camp, xenon lamp, chemical lamp, electrodeless discharge lamp, LED lamp, etc. that emit light in the wavelength range of 150 to 450 nm Usually, ultraviolet rays of 30 to 3,000 mJ / cm 2 and preferably 100 to 1500 mJ / cm 2 can be irradiated.
자외선 조사 후는, 필요에 따라 가열을 실시하여 경화의 완전을 도모할 수도 있다.After ultraviolet irradiation, you may heat as needed and can complete hardening.
도공 막 두께(경화 후의 막 두께)로서는, 통상, 활성 에너지선 경화성의 도막으로서 광중합 개시제(D)가 균일하게 반응할 수 있도록 광선 투과를 감안하면 1∼1,000㎛이며, 바람직하게는 2∼500㎛이며, 특히 바람직하게는 3∼200㎛이다.As coating film thickness (film thickness after hardening), it is 1-1,000 micrometers normally, considering light transmission so that a photoinitiator (D) may react uniformly as an active energy ray curable coating film, Preferably it is 2-500 micrometers It is 3-200 micrometers especially preferably.
본 발명의 활성 에너지선 경화성 수지 조성물은 코팅제로서 사용하는 것이 바람직하고, 특히 하드 코트용 코팅제나 광학 필름용 코팅제로서 사용하는 것이 바람직하다.It is preferable to use the active energy ray curable resin composition of this invention as a coating agent, and it is especially preferable to use it as a coating agent for hard coats, and the coating agent for optical films.
또, 본 발명에서는, 활성 에너지선 경화성 수지 조성물을 사이즈 15cm×15 cm로 두께 100㎛의 폴리에틸렌테레프탈레이트(PET) 필름에, 경화 후의 도막이 10㎛의 두께가 되도록 도공하고, 온도 60℃에서 3분간 건조시킨 후, PET 필름면으로부터의 높이 18cm의 위치에 80W의 고압 수은 등을 준비하고, 5.1m/min의 속도로 적산 조사량이 500mJ/㎠가 되도록 자외선을 조사함으로써, 경화 도막을 얻을 수 있다. 그 경화 도막을 10cm×10cm가 되도록 자르고, 그 자른 경화 도막의 네 귀퉁이의 튀어오른 높이의 평균값이 40mm 이하, 특히 30mm 이하, 또한, 25mm 이하인 경화 도막이 되는 코팅제로 하는 것이 바람직하다.In the present invention, the active energy ray-curable resin composition is coated on a polyethylene terephthalate (PET) film having a thickness of 15 cm x 15 cm so as to have a thickness of 10 μm, and the coating film after curing is formed at a temperature of 60 ° C. for 3 minutes. After drying, 80 W high-pressure mercury etc. are prepared in the position of 18 cm in height from PET film surface, and a cured coating film can be obtained by irradiating an ultraviolet-ray so that accumulated irradiation amount may be 500 mJ / cm <2> at the speed of 5.1 m / min. It is preferable to set it as the coating agent used as the cured coating film which cut | disconnects the cured coating film so that it may become 10 cm x 10 cm, and the average value of the jumped height of the four corners of the cut cured coating film is 40 mm or less, especially 30 mm or less, and 25 mm or less.
또한, 본 발명에서는 활성 에너지선 경화성 수지 조성물을, 사이즈 15cm×15cm로 두께 125㎛의 역접착 PET 필름에, 경화 후의 도막이 10㎛의 두께가 되도록 도공하고, 온도 60℃에서 3분간 건조시킨 후, 역접착 PET 필름면으로부터의 높이 18cm의 위치에 80W의 고압 수은등을 준비하고, 5.1m/min의 속도로 적산 조사량이 500mJ/㎠가 되도록 자외선을 조사함으로써, 경화 도막을 얻을 수 있다. 그 경화 도막에서, JIS K 5600-5-1에 준하여 원통형 맨드릴 굴곡 시험기를 사용하여 굴곡성의 평가를 실시하고, 평가용 경화 도막을 시험봉에 휘감았을 때에, 갈라짐 또는 박리가 생기는 최대의 지름(정수값, mm)이 20mm 이하, 특히는 15mm 이하, 또한, 10mm 이하, 특히 8mm 이하인 코팅제로 하는 것이 바람직하다.In the present invention, the active energy ray-curable resin composition is coated onto a 125 μm-thick reverse-adhesive PET film at a size of 15 cm × 15 cm so that the coating film after curing is 10 μm thick, and dried at a temperature of 60 ° C. for 3 minutes, A cured coating film can be obtained by preparing an 80 W high-pressure mercury lamp at a position of 18 cm in height from the back-adhesive PET film surface, and irradiating ultraviolet rays so that the accumulated irradiation amount is 500 mJ / cm 2 at a speed of 5.1 m / min. In the cured coating film, when the bendability was evaluated using a cylindrical mandrel bending tester in accordance with JIS K 5600-5-1, and the cured coating film for evaluation was wrapped around the test rod, the largest diameter (constant) Value, mm) is preferably 20 mm or less, particularly 15 mm or less, and 10 mm or less, in particular 8 mm or less.
그리고, 본 발명에서는 활성 에너지선 경화성 수지 조성물을, 사이즈 15cm×15cm로 두께 125㎛의 역접착 PET 필름에, 경화 후의 도막이 10㎛의 두께가 되도록 도공하고, 온도 60℃에서 3분간 건조시킨 후, 역접착 PET 필름면으로부터의 높이 18cm의 위치에 80W의 고압 수은등을 준비하고, 5.1m/min의 속도로 적산 조사량이 500mJ/㎠가 되도록 자외선을 조사함으로써, 경화 도막을 얻을 수 있다. 그 경화 도막에서 스틸울(닛폰스틸울사 제조, 본스타＃0000)을 사용하여 500g의 하중을 걸면서 경화 도막 표면을 10왕복시킨 후, 표면의 손상된 정도를 육안으로 관찰한 경우에서도, 도막 표면에 흠집이 없는 것이 바람직하다.In the present invention, the active energy ray-curable resin composition is coated on a 125 μm-thick non-adhesive PET film at a size of 15 cm × 15 cm so that the coating film after curing is 10 μm thick, and dried at a temperature of 60 ° C. for 3 minutes, A cured coating film can be obtained by preparing an 80 W high-pressure mercury lamp at a position of 18 cm in height from the back-adhesive PET film surface, and irradiating ultraviolet rays so that the accumulated irradiation amount is 500 mJ / cm 2 at a speed of 5.1 m / min. Even if the surface of the cured coating film was reciprocated ten times while applying 500 g of load using steel wool (Bonsta ＃ 0000, manufactured by Nippon Steel Wool Co., Ltd.) in the cured coating film, the degree of damage of the surface was visually observed. It is desirable that there are no scratches.
본 발명의 제1 요지에 관한 발명은, 펜타에리쓰리톨과 (메타)아크릴산과의 반응물인 상기 (메타)아크릴레이트(a1)∼(a4)의 혼합물(A) 중의 (메타)아크릴레이트(a1)∼(a3)와 다가 이소시아네이트(CA)가 반응한 우레탄(메타)아크릴레이트계 조성물［I］를 함유하여 이루어지며, 상기 혼합물(A)의 수산기가 200mgKOH/g 이상인 활성 에너지선 경화성 수지 조성물이다. 이 활성 에너지선 경화성 수지 조성물은, 경화 수축이 작기 때문에 컬되기 어렵고, 경도 및 굴곡성이 뛰어난 경화 도막을 형성할 수 있으며, 또한. 경화 전의 미경화 상태의 도막이라도 도막 표면이 달라붙지 않아, 택 프리인 도막 표면을 형성할 수 있다는 효과를 갖는 것이며, 특히 코팅제(또한 하드 코트용 코팅제나 광학 필름용 코팅제)로서 유용하고, 또, 도료, 잉크등으로서도 유용하다.The invention which concerns on the 1st summary of this invention is a (meth) acrylate (a1) in the mixture (A) of the said (meth) acrylate (a1)-(a4) which is a reactant of pentaerythritol and (meth) acrylic acid. (A) and urethane (meth) acrylate-based composition [I] to which polyvalent isocyanate (CA) reacted, wherein the hydroxyl group of the mixture (A) is 200 mgKOH / g or more. . This active energy ray curable resin composition is hard to curl because hardening shrinkage is small, and can form the cured coating film excellent in hardness and flexibility. Even if the coating film of the uncured state before hardening does not adhere to the coating film surface, it has the effect that a tack-free coating film surface can be formed, and it is especially useful as a coating agent (a coating agent for hard coats, and a coating agent for optical films), It is also useful as a paint or ink.
본 발명의 제2 요지에 관한 발명은, 펜타에리쓰리톨과 (메타)아크릴산과의 반응물인 상기 (메타)아크릴레이트(a1)∼(a4)의 혼합물(A) 중의 (메타)아크릴레이트(a1)∼(a3)와 다가 이소시아네이트(CA)가 반응한 우레탄(메타)아크릴레이트계 조성물［I］, 및, 디펜타에리쓰리톨과 (메타)아크릴산과의 반응물인 하기 (메타)아크릴레이트(b1)∼(b6)의 혼합물(B) 중의 (메타)아크릴레이트(b1)∼(b5)와 다가 이소시아네이트(CB)가 반응한 우레탄(메타)아크릴레이트계 조성물［II］를 함유하며, 상기 혼합물(A)의 수산기값이 200mgKOH/g 이상인 것과 동시에, 상기 혼합물(B)의 수산기값이 40mgKOH/g 이상인 활성 에너지선 경화성 수지 조성물이다. 이 활성 에너지선 경화성 수지 조성물은 경화 수축이 작기 때문에 컬되기 어렵고, 경도 및 굴곡성이 뛰어난 경화 도막을 형성할 수 있다는 효과를 갖는 것이며, 특히 코팅제(또한 하드 코트용 코팅제나 광학 필름용 코팅제)로서 유용하고, 또, 도료, 잉크 등으로서도 유용하다.The invention according to the second aspect of the present invention is a (meth) acrylate (a1) in a mixture (A) of the above-mentioned (meth) acrylates (a1) to (a4) which are reactants of pentaerythritol and (meth) acrylic acid. The following (meth) acrylate (b1) which is a urethane (meth) acrylate type composition [I] to which (a3) and polyhydric isocyanate (CA) reacted, and the reactant of dipentaerythritol with (meth) acrylic acid Urethane (meth) acrylate-based composition [II] in which (meth) acrylates (b1) to (b5) and polyvalent isocyanate (CB) reacted in a mixture (B) of (b) to (b6). The hydroxyl value of A) is 200 mgKOH / g or more, and the hydroxyl value of the said mixture (B) is 40 mgKOH / g or more, and is an active-energy-ray-curable resin composition. This active energy ray-curable resin composition has the effect of being hard to curl because of its small shrinkage, and having an effect of forming a cured coating film excellent in hardness and flexibility, and is particularly useful as a coating agent (and a coating agent for hard coat or coating agent for optical film). Moreover, it is useful also as a coating material, an ink, etc.
본 발명의 제3의 요지에 관한 발명은, 상기［α］의 (메타)아크릴레이트(a1)∼(a3), 상기［β］의(메타)아크릴레이트(b1)∼(b5), 및, 다가 이소시아네이트(CC)가 반응한 우레탄(메타)아크릴레이트계 조성물［III］를 함유하는 활성 에너지선 경화성 수지 조성물이다. 이 활성 에너지선 경화성 수지 조성물은, 경화 수축이 작기 때문에 컬하기 어렵고, 경도, 굴곡성 및 내찰상성이 뛰어난 경화 도막을 형성할 수 있다는 효과를 갖는 것이며, 특히 코팅제(또한 하드 코트용 코팅제나 광학 필름용 코팅제)로서 유용하다. 또, 도료, 잉크 등으로서도 유용하다.The invention according to the third aspect of the present invention includes the (meth) acrylates (a1) to (a3) of the above [α], the (meth) acrylates (b1) to (b5) of the above [β], and It is an active energy ray curable resin composition containing urethane (meth) acrylate type composition [III] which polyvalent isocyanate (CC) reacted. This active energy ray curable resin composition has the effect of being hard to curl because of its small shrinkage, and having the effect of being able to form a cured coating film excellent in hardness, flexibility and scratch resistance, and in particular, a coating agent (also for a hard coat coating agent and an optical film). Coating agent). It is also useful as a paint, ink, and the like.
실시예Example
이하, 실시예를 들어 본 발명을 더욱 구체적으로 설명하지만, 본 발명은 그 요지를 넘지 않는 이상 이하의 실시예로 한정되는 것은 아니다. 또한, 실시예 중, 「부」, 「%」는 중량 기준을 의미한다.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 addition, "part" and "%" mean a basis of weight in an Example.
＜＜우레탄(메타)아크릴레이트계 조성물［I］를 사용한 실시예＞＞ << Example using urethane (meth) acrylate type composition [I] >>
이하와 같이 우레탄 아크릴레이트계 조성물［I］(［I-1］∼［I-4］), 또한 비교를 위한 우레탄 아크릴레이트계 조성물［I'］(［I'-1］∼［I'-4］)를 준비했다.Urethane acrylate composition [I] ([I-1]-[I-4]) as described below, and urethane acrylate composition [I '] ([I'-1]-[I'-] for further comparison 4]).
〔우레탄 아크릴레이트계 조성물［I-1］의 제조〕 [Production of Urethane Acrylate Composition [I-1]]
온도계, 교반기, 수냉 콘덴서, 질소 가스 취입구를 구비한 4구 플라스크에, 이소포론디이소시아네이트(C-1) 36g, 수산기값 288mgKOH/g의 아크릴레이트 혼합물(A-1)(펜타에리쓰리톨의 아크릴산 부가물) 64g, 용제로서 초산에틸 100g, 중합 금지제로서 4-메톡시페놀 0.08g, 반응 촉매로서 디부틸주석디라우레이트 0.05g을 넣고, 60℃에서 반응시켜서, 잔존 이소시아네이트기가 0.1%가 된 시점에서 반응을 종료하고, 우레탄 아크릴레이트계 조성물［I-1］을 얻었다(수지분 농도 50%). In a four-necked flask equipped with a thermometer, a stirrer, a water cooling condenser, and a nitrogen gas inlet, an acrylate mixture (A-1) of 36 g of isophorone diisocyanate (C-1) and a hydroxyl value of 288 mgKOH / g (of pentaerythritol 64 g of acrylic acid adduct), 100 g of ethyl acetate as a solvent, 0.08 g of 4-methoxyphenol as a polymerization inhibitor, and 0.05 g of dibutyltin dilaurate as a reaction catalyst were added and reacted at 60 ° C. Reaction was complete | finished at the time of the completion | finish and the urethane acrylate composition [I-1] was obtained (resin content concentration 50%).
얻어진 우레탄 아크릴레이트계 조성물［I-1］의 중량 평균 분자량은 4,700, 20℃에서의 점도는 80mPa·s였다. 또한, 20℃에서의 점도의 측정은 B형 점도계를 이용해서 실시했다. 20℃에서의 점도 측정은 이하 같다.As for the weight average molecular weight of obtained urethane acrylate composition [I-1], the viscosity in 4,700 and 20 degreeC was 80 mPa * s. In addition, the measurement of the viscosity in 20 degreeC was implemented using the Brookfield viscometer. The viscosity measurement in 20 degreeC is as follows.
또한, 아크릴레이트 혼합물(A-1) 중에 있어서의 하기 성분 (a1)∼(a4)의 합계에 대한 각 성분의 함유 비율은 이하와 같다.In addition, the content rate of each component with respect to the sum total of the following components (a1)-(a4) in an acrylate mixture (A-1) is as follows.
(a1) 펜타에리쓰리톨 모노아크릴레이트 4%(a1) pentaerythritol monoacrylate 4%
(a2) 펜타에리쓰리톨 디아크릴레이트 29%(a2) Pentaerythritol diacrylate 29%
(a3) 펜타에리쓰리톨 트리아크릴레이트 49%(a3) pentaerythritol triacrylate 49%
(a4) 펜타에리쓰리톨 테트라아크릴레이트 18%(a4) pentaerythritol tetraacrylate 18%
또한, 혼합물 중의 각 성분의 함유 비율은 액체 크로마토 그래프(Agilent 사제, 「Technology HP 1100」)에 컬럼(Imtakt사 제조, CadenzaCD-C18100×3mm 3㎛)을 사용하는 것으로 측정된다.In addition, the content rate of each component in a mixture is measured by using a column (Imtakt company make, CadenzaCD-C18100x3mm3micrometer) for the liquid chromatograph ("Technology HP 1100" by Agilent).
〔우레탄 아크릴레이트계 조성물［I-2］의 제조〕 [Production of Urethane Acrylate-based Composition [I-2]]
온도계, 교반기, 수냉 콘덴서, 질소 가스 취입구를 구비한 4구 플라스크에, 수첨화 자일렌 디이소시아네이트(C-2) 33g, 수산기값 288mgKOH/g의 아크릴레이트 혼합물(A-1)(펜타에리쓰리톨의 아크릴산 부가물) 67g, 용제로서 초산에틸 100g, 중합 금지제로서 4-메톡시페놀 0.08g, 반응 촉매로서 디부틸주석디라우레이트 0.05g을 넣고, 60℃에서 반응시켜서, 잔존 이소시아네이트기가 0.1%가 된 시점에서 반응을 종료하고, 우레탄 아크릴레이트계 조성물［I-2］를 얻었다(수지분 농도 50%). In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, an acrylate mixture (A-1) having 33 g of hydrogenated xylene diisocyanate (C-2) and a hydroxyl value of 288 mgKOH / g (pentaeryz) 67 g of acrylic acid adduct of lititol, 100 g of ethyl acetate as a solvent, 0.08 g of 4-methoxyphenol as a polymerization inhibitor, 0.05 g of dibutyltin dilaurate as a reaction catalyst, were reacted at 60 ° C, and the remaining isocyanate group was 0.1. The reaction was complete | finished when it became% and the urethane acrylate composition [I-2] was obtained (resin concentration 50%).
얻어진 우레탄 아크릴레이트계 조성물［I-2］의 중량 평균 분자량은 6,200, 20℃에서의 점도는 65mPa·s였다.As for the weight average molecular weight of obtained urethane acrylate composition [I-2], the viscosity in 6,200 and 20 degreeC was 65 mPa * s.
〔우레탄 아크릴레이트계 조성물［I-3］의 제조〕 [Production of Urethane Acrylate Composition [I-3]]
온도계, 교반기, 수냉 콘덴서, 질소 가스 취입구를 구비한 4구 플라스크에, 톨릴렌 디이소시아네이트(C-3) 43g, 수산기값 288 mgKOH/g의 아크릴레이트 혼합물(A-1)(펜타에리쓰리톨의 아크릴산 부가물) 97g, 용제로서 초산에틸 60g, 중합 금지제로서 4-메톡시페놀 0.08g, 반응 촉매로서 디부틸주석디라우레이트 0.05g을 넣고, 60℃에서 반응시켜서, 잔존 이소시아네이트기가 0.1%가 된 시점에서 반응을 종료하고, 우레탄 아크릴레이트계 조성물［I-3］을 얻었다(수지분 농도 70%).In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, an acrylate mixture (A-1) having 43 g of tolylene diisocyanate (C-3) and a hydroxyl value of 288 mgKOH / g (pentaerythritol Acrylic acid adduct) 97 g, ethyl acetate 60 g as a solvent, 0.08 g of 4-methoxyphenol as a polymerization inhibitor, 0.05 g of dibutyltin dilaurate as a reaction catalyst were added and reacted at 60 degreeC, and the remaining isocyanate group was 0.1%. The reaction was complete | finished at the time of becoming it, and urethane acrylate composition [I-3] was obtained (resin concentration 70%).
얻어진 우레탄 아크릴레이트계 조성물［I-3］의 중량 평균 분자량은 7, 300, 20℃에서의 점도는 161,000mPa·s였다.As for the weight average molecular weight of obtained urethane acrylate composition [I-3], the viscosity in 7, 300 and 20 degreeC was 161,000 mPa * s.
〔우레탄 아크릴레이트계 조성물［I-4］의 제조〕 [Production of Urethane Acrylate-based Composition [I-4]]
온도계, 교반기, 수냉 콘덴서, 질소 가스 취입구를 구비한 4구 플라스크에, 크실렌 디이소시아네이트(C-4) 48g, 수산기값 288mgKOH/g의 아크릴레이트 혼합물(A-1)(펜타에리쓰리톨의 아크릴산 부가물) 90g, 용제로서 초산에틸 60g, 중합 금지제로서 4-메톡시페놀 0.08g, 반응 촉매로서 디부틸주석디라우레이트 0.05g을 넣고, 60℃에서 반응시켜, 잔존 이소시아네이트기가 0.1%가 된 시점에서 반응을 종료하고, 우레탄 아크릴레이트계 조성물［I-4］를 얻었다(수지분 농도 70%).In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 48 g of xylene diisocyanate (C-4) and an acrylate mixture (A-1) having a hydroxyl value of 288 mg KOH / g (acrylic acid of pentaerythritol) Additive) 90 g, 60 g of ethyl acetate as a solvent, 0.08 g of 4-methoxyphenol as a polymerization inhibitor, 0.05 g of dibutyltin dilaurate as a reaction catalyst were added and reacted at 60 ° C, whereby the remaining isocyanate group became 0.1%. Reaction was terminated at the time point and the urethane acrylate composition [I-4] was obtained (resin concentration 70%).
얻어진 우레탄 아크릴레이트계 조성물［I-4］의 중량 평균 분자량은 12,000, 20℃에서의 점도는 고점도이기 때문에 측정을 실시하지 않았다.Since the viscosity in 12,000 and 20 degreeC of the weight average molecular weight of obtained urethane acrylate composition [I-4] is high viscosity, it was not measured.
〔우레탄 아크릴레이트계 조성물［I'-1］의 제조〕 [Production of Urethane Acrylate-based Composition [I'-1]]
온도계, 교반기, 수냉 콘덴서, 질소 가스 취입구를 구비한 플라스크에, 이소포론 디이소시아네이트(C-1) 38.4g, 수산기값 120mgKOH/g의 아크릴레이트 혼합물(A'-1)(펜타에리쓰리톨의 아크릴산 부가물) 161.6g을 넣고, 중합 금지제로서 하이드로퀴논메틸에테르 0.01g, 반응 촉매로서 디부틸주석디라우레이트 0.01g을 넣고, 60℃에서 8시간 잔존시켜서, 잔존 이소시아네이트기가 0.3% 이하가 된 시점에서 반응을 종료하고, 우레탄 아크릴레이트계 조성물［I'-1］을 얻었다(수지분 농도 100%).In a flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, an acrylate mixture (A'-1) having 38.4 g of isophorone diisocyanate (C-1) and a hydroxyl value of 120 mgKOH / g (of pentaerythritol 161.6 g of acrylic acid adduct) was added, 0.01 g of hydroquinone methyl ether as a polymerization inhibitor and 0.01 g of dibutyltin dilaurate were added as a reaction catalyst, and the remaining isocyanate group was 0.3% or less after remaining at 60 ° C for 8 hours. Reaction was complete | finished at the time point, and urethane acrylate composition [I'-1] was obtained (resin content concentration 100%).
얻어진 우레탄 아크릴레이트계 조성물［I'-1］의 중량 평균 분자량은 1, 400, 60℃에서의 점도는 3,000mPa·s였다. 단, 고점도였기 때문에 E형 점도계를 사용하여 측정을 실시했다.As for the weight average molecular weight of obtained urethane acrylate composition [I'-1], the viscosity in 1, 400 and 60 degreeC was 3,000 mPa * s. However, since it was high viscosity, it measured using the E-type viscosity meter.
또한, 아크릴레이트 혼합물(A'-1) 중에 있어서의 하기 성분 (a1)∼(a4)의 합계에 대한 각 성분의 함유 비율은 이하와 같다.In addition, the content rate of each component with respect to the sum total of the following components (a1)-(a4) in an acrylate mixture (A'-1) is as follows.
(a2) 펜타에리쓰리톨 디아크릴레이트 5%(a2) pentaerythritol diacrylate 5%
(a3) 펜타에리쓰리톨 트리아크릴레이트 50%(a3) pentaerythritol triacrylate 50%
(a4) 펜타에리쓰리톨 테트라아크릴레이트 45%(a4) pentaerythritol tetraacrylate 45%
단, (a1) 펜타에리쓰리톨 모노아크릴레이트에 관해서는 함유량이 측정 한계 이하였기 때문에, (a2)∼(a4) 성분의 함유 비율을 나타냈다.However, since content was below the measurement limit about pentaerythritol monoacrylate (a1), the content rate of (a2)-(a4) component was shown.
〔우레탄 아크릴레이트계 조성물［I'-2］의 제조〕 [Production of Urethane Acrylate-based Composition [I'-2]]
온도계, 교반기, 수냉 콘덴서, 질소 가스 취입구를 구비한 4구 플라스크에, 이소포론 디이소시아네이트(C-1) 37g, 수산기값 288 mgKOH/g의 아크릴레이트 혼합물(A-1)(펜타에리쓰리톨의 아크릴산 부가물) 14g, 아디핀산과 네오펜틸글리콜로 이루어진 폴리에스테르폴리올(DIC사 제조, 「ODX-2044」, 수평균 분자량：약 2,000) 114g, 중합 금지제로서 4-메톡시페놀 0.08g, 반응 촉매로서 디부틸주석디라우레이트 0.05g을 넣고, 60℃에서 반응시켜서, 잔존 이소시아네이트기가 3.9%가 된 시점에서 수산기값 288mgKOH/g의 아크릴레이트 혼합물(A-1)(펜타에리쓰리톨의 아크릴산 부가물) 35g을 더하고, 다시 60℃에서 반응시켰다. 잔존 이소시아네이트기가 0.1%가 된 시점에서 반응을 종료하고, 우레탄 아크릴레이트계 조성물［I'-2］를 얻었다(수지분 농도 100%).In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 37 g of isophorone diisocyanate (C-1) and an acrylate mixture (A-1) having a hydroxyl value of 288 mgKOH / g (pentaerythritol 14 g of acrylic acid adducts), polyester polyol consisting of adipic acid and neopentyl glycol (manufactured by DIC Corporation, "ODX-2044", number average molecular weight: about 2,000) 114 g, 4-methoxyphenol 0.08 g, as a polymerization inhibitor, 0.05 g of dibutyltin dilaurate was added as a reaction catalyst and reacted at 60 DEG C, and when the remaining isocyanate group became 3.9%, an acrylate mixture (A-1) having a hydroxyl value of 288 mgKOH / g (acrylic acid of pentaerythritol) Adduct) 35 g was added and reacted again at 60 ° C. Reaction was complete | finished when the remaining isocyanate group became 0.1%, and urethane acrylate composition [I'-2] was obtained (resin content concentration 100%).
또한, 상기 순서에 의하면, 얻어진 우레탄 아크릴레이트계 조성물［I'-2］에는 (A-1) 및 (C-1)만의 반응물은 없게 된다.In addition, according to the said procedure, in the obtained urethane acrylate composition [I'-2], there is no reactant only for (A-1) and (C-1).
얻어진 우레탄 아크릴레이트계 조성물［I'-2］의 중량 평균 분자량은 18,000, 60℃에서의 점도는 700,000mPa·s였다. 단, 고점도였기 때문에 E형 점도계를 사용하여 측정을 실시했다.The weight average molecular weight of the obtained urethane acrylate composition [I'-2] was 18,000, and the viscosity in 60 degreeC was 700,000 mPa * s. However, since it was high viscosity, it measured using the E-type viscosity meter.
〔우레탄 아크릴레이트계 조성물［I'-3］의 제조〕 [Production of Urethane Acrylate-based Composition [I'-3]]
온도계, 교반기, 수냉 콘덴서, 질소 가스 취입구를 구비한 4구 플라스크에, 이소포론 디이소시아네이트(C-1) 25.8g, 수산기값 184.2mgKOH/g의 아크릴레이트 혼합물(A'-2)(펜타에리쓰리톨의 아크릴산 부가물) 74.2g, 용제로서 초산에틸 100g, 중합 금지제로서 4-메톡시페놀 0.08g, 반응 촉매로서 디부틸주석디라우레이트 0.05g을 넣고, 60℃에서 반응시켜서, 잔존 이소시아네이트기가 0.1%가 된 시점에서 반응을 종료하고, 우레탄 아크릴레이트계 조성물［I'-3］을 얻었다(수지분 농도 50%).In a four-necked flask equipped with a thermometer, a stirrer, a water cooling condenser, and a nitrogen gas inlet, an acrylate mixture (A'-2) having 25.8 g of isophorone diisocyanate (C-1) and a hydroxyl value of 184.2 mgKOH / g (pentaene Acrylic acid adduct of rititol) 74.2 g, ethyl acetate 100 g as solvent, 0.08 g of 4-methoxyphenol as a polymerization inhibitor, 0.05 g of dibutyltin dilaurate as a reaction catalyst, and reacted at 60 ° C Reaction was complete | finished when group became 0.1%, and urethane acrylate composition [I'-3] was obtained (resin content concentration 50%).
얻어진 우레탄 아크릴레이트계 조성물［I'-3］의 중량 평균 분자량은 2,100, 20℃에서의 점도는 73mPa·s였다.The weight average molecular weight of obtained urethane acrylate composition [I'-3] was 2,100, and the viscosity in 20 degreeC was 73 mPa * s.
또한, 아크릴레이트 혼합물(A'-2) 중에 있어서의 하기 성분 (a1)∼(a4)의 합계에 대한 각 성분의 함유 비율은 이하와 같다.In addition, the content rate of each component with respect to the sum total of the following components (a1)-(a4) in an acrylate mixture (A'-2) is as follows.
(a1) 펜타에리쓰리톨 모노아크릴레이트 1.6%(a1) pentaerythritol monoacrylate 1.6%
(a2) 펜타에리쓰리톨 디아크릴레이트 14.6%(a2) pentaerythritol diacrylate 14.6%
(a3) 펜타에리쓰리톨 트리아크릴레이트 49.6%(a3) pentaerythritol triacrylate 49.6%
(a4) 펜타에리쓰리톨 테트라아크릴레이트 34.2%(a4) pentaerythritol tetraacrylate 34.2%
〔우레탄 아크릴레이트계 조성물［I'-4］의 제조〕 [Production of Urethane Acrylate-based Composition [I'-4]]
온도계, 교반기, 수냉 콘덴서, 질소 가스 취입구를 구비한 4구 플라스크에, 수첨화 자일렌 디이소시아네이트(C-2) 23.3g, 수산기값 184.2mgKOH/g의 아크릴레이트 혼합물(A'-2)(펜타에리쓰리톨의 아크릴산 부가물) 76.7g, 용제로서 초산에틸 100g, 중합 금지제로서 4-메톡시페놀 0.08g, 반응 촉매로서 디부틸주석디라우레이트 0.05g을 넣고, 60℃에서 반응시켜서, 잔존 이소시아네이트기가 0.1%가 된 시점에서 반응을 종료하고, 우레탄 아크릴레이트계 조성물［I'-4］를 얻었다(수지분 농도 50%).In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, an acrylate mixture (A'-2) having 23.3 g of hydrogenated xylene diisocyanate (C-2) and a hydroxyl value of 184.2 mgKOH / g ( 76.7 g of acrylic acid adduct of pentaerythritol), 100 g of ethyl acetate as a solvent, 0.08 g of 4-methoxyphenol as a polymerization inhibitor, 0.05 g of dibutyltin dilaurate as a reaction catalyst were added and reacted at 60 ° C, Reaction was complete | finished when the remaining isocyanate group became 0.1%, and urethane acrylate composition [I'-4] was obtained (resin content concentration 50%).
얻어진 우레탄 아크릴레이트계 조성물［I'-4］의 중량 평균 분자량은 2, 200, 20℃에서의 점도는 85 mPa·s였다.The viscosity in 2, 200 and 20 degreeC of the weight average molecular weight of the obtained urethane acrylate composition [I'-4] was 85 mPa * s.
＜실시예 1∼4, 비교예 1∼4＞ <Examples 1-4, Comparative Examples 1-4>
〔활성 에너지선 경화성 수지 조성물의 제조〕 [Production of Active Energy Ray Curable Resin Composition]
상기에서 얻어진 우레탄 아크릴레이트계 조성물(［I］,［I'］)에, 광중합 개시제(D)로서 1-히드록시시클로헥실페닐케톤(IGM사 제조, 「옴니랏드 184」)을 경화 성분 100부에 대해서 4부 배합하고, 활성 에너지선 경화성 수지 조성물을 얻었다. 100 parts of hardening components to the urethane acrylate composition ([I], [I ']) obtained above as a photoinitiator (D) 1-hydroxycyclohexyl phenyl ketone (IGM Corporation make, "omnilad 184"). It mix | blended 4 parts about and obtained the active energy ray curable resin composition.
또한, 실시예 3, 4, 비교예 1, 2에 대해서는, 얻어진 우레탄 아크릴레이트계 조성물(［I］,［I'］)을 수지분 50%가 되도록 초산에틸에 의해서 희석한 것 이외는, 상기와 같이 하여 활성 에너지선 경화성 수지 조성물을 얻었다.In addition, about Example 3, 4 and Comparative Examples 1 and 2, except that the obtained urethane acrylate composition ([I], [I ']) was diluted with ethyl acetate so that it might become a resin content 50%, In this manner, an active energy ray curable resin composition was obtained.
얻어진 활성 에너지선 경화성 수지 조성물에 대해서, 하기와 같이 경화 전의 도막(건조 도막)을 형성하여 도막의 달라붙음을 평가했다. 또한, 하기와 같이 경화 도막을 형성하여 경화 도막의 경도, 굴곡성을 평가했다. 평가 결과는 후기의 표 1과 같다.About the obtained active energy ray curable resin composition, the coating film (drying coating film) before hardening was formed as follows, and the sticking of the coating film was evaluated. Moreover, the cured coating film was formed as follows and the hardness and the flexibility of the cured coating film were evaluated. The evaluation results are shown in Table 1 of the later.
〔건조 도막의 달라붙음〕 [Sticking of dry coating film]
상기에서 얻어진 활성 에너지선 경화성 수지 조성물을 역(易)접착 PET 필름(토요보사 제조, 「A4300」, 사이즈 15cm×15cm, 두께 125㎛) 기판 상에 바 코터를 사용하여, 경화 후의 도막이 10㎛의 두께가 되도록 도공하고, 60℃에서 3분간 건조했다. 얻어진 경화 전의 도막을, 택킹 시험기(레스카사 제조, 「TAC-II」)를 사용하여 압입 속도 120mm/min, 인양 속도 600 mm/min, 압력 20.4gf, 가압 시간 1.0초간의 조건으로 프로브택 시험을 실시했다.The coating film after hardening of the active-energy-ray-curable resin composition obtained above on the back stick PET film (Toyobo Co., Ltd. make, "A4300", size 15 cm x 15 cm, thickness 125 micrometers) board | substrate was used, and the coating film after hardening is 10 micrometers. Coating was carried out so as to be thick and dried at 60 ° C. for 3 minutes. Probe-tack test was carried out on the obtained coating film before curing using a tagging tester (manufactured by Lesca, "TAC-II") under conditions of indentation speed 120 mm / min, lifting speed 600 mm / min, pressure 20.4 gf, and pressurization time 1.0 seconds. Carried out.
〔경화 도막의 경도〕 [Hardness of the cured coating film]
상기에서 얻어진 활성 에너지선 경화성 수지 조성물을 역접착 PET 필름(토요보사 제조, 「A4300」, 사이즈 15cm×15cm, 두께 125㎛) 기판 상에 바 코터를 사용하여 경화 후의 도막이 10㎛의 두께가 되도록 도공하고, 60℃에서 3분간 건조한 후, 고압 수은등 80W, 1등을 사용하여, 18cm의 높이로부터 5.1m/min의 컨베이어 속도로 2패스의 자외선 조사(적산 조사량 500mJ/㎠)를 실시하고, 경화 도막을 형성했다. 역접착 PET 필름 상에 도공한 상기 경화 도막에 대해서, JIS K-5600에 준하여 시험을 실시하고 연필 경도를 측정했다.The active energy ray curable resin composition obtained above is coated on a back-stick PET film (Toyobo Co., Ltd., "A4300", size 15 cm x 15 cm, thickness 125 µm) using a bar coater so that the coating film after curing becomes 10 µm thick. After drying at 60 ° C. for 3 minutes, using a high-pressure mercury lamp 80 W and one lamp, two passes of ultraviolet irradiation (accumulated irradiation amount 500 mJ / cm 2) were carried out at a conveyor speed of 5.1 m / min from a height of 18 cm to form a cured coating film. Formed. About the said cured coating film coated on the reverse adhesion PET film, it tested according to JISK-5600 and measured pencil hardness.
〔경화 도막의 굴곡성〕 [Flexibility of Cured Coating Film]
상기의 경도 평가와 동일하게 하여 경화 도막을 형성하고, 역접착 PET 필름 상에 도공한 경화 도막에 대해서, JIS K 5600-5-1에 준하여 원통형 맨드릴 굴곡 시험기를 사용하여 굴곡성의 평가를 실시했다. 평가용 경화 도막을, 도막면이 외측이 되도록 시험봉에 휘감았을 때에, 갈라짐 또는 박리가 생기는 최대의 지름(정수값, mm)을 측정했다. 값이 작을수록 굴곡성이 높은 도막인 것을 의미한다.The cured coating film was formed in the same manner as the above hardness evaluation, and the curable coating film coated on the anti-adhesive PET film was evaluated for flexibility using a cylindrical mandrel bending tester in accordance with JIS K 5600-5-1. When the cured coating film for evaluation was wound around the test rod so that the coating film surface became an outer side, the largest diameter (an integer value, mm) which a crack or peeling generate | occur | produced was measured. The smaller the value, the higher the flexibility.
상기 평가 결과로부터 실시예 1∼4의 우레탄 아크릴레이트계 조성물［I］를 함유하는 활성 에너지선 경화성 수지 조성물로 얻어지는 경화 도막은, 경도 및 굴곡성이 뛰어날 뿐만 아니라, 경화 전의 미경화 상태의 도막에서도 달라붙음이 없다는 것을 알 수 있다. The cured coating film obtained by the active energy ray curable resin composition containing the urethane acrylate composition [I] of Examples 1-4 from the said evaluation result is not only excellent in hardness and flexibility, but also in the uncured coating film before hardening. You can see that there is no attachment.
한편, 특정 우레탄 아크릴레이트계 조성물［I］이외의 우레탄 아크릴레이트계 조성물을 사용한 각 비교예에서 비교예 1은 경화 도막의 굴곡성이 떨어지는 것이며, 또한, 경화 전의 도막은 달라붙음을 갖는 것이었다. 또, 비교예 2는 경화 도막의 경도가 떨어지는 것이며, 또한, 경화 전의 도막은 달라붙음을 갖는 것이었다. 비교예 3 및 4에서는, 경화 도막의 굴곡성이 떨어지는 것이었다.On the other hand, in each comparative example using the urethane acrylate composition other than specific urethane acrylate composition [I], the comparative example 1 was inferior to the flexibility of a cured coating film, and the coating film before hardening had sticking. Moreover, the comparative example 2 had the hardness of the cured coating film falling, and the coating film before hardening had sticking. In Comparative Examples 3 and 4, the flexibility of the cured coating film was inferior.
이들로부터, 상기 실시예 1∼4의 활성 에너지선 경화성 수지 조성물이 택 프리이며, 경도 및 굴곡성에 양호하고, 코팅제 등, 특히 하드 코트용 코팅제나 광학 필름용 코팅제의 용도에 대해 유용하다는 것을 알 수 있다.From these, it can be seen that the active energy ray-curable resin compositions of Examples 1 to 4 are tack free, are good in hardness and flexibility, and are useful for the use of coatings for hard coats and coatings for optical films, such as coatings. have.
＜＜우레탄(메타)아크릴레이트계 조성물［I］및［II］를 사용한 실시예＞＞ << Example using urethane (meth) acrylate type composition [I] and [II] >>
이하와 같이 우레탄 아크릴레이트계 조성물［I］(［I-5］∼［I-7］),［II］(［II-1］∼［II-2］), 또한 비교를 위한 우레탄 아크릴레이트계 조성물［I'］(［I'-5］∼［I'-7］)를 준비했다.Urethane acrylate composition [I] ([I-5]-[I-7]), [II] ([II-1]-[II-2]), a urethane acrylate system for comparison as follows Composition [I '] ([I'-5]-[I'-7]) was prepared.
〔우레탄 아크릴레이트계 조성물［I-5］〕 [Urethane acrylate composition [I-5]]
온도계, 교반기, 수냉 콘덴서, 질소 가스 취입구를 구비한 4구 플라스크에, 이소포론 디이소시아네이트(C-1) 36g, 수산기값 288mgKOH/g의 아크릴레이트 혼합물(A-1)(펜타에리쓰리톨의 아크릴산 부가물) 64g, 용제로서 초산에틸 100g, 중합 금지제로서 4-메톡시페놀 0.08g, 반응 촉매로서 디부틸주석디라우레이트 0.05g을 넣고, 60℃에서 반응시켜, 잔존 이소시아네이트기가 0.1%가 된 시점에서 반응을 종료하고, 우레탄 아크릴레이트계 조성물［I-5］를 얻었다(수지분 농도 50%).In a four-necked flask equipped with a thermometer, a stirrer, a water cooling condenser, and a nitrogen gas inlet, an acrylate mixture (A-1) having 36 g of isophorone diisocyanate (C-1) and a hydroxyl value of 288 mgKOH / g (of pentaerythritol 64 g of acrylic acid adduct), 100 g of ethyl acetate as a solvent, 0.08 g of 4-methoxyphenol as a polymerization inhibitor, and 0.05 g of dibutyltin dilaurate as a reaction catalyst were added and reacted at 60 ° C. Reaction was complete | finished at the time of the completion | finish, and urethane acrylate composition [I-5] was obtained (resin content concentration 50%).
얻어진 우레탄 아크릴레이트계 조성물［I-5］의 중량 평균 분자량은 4,700, 20℃에서의 점도는 80mPa·s였다. 또한, 20℃에서의 점도의 측정은 B형 점도계를 사용하여 실시했다. 20℃에서의 점도 측정은 이하와 같다.The weight average molecular weight of the obtained urethane acrylate composition [I-5] was 4,700, and the viscosity in 20 degreeC was 80 mPa * s. In addition, the measurement of the viscosity in 20 degreeC was performed using the Brookfield viscometer. The viscosity measurement at 20 degreeC is as follows.
또한, 아크릴레이트 혼합물(A-1) 중에 있어서의 하기 성분 (a1)∼(a4)의 합계에 대한 각 성분의 함유 비율은 이하와 같다.In addition, the content rate of each component with respect to the sum total of the following components (a1)-(a4) in an acrylate mixture (A-1) is as follows.
(a1) 펜타에리쓰리톨 모노아크릴레이트 4%(a1) pentaerythritol monoacrylate 4%
(a2) 펜타에리쓰리톨 디아크릴레이트 29%(a2) pentaerythritol diacrylate 29%
(a3) 펜타에리쓰리톨 트리아크릴레이트 49%(a3) pentaerythritol triacrylate 49%
(a4) 펜타에리쓰리톨 테트라아크릴레이트 18%(a4) pentaerythritol tetraacrylate 18%
〔우레탄 아크릴레이트계 조성물［I-6］의 제조〕 [Production of Urethane Acrylate Composition [I-6]]
온도계, 교반기, 수냉 콘덴서, 질소 가스 취입구를 구비한 4구 플라스크에, 수첨화 자일렌 디이소시아네이트(C-2) 33g, 수산기값 288mgKOH/g의 아크릴레이트 혼합물(A-1)(펜타에리쓰리톨의 아크릴산 부가물) 67g, 용제로서 초산에틸 100g, 중합 금지제로서 4-메톡시페놀 0.08g, 반응 촉매로서 디부틸주석디라우레이트 0.05g을 넣고, 60℃에서 반응시켜, 잔존 이소시아네이트기가 0.1%가 된 시점에서 반응을 종료하고, 우레탄 아크릴레이트계 조성물［I-6］을 얻었다(수지분 농도 50%). In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, an acrylate mixture (A-1) having 33 g of hydrogenated xylene diisocyanate (C-2) and a hydroxyl value of 288 mgKOH / g (pentaeryz) 67 g of acrylic acid adduct of lititol, 100 g of ethyl acetate as a solvent, 0.08 g of 4-methoxyphenol as a polymerization inhibitor, 0.05 g of dibutyltin dilaurate as a reaction catalyst, were reacted at 60 ° C, and the residual isocyanate group was 0.1. The reaction was complete | finished when it became% and the urethane acrylate composition [I-6] was obtained (resin concentration 50%).
얻어진 우레탄 아크릴레이트계 조성물［I-6］의 중량 평균 분자량은 6,200, 20℃에서의 점도는 65mPa·s였다.The viscosity in 6,200 and 20 degreeC of the weight average molecular weight of obtained urethane acrylate composition [I-6] was 65 mPa * s.
〔우레탄 아크릴레이트계 조성물［I-7］의 제조〕 [Production of Urethane Acrylate-based Composition [I-7]]
온도계, 교반기, 수냉 콘덴서, 질소 가스 취입구를 구비한 4구 플라스크에, 자일렌 디이소시아네이트(C-4) 32g, 수산기값 288mgKOH/g의 아크릴레이트 혼합물(A-1)(펜타에리쓰리톨의 아크릴산 부가물) 68g, 용제로서 초산에틸 100g, 중합 금지제로서 4-메톡시페놀 0.08g, 반응 촉매로서 디부틸주석디라우레이트 0.05g을 넣고, 60℃에서 반응시켜서, 잔존 이소시아네이트기가 0.1%가 된 시점에서 반응을 종료하고, 우레탄 아크릴레이트계 조성물［I-7］을 얻었다(수지분 농도 50%). In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, an acrylate mixture (A-1) of 32 g of xylene diisocyanate (C-4) and a hydroxyl value of 288 mgKOH / g (of pentaerythritol 68 g of acrylic acid adduct), 100 g of ethyl acetate as a solvent, 0.08 g of 4-methoxyphenol as a polymerization inhibitor, and 0.05 g of dibutyltin dilaurate as a reaction catalyst were added and reacted at 60 ° C. Reaction was complete | finished at the time of the completion | finish, and urethane acrylate composition [I-7] was obtained (resin content concentration 50%).
얻어진 우레탄 아크릴레이트계 조성물［I-7］의 중량 평균 분자량은 5,900, 20℃에서의 점도는 50mPa·s였다.The weight average molecular weight of the obtained urethane acrylate composition [I-7] was 5,900, and the viscosity in 20 degreeC was 50 mPa * s.
〔우레탄 아크릴레이트계 조성물［II-1］의 제조〕 [Manufacture of urethane acrylate composition [II-1]]
온도계, 교반기, 수냉 콘덴서, 질소 가스 취입구를 구비한 4구 플라스크에, 수첨화 자일렌 디이소시아네이트(C-2) 27.9g, 수산기값 96 mgKOH/g의 아크릴레이트 혼합물(B-1)(디펜타에리쓰리톨의 아크릴산 부가물) 172.1g, 중합 금지제로서 4-메톡시페놀 0.08g, 반응 촉매로서 디부틸주석디라우레이트 0.1g을 넣고, 60℃에서 반응시켜, 잔존 이소시아네이트기가 0.1%가 된 시점에서 반응을 종료하고, 우레탄 아크릴레이트계 조성물［II-1］을 얻었다(수지분 농도 100%).In a four-necked flask equipped with a thermometer, a stirrer, a water cooling condenser, and a nitrogen gas inlet, an acrylate mixture (B-1) having 27.9 g of hydrogenated xylene diisocyanate (C-2) and a hydroxyl value of 96 mgKOH / g (di 172.1 g of acrylic acid adduct of pentaerythritol), 0.08 g of 4-methoxyphenol as a polymerization inhibitor, and 0.1 g of dibutyltin dilaurate as a reaction catalyst were added and reacted at 60 ° C. Reaction was complete | finished and the urethane acrylate composition [II-1] was obtained (resin content 100%).
얻어진 우레탄 아크릴레이트계 조성물［II-1］의 중량 평균 분자량은 5,500, 60℃에서의 점도는 39,400mPa·s였다. 또한, 60℃에서의 점도의 측정은 E형 점도계를 사용하여 실시했다. 60℃에서의 점도 측정은 이하와 같다.The viscosity in 5,500 and 60 degreeC of the weight average molecular weight of obtained urethane acrylate composition [II-1] was 39,400 mPa * s. In addition, the measurement of the viscosity in 60 degreeC was performed using the E-type viscosity meter. The viscosity measurement at 60 degreeC is as follows.
또한, 아크릴레이트 혼합물(B-1) 중에 있어서의 하기 성분 (b1)∼(b6)의 합계에 대한 각 성분의 함유 비율은 이하와 같다.In addition, the content rate of each component with respect to the sum total of the following components (b1)-(b6) in an acrylate mixture (B-1) is as follows.
(b4) 디펜타에리쓰리톨 테트라아크릴레이트 18%(b4) dipentaerythritol tetraacrylate 18%
(b5) 디펜타에리쓰리톨 펜타아크릴레이트 51%(b5) dipentaerythritol pentaacrylate 51%
(b6) 디펜타에리쓰리톨 헥사아크릴레이트 31% (b6) dipentaerythritol hexaacrylate 31%
단, (b1) 디펜타에리쓰리톨 모노아크릴레이트, (b2) 디펜타에리쓰리톨 디아크릴레이트, (b3) 디펜타에리쓰리톨 트리아크릴레이트에 관해서는 함유량이 측정 한계치 이하였기 때문에, (b4)∼(b6) 성분의 함유 비율을 나타냈다.However, since content was below the measurement limit regarding (b1) dipentaerythritol monoacrylate, (b2) dipentaerythritol diacrylate, and (b3) dipentaerythritol triacrylate, (b4 The content rate of (a)-(b6) component was shown.
〔우레탄 아크릴레이트계 조성물［II-2］의 제조〕 [Production of Urethane Acrylate Composition [II-2]]
온도계, 교반기, 수냉 콘덴서, 질소 가스 취입구를 구비한 4구 플라스크에, 이소포론 디이소시아네이트(C-1) 31.3g, 수산기값 96 mgKOH/g의 아크릴레이트 혼합물(B-1)(디펜타에리쓰리톨의 아크릴산 부가물) 168.7g, 중합 금지제로서 4-메톡시페놀 0.08g, 반응 촉매로서 디부틸주석디라우레이트 0.1g을 넣고, 60℃에서 반응시켜, 잔존 이소시아네이트기가 0.1%가 된 시점에서 반응을 종료하고, 우레탄 아크릴레이트계 조성물［II-2］를 얻었다(수지분 농도 100%). 얻어진 우레탄 아크릴레이트계 조성물［II-2］의 중량 평균 분자량은 67,000, 60℃에서의 점도는 65,000mPa·s였다.In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, an acrylate mixture (B-1) having 31.3 g of isophorone diisocyanate (C-1) and a hydroxyl value of 96 mgKOH / g (Dipenta Acrylic acid adduct of rititol) 168.7 g, 4-methoxy phenol 0.08 g as a polymerization inhibitor, 0.1 g of dibutyltin dilaurate as a reaction catalyst was added and reacted at 60 DEG C, and the remaining isocyanate group became 0.1%. Was completed, and urethane acrylate composition [II-2] was obtained (resin content 100%). The weight average molecular weight of obtained urethane acrylate composition [II-2] was 67,000, and the viscosity in 60 degreeC was 65,000 mPa * s.
〔우레탄 아크릴레이트계 조성물［II-3］의 제조〕 [Production of Urethane Acrylate Composition [II-3]]
온도계, 교반기, 수냉 콘덴서, 질소 가스 취입구를 구비한 4구 플라스크에, 이소포론 디이소시아네이트(C-1) 13.2g, 수산기값 50mgKOH/g의 아크릴레이트 혼합물(B-2)(디펜타에리쓰리톨의 아크릴산 부가물) 186.8g, 중합 금지제로서 4-메톡시페놀 0.08g, 반응 촉매로서 디부틸주석디라우레이트 0.1g을 넣고, 60℃에서 반응시켜, 잔존 이소시아네이트기가 0.1%가 된 시점에서 반응을 종료하고, 우레탄 아크릴레이트계 조성물［II-3］을 얻었다(수지분 농도 100%). In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 13.2 g of isophorone diisocyanate (C-1) and an acrylate mixture (B-2) having a hydroxyl value of 50 mgKOH / g (Dipentaeryth 186.8 g of acrylic acid adduct of lititol, 0.08 g of 4-methoxyphenol as a polymerization inhibitor, and 0.1 g of dibutyltin dilaurate as a reaction catalyst were added and reacted at 60 ° C, when the remaining isocyanate group became 0.1%. Reaction was complete | finished and urethane acrylate composition [II-3] was obtained (resin content concentration 100%).
얻어진 우레탄 아크릴레이트계 조성물［II-3］의 중량 평균 분자량은 2,000 60℃에서의 점도는 1,700mPa·s였다.The viscosity in 2,000-60 degreeC of the weight average molecular weight of obtained urethane acrylate composition [II-3] was 1,700 mPa * s.
또한, 아크릴레이트 혼합물(B-2) 중에 있어서의 하기 성분 (b1)∼(b6)의 합계에 대한 각 성분의 함유 비율은 이하와 같다.In addition, the content rate of each component with respect to the sum total of the following components (b1)-(b6) in an acrylate mixture (B-2) is as follows.
(b4) 디펜타에리쓰리톨 테트라아크릴레이트 6%(b4) Dipentaerythritol tetraacrylate 6%
(b5) 디펜타에리쓰리톨 펜타아크릴레이트 54%(b5) dipentaerythritol pentaacrylate 54%
(b6) 디펜타에리쓰리톨 헥사아크릴레이트 40% (b6) dipentaerythritol hexaacrylate 40%
단, (b1) 디펜타에리쓰리톨 모노아크릴레이트, (b2) 디펜타에리쓰리톨 디아크릴레이트, (b3) 디펜타에리쓰리톨 트리아크릴레이트에 관해서는 함유량이 측정 한계치 이하였기 때문에, (b4)∼(b6) 성분의 함유 비율을 나타냈다.However, since content was below the measurement limit regarding (b1) dipentaerythritol monoacrylate, (b2) dipentaerythritol diacrylate, and (b3) dipentaerythritol triacrylate, (b4 The content rate of (a)-(b6) component was shown.
〔우레탄 아크릴레이트계 조성물［I'-5］의 제조〕 [Production of Urethane Acrylate Composition [I'-5]]
온도계, 교반기, 수냉 콘덴서, 질소 가스 취입구를 구비한 플라스크에, 이소포론 디이소시아네이트(C-1) 38.4g, 수산기값 118mgKOH/g의 아크릴레이트 혼합물(A'-1)(펜타에리쓰리톨의 아크릴산 부가물) 161.6g을 넣고, 중합 금지제로서 하이드로퀴논메틸에테르 0.01g, 반응 촉매로서 디부틸주석디라우레이트 0.01g을 넣고, 60℃에서 8시간 반응시켜, 잔존 이소시아네이트기가 0.3% 이하가 된 시점에서 반응을 종료하고, 우레탄 아크릴레이트계 조성물［I'-5］를 얻었다(수지분 농도 100%). In a flask equipped with a thermometer, a stirrer, a water cooling condenser, and a nitrogen gas inlet, an acrylate mixture (A'-1) having 38.4 g of isophorone diisocyanate (C-1) and a hydroxyl value of 118 mgKOH / g (of pentaerythritol 161.6 g of acrylic acid adduct) was added, 0.01 g of hydroquinone methyl ether as a polymerization inhibitor, and 0.01 g of dibutyltin dilaurate as a reaction catalyst were added and reacted at 60 ° C for 8 hours, whereby the remaining isocyanate group became 0.3% or less. Reaction was complete | finished at the time point, and urethane acrylate composition [I'-5] was obtained (resin content concentration 100%).
얻어진 우레탄 아크릴레이트계 조성물［I'-5］의 중량 평균 분자량은 1,400, 60℃에서의 점도는 3,000mPa·s였다.As for the weight average molecular weight of obtained urethane acrylate composition [I'-5], the viscosity in 1,400 and 60 degreeC was 3,000 mPa * s.
또한, 아크릴레이트 혼합물(A'-1) 중에 있어서의 하기 성분(a1)∼(a4)의 합계에 대한 각 성분의 함유 비율은 이하와 같다.In addition, the content rate of each component with respect to the sum total of the following components (a1)-(a4) in an acrylate mixture (A'-1) is as follows.
(a2) 펜타에리쓰리톨 디아크릴레이트 5%(a2) pentaerythritol diacrylate 5%
(a3) 펜타에리쓰리톨 트리아크릴레이트 50%(a3) pentaerythritol triacrylate 50%
(a4) 펜타에리쓰리톨 테트라아크릴레이트 45%(a4) pentaerythritol tetraacrylate 45%
단, (a1) 펜타에리쓰리톨 모노아크릴레이트에 관해서는 함유량이 측정 한계치 이하였기 때문에, (a2)∼(a4) 성분의 함유 비율을 나타냈다.However, since content was below the measurement limit value about (a1) pentaerythritol monoacrylate, the content rate of (a2)-(a4) component was shown.
〔우레탄 아크릴레이트계 조성물［I'-6］의 제조〕 [Production of Urethane Acrylate-based Composition [I'-6]]
온도계, 교반기, 수냉 콘덴서, 질소 가스 취입구를 구비한 4구 플라스크에, 수첨화 자일렌 디이소시아네이트(C-2) 23.3g, 수산기값 184.2mgKOH/g의 아크릴레이트 혼합물(A'-2)(펜타에리쓰리톨의 아크릴산 부가물) 76.7g, 용제로서 초산 에틸 100g, 중합 금지제로서 4-메톡시페놀 0.08g, 반응 촉매로서 디부틸주석디라우레이트 0.05g을 넣고, 60℃에서 반응시켜, 잔존 이소시아네이트기가 0.1%가 된 시점에서 반응을 종료하고, 우레탄 아크릴레이트계 조성물［I'-6］을 얻었다(수지분 농도 50%). 얻어진 우레탄 아크릴레이트계 조성물［I'-6］의 중량 평균 분자량은 2,200, 20℃에서의 점도는 85 mPa·s였다.In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, an acrylate mixture (A'-2) having 23.3 g of hydrogenated xylene diisocyanate (C-2) and a hydroxyl value of 184.2 mgKOH / g ( 76.7 g of acrylic acid adduct of pentaerythritol), 100 g of ethyl acetate as a solvent, 0.08 g of 4-methoxyphenol as a polymerization inhibitor, 0.05 g of dibutyltin dilaurate as a reaction catalyst were added and reacted at 60 ° C, Reaction was complete | finished when the remaining isocyanate group became 0.1%, and urethane acrylate composition [I'-6] was obtained (resin content concentration 50%). The viscosity in 2,200 and 20 degreeC of the weight average molecular weight of obtained urethane acrylate composition [I'-6] was 85 mPa * s.
또한, 아크릴레이트 혼합물(A'-2) 중에 있어서의 하기 성분(a1)∼(a4)의 합계에 대한 각 성분의 함유 비율은 이하와 같다.In addition, the content rate of each component with respect to the sum total of the following components (a1)-(a4) in an acrylate mixture (A'-2) is as follows.
(a1) 펜타에리쓰리톨 모노아크릴레이트 1.6%(a1) pentaerythritol monoacrylate 1.6%
(a2) 펜타에리쓰리톨 디아크릴레이트 14.6%(a2) pentaerythritol diacrylate 14.6%
(a3) 펜타에리쓰리톨 트리아크릴레이트 49.6%(a3) pentaerythritol triacrylate 49.6%
(a4) 펜타에리쓰리톨 테트라아크릴레이트 34.2%(a4) pentaerythritol tetraacrylate 34.2%
〔우레탄 아크릴레이트계 조성물［I'-7］의 제조〕 [Production of Urethane Acrylate-based Composition [I'-7]]
온도계, 교반기, 수냉 콘덴서, 질소 가스 취입구를 구비한 4구 플라스크에, 이소포론 디이소시아네이트(C-1) 25.8g, 수산기값 184.2mgKOH/g의 아크릴레이트 혼합물(A'-2)(펜타에리쓰리톨의 아크릴산 부가물) 74.2g, 용제로서 초산에틸 100g, 중합 금지제로서 4-메톡시페놀 0.08g, 반응 촉매로서 디부틸주석디라우레이트 0.05g을 넣고, 60℃에서 반응시켜서, 잔존 이소시아네이트기가 0.1%가 된 시점에서 반응을 종료하고, 우레탄 아크릴레이트계 조성물［I'-7］을 얻었다(수지분 농도 50%).In a four-necked flask equipped with a thermometer, a stirrer, a water cooling condenser, and a nitrogen gas inlet, an acrylate mixture (A'-2) having 25.8 g of isophorone diisocyanate (C-1) and a hydroxyl value of 184.2 mgKOH / g (pentaene Acrylic acid adduct of rititol) 74.2 g, ethyl acetate 100 g as solvent, 0.08 g of 4-methoxyphenol as a polymerization inhibitor, 0.05 g of dibutyltin dilaurate as a reaction catalyst, and reacted at 60 ° C Reaction was complete | finished when group became 0.1%, and urethane acrylate composition [I'-7] was obtained (resin concentration 50%).
얻어진 우레탄 아크릴레이트계 조성물［I'-7］의 중량 평균 분자량은 2,100, 20℃에서의 점도는 73mPa·s였다.The viscosity in 2,100 and 20 degreeC of the weight average molecular weight of obtained urethane acrylate composition [I'-7] was 73 mPa * s.
＜실시예 5∼12, 비교예 5∼9＞ <Examples 5-12, Comparative Examples 5-9>
〔활성 에너지선 경화성 수지 조성물의 제조〕 [Production of Active Energy Ray Curable Resin Composition]
상기에서 얻어진 우레탄 아크릴레이트계 조성물(［I］,［II］,［I'］)을 하기 표 2에 나타내는 바와 같은 배합 조성으로 하고, 광중합 개시제(D)로서 1-히드록시시클로헥실페닐케톤(IGM사 제조, 「옴니랏드 184」)을 경화 성분 100부에 대해서 4부 배합하여, 에너지선 경화성 수지 조성물을 얻었다.The urethane acrylate composition ([I], [II], [I ']) obtained above is made into the compounding composition as shown in following Table 2, and it is 1-hydroxycyclohexyl phenyl ketone (D) as a photoinitiator (D). IGM Corporation make "omni rod 184") 4 parts with respect to 100 parts of hardening components, and obtained the energy-beam curable resin composition.
얻어진 활성 에너지선 경화성 수지 조성물에 대해서, 하기와 같이 경화 도막을 형성하고 경화 도막의 경도, 굴곡성을 평가했다. 평가 결과는 하기 표 2와 같다.About the obtained active energy ray curable resin composition, the cured coating film was formed as follows and the hardness and the flexibility of the cured coating film were evaluated. Evaluation results are shown in Table 2 below.
〔경화 도막의 경도〕 [Hardness of the cured coating film]
상기에서 얻어진 활성 에너지선 경화성 수지 조성물을, 역접착 PET 필름(토요보사 제조, 「A4300」, 사이즈 15cm×15cm, 두께 125㎛) 기판 상에 바 코터를 사용하여 경화 후의 도막이 10㎛의 두께가 되도록 도공하고, 60℃에서 3분간 건조한 후, 고압 수은등 80W, 1등을 사용하여 18cm의 높이로부터 5.1m/min의 컨베이어 속도로 2패스의 자외선 조사(적산 조사량 500mJ/㎠)를 실시하여 경화 도막을 형성했다. 역접착 PET 필름상에 도공한 상기 경화 도막에 대해서, JIS K -5600에 준하여 시험을 실시하고 연필 경도를 측정했다.The active energy ray-curable resin composition obtained above was used as a bar coater on a reverse-adhesive PET film (Toyobo Co., Ltd., "A4300", size 15 cm x 15 cm, thickness 125 µm), so that the coating film after curing became a thickness of 10 µm. After coating and drying at 60 ° C. for 3 minutes, using a high-pressure mercury lamp 80 W and a 1 lamp, two passes of ultraviolet irradiation (accumulated irradiation amount 500 mJ / cm 2) are carried out at a conveyor speed of 5.1 m / min from a height of 18 cm to form a cured coating film. Formed. About the said cured coating film coated on the non-adhesive PET film, it tested according to JIS K-5600 and measured the pencil hardness.
〔경화 도막의 굴곡성〕 [Flexibility of Cured Coating Film]
상기의 경도 평가와 같이 하여 경화 도막을 형성하고, 역접착 PET 필름 상에 도공한 경화 도막에 대해서, JIS K 5600-5-1에 준하여 원통형 맨드릴 굴곡 시험기를 사용하여 굴곡성의 평가를 실시했다. 평가용 경화 도막을, 도막면이 외측이 되도록 시험봉에 휘감았을 때에, 갈라짐 또는 박리가 생기는 최대의 지름(정수값, mm)을 측정했다. 값이 작을수록 굴곡성이 높은 도막인 것을 의미한다.The cured coating film was formed in the same manner as the above hardness evaluation, and the curable coating film coated on the anti-adhesive PET film was evaluated for flexibility by using a cylindrical mandrel bending tester in accordance with JIS K 5600-5-1. When the cured coating film for evaluation was wound around the test rod so that the coating film surface became an outer side, the largest diameter (an integer value, mm) which a crack or peeling generate | occur | produced was measured. The smaller the value, the higher the flexibility.
상기 평가 결과로부터, 실시예 5∼12의 우레탄 아크릴레이트계 조성물［I］및［II］를 함유하는 활성 에너지선 경화성 수지 조성물로부터 얻어지는 경화 도막은, 경도 및 굴곡성의 양쪽 모두가 뛰어나는 것을 알 수 있다. 한편, 우레탄 아크릴레이트계 조성물［I］를 함유하지 않고, 우레탄 아크릴레이트계 조성물［II］만을 사용한 비교예 5에서는, 경화 도막의 굴곡성이 떨어지는 것이었다. 또한, 수산기값이 낮은 아크릴레이트 혼합물을 사용하여 조제한 우레탄 아크릴레이트계 조성물을 함유하는 비교예 6 및 7에 대해도, 경화 도막의 굴곡성이 떨어지는 것이었다.From the said evaluation result, it turns out that the cured coating film obtained from the active-energy-ray-curable resin composition containing the urethane acrylate composition [I] and [II] of Examples 5-12 is excellent in both hardness and flexibility. have. On the other hand, in Comparative Example 5 using only the urethane acrylate composition [I] and using only the urethane acrylate composition [II], the flexibility of the cured coating film was inferior. Moreover, the curability of the cured coating film was also inferior with respect to Comparative Examples 6 and 7 containing the urethane acrylate composition prepared using the acrylate mixture with low hydroxyl value.
또, 수산기값의 약간 높은 아크릴레이트 혼합물을 사용한 조제한 우레탄 아크릴레이트계 조성물을 함유하는 비교예 8 및 9에 대해도, 경화 도막의 굴곡성이 떨어지는 것이었다.Moreover, the curability of the cured coating film was also inferior to Comparative Examples 8 and 9 containing the urethane acrylate composition prepared using a slightly higher acrylate mixture having a hydroxyl value.
이것으로부터, 상기 실시예 5∼12의 활성 에너지선 경화성 수지 조성물이 경도 및 굴곡성에 양호하고, 코팅제등, 특히 하드 코트용 코팅제나 광학 필름용 코팅제의 용도에 대해 유용하다는 것을 알 수 있다.From this, it turns out that the active energy ray curable resin composition of Examples 5-12 is favorable to hardness and bendability, and it is useful about a coating agent etc., especially the use of the coating agent for hard coats, and the coating agent for optical films.
＜＜우레탄(메타)아크릴레이트계 조성물［III］를 사용한 실시예＞＞<< Example using urethane (meth) acrylate type composition [III] >>
우레탄(메타)아크릴레이트계 조성물의 제조에 앞서, 이하와 같이 혼합물(A), 혼합물(A')(비교예용), 혼합물(B), 다가 이소시아네이트(C), 광중합 개시제(D)를 준비했다. Prior to the preparation of the urethane (meth) acrylate-based composition, a mixture (A), a mixture (A ') (for comparative purposes), a mixture (B), a polyvalent isocyanate (C) and a photopolymerization initiator (D) were prepared as follows. .
〔혼합물(A)〕[Mixture (A)]
·A-1：수산기값 288mgKOH/g의 펜타에리쓰리톨의 아크릴산 부가물에서, 하기와 같이 성분 (a1)∼(a4)의 합계에 대한 각 성분의 함유 비율은 이하와 같다.A-1: The content rate of each component with respect to the sum total of component (a1)-(a4) is as follows in the acrylic acid adduct of pentaerythritol with a hydroxyl value of 288 mgKOH / g.
(a1) 펜타에리쓰리톨 모노 아크릴레이트 4%(a1) pentaerythritol mono acrylate 4%
(a2) 펜타에리쓰리톨 디아크릴레이트 29%(a2) pentaerythritol diacrylate 29%
(a3) 펜타에리쓰리톨 트리아크릴레이트 49%(a3) pentaerythritol triacrylate 49%
(a4) 펜타에리쓰리톨 테트라아크릴레이트 18%(a4) Pentaerythritol tetraacrylate 18%
〔혼합물(A')(비교예용)〕[Mixture A '(for comparative example)]
·A'-1：수산기값 118 mgKOH/g의 펜타에리쓰리톨의 아크릴산 부가물에서, 하기 성분(a1)∼(a4)의 합계에 대한 각 성분의 함유 비율은 이하와 같다.A'-1: The content rate of each component with respect to the sum total of the following components (a1)-(a4) in the acrylic acid adduct of pentaerythritol with a hydroxyl value of 118 mgKOH / g is as follows.
(a2) 펜타에리쓰리톨 디아크릴레이트 5%(a2) pentaerythritol diacrylate 5%
(a3) 펜타에리쓰리톨 트리아크릴레이트 50%(a3) Pentaerythritol triacrylate 50%
(a4) 펜타에리쓰리톨 테트라아크릴레이트 45% (a4) pentaerythritol tetraacrylate 45%
단, (a1) 펜타에리쓰리톨 모노아크릴레이트에 관해서는 함유량이 측정 한계치 이하였기 때문에, (a2)∼(a4) 성분의 함유 비율을 나타냈다.However, since content was below the measurement limit value about (a1) pentaerythritol monoacrylate, the content rate of (a2)-(a4) component was shown.
·A'-2：수산기값 184.2mgKOH/g의 펜타에리쓰리톨의 아크릴산 부가물에서, 하기 성분(a1)∼(a4)의 합계에 대한 각 성분의 함유 비율은 이하와 같다.A'-2: The content rate of each component with respect to the sum total of the following components (a1)-(a4) in the acrylic acid adduct of pentaerythritol with a hydroxyl value of 184.2 mgKOH / g is as follows.
(a1) 펜타에리쓰리톨 모노 아크릴레이트 1.6%(a1) pentaerythritol mono acrylate 1.6%
(a2) 펜타에리쓰리톨 디아크릴레이트 14.6%(a2) pentaerythritol diacrylate 14.6%
(a3) 펜타에리쓰리톨 트리아크릴레이트 49.6%(a3) Pentaerythritol triacrylate 49.6%
(a4) 펜타에리쓰리톨 테트라 아크릴레이트 34.2%(a4) pentaerythritol tetra acrylate 34.2%
〔혼합물(B)〕[Mixture (B)]
·B-1：수산기값 96 mgKOH/g의 디펜타에리쓰리톨의 아크릴산 부가물에서, 하기 성분(b1)∼(b6)의 합계에 대한 각 성분의 함유 비율은 이하와 같다.B-1: The content rate of each component with respect to the sum total of the following components (b1)-(b6) in the acrylic acid adduct of dipentaerythritol with a hydroxyl value of 96 mgKOH / g is as follows.
(b4) 디펜타에리쓰리톨 테트라아크릴레이트 18%(b4) dipentaerythritol tetraacrylate 18%
(b5) 디펜타에리쓰리톨 펜타아크릴레이트 51%(b5) dipentaerythritol pentaacrylate 51%
(b6) 디펜타에리쓰리톨 헥사아크릴레이트 31% (b6) dipentaerythritol hexaacrylate 31%
단, (b1) 디펜타에리쓰리톨 모노아크릴레이트, (b2) 디펜타에리쓰리톨 디아크릴레이트, (b3) 디펜타에리쓰리톨 트리아크릴레이트에 관해서는 함유량이 측정 한계치 이하였기 때문에, (b4)∼(b6) 성분의 함유 비율을 나타냈다.However, since content was below the measurement limit regarding (b1) dipentaerythritol monoacrylate, (b2) dipentaerythritol diacrylate, and (b3) dipentaerythritol triacrylate, (b4 The content rate of (a)-(b6) component was shown.
·B-2：수산기값 54mgKOH/g의 디펜타에리쓰리톨의 아크릴산 부가물에서, 하기 성분(b1)∼(b6)의 합계에 대한 각 성분의 함유 비율은 이하와 같다.B-2: The content rate of each component with respect to the sum total of the following components (b1)-(b6) in the acrylic acid adduct of dipentaerythritol with a hydroxyl value of 54 mgKOH / g is as follows.
(b4) 디펜타에리쓰리톨 테트라아크릴레이트 6%(b4) dipentaerythritol tetraacrylate 6%
(b5) 디펜타에리쓰리톨 펜타아크릴레이트 54%(b5) dipentaerythritol pentaacrylate 54%
(b6) 디펜타에리쓰리톨 헥사아크릴레이트 40% (b6) dipentaerythritol hexaacrylate 40%
단, (b1) 디펜타에리쓰리톨 모노아크릴레이트, (b2) 디펜타에리쓰리톨 디아크릴레이트, (b3) 디펜타에리쓰리톨 트리아크릴레이트에 관해서는 함유량이 측정 한계치 이하였기 때문에, (b4)∼(b6) 성분의 함유 비율을 나타냈다.However, since content was below the measurement limit regarding (b1) dipentaerythritol monoacrylate, (b2) dipentaerythritol diacrylate, and (b3) dipentaerythritol triacrylate, (b4 The content rate of (a)-(b6) component was shown.
〔다가 이소시아네이트(C)〕[Polyvalent isocyanate (C)]
·C-1： 이소포론 디이소시아네이트C-1: isophorone diisocyanate
·C-2：수첨화 자일렌 디이소시아네이트C-2 ： Hydrated xylene diisocyanate
·C-4：자일렌 디이소시아네이트C-4: xylene diisocyanate
〔광중합 개시제(D)〕[Photoinitiator (D)]
·D-1：1-히드록시시클로헥실페닐케톤(IGM사 제조, 「옴니랏드 184」)D-1: 1-hydroxycyclohexylphenyl ketone (IGM Corporation make, `` omnilad 184 '')
〔합성예 1：우레탄 아크릴레이트계 조성물(III-1)〕 [Synthesis example 1: urethane acrylate composition (III-1)]
온도계, 교반기, 수냉 콘덴서, 질소 가스 취입구를 구비한 4구 플라스크에, 수첨화 자일렌 디이소시아네이트(C-2) 24g, 수산기값 288mgKOH/g의 아크릴레이트 혼합물(A-1)(펜타에리쓰리톨의 아크릴산 부가물) 33g, 수산기값 96mgKOH/g의 아크릴레이트 혼합물(B-1)(디펜타에리쓰리톨의 아크릴산 부가물) 43g, 용제로서 초산에틸 100g, 중합 금지제로서 4-메톡시페놀 0.08g, 반응 촉매로서 디부틸주석디라우레이트 0.05g을 넣고, 60℃에서 반응시켜서, 잔존 이소시아네이트기가 0.1%가 된 시점에서 반응을 종료하고, 우레탄 아크릴레이트계 조성물(III-1)을 얻었다(수지분 농도 50%).In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, an acrylate mixture (A-1) (pentaeryz) having 24 g of hydrogenated xylene diisocyanate (C-2) and a hydroxyl value of 288 mgKOH / g 33 g of acrylic acid adduct of lititol, 43 g of acrylate mixture (B-1) (acrylic acid adduct of dipentaerythritol) having a hydroxyl value of 96 mgKOH / g, 100 g of ethyl acetate as a solvent, 4-methoxyphenol as a polymerization inhibitor 0.05 g of dibutyltin dilaurate was added as 0.08 g and a reaction catalyst, it was made to react at 60 degreeC, reaction was complete | finished when the remaining isocyanate group became 0.1%, and urethane acrylate composition (III-1) was obtained ( Resin concentration 50%).
얻어진 우레탄 아크릴레이트계 조성물(III-1)의 중량 평균 분자량은 4,900, 20℃에서의 점도는 40mPa·s였다. 또한, 20℃에서의 점도의 측정은 B형 점도계를 이용해서 실시했다. 20℃에서의 점도 측정은 이하와 같다.The viscosity in 4,900 and 20 degreeC of the weight average molecular weight of obtained urethane acrylate composition (III-1) was 40 mPa * s. In addition, the measurement of the viscosity in 20 degreeC was implemented using the Brookfield viscometer. The viscosity measurement at 20 degreeC is as follows.
〔합성예 2：우레탄 아크릴레이트계 조성물(III-2)〕 [Synthesis example 2: urethane acrylate composition (III-2)]
온도계, 교반기, 수냉 콘덴서, 질소 가스 취입구를 구비한 4구 플라스크에, 자일렌 디이소시아네이트(C-4) 23g, 수산기값 288 mgKOH/g의 아크릴레이트 혼합물(A-1)(펜타에리쓰리톨의 아크릴산 부가물) 33g, 수산기값 96 mgKOH/g의 아크릴레이트 혼합물(B-1)(디펜타에리쓰리톨의 아크릴산 부가물) 44g, 용제로서 초산에틸 100g, 중합 금지제로서 4-메톡시페놀 0.08g, 반응 촉매로서 디부틸주석디라우레이트 0.05g을 넣고, 60℃에서 반응시켜서, 잔존 이소시아네이트기가 0.1%가 된 시점에서 반응을 종료하고, 우레탄 아크릴레이트계 조성물(III-2)을 얻었다(수지분 농도 50%).In a four-necked flask equipped with a thermometer, a stirrer, a water cooling condenser, and a nitrogen gas inlet, an acrylate mixture (A-1) (pentaerythritol) having 23 g of xylene diisocyanate (C-4) and a hydroxyl value of 288 mgKOH / g Acrylic acid adduct) 33g, acrylate mixture (B-1) (hydroxyl adduct of dipentaerythritol) 44 g of hydroxyl value 96 mgKOH / g, 100 g of ethyl acetate as a solvent, 4-methoxyphenol as a polymerization inhibitor 0.05 g of dibutyltin dilaurate was added as 0.08 g and a reaction catalyst, and it was made to react at 60 degreeC, reaction was complete | finished when the remaining isocyanate group became 0.1%, and urethane acrylate composition (III-2) was obtained ( Resin concentration 50%).
얻어진 우레탄 아크릴레이트계 조성물(III-2)의 중량 평균 분자량은 4,600, 20℃에서의 점도는 30mPa·s였다.The weight average molecular weight of obtained urethane acrylate composition (III-2) was 4,600, and the viscosity in 20 degreeC was 30 mPa * s.
〔합성예 3：우레탄 아크릴레이트계 조성물(III-3)〕 [Synthesis example 3: urethane acrylate composition (III-3)]
온도계, 교반기, 수냉 콘덴서, 질소 가스 취입구를 구비한 4구 플라스크에, 수첨화 자일렌 디이소시아네이트(C-2) 24g, 수산기값 288mgKOH/g의 아크릴레이트 혼합물(A-1)(펜타에리쓰리톨의 아크릴산 부가물) 35g, 수산기값 54 mgKOH/g의 아크릴레이트 혼합물(B-2)(디펜타에리쓰리톨의 아크릴산 부가물) 81g, 용제로서 초산에틸 60g, 중합 금지제로서 4-메톡시페놀 0.08g, 반응 촉매로서 디부틸주석디라우레이트 0.05g을 넣고, 60℃에서 반응시켜, 잔존 이소시아네이트기가 0.1%가 된 시점에서 반응을 종료하고, 우레탄 아크릴레이트계 조성물(III-3)을 얻었다(수지분 농도 70%).In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, an acrylate mixture (A-1) (pentaeryz) having 24 g of hydrogenated xylene diisocyanate (C-2) and a hydroxyl value of 288 mgKOH / g Acrylic acid adduct of lithol) 35 g, acrylate mixture (B-2) (acrylic acid adduct of dipentaerythritol) having a hydroxyl value of 54 mgKOH / g, 60 g of ethyl acetate as a solvent, 4-methoxy as a polymerization inhibitor 0.08 g of phenol and 0.05 g of dibutyltin dilaurate were added as a reaction catalyst, and reacted at 60 degreeC, reaction was complete | finished when the remaining isocyanate group became 0.1%, and urethane acrylate composition (III-3) was obtained. (70% resin fraction concentration).
얻어진 우레탄 아크릴레이트계 조성물(III-3)의 중량 평균 분자량은 3,300, 20℃에서의 점도는 460mPa·s였다.The viscosity in 3,300 and 20 degreeC of the weight average molecular weight of obtained urethane acrylate composition (III-3) was 460 mPa * s.
〔합성예 4：우레탄 아크릴레이트계 조성물(III-4)〕 [Synthesis example 4: urethane acrylate composition (III-4)]
온도계, 교반기, 수냉 콘덴서, 질소 가스 취입구를 구비한 4구 플라스크에, 이소포론 디이소시아네이트(C-1) 39g, 수산기값 288mgKOH/g의 아크릴레이트 혼합물(A-1)(펜타에리쓰리톨의 아크릴산 부가물) 49g, 수산기값 54 mgKOH/g의 아크릴레이트 혼합물(B-2)(디펜타에리쓰리톨의 아크릴산 부가물) 112g, 중합 금지제로서 4-메톡시페놀 0.08g, 반응 촉매로서 디부틸주석디라우레이트 0.05g을 넣고, 60℃에서 반응시켜서, 잔존 이소시아네이트기가 0.1%가 된 시점에서 반응을 종료하고, 우레탄 아크릴레이트계 조성물(III-3)을 얻었다(수지분 농도 100%).In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, an acrylate mixture (A-1) of 39 g of isophorone diisocyanate (C-1) and a hydroxyl value of 288 mgKOH / g (of pentaerythritol Acrylic acid adducts) 49 g, hydroxyl value 54 mgKOH / g (g-2) (acrylic acid adduct of dipentaerythritol) 112 g, 0.08 g of 4-methoxyphenols as a polymerization inhibitor, di as a reaction catalyst 0.05 g of butyltin dilaurate was added and reacted at 60 degreeC, reaction was complete | finished when the remaining isocyanate group became 0.1%, and urethane acrylate composition (III-3) was obtained (resin content concentration 100%).
얻어진 우레탄 아크릴레이트계 조성물(III-4)의 중량 평균 분자량은 3,800이었다. 매우 고점도였기 때문에 점도는 측정할 수 없었다.The weight average molecular weight of obtained urethane acrylate composition (III-4) was 3,800. The viscosity could not be measured because it was very high viscosity.
〔합성예 5：우레탄 아크릴레이트계 조성물(III'-1)〕 [Synthesis example 5: urethane acrylate composition (III'-1)]
온도계, 교반기, 수냉 콘덴서, 질소 가스 취입구를 구비한 4구 플라스크에, 수첨화 자일렌 디이소시아네이트(C-2) 22g, 수산기값 118mgKOH/g의 아크릴레이트 혼합물(A'-1)(펜타에리쓰리톨의 아크릴산 부가물) 78g, 수산기값 96mgKOH/g의 아크릴레이트 혼합물(B-1)(디펜타에리쓰리톨의 아크릴산 부가물) 40g, 용제로서 초산에틸 60g, 중합 금지제로서 4-메톡시페놀 0.08g, 반응 촉매로서 디부틸주석디라우레이트 0.05g을 넣고, 60℃에서 반응시켜, 잔존 이소시아네이트기가 0.1%가 된 시점에서 반응을 종료하고, 우레탄 아크릴레이트계 조성물(III'-1)을 얻었다(수지분 농도 70%).In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, an acrylate mixture (A'-1) having 22 g of hydrogenated xylene diisocyanate (C-2) and a hydroxyl value of 118 mgKOH / g (pentaene Acrylic acid adduct of rititol) 78 g, acrylate mixture (B-1) (hydroxyl adduct of dipentaerythritol) with hydroxyl value of 96 mgKOH / g, 40 g of ethyl acetate as solvent, 4-methoxy as polymerization inhibitor 0.08 g of phenol and 0.05 g of dibutyltin dilaurate were added as a reaction catalyst, and reacted at 60 degreeC, reaction was complete | finished when the remaining isocyanate group became 0.1%, and urethane acrylate composition (III'-1) was terminated. It was obtained (resin concentration 70%).
얻어진 우레탄 아크릴레이트계 조성물(III'-1)의 중량 평균 분자량은 1,700, 20℃에서의 점도는 140mPa·s였다.The viscosity in 1,700 and 20 degreeC of the weight average molecular weight of obtained urethane acrylate composition (III'-1) was 140 mPa * s.
〔합성예 6：우레탄 아크릴레이트계 조성물(III'-2)〕 [Synthesis example 6: urethane acrylate composition (III'-2)]
온도계, 교반기, 수냉 콘덴서, 질소 가스 취입구를 구비한 4구 플라스크에, 수첨화 자일렌 디이소시아네이트(C-2) 21.3g, 수산기값 184.2mgKOH/g의 아크릴레이트 혼합물(A'-2)(펜타에리쓰리톨의 아크릴산 부가물) 61.0g, 수산기값 96mgKOH/g의 아크릴레이트 혼합물(B-1)(디펜타에리쓰리톨의 아크릴산 부가물) 17.6g, 용제로서 초산에틸 100g, 중합 금지제로서 4-메톡시페놀 0.08g, 반응 촉매로서 디부틸주석디라우레이트 0.05g을 넣고, 60℃에서 반응시켜, 잔존 이소시아네이트기가 0.1%가 된 시점에서 반응을 종료하고, 우레탄 아크릴레이트계 조성물(III'-2)을 얻었다(수지분 농도 50%).In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen gas inlet, an acrylate mixture (A'-2) having 21.3 g of hydrogenated xylene diisocyanate (C-2) and a hydroxyl value of 184.2 mgKOH / g ( 61.0 g of acrylic acid adduct of pentaerythritol), 17.6 g of an acrylate mixture (B-1) (acrylic acid adduct of dipentaerythritol) having a hydroxyl value of 96 mgKOH / g, 100 g of ethyl acetate as a solvent, a polymerization inhibitor 0.08 g of 4-methoxyphenol and 0.05 g of dibutyltin dilaurate were added as a reaction catalyst, and reacted at 60 degreeC, reaction was complete | finished when the remaining isocyanate group became 0.1%, and urethane acrylate composition (III ') was carried out. -2) was obtained (resin concentration 50%).
얻어진 우레탄 아크릴레이트계 조성물(III'-2)의 중량 평균 분자량은 2,300, 20℃에서의 점도는 65 mPa·s였다.The viscosity in 2,300 and 20 degreeC of the weight average molecular weight of obtained urethane acrylate composition (III'-2) was 65 mPa * s.
〔합성예 7：우레탄 아크릴레이트계 조성물(III'-3)〕 [Synthesis example 7: Urethane acrylate composition (III'-3)]
온도계, 교반기, 수냉 콘덴서, 질소 가스 취입구를 구비한 4구 플라스크에, 자일렌디이소시아네이트(C-4) 32g, 수산기값 288mgKOH/g의 아크릴레이트 혼합물(A-1)(펜타에리쓰리톨의 아크릴산 부가물) 68g, 용제로서 초산에틸 100g, 중합 금지제로서 4-메톡시페놀 0.08g, 반응 촉매로서 디부틸주석디라우레이트 0.05g을 넣고, 60℃에서 반응시켜, 잔존 이소시아네이트기가 0.1%가 된 시점에서 반응을 종료하고, 우레탄 아크릴레이트계 조성물(III'-3)을 얻었다(수지분 농도 50%).In a four-necked flask equipped with a thermometer, a stirrer, a water cooling condenser, and a nitrogen gas inlet, an acrylate mixture (A-1) having 32 g of xylene diisocyanate (C-4) and a hydroxyl value of 288 mgKOH / g (acrylic acid of pentaerythritol) Additive) 68 g, 100 g of ethyl acetate as a solvent, 0.08 g of 4-methoxyphenol as a polymerization inhibitor, 0.05 g of dibutyltin dilaurate as a reaction catalyst were added and reacted at 60 degreeC, and the remaining isocyanate group became 0.1%. Reaction was complete | finished at the time point, and urethane acrylate composition (III'-3) was obtained (resin concentration 50%).
얻어진 우레탄 아크릴레이트계 조성물(III'-3)의 중량 평균 분자량은 5,900, 20℃에서의 점도는 50mPa·s였다.The weight average molecular weight of obtained urethane acrylate composition (III'-3) was 5,900, and the viscosity in 20 degreeC was 50 mPa * s.
〔합성예 8：우레탄 아크릴레이트계 조성물(III'-4)의 제조〕 [Synthesis example 8: manufacture of urethane acrylate composition (III'-4)]
온도계, 교반기, 수냉 콘덴서, 질소 가스 취입구를 구비한 4구 플라스크에, 수첨화 자일렌 디이소시아네이트(C-2) 28g, 수산기값 96 mgKOH/g의 아크릴레이트 혼합물(B-1)(디펜타에리쓰리톨의 아크릴산 부가물) 172g, 중합 금지제로서 4-메톡시페놀 0.08g, 반응 촉매로서 디부틸주석디라우레이트 0.1g을 넣고, 60℃에서 반응시켜, 잔존 이소시아네이트기가 0.1%가 된 시점에서 반응을 종료하고, 우레탄 아크릴레이트계 조성물(III'-4)을 얻었다(수지분 농도 100%).In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen gas inlet, an acrylate mixture (B-1) having 28 g of hydrogenated xylene diisocyanate (C-2) and a hydroxyl value of 96 mgKOH / g (Dipenta) 172 g of acrylic acid adduct of erythritol), 0.08 g of 4-methoxyphenol as a polymerization inhibitor, 0.1 g of dibutyltin dilaurate as a reaction catalyst were added and reacted at 60 degreeC, and the remaining isocyanate group became 0.1%. The reaction was terminated at and the urethane acrylate composition (III'-4) was obtained (resin concentration 100%).
얻어진 우레탄 아크릴레이트계 조성물(III'-4)의 중량 평균 분자량은 5,500, 60℃에서의 점도는 39,400mPa·s였다. 또한, 60℃에서의 점도의 측정은 E형 점도계를 사용하여 실시했다.The weight average molecular weight of obtained urethane acrylate composition (III'-4) was 5,500, and the viscosity in 60 degreeC was 39,400 mPa * s. In addition, the measurement of the viscosity in 60 degreeC was performed using the E-type viscosity meter.
＜실시예 13∼16, 비교예 10∼13＞ <Examples 13-16, Comparative Examples 10-13>
〔활성 에너지선 경화성 수지 조성물〕 [Active energy ray curable resin composition]
상기에서 얻어진 우레탄 아크릴레이트계 조성물(III-1∼4, III'-1∼4)에, 광중합 개시제(D)로서 1-히드록시시클로헥실페닐케톤(IGM사 제조, 「옴니랏드 184」)을 경화 성분 100부에 대해서 4부 배합하여 활성 에너지선 경화성 수지 조성물을 얻었다.In the urethane acrylate composition (III-1 to 4, III'-1 to 4) obtained above, 1-hydroxycyclohexylphenyl ketone (manufactured by IMG Corporation, "Omnilad 184") is used as the photopolymerization initiator (D). Four parts were mix | blended with respect to 100 parts of hardening components, and the active energy ray curable resin composition was obtained.
얻어진 활성 에너지선 경화성 수지 조성물에 대해서, 하기와 같이 경화 도막을 형성해, 경화 도막의 경도, 굴곡성, 내찰상성을 평가했다. 평가 결과는 하기 표 3과 같다.About the obtained active energy ray curable resin composition, the cured coating film was formed as follows and the hardness, the bending property, and the scratch resistance of the cured coating film were evaluated. Evaluation results are shown in Table 3 below.
〔경화 도막의 경도〕 [Hardness of the cured coating film]
상기에서 얻어진 활성 에너지선 경화성 수지 조성물을, 역접착 PET 필름(토요보사 제조, 「A4300」, 사이즈 15cm×15cm, 두께 125㎛) 기판 상에 바 코터를 이용하고, 경화 후의 도막이 10㎛의 두께가 되도록) 도공하고, 60℃에서 3분간 건조한 후, 고압 수은등 80W, 1등을 사용하여, 18cm의 높이로부터 5.1m/min의 컨베이어 속도로 2 패스의 자외선 조사(적산 조사량 500 mJ/㎠)를 실시하여 경화 도막을 형성했다.The active energy ray curable resin composition obtained above was subjected to a bar coater on a reverse-adhesive PET film (Toyobo Co., Ltd., "A4300", size 15 cm x 15 cm, thickness 125 µm), and the coating film after curing had a thickness of 10 µm. After coating and drying at 60 ° C. for 3 minutes, using a high-pressure mercury lamp 80 W and one lamp, two passes of ultraviolet irradiation (accumulated irradiation amount 500 mJ / cm 2) are carried out at a conveyor speed of 5.1 m / min from a height of 18 cm. To form a cured coating film.
역접착 PET 필름상에 도공한 상기 경화 도막에 대해서, JIS K-5600에 준하고 시험을 실시하여 연필 경도를 측정했다.About the said cured coating film coated on the non-adhesive PET film, it tested according to JISK-5600 and measured the pencil hardness.
〔경화 도막의 굴곡성〕 [Flexibility of Cured Coating Film]
상기의 경도 평가와 동일하게 하여 경화 도막을 형성하고, 역접착 PET 필름상에 도공한 경화 도막에 대해서, JIS K 5600-5-1에 준하여 원통형 맨드릴 굴곡 시험기를 사용하여 굴곡성의 평가를 실시했다. 평가용 경화 도막을, 도막면이 외측이 되도록 시험봉에 휘감았을 때에, 갈라짐 또는 박리가 생기는 최대의 지름(정수값, mm)을 측정했다. 값이 작을수록 굴곡성의 높은 도막인 것을 의미한다.The cured coating film was formed in the same manner as the above hardness evaluation, and the curable coating film coated on the anti-adhesive PET film was evaluated for flexibility using a cylindrical mandrel bending tester in accordance with JIS K 5600-5-1. When the cured coating film for evaluation was wound around the test rod so that the coating film surface became an outer side, the largest diameter (an integer value, mm) which a crack or peeling generate | occur | produced was measured. The smaller the value, the more flexible the coating.
〔경화 도막의 내찰상성〕 [Scratch resistance of the cured coating film]
상기의 경도 평가와 동일하게 하여 경화 도막을 형성하고, 역접착 PET 필름상에 도공한 경화 도막에 대해서, 스틸울(닛폰스틸울사 제조, 본 스타＃0000)을 사용하여 500g의 하중을 걸치면서 경화 도막의 표면을 10왕복시킨 후, 표면의 손상되어 정도를 육안으로 관찰했다.The cured coating film was formed in the same manner as the above hardness evaluation, and the cured coating film coated on the non-adhesive PET film was cured while applying a load of 500 g using steel wool (manufactured by Nippon Steel Wool Co., Ltd.). After reciprocating the surface of the coating film 10 times, the degree of damage to the surface was visually observed.
(평가)(evaluation)
○···흠집을 확인할 수 없는 것○ ... not able to confirm scratch
×···흠집을 확인할 수 있는 것× ··· Can identify scratches
상기 평가 결과로부터, 실시예 13∼16의 우레탄 아크릴레이트계 조성물［III］를 함유하는 활성 에너지선 경화성 수지 조성물로부터 얻어지는 경화 도막은, 경도 및 굴곡성 뿐만 아니라, 내찰상성에도 뛰어난 것을 알 수 있다. From the said evaluation result, it turns out that the cured coating film obtained from the active-energy-ray-curable resin composition containing the urethane acrylate composition [III] of Examples 13-16 is excellent not only in hardness and flexibility but also in scratch resistance.
한편, 수산기값이 200mgKOH/g 미만의 저수산기값의 펜타에리쓰리톨의 아크릴산 부가물(A'-1)을 사용한 비교예 10의 경우, 혼합물(A) 및 (B) 중, 디펜타에리쓰리톨의 아크릴산 부가물(B-1)만을 사용한 비교예 13의 경우는, 경화 도막의 굴곡성이 떨어지는 것이었다. 또, 수산기값이 조금 낮은 펜타에리쓰리톨의 아크릴산 부가물(A'-2)을 사용한 비교예 11의 경우에서는, 경도가 조금 떨어지고, 내찰상성이 떨어지는 것이었다. 또한, 혼합물(A) 및 (B) 중, 고수산기가의 펜타에리쓰리톨의 아크릴산 부가물(A-1)만을 사용한 비교예 12의 경우, 경화 도막의 내찰상성이 떨어지는 것이었다. On the other hand, in the case of the comparative example 10 which used the acrylic acid adduct (A'-1) of the pentaerythritol of the low hydroxyl value of less than 200 mgKOH / g, in a mixture (A) and (B), dipentaeryth In the case of the comparative example 13 using only the acrylic acid addition product (B-1) of lititol, the curability of the cured coating film was inferior. Moreover, in the case of the comparative example 11 which used the acrylic acid adduct (A'-2) of pentaerythritol which has a little hydroxyl value, the hardness fell slightly and it was inferior to scratch resistance. In addition, in the comparative example 12 which used only the acrylic acid addition product (A-1) of pentaerythritol of a high hydroxyl value in mixture (A) and (B), it was inferior to the scratch resistance of a cured coating film.
이것들로부터, 실시예 13∼16의 활성 에너지선 경화성 수지 조성물이 경도, 굴곡성에 더하여 내찰상성에도 양호하고, 코팅제등, 특히 하드 코트용 코팅제나 광학 필름용 코팅제의 용도에 대해 유용하다는 것을 알 수 있다.From these, it turns out that the active energy ray curable resin composition of Examples 13-16 is favorable also to abrasion resistance in addition to hardness and flexibility, and is useful for the use of a coating agent, especially a hard coat coating agent and an optical film coating agent. have.
상기 실시예에 대해서는, 본 발명에 있어서의 구체적인 형태에 대해 나타냈지만, 상기 실시예는 단순한 예시에 지나지 않으며, 한정적으로 해석되는 것은 아니다. 당업자에게 분명한 여러 가지 변형은, 본 발명의 범위내인 것이 기대되고 있다.Although the said Example was shown about the specific form in this invention, the said Example is only a mere illustration and is not interpreted limitedly. Various modifications apparent to those skilled in the art are expected to be within the scope of the present invention.
본 발명의 활성 에너지선 경화성 수지 조성물은, 경화 도막을 형성했을 때에, 경화 수축이 작기 때문에 컬하기 어렵고, 경도 및 굴곡성이 뛰어난 도막을 형성할 수 있는 것이며, 코팅제, 특히 하드 코트용 코팅제나 광학 필름용 코팅제로서 유용하다. 또, 도료, 잉크 등으로서도 유용하다. 또한, 필름 상에 활성 에너지선 경화성 수지 조성물층이 형성된 미경화 상태의 적층 필름의 수지 조성물측을 성형물에 붙인 후, 활성 에너지선 경화를 실시하는 것으로, 여러 가지의 성형물에 용이하게 경화막을 형성할 수 있다.When the cured coating film is formed, the active energy ray-curable resin composition of the present invention is hard to curl because of its small shrinkage, and can form a coating film excellent in hardness and flexibility, and is a coating agent, in particular, a coating agent or an optical film for a hard coat. It is useful as a coating agent for. It is also useful as a paint, ink, and the like. Moreover, after attaching the resin composition side of the uncured laminated | multilayer film in which the active energy ray curable resin composition layer was formed on the film to a molded object, hardening of an active energy ray can be performed, and a cured film can be easily formed in various molded objects. Can be.
Claims (15)
(a1) 펜타에리쓰리톨 모노(메타)아크릴레이트
(a2) 펜타에리쓰리톨 디(메타)아크릴레이트
(a3) 펜타에리쓰리톨 트리(메타)아크릴레이트
(a4) 펜타에리쓰리톨 테트라(메타)아크릴레이트(Meth) acrylates (a1) to (a3) and polyhydric isocyanate (CA) in a mixture (A) of the following (meth) acrylates (a1) to (a4) which are reactants of pentaerythritol and (meth) acrylic acid The urethane (meth) acrylate type composition [I] which reacted), and the hydroxyl value of the said mixture (A) is 200 mgKOH / g or more, The active energy ray curable resin composition characterized by the above-mentioned.
(a1) pentaerythritol mono (meth) acrylate
(a2) pentaerythritol di (meth) acrylate
(a3) pentaerythritol tri (meth) acrylate
(a4) pentaerythritol tetra (meth) acrylate
혼합물(A)
(a1) 펜타에리쓰리톨 모노(메타)아크릴레이트
(a2) 펜타에리쓰리톨 디(메타)아크릴레이트
(a3) 펜타에리쓰리톨 트리(메타)아크릴레이트
(a4) 펜타에리쓰리톨 테트라(메타)아크릴레이트
혼합물(B)
(b1) 디펜타에리쓰리톨 모노(메타)아크릴레이트
(b2) 디펜타에리쓰리톨 디(메타)아크릴레이트
(b3) 디펜타에리쓰리톨 트리(메타)아크릴레이트
(b4) 디펜타에리쓰리톨 테트라(메타)아크릴레이트
(b5) 디펜타에리쓰리톨 펜타(메타)아크릴레이트
(b6) 디펜타에리쓰리톨 헥사(메타)아크릴레이트(Meth) acrylates (a1) to (a3) and polyhydric isocyanate (CA) in a mixture (A) of the following (meth) acrylates (a1) to (a4) which are reactants of pentaerythritol and (meth) acrylic acid Mixture (B) of the following (meth) acrylate (b1)-(b6) which is a reaction product of urethane (meth) acrylate type composition [I] which reacted with, and dipentaerythritol and (meth) acrylic acid It contains urethane (meth) acrylate type composition [II] which (meth) acrylate (b1)-(b5) and polyhydric isocyanate (CB) reacted, and the hydroxyl value of the said mixture (A) is 200 mgKOH / g or more. Simultaneously, the hydroxyl value of the said mixture (B) is 40 mgKOH / g or more, The active energy ray curable resin composition characterized by the above-mentioned.
Mixture (A)
(a1) pentaerythritol mono (meth) acrylate
(a2) pentaerythritol di (meth) acrylate
(a3) pentaerythritol tri (meth) acrylate
(a4) pentaerythritol tetra (meth) acrylate
Mixture (B)
(b1) dipentaerythritol mono (meth) acrylate
(b2) dipentaerythritol di (meth) acrylate
(b3) dipentaerythritol tri (meth) acrylate
(b4) dipentaerythritol tetra (meth) acrylate
(b5) dipentaerythritol penta (meth) acrylate
(b6) dipentaerythritol hexa (meth) acrylate
［α］펜타에리쓰리톨과 (메타)아크릴산과의 반응물인 하기 (메타)아크릴레이트(a1)∼(a4)의 혼합물(A)의 수산기값이 200mgKOH/g 이상이며, 상기 혼합물(A) 중의 (메타)아크릴레이트(a1)∼(a3).
(a1) 펜타에리쓰리톨 모노(메타)아크릴레이트
(a2) 펜타에리쓰리톨 디(메타)아크릴레이트
(a3) 펜타에리쓰리톨 트리(메타)아크릴레이트
(a4) 펜타에리쓰리톨 테트라(메타)아크릴레이트
［β] 디펜타에리쓰리톨과 (메타)아크릴산과의 반응물인 하기 (메타)아크릴레이트(b1)∼(b6)의 혼합물(B)의 수산기값이 40mgKOH/g 이상이며, 상기 혼합물(B) 중의 (메타)아크릴레이트(b1)∼(b5).
(b1) 디펜타에리쓰리톨 모노(메타)아크릴레이트
(b2) 디펜타에리쓰리톨 디(메타)아크릴레이트
(b3) 디펜타에리쓰리톨 트리(메타)아크릴레이트
(b4) 디펜타에리쓰리톨 테트라(메타)아크릴레이트
(b5) 디펜타에리쓰리톨 펜타(메타)아크릴레이트
(b6) 디펜타에리쓰리톨 헥사(메타)아크릴레이트Urethane (meth) which (meth) acrylate (a1)-(a3) which is the following [(alpha)), (meth) acrylate (b1)-(b5) which is the following [(beta)), and the polyvalent isocyanate (CC) reacted. An acrylate composition [III] is contained, The active energy ray curable resin composition characterized by the above-mentioned.
The hydroxyl value of the mixture (A) of the following (meth) acrylate (a1)-(a4) which is a reaction of [(alpha)] pentaerythritol and (meth) acrylic acid is 200 mgKOH / g or more, and in the said mixture (A) (Meth) acrylate (a1)-(a3).
(a1) pentaerythritol mono (meth) acrylate
(a2) pentaerythritol di (meth) acrylate
(a3) pentaerythritol tri (meth) acrylate
(a4) pentaerythritol tetra (meth) acrylate
[Beta] The hydroxyl value of the mixture (B) of the following (meth) acrylate (b1)-(b6) which is a reactant of dipentaerythritol with (meth) acrylic acid is 40 mgKOH / g or more, The said mixture (B) (Meth) acrylate (b1)-(b5) in the medium.
(b1) dipentaerythritol mono (meth) acrylate
(b2) dipentaerythritol di (meth) acrylate
(b3) dipentaerythritol tri (meth) acrylate
(b4) dipentaerythritol tetra (meth) acrylate
(b5) dipentaerythritol penta (meth) acrylate
(b6) dipentaerythritol hexa (meth) acrylate
상기 (메타)아크릴레이트(a1)∼(a4)의 혼합물(A) 중의 펜타에리쓰리톨 디(메타)아크릴레이트(a2)의 함유 비율이 10∼50중량%인 것을 특징으로 하는 활성 에너지선 경화성 수지 조성물.The method according to any one of claims 1 to 3,
Active energy ray-curable, wherein the content ratio of pentaerythritol di (meth) acrylate (a2) in the mixture (A) of the (meth) acrylates (a1) to (a4) is 10 to 50% by weight. Resin composition.
상기 (메타)아크릴레이트(a1)∼(a3)의 합계에 대한 펜타에리쓰리톨 디(메타)아크릴레이트(a2)의 함유 비율이 15∼55중량%인 것을 특징으로 하는 활성 에너지선 경화성 수지 조성물.The method according to any one of claims 1 to 4,
The content ratio of pentaerythritol di (meth) acrylate (a2) with respect to the sum total of said (meth) acrylate (a1)-(a3) is 15-55 weight%, The active energy ray curable resin composition characterized by the above-mentioned. .
상기 우레탄(메타)아크릴레이트계 조성물［I］의 중량 평균 분자량이 1,000∼20,000인 것을 특징으로 하는 활성 에너지선 경화성 수지 조성물.The method according to any one of claims 1, 2, 4, 5,
The weight average molecular weight of the said urethane (meth) acrylate type composition [I] is 1,000-20,000, The active energy ray curable resin composition characterized by the above-mentioned.
상기 (메타)아크릴레이트(b1)∼(b6)의 혼합물(B) 중의 디펜타에리쓰리톨 펜타(메타)아크릴레이트(b5)의 함유 비율이 15∼60중량%인 것을 특징으로 하는 활성 에너지선 경화성 수지 조성물.The method according to any one of claims 2 to 6,
The active energy ray is 15-60 weight% of the content rate of dipentaerythritol penta (meth) acrylate (b5) in the mixture (B) of said (meth) acrylate (b1)-(b6). Curable Resin Composition.
상기 (메타)아크릴레이트(b1)∼(b5)의 합계에 대한 디펜타에리쓰리톨 펜타(메타)아크릴레이트(b5)의 함유 비율이 45∼90중량%인 것을 특징으로 하는 활성 에너지선 경화성 수지 조성물.The method according to any one of claims 2 to 7,
Active energy ray curable resin whose content ratio of dipentaerythritol penta (meth) acrylate (b5) with respect to the sum total of said (meth) acrylate (b1)-(b5) is 45-90 weight%. Composition.
상기 (메타)아크릴레이트(b1)∼(b6)의 혼합물(B) 중의 디펜타에리쓰리톨 테트라(메타)아크릴레이트(b4)의 함유 비율이 1∼35중량%인 것을 특징으로 하는 활성 에너지선 경화성 수지 조성물.The method according to any one of claims 2 to 8,
An active energy ray, wherein the content ratio of dipentaerythritol tetra (meth) acrylate (b4) in the mixture (B) of the (meth) acrylates (b1) to (b6) is 1 to 35% by weight. Curable Resin Composition.
상기 (메타)아크릴레이트(b1)∼(b5) 합계에 대한 디펜타에리쓰리톨 테트라(메타)아크릴레이트(b4)의 함유 비율이 2∼40중량%인 것을 특징으로 하는 활성 에너지선 경화성 수지 조성물.The method according to any one of claims 2 to 9,
The content ratio of dipentaerythritol tetra (meth) acrylate (b4) to the total of the (meth) acrylates (b1) to (b5) is 2 to 40% by weight, wherein the active energy ray curable resin composition .
상기 우레탄(메타)아크릴레이트계 조성물［II］의 중량 평균 분자량이 1,000∼20,000인 것을 특징으로 하는 활성 에너지선 경화성 수지 조성물.The method according to any one of claims 2, 4 to 10,
The weight average molecular weight of the said urethane (meth) acrylate type composition [II] is 1,000-20,000, The active energy ray curable resin composition characterized by the above-mentioned.
상기 우레탄(메타)아크릴레이트계 조성물［III］의 중량 평균 분자량이 1,000∼20,000인 것을 특징으로 하는 활성 에너지선 경화성 수지 조성물.The method according to any one of claims 3 to 5, 7 to 10,
The weight average molecular weight of the said urethane (meth) acrylate type composition [III] is 1,000-20,000, The active energy ray curable resin composition characterized by the above-mentioned.
하드 코트용 코팅제로서 사용하는 것을 특징으로 하는 코팅제.The method according to claim 13,
A coating agent used as a coating agent for hard coats.
광학 필름용 코팅제로서 사용하는 것을 특징으로 하는 코팅제.The method according to claim 13,
A coating agent, which is used as a coating agent for an optical film.
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| JP2009286924A (en) | 2008-05-30 | 2009-12-10 | Jsr Corp | Curable composition |
| JP2010077292A (en) | 2008-09-26 | 2010-04-08 | Dic Corp | Active energy ray-curable resin composition for coating and film base |
| JP2010180319A (en) | 2009-02-05 | 2010-08-19 | Kyoeisha Chem Co Ltd | Urethane (meth)acrylate and coating agent containing the same |
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| JP2016104859A (en) * | 2014-11-25 | 2016-06-09 | 日本合成化学工業株式会社 | Active energy ray-curable resin composition and coating agent |
| KR20170017924A (en) * | 2014-06-13 | 2017-02-15 | 도아고세이가부시키가이샤 | Curable composition |
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| TWI515272B (en) * | 2011-03-08 | 2016-01-01 | Nippon Synthetic Chem Ind | Active energy ray hardening resin composition and coating agent |
| CN107709396B (en) * | 2015-06-04 | 2020-11-27 | Dic株式会社 | Urethane (meth) acrylate resin and laminated film |
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| JP2009286924A (en) | 2008-05-30 | 2009-12-10 | Jsr Corp | Curable composition |
| JP2010077292A (en) | 2008-09-26 | 2010-04-08 | Dic Corp | Active energy ray-curable resin composition for coating and film base |
| JP2010180319A (en) | 2009-02-05 | 2010-08-19 | Kyoeisha Chem Co Ltd | Urethane (meth)acrylate and coating agent containing the same |
| JP2012229412A (en) | 2011-04-13 | 2012-11-22 | Nippon Synthetic Chem Ind Co Ltd:The | Resin composition and coating agent |
| KR20170017924A (en) * | 2014-06-13 | 2017-02-15 | 도아고세이가부시키가이샤 | Curable composition |
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