TW202003599A - (meth)acrylate compound, curable composition, cured product and article - Google Patents
(meth)acrylate compound, curable composition, cured product and article Download PDFInfo
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- TW202003599A TW202003599A TW108117826A TW108117826A TW202003599A TW 202003599 A TW202003599 A TW 202003599A TW 108117826 A TW108117826 A TW 108117826A TW 108117826 A TW108117826 A TW 108117826A TW 202003599 A TW202003599 A TW 202003599A
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- Prior art keywords
- meth
- compound
- acrylate
- curable composition
- epoxy
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- -1 acrylate compound Chemical class 0.000 title claims abstract description 181
- 239000000203 mixture Substances 0.000 title claims description 83
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 41
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims abstract description 27
- 125000003118 aryl group Chemical group 0.000 claims abstract description 16
- 125000001424 substituent group Chemical group 0.000 claims abstract description 14
- 239000003822 epoxy resin Substances 0.000 claims description 70
- 229920000647 polyepoxide Polymers 0.000 claims description 70
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 69
- 239000004593 Epoxy Substances 0.000 claims description 31
- 239000011248 coating agent Substances 0.000 claims description 24
- 239000004925 Acrylic resin Substances 0.000 claims description 21
- 238000000576 coating method Methods 0.000 claims description 19
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- GGNQRNBDZQJCCN-UHFFFAOYSA-N benzene-1,2,4-triol Chemical compound OC1=CC=C(O)C(O)=C1 GGNQRNBDZQJCCN-UHFFFAOYSA-N 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 9
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 7
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 3
- 150000004292 cyclic ethers Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 51
- 230000000052 comparative effect Effects 0.000 description 33
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 27
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 24
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 23
- CSTYUNFMCWVYJF-UHFFFAOYSA-N 4-methyl-1,3-dioxetan-2-one Chemical compound CC1OC(=O)O1 CSTYUNFMCWVYJF-UHFFFAOYSA-N 0.000 description 18
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 18
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 17
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 16
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 10
- 150000002148 esters Chemical group 0.000 description 10
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 230000001186 cumulative effect Effects 0.000 description 7
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 7
- 150000002596 lactones Chemical class 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 6
- 229930185605 Bisphenol Natural products 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 125000005702 oxyalkylene group Chemical group 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 5
- 235000004515 gallic acid Nutrition 0.000 description 5
- 229940074391 gallic acid Drugs 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 229920000193 polymethacrylate Polymers 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 239000004843 novolac epoxy resin Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 3
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000005587 carbonate group Chemical group 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 229910001507 metal halide Inorganic materials 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 125000006353 oxyethylene group Chemical group 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- FOWDZVNRQHPXDO-UHFFFAOYSA-N propyl hydrogen carbonate Chemical compound CCCOC(O)=O FOWDZVNRQHPXDO-UHFFFAOYSA-N 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical group C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 2
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- LLPKQRMDOFYSGZ-UHFFFAOYSA-N 2,5-dimethyl-1h-imidazole Chemical compound CC1=CN=C(C)N1 LLPKQRMDOFYSGZ-UHFFFAOYSA-N 0.000 description 2
- CZAZXHQSSWRBHT-UHFFFAOYSA-N 2-(2-hydroxyphenyl)-3,4,5,6-tetramethylphenol Chemical compound OC1=C(C)C(C)=C(C)C(C)=C1C1=CC=CC=C1O CZAZXHQSSWRBHT-UHFFFAOYSA-N 0.000 description 2
- BOZRCGLDOHDZBP-UHFFFAOYSA-N 2-ethylhexanoic acid;tin Chemical compound [Sn].CCCCC(CC)C(O)=O BOZRCGLDOHDZBP-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- PGSWEKYNAOWQDF-UHFFFAOYSA-N 3-methylcatechol Chemical compound CC1=CC=CC(O)=C1O PGSWEKYNAOWQDF-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- ZMHZSHHZIKJFIR-UHFFFAOYSA-N octyltin Chemical compound CCCCCCCC[Sn] ZMHZSHHZIKJFIR-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 description 1
- HGCMSCWGVAYWHR-UHFFFAOYSA-N 1,3,5-trimethyl-2-[[phenyl-[(2,4,6-trimethylphenyl)methyl]phosphoryl]methyl]benzene Chemical compound CC1=CC(C)=CC(C)=C1CP(=O)(C=1C=CC=CC=1)CC1=C(C)C=C(C)C=C1C HGCMSCWGVAYWHR-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- FNOZYFSGNFPIIH-UHFFFAOYSA-N 1,4-diethylimidazole Chemical compound CCC1=CN(CC)C=N1 FNOZYFSGNFPIIH-UHFFFAOYSA-N 0.000 description 1
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- ARNKHYQYAZLEEP-UHFFFAOYSA-N 1-naphthalen-1-yloxynaphthalene Chemical compound C1=CC=C2C(OC=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ARNKHYQYAZLEEP-UHFFFAOYSA-N 0.000 description 1
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 1
- KWHSRIVTVJILDJ-UHFFFAOYSA-N 2-(diphenylphosphorylmethyl)-1,3,5-trimethoxybenzene Chemical compound COC1=CC(OC)=CC(OC)=C1CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 KWHSRIVTVJILDJ-UHFFFAOYSA-N 0.000 description 1
- LESMLVDJJCWZAJ-UHFFFAOYSA-N 2-(diphenylphosphorylmethyl)-1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 LESMLVDJJCWZAJ-UHFFFAOYSA-N 0.000 description 1
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- DORYUYZNWCZQOL-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-phenylphenyl)butan-1-one Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 DORYUYZNWCZQOL-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
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- SVIQBUBNVYWIDV-UHFFFAOYSA-N 2-methoxy-2-(2-methoxyphenyl)-1-phenylethanone Chemical compound C=1C=CC=C(OC)C=1C(OC)C(=O)C1=CC=CC=C1 SVIQBUBNVYWIDV-UHFFFAOYSA-N 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 1
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- NJFUXFRJVIXVSG-UHFFFAOYSA-M tetramethylphosphanium;chloride Chemical compound [Cl-].C[P+](C)(C)C NJFUXFRJVIXVSG-UHFFFAOYSA-M 0.000 description 1
- QBAUHKSMFOSSGE-UHFFFAOYSA-M tetrapropylphosphanium;chloride Chemical compound [Cl-].CCC[P+](CCC)(CCC)CCC QBAUHKSMFOSSGE-UHFFFAOYSA-M 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
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- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
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- AVCVDUDESCZFHJ-UHFFFAOYSA-N triphenylphosphane;hydrochloride Chemical compound [Cl-].C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 AVCVDUDESCZFHJ-UHFFFAOYSA-N 0.000 description 1
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- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 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
- 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
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/96—Esters of carbonic or haloformic acids
-
- 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
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
-
- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本發明關於低黏度且具有優異的硬化性，而硬化物具有優異的耐熱性之(甲基)丙烯酸酯化合物、含有其之硬化性組成物、前述硬化性組成物之硬化物、及具有前述硬化物的塗膜之物品。 The present invention relates to a (meth)acrylate compound having a low viscosity and excellent curability, and a cured product having excellent heat resistance, a curable composition containing the same, a cured product of the aforementioned curable composition, and the aforementioned cured product Articles coated with paint.
近年來，藉由紫外線等的活性能量線而能硬化的活性能量線硬化性組成物，或藉由熱而能硬化的熱硬化性組成物等之硬化性組成物，被廣泛地使用在油墨、塗料、塗覆劑、接著劑、光學構件等之領域。其中，就前述塗覆劑用途而言，一般要求在可對各種基材表面賦予式樣設計性之同時具有優異的硬化性，而且可形成能防止基材表面的劣化之塗膜。再者，近年來，產業界要求能形成硬化塗膜的材料，其係不僅硬化性，而且具備即使在各式各樣的溫度環境下都能保護被塗物的水準之耐熱性等性能。 In recent years, curable compositions such as active energy ray curable compositions that can be cured by active energy rays such as ultraviolet rays, or thermosetting compositions that can be cured by heat, have been widely used in inks, The field of coatings, coating agents, adhesives, optical components, etc. Among them, for the application of the aforementioned coating agent, it is generally required to provide design designability to various substrate surfaces while having excellent curability, and to form a coating film capable of preventing deterioration of the substrate surface. In addition, in recent years, the industry has demanded materials that can form a cured coating film, which is not only curable, but also has a level of heat resistance and other properties that can protect the coated object even in various temperature environments.
就提升硬化塗膜的耐熱性之技術而言，已知含有下述通式(1)所示的二(甲基)丙烯酸酯之硬化性組成物等(例如，參照專利文獻1)。 As a technique for improving the heat resistance of a cured coating film, a curable composition containing a di(meth)acrylate represented by the following general formula (1) is known (for example, refer to Patent Document 1).
[式(1)中，R1表示氫原子或甲基]。 [In formula (1), R 1 represents a hydrogen atom or a methyl group]
然而，該硬化性組成物係黏度高，而且於硬化性及硬化塗膜的耐熱性，亦無法滿足近來愈加提高的要求性能。 However, the curable composition system has a high viscosity, and the curability and the heat resistance of the cured coating film cannot satisfy the performance requirements that have been increasing recently.
於是，要求低黏度且具有優異的硬化性，而且能形成具有優異的耐熱性之硬化物的材料。 Therefore, there is a demand for a material with low viscosity and excellent curability, and capable of forming a cured product with excellent heat resistance.
[專利文獻1]日本特開2005-314320號公報 [Patent Document 1] Japanese Unexamined Patent Publication No. 2005-314320
本發明所欲解決的課題在於提供：低黏度且具有優異的硬化性，而且能形成耐熱性優異的硬化物之(甲基)丙烯酸酯化合物；含有其之硬化性組成物；前述硬化性組成物之硬化物；以及具有前述硬化物的塗膜之物品。 The problem to be solved by the present invention is to provide: a (meth)acrylate compound having a low viscosity, excellent curability, and capable of forming a cured product having excellent heat resistance; a curable composition containing it; and the aforementioned curable composition Hardened product; and articles with the coating film of the aforementioned hardened product.
本發明人等為了解決上述課題而專心致力地檢討的結果，發現藉由使用一種以含有酚性羥基的化合物、與環狀碳酸酯化合物或環狀醚化合物、與不飽和單羧酸作為必須的反應原料之(甲基)丙烯酸酯化合物可解決上述課題，而完成了本發明， 其中該含有酚性羥基的化合物包含至少具有3個羥基作為芳香環上的取代基之酚化合物。 In order to solve the above-mentioned problems, the present inventors intensively reviewed the results and found that by using a compound containing a phenolic hydroxyl group, a cyclic carbonate compound or a cyclic ether compound, and an unsaturated monocarboxylic acid as essential The (meth)acrylate compound of the reaction raw material can solve the above-mentioned problems and completed the present invention, wherein the phenolic hydroxyl group-containing compound contains a phenol compound having at least three hydroxyl groups as a substituent on the aromatic ring.
即，本發明關於(甲基)丙烯酸酯化合物、含有其之硬化性組成物、前述硬化性組成物之硬化物及具有前述硬化物的硬化塗膜之物品，該(甲基)丙烯酸酯化合物係以含有酚性羥基的化合物(A)、與環狀碳酸酯化合物(B1)或環狀醚化合物(B2)、與不飽和單羧酸(C)作為必須的反應原料之(甲基)丙烯酸酯樹脂，其特徵為前述含有酚性羥基的化合物(A)係含有至少具有3個羥基作為芳香環上的取代基之酚化合物者。 That is, the present invention relates to a (meth)acrylate compound, a curable composition containing the same, a cured product of the curable composition, and an article having a cured coating film of the cured product. The (meth)acrylate compound is (Meth) acrylate containing phenolic hydroxyl-containing compound (A), cyclic carbonate compound (B1) or cyclic ether compound (B2), and unsaturated monocarboxylic acid (C) as essential reaction raw materials The resin is characterized in that the phenolic hydroxyl group-containing compound (A) contains a phenol compound having at least three hydroxyl groups as substituents on the aromatic ring.
本發明之(甲基)丙烯酸酯化合物，由於低黏度且具有優異的硬化性，能形成耐熱性優異的硬化物，故含有前述(甲基)丙烯酸酯化合物與光聚合起始劑之硬化性組成物可作為塗覆劑或接著劑使用，尤其可適合作為塗覆劑使用。 Since the (meth)acrylate compound of the present invention has a low viscosity and has excellent curability and can form a cured product with excellent heat resistance, the curable composition containing the aforementioned (meth)acrylate compound and a photopolymerization initiator The substance can be used as a coating agent or an adhesive, and is particularly suitable as a coating agent.
本發明之(甲基)丙烯酸酯化合物，係以含有酚性羥基的化合物(A)、與環狀碳酸酯化合物(B1)或環狀醚化合物(B2)、與不飽和單羧酸(C)作為必須的反應原料之(甲基)丙烯酸酯化合物，其特徵為：前述含有酚性羥基的化合物(A)係含有至少具有3個羥基作為芳香環上的取代基之酚化合物者。 The (meth)acrylate compound of the present invention is composed of a compound (A) containing a phenolic hydroxyl group, a cyclic carbonate compound (B1) or a cyclic ether compound (B2), and an unsaturated monocarboxylic acid (C) The (meth)acrylate compound as an essential reaction raw material is characterized in that the phenolic hydroxyl group-containing compound (A) is a phenol compound containing at least three hydroxyl groups as substituents on the aromatic ring.
還有，於本發明中，「(甲基)丙烯酸酯」，就是意指丙烯酸酯及/或甲基丙烯酸酯。又，「(甲基)丙烯醯基」，就是 意指丙烯醯基及/或甲基丙烯醯基。再者，「(甲基)丙烯酸」，就是意指丙烯酸及/或甲基丙烯酸。 In addition, in the present invention, "(meth)acrylate" means acrylate and/or methacrylate. In addition, "(meth)acryloyl" means acryloyl and/or methacryloyl. Furthermore, "(meth)acrylic acid" means acrylic acid and/or methacrylic acid.
作為前述含有酚性羥基的化合物(A)，係必須含有至少具有3個羥基作為芳香環上的取代基之酚化合物者。 The phenolic hydroxyl group-containing compound (A) must contain at least three hydroxyl groups as substituents on the aromatic ring.
前述至少具有3個羥基作為芳香環上的取代基之酚化合物，只要具有3個羥基作為芳香環上的取代基，則沒有特別的限制，亦可具有其它的取代基。 The phenol compound having at least three hydroxyl groups as substituents on the aromatic ring is not particularly limited as long as it has three hydroxyl groups as substituents on the aromatic ring, and may have other substituents.
作為前述至少具有3個羥基作為芳香環上的取代基之酚化合物，可舉出例如下述結構式(1-1)~(1-3)所示的化合物。 Examples of the phenol compound having at least three hydroxyl groups as substituents on the aromatic ring include compounds represented by the following structural formulas (1-1) to (1-3).
上述結構式(1-1)~(1-3)中，R1係碳原子數1~20的烷基、碳原子數1~20的烷氧基、芳基、鹵素原子之任一者。又，p為0或1以上之整數，較佳為0或1~3，更佳為0或1，進一步較佳為0。q為3。還有，關於上述結構式中之芳香環上的取代基之位置則為任意，可在例如結構式(1-2)之萘環中的任一環上取代，於結構式(1-3)中，係表示可在1分子中存在的苯環之任一環上取代，表示1分子中的取代基之個數為p及q。 In the above structural formulae (1-1) to (1-3), R 1 is any one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, and a halogen atom. In addition, p is an integer of 0 or more, preferably 0 or 1 to 3, more preferably 0 or 1, even more preferably 0. q is 3. In addition, the position of the substituent on the aromatic ring in the above structural formula is arbitrary, and may be substituted on any ring in the naphthalene ring of the structural formula (1-2), for example, in the structural formula (1-3) , Means that it can be substituted on any one of the benzene rings present in one molecule, and that the number of substituents in one molecule is p and q.
於上述結構式(1-1)~(1-3)所示的化合物之中，在結構式(1-1)中，p為0且q為3的三羥基苯，從可得到低黏度且具有優異的硬化性，而且能形成具有優異的耐熱性之硬化物的 (甲基)丙烯酸酯化合物來看為較佳，進一步具體而言，更佳為在1位、2位與3位具有羥基的1,2,3-三羥基苯(以下亦稱為「五倍子酚」)或在1位、2位與4位具有羥基的1,2,4-三羥基苯。 Among the compounds represented by the above structural formulas (1-1) to (1-3), in the structural formula (1-1), trihydroxybenzene where p is 0 and q is 3, from which low viscosity and A (meth)acrylate compound that has excellent hardenability and can form a hardened product with excellent heat resistance is preferable, and more specifically, it is more preferable to have a hydroxyl group at the 1, 2, and 3 positions. 1,2,3-trihydroxybenzene (hereinafter also called "gallophenol") or 1,2,4-trihydroxybenzene having hydroxyl groups at the 1, 2 and 4 positions.
作為前述環狀碳酸酯化合物(B1)，可舉出例如碳酸伸乙酯、碳酸伸丙酯、碳酸伸丁酯、碳酸伸戊酯等。此等之環狀碳酸酯化合物可單獨使用，也可併用2種以上。又，於此等之中，從可得到低黏度且具有優異的硬化性，而且能形成具有優異的耐熱性之硬化物的(甲基)丙烯酸酯化合物來看，較佳為碳酸伸乙酯或碳酸伸丙酯。 Examples of the cyclic carbonate compound (B1) include ethyl carbonate, propyl carbonate, butyl carbonate, and pentyl carbonate. These cyclic carbonate compounds may be used alone or in combination of two or more. Among these, from the viewpoint of obtaining a (meth)acrylate compound that can obtain a low viscosity, has excellent curability, and can form a cured product having excellent heat resistance, ethyl carbonate or Propylene carbonate.
作為前述環狀醚化合物(B2)，可舉出例如環氧乙烷、環氧丙烷、四氫呋喃等。此等之環狀醚化合物可單獨使用，也可併用2種以上。又，於此等之中，從可得到低黏度且具有優異的硬化性，而且能形成具有優異的耐熱性之硬化物的(甲基)丙烯酸酯化合物來看，較佳為環氧乙烷或環氧丙烷。 Examples of the cyclic ether compound (B2) include ethylene oxide, propylene oxide, and tetrahydrofuran. These cyclic ether compounds may be used alone or in combination of two or more. Among these, from the viewpoint of obtaining a (meth)acrylate compound that can obtain a low viscosity, has excellent curability, and can form a cured product having excellent heat resistance, ethylene oxide or Propylene oxide.
前述含有酚性羥基的化合物(A)與前述環狀碳酸酯化合物(B1)之莫耳比[(B1)/(A)]或前述含有酚性羥基的化合物(A)與前述環狀醚化合物(B2)之莫耳比[(B2)/(A)]，從可得到具有低黏度且具有優異的硬化性，而且能形成具有優異的耐熱性之硬化物的(甲基)丙烯酸酯化合物來看，較佳為3以上。 The molar ratio [(B1)/(A)] of the phenolic hydroxyl group-containing compound (A) and the cyclic carbonate compound (B1) or the phenolic hydroxyl group-containing compound (A) and the cyclic ether compound The molar ratio of (B2) [(B2)/(A)] can be obtained from a (meth)acrylate compound that has a low viscosity and has excellent curability and can form a cured product with excellent heat resistance See, it is preferably 3 or more.
所謂的前述不飽和單羧酸(C)，就是指在一分子中具有(甲基)丙烯醯基與羧基的化合物，可舉出例如丙烯酸、甲基丙烯酸等。又，作為前述不飽和單羧酸(C)，亦可使用下述結構式(2)所示的化合物。再者，亦可使用前述不飽和單羧酸(C)之酯化物、醯鹵、酸酐等。此等之不飽和單羧酸(C)可單獨使用，也可併用2種以上。 The aforementioned unsaturated monocarboxylic acid (C) refers to a compound having a (meth)acryloyl group and a carboxyl group in one molecule, and examples thereof include acrylic acid and methacrylic acid. As the unsaturated monocarboxylic acid (C), a compound represented by the following structural formula (2) can also be used. In addition, esterification of the aforementioned unsaturated monocarboxylic acid (C), halides, acid anhydrides, etc. may also be used. These unsaturated monocarboxylic acids (C) may be used alone or in combination of two or more.
[式中，X表示碳數1~10的伸烷基鏈、聚氧化烯鏈、(聚)酯鏈、芳香族烴鏈或(聚)碳酸酯鏈，在結構中亦可具有鹵素原子或烷氧基等；Y係氫原子或甲基]。 [In the formula, X represents a C1-C10 alkylene chain, polyoxyalkylene chain, (poly)ester chain, aromatic hydrocarbon chain or (poly)carbonate chain, and may have a halogen atom or an alkyl group in the structure Oxygen, etc.; Y hydrogen atom or methyl group].
作為前述聚氧化烯鏈，可舉出例如聚氧乙烯鏈、聚氧丙烯鏈等。 Examples of the polyoxyalkylene chains include polyoxyethylene chains and polyoxypropylene chains.
作為前述(聚)酯鏈，可舉出例如下述結構式(3)所示的(聚)酯鏈。 Examples of the (poly)ester chain include (poly)ester chains represented by the following structural formula (3).
(式中，R1係碳原子數1~10的伸烷基，n為1~5之整數)。 (In the formula, R 1 is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5).
作為前述芳香族烴鏈，可舉出例如伸苯基鏈、伸萘基鏈、伸聯苯基鏈、苯基伸萘基鏈、伸聯萘基鏈等。又，作為部分結構，亦可使用具有苯環、萘環、蒽環、菲環等芳香環的烴鏈。 Examples of the aromatic hydrocarbon chain include a phenylene chain, a naphthyl chain, a biphenylene chain, a phenyl naphthyl chain, and a biphenylene chain. In addition, as a partial structure, a hydrocarbon chain having an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring can also be used.
作為前述(聚)碳酸酯鏈，可舉出例如下述結構式(4)所示的(聚)碳酸酯鏈。 Examples of the (poly)carbonate chain include (poly)carbonate chains represented by the following structural formula (4).
(式中R2係碳原子數1~10的伸烷基，n為1~5之整數)。 (In the formula, R 2 is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5).
作為前述不飽和單羧酸(C)之酯化物，可舉出例如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸2-乙基己酯等之(甲基)丙烯酸烷酯化合物；(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸羥基丙酯、(甲基)丙烯酸羥基丁酯等之含有羥基的(甲基)丙烯酸酯化合物；(甲基)丙烯酸二甲基胺基乙酯、(甲基)丙烯酸二乙基胺基乙酯等之含有氮的(甲基)丙烯酸酯化合物；(甲基)丙烯酸環氧丙酯、(甲基)丙烯酸四氫糠酯、(甲基)丙烯酸
作為前述不飽和單羧酸(C)之醯鹵，可舉出例如(甲基)丙烯醯氯等。 Examples of the acyl halide of the unsaturated monocarboxylic acid (C) include (meth)acryloyl chloride and the like.
作為前述不飽和單羧酸(C)之酸酐，可舉出例如(甲基)丙烯酸酐等。 Examples of the acid anhydride of the unsaturated monocarboxylic acid (C) include (meth)acrylic anhydride.
前述環狀碳酸酯化合物(B1)與前述不飽和羧酸(C)之莫耳比[(C)/(B1)]或前述環狀醚化合物(B2)與前述不飽和羧酸(C)之莫耳比[(C)/(B2)]，從可得到低黏度且具有優異的硬化性，而且能形成具有優異的耐熱性之硬化物的(甲基)丙烯酸酯化合物來看，較佳為0.65以上，更佳為0.65~1.05之範圍。 The molar ratio of the cyclic carbonate compound (B1) to the unsaturated carboxylic acid (C) [(C)/(B1)] or the cyclic ether compound (B2) and the unsaturated carboxylic acid (C) The molar ratio [(C)/(B2)], from the viewpoint of obtaining a (meth)acrylate compound that has a low viscosity, has excellent curability, and can form a cured product having excellent heat resistance, is preferably Above 0.65, more preferably in the range of 0.65 to 1.05.
本發明之(甲基)丙烯酸酯化合物的重量平均分子量從低黏度且具有優異的硬化性來看，較佳為1,000以下。 The weight average molecular weight of the (meth)acrylate compound of the present invention is preferably 1,000 or less from the viewpoint of low viscosity and excellent curability.
還有，於本發明中，重量平均分子量(Mw)表示藉由凝膠滲透層析(GPC)法所測定之值。 In the present invention, the weight average molecular weight (Mw) represents the value measured by the gel permeation chromatography (GPC) method.
本發明之(甲基)丙烯酸酯化合物之製造方法係沒 有特別的限制，可適宜地藉由眾所周知之方法製造。例如，能夠以使反應原料全部整批地反應之方法來製造，也能夠以使反應原料依序反應之方法來製造。其中，從反應之控制容易來看，可藉由以下來進行：先使含有酚性羥基的化合物與環狀碳酸酯化合物或環狀醚化合物，在鹼性觸媒之存在下，於100~200℃之溫度範圍進行反應之後，接著使不飽和羧酸或其酯化物在酸性觸媒之存在下，於60~140℃之溫度範圍進行反應。還有，本反應在減壓下、常壓下、加壓下皆可進行。 The method for producing the (meth)acrylate compound of the present invention is not particularly limited, and can be suitably produced by a well-known method. For example, it can be manufactured by a method of reacting all the reaction raw materials in batches, or by a method of sequentially reacting the reaction raw materials. Among them, from the point of view of easy control of the reaction, it can be performed by the following: first, a compound containing a phenolic hydroxyl group and a cyclic carbonate compound or a cyclic ether compound, in the presence of an alkaline catalyst, at 100 to 200 After the reaction in the temperature range of ℃, the unsaturated carboxylic acid or its ester compound is then reacted in the temperature range of 60-140 ℃ in the presence of an acid catalyst. In addition, this reaction can be performed under reduced pressure, normal pressure, and pressure.
本發明之(甲基)丙烯酸酯化合物可藉由添加光聚合起始劑，而作為硬化性組成物使用。 The (meth)acrylate compound of the present invention can be used as a curable composition by adding a photopolymerization initiator.
作為前述光聚合起始劑，可舉出例如1-羥基環己基苯基酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、1-[4-(2-羥基乙氧基)苯基]-2-羥基-2-甲基-1-丙烷-1-酮、噻噸酮(Thioxanthone)及噻噸酮衍生物、2,2’-二甲氧基-1,2-二苯基乙烷-1-酮、二苯基(2,4,6-三甲氧基苯甲醯基)膦氧化物、2,4,6-三甲基苯甲醯基二苯基膦氧化物、雙(2,4,6-三甲基苯甲醯基)苯基膦氧化物、2-甲基-1-(4-甲硫基苯基)-2-
作為前述其它的光聚合起始劑之市售品，可舉出例如「Omnirad-1173」、「Omnirad-184」、「Omnirad-127」、「Omnirad-2959」、「Omnirad-369」、「Omnirad-379」、「Omnirad-907」、「Omnirad-4265」、「Omnirad-1000」、「Omnirad-651」、「Omnirad-TPO」、「Omnirad-819」、「Omnirad-2022」、「Omnirad-2100」、「Omnirad-754」、「Omnirad-784」、「Omnirad-500」、「Omnirad-81」(IGM 公司製)、「Kayacure-DETX」、「Kayacure-MBP」、「Kayacure-DMBI」、「Kayacure-EPA」、「Kayacure-OA」(日本化藥股份有限公司製)、「Vicure-10」、「Vicure-55」(STAUFFER CHEMICAL公司製)、「Trigonal P1」(AKZO公司製)、「Sandoray 1000」(SANDOZ公司製)、「DEAP」(APJOHN公司製)、「Quantacure-PDO」、「Quantacure-ITX」、「Quantacure-EPD」(WARD BLENKINSOP公司製)、「Runtecure-1104」(Runtec公司製)等。 As the commercially available products of the aforementioned other photopolymerization initiators, for example, "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad-2959", "Omnirad-369", "Omnirad" -379", "Omnirad-907", "Omnirad-4265", "Omnirad-1000", "Omnirad-651", "Omnirad-TPO", "Omnirad-819", "Omnirad-2022", "Omnirad-2100" '', ``Omnirad-754'', ``Omnirad-784'', ``Omnirad-500'', ``Omnirad-81'' (manufactured by IGM), ``Kayacure-DETX'', ``Kayacure-MBP'', ``Kayacure-DMBI'', `` Kayacure-EPA, ``Kayacure-OA'' (manufactured by Nippon Kayaku Co., Ltd.), ``Vicure-10'', ``Vicure-55'' (manufactured by STAUFFER CHEMICAL), ``Trigonal P1'' (manufactured by AKZO), ``Sandoray 1000'' (manufactured by SANDOZ), ``DEAP'' (manufactured by APJOHN), ``Quantacure-PDO'', ``Quantacure-ITX'', ``Quantacure-EPD'' (manufactured by WARD BLENKINSOP), ``Runtecure-1104'' (manufactured by Runtec) )Wait.
前述光聚合起始劑之添加量，較佳為例如在前述硬化性組成物中以1~20質量%之範圍使用。 The added amount of the photopolymerization initiator is preferably used in the range of 1 to 20% by mass in the curable composition, for example.
本發明之硬化性組成物在不妨礙本發明的效果之範圍內，亦可包含環氧(甲基)丙烯酸酯樹脂(D)。 The curable composition of the present invention may contain an epoxy (meth)acrylate resin (D) as long as the effect of the present invention is not hindered.
作為前述環氧(甲基)丙烯酸酯樹脂(D)，並沒有特別的限制，但可舉出例如以環氧樹脂(d1)與不飽和單羧酸(d2)作為必須的反應原料者。前述環氧樹脂(d1)只要是在樹脂中具有複數的環氧基，且與前述含有羧基的(甲基)丙烯酸酯化合物反應，而可形成環氧(甲基)丙烯酸酯樹脂者，則其具體結構並沒有特別的限定。作為前述環氧樹脂(d1)，可舉出例如雙酚型環氧樹脂、氫化雙酚型環氧樹脂、聯苯酚型環氧樹脂、氫化聯苯酚型環氧樹脂、伸苯基醚型環氧樹脂、伸萘基醚型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、雙酚酚醛清漆型環氧樹脂、萘酚酚醛清漆型環氧樹脂、苯酚芳烷基型環氧樹脂、萘酚芳烷基型環氧樹脂、二環戊二烯-苯酚加成反應型環氧樹脂、聯苯基芳烷基型環氧樹脂、茀型環氧樹脂、呫噸型環氧樹脂、二羥基苯型環氧樹脂、三羥基苯型環氧樹脂等。此等之環氧樹脂(d1)可單 獨使用，也可併用2種以上。又，於此等之中，從可得到能形成耐熱性及介電特性優異的硬化物之環氧(甲基)丙烯酸酯樹脂組成物來看，較佳為雙酚型環氧樹脂、氫化雙酚型環氧樹脂、聯苯酚型環氧樹脂、氫化聯苯酚型環氧樹脂、萘酚型環氧樹脂、二羥基苯型環氧樹脂，更佳為雙酚型環氧樹脂或氫化雙酚型環氧樹脂、二羥基苯型環氧樹脂。 The epoxy (meth)acrylate resin (D) is not particularly limited, but examples thereof include epoxy resin (d1) and unsaturated monocarboxylic acid (d2) as essential reaction raw materials. As long as the epoxy resin (d1) has plural epoxy groups in the resin and reacts with the carboxyl group-containing (meth)acrylate compound to form an epoxy (meth)acrylate resin, then The specific structure is not particularly limited. Examples of the epoxy resin (d1) include bisphenol-type epoxy resins, hydrogenated bisphenol-type epoxy resins, biphenol-type epoxy resins, hydrogenated biphenol-type epoxy resins, and phenylene ether-type epoxy resins. Resin, naphthyl ether epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol novolac epoxy resin, naphthol novolac epoxy resin, phenol aralkyl Type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, biphenyl aralkyl type epoxy resin, stilbene type epoxy resin, xanthene type Epoxy resin, dihydroxybenzene epoxy resin, trihydroxybenzene epoxy resin, etc. These epoxy resins (d1) can be used alone or in combination of two or more. Among these, from the viewpoint of obtaining an epoxy (meth)acrylate resin composition capable of forming a cured product excellent in heat resistance and dielectric properties, bisphenol-type epoxy resin and hydrogenated bis Phenolic epoxy resin, biphenol epoxy resin, hydrogenated biphenol epoxy resin, naphthol epoxy resin, dihydroxy benzene epoxy resin, more preferably bisphenol epoxy resin or hydrogenated bisphenol epoxy resin Epoxy resin, dihydroxybenzene epoxy resin.
作為前述雙酚型環氧樹脂，可舉出例如雙酚A型環氧樹脂、雙酚AP型環氧樹脂、雙酚B型環氧樹脂、雙酚BP型環氧樹脂、雙酚E型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂等。 Examples of the bisphenol epoxy resin include bisphenol A epoxy resin, bisphenol AP epoxy resin, bisphenol B epoxy resin, bisphenol BP epoxy resin, and bisphenol E ring. Oxygen resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, etc.
作為前述氫化雙酚型環氧樹脂，可舉出例如氫化雙酚A型環氧樹脂、氫化雙酚B型環氧樹脂、氫化雙酚E型環氧樹脂、氫化雙酚F型環氧樹脂、氫化雙酚S型環氧樹脂等。 Examples of the hydrogenated bisphenol epoxy resin include hydrogenated bisphenol A epoxy resin, hydrogenated bisphenol B epoxy resin, hydrogenated bisphenol E epoxy resin, hydrogenated bisphenol F epoxy resin, Hydrogenated bisphenol S-type epoxy resin, etc.
作為前述聯苯酚型環氧樹脂，可舉出例如4,4’-聯苯酚型環氧樹脂、2,2’-聯苯酚型環氧樹脂、四甲基-4,4’-聯苯酚型環氧樹脂、四甲基-2,2’-聯苯酚型環氧樹脂等。 Examples of the biphenol-type epoxy resin include 4,4'-biphenol-type epoxy resin, 2,2'-biphenol-type epoxy resin, and tetramethyl-4,4'-biphenol-type ring. Oxygen resin, tetramethyl-2,2'-biphenol epoxy resin, etc.
作為前述氫化聯苯酚型環氧樹脂，可舉出例如氫化4,4’-聯苯酚型環氧樹脂、氫化2,2’-聯苯酚型環氧樹脂、氫化四甲基-4,4’-聯苯酚型環氧樹脂、氫化四甲基-2,2’-聯苯酚型環氧樹脂等。 Examples of the hydrogenated biphenol-type epoxy resin include hydrogenated 4,4′-biphenol-type epoxy resin, hydrogenated 2,2′-biphenol-type epoxy resin, and hydrogenated tetramethyl-4,4′- Biphenol epoxy resin, hydrogenated tetramethyl-2,2'-biphenol epoxy resin, etc.
作為前述二羥基苯型環氧樹脂，可舉出例如兒茶酚型環氧樹脂、間苯二酚型環氧樹脂、氫醌型環氧樹脂等。 Examples of the dihydroxybenzene type epoxy resin include catechol type epoxy resin, resorcinol type epoxy resin, and hydroquinone type epoxy resin.
當前述環氧樹脂為前述雙酚型環氧樹脂、前述氫化雙酚型環氧樹脂、前述聯苯酚型環氧樹脂、前述氫化聯苯酚型環氧樹脂、萘酚型環氧樹脂、二羥基苯型環氧樹脂之任一者時，從 可得到低黏度且具有優異的硬化性，能形成耐熱性優異的硬化物之環氧(甲基)丙烯酸酯樹脂組成物來看，前述環氧樹脂之環氧當量較佳為110~400g/當量之範圍。 When the epoxy resin is the bisphenol epoxy resin, the hydrogenated bisphenol epoxy resin, the biphenol epoxy resin, the hydrogenated biphenol epoxy resin, the naphthol epoxy resin, dihydroxybenzene In the case of any type of epoxy resin, from the viewpoint of obtaining an epoxy (meth)acrylate resin composition that has a low viscosity, has excellent curability, and can form a cured product with excellent heat resistance, the The epoxy equivalent is preferably in the range of 110 to 400 g/equivalent.
作為前述不飽和單羧酸(d2)，可使用作為上述之不飽和單羧酸(C)而例示者，前述不飽和單羧酸(d2)可單獨使用，也可併用2種以上。 As the unsaturated monocarboxylic acid (d2), those exemplified as the above-mentioned unsaturated monocarboxylic acid (C) may be used, and the unsaturated monocarboxylic acid (d2) may be used alone or in combination of two or more kinds.
作為前述環氧(甲基)丙烯酸酯樹脂(D)，較佳為在同一分子內具有環氧基及(甲基)丙烯醯基者。 The epoxy (meth)acrylate resin (D) is preferably one having an epoxy group and a (meth)acryloyl group in the same molecule.
又，作為前述環氧(甲基)丙烯酸酯樹脂(D)，更佳為相對於前述環氧樹脂(d1)所具有的環氧基1莫耳，前述不飽和單羧酸之莫耳數為0.25~0.75之範圍者。 Further, the epoxy (meth)acrylate resin (D) is more preferably 1 mole relative to the epoxy group of the epoxy resin (d1), and the number of moles of the unsaturated monocarboxylic acid is In the range of 0.25~0.75.
前述環氧(甲基)丙烯酸酯樹脂(D)之(甲基)丙烯醯基當量，從可得到能形成耐熱性優異的硬化物之硬化性組成物來看，較佳為200~800g/當量之範圍。又，前述環氧(甲基)丙烯酸酯樹脂(D)之環氧當量較佳為300~900g/當量之範圍。 The (meth)acryloyl equivalent of the epoxy (meth)acrylate resin (D) is preferably 200 to 800 g/equivalent from the viewpoint of obtaining a curable composition capable of forming a cured product having excellent heat resistance. Scope. In addition, the epoxy equivalent of the epoxy (meth)acrylate resin (D) is preferably in the range of 300 to 900 g/equivalent.
前述環氧(甲基)丙烯酸酯樹脂(D)之酸價，從可得到能形成耐熱性優異的硬化物之硬化性組成物來看，較佳為3mgKOH/g以下，更佳為2mgKOH/g以下。又，前述環氧(甲基)丙烯酸酯樹脂(D)之羥值較佳為300mgKOH/g以下。 The acid value of the epoxy (meth)acrylate resin (D) is preferably 3 mgKOH/g or less, more preferably 2 mgKOH/g from the viewpoint of obtaining a curable composition capable of forming a cured product having excellent heat resistance. the following. In addition, the hydroxyl value of the epoxy (meth)acrylate resin (D) is preferably 300 mgKOH/g or less.
前述環氧樹脂(d1)與前述不飽和單羧酸(d2)之反應較佳為在鹼性觸媒之存在下進行。 The reaction of the epoxy resin (d1) and the unsaturated monocarboxylic acid (d2) is preferably carried out in the presence of an alkaline catalyst.
作為前述鹼性觸媒，可舉出例如N-甲基
前述鹼性觸媒之使用量係相對於前述環氧樹脂(d1)與前述不飽和單羧酸(d2)之合計100質量份，而較佳為0.01~0.5質量份之範圍，更佳為0.01~0.4之範圍。 The amount of the basic catalyst used is 100 parts by mass relative to the total of the epoxy resin (d1) and the unsaturated monocarboxylic acid (d2), preferably 0.01 to 0.5 parts by mass, more preferably 0.01 ~0.4 range.
於前述環氧樹脂(d1)與前述不飽和單羧酸(d2)之反應中使用了鹼性觸媒時，可在反應後分離、去除前述鹼性觸媒而使用，亦可不分離、去除前述鹼性觸媒，而以酸性化合物使其失去活性而使用。 When an alkaline catalyst is used in the reaction between the epoxy resin (d1) and the unsaturated monocarboxylic acid (d2), the alkaline catalyst can be separated and removed after the reaction, or it can be used without separation or removal. It is used as an alkaline catalyst, which is deactivated by acidic compounds.
作為前述酸性化合物，可舉出例如鹽酸、硫酸、磷酸等之無機酸、甲磺酸、對甲苯磺酸、草酸等之有機酸等。此等之酸性化合物可單獨使用，也可併用2種以上。 Examples of the acidic compound include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid. These acidic compounds may be used alone or in combination of two or more.
前述環氧(甲基)丙烯酸酯樹脂(D)之製造方法沒有特別的限定，可用任何方法製造。例如，可利用使反應原料全部整批地反應之方法來製造，也可利用使反應原料依序反應之方法來製造。其中，從反應之控制容易來看，可藉由以下方法等來進行：先使環氧樹脂(d1)與不飽和單羧酸(d2)在鹼性觸媒之存在下，於80~140℃之溫度範圍進行反應，接著添加酸性化合物，於50~100℃之溫度範圍混合，以使鹼性觸媒失去活性。 The production method of the aforementioned epoxy (meth)acrylate resin (D) is not particularly limited, and can be produced by any method. For example, it can be manufactured by a method of reacting all the reaction raw materials in batches, or by a method of sequentially reacting the reaction raw materials. Among them, from the point of view of easy control of the reaction, it can be carried out by the following methods: first, the epoxy resin (d1) and the unsaturated monocarboxylic acid (d2) in the presence of an alkaline catalyst at 80 ~ 140 ℃ The reaction is carried out in the temperature range, and then the acidic compound is added and mixed in the temperature range of 50~100 ℃ to make the alkaline catalyst inactive.
前述環氧(甲基)丙烯酸酯樹脂(D)之含量，在前述硬化性組成物固體成分中較佳為2~90質量%。 The content of the epoxy (meth)acrylate resin (D) in the solid content of the curable composition is preferably 2 to 90% by mass.
又，前述環氧(甲基)丙烯酸酯(D)與前述(甲基)丙烯酸酯化合物之質量比例[{(甲基)丙烯酸酯化合物}/{環氧(甲基)丙烯酸酯(D)}]，從可得到低黏度且具有優異的硬化性，而且能形成具有優異的耐熱性之硬化物的硬化性組成物來看，較佳為10/90~90/10之範圍。 Furthermore, the mass ratio of the epoxy (meth)acrylate (D) to the (meth)acrylate compound [{(meth)acrylate compound}/{epoxy (meth)acrylate (D)} ] From the viewpoint of obtaining a curable composition having a low viscosity, excellent curability, and a cured product having excellent heat resistance, it is preferably in the range of 10/90 to 90/10.
另外，本發明之硬化性組成物亦可含有本發明之(甲基)丙烯酸酯化合物以外之其它的(甲基)丙烯酸酯單體。 In addition, the curable composition of the present invention may contain (meth)acrylate monomers other than the (meth)acrylate compound of the present invention.
作為前述其它的(甲基)丙烯酸酯單體，可舉出例如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸辛酯等之脂肪族單(甲基)丙烯酸酯化合物；(甲基)丙烯酸環己酯、(甲基)丙烯酸異
又，作為前述其它的(甲基)丙烯酸酯單體，除了上述之外，還可使用以前述至少具有3個羥基作為芳香環上的取代基之酚化合物以外的酚化合物(以下，亦稱為「其它的酚化合物」)、與環狀碳酸酯化合物或環狀醚化合物、與不飽和單羧酸作為必須的反應原料之(甲基)丙烯酸酯單體。 In addition, as the other (meth)acrylate monomers, in addition to the above, phenol compounds other than the phenol compounds having at least three hydroxyl groups as substituents on the aromatic ring (hereinafter, also referred to as "Other phenol compounds"), (meth)acrylate monomers with cyclic carbonate compounds or cyclic ether compounds, and unsaturated monocarboxylic acids as essential raw materials for the reaction.
作為前述其它的酚化合物，可舉出例如甲酚、二甲苯酚、兒茶酚、間苯二酚、氫醌、3-甲基兒茶酚、4-甲基兒茶酚、4-烯丙基焦兒茶酚、1-萘酚、2-萘酚、1,3-萘二酚、1,5-萘二酚、2,6-萘二酚、2,7-萘二酚、氫化雙酚、氫化聯苯酚、聚伸苯基醚型二醇、聚伸萘基醚型二醇、苯酚酚醛清漆樹脂、甲酚酚醛清漆樹脂、雙酚酚醛清漆型樹脂、萘酚酚醛清漆型樹脂、苯酚芳烷基型樹脂、萘酚芳烷基型樹脂、含有環結構的酚樹脂等。 Examples of the aforementioned other phenol compounds include cresol, xylenol, catechol, resorcinol, hydroquinone, 3-methylcatechol, 4-methylcatechol, 4-allyl Pyrogallate, 1-naphthol, 2-naphthol, 1,3-naphthalenediol, 1,5-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, hydrogenated bisphenol Phenol, hydrogenated biphenol, polyphenylene ether glycol, polynaphthyl ether glycol, phenol novolak resin, cresol novolak resin, bisphenol novolak resin, naphthol novolak resin, phenol Aralkyl type resin, naphthol aralkyl type resin, phenol resin containing ring structure, etc.
作為前述環狀碳酸酯化合物及前述環狀醚化合物，可使用與上述之環狀碳酸酯化合物(B1)及上述之環狀醚化合物(B2)同樣者。 As the cyclic carbonate compound and the cyclic ether compound, the same ones as the cyclic carbonate compound (B1) and the cyclic ether compound (B2) described above can be used.
作為前述不飽和羧酸，可使用與上述之不飽和羧酸(C)同樣者。 As the unsaturated carboxylic acid, the same as the above-mentioned unsaturated carboxylic acid (C) can be used.
前述其它的(甲基)丙烯酸酯單體之含量，較佳為在本發明之硬化性組成物中為90質量%以下。 The content of the aforementioned other (meth)acrylate monomer is preferably 90% by mass or less in the curable composition of the present invention.
本發明之硬化性組成物亦可因塗敷黏度調節等之目的而含有有機溶劑，其種類或添加量係因應所欲的性能而被適宜選擇及調整。 The curable composition of the present invention may also contain an organic solvent for the purpose of coating viscosity adjustment, etc. The type or amount of addition is appropriately selected and adjusted according to the desired performance.
作為前述有機溶劑，可舉出例如甲基乙基酮、丙酮、異丁酮等之酮溶劑；四氫呋喃、二氧戊環等之環狀醚溶劑；乙酸甲酯、乙酸乙酯、乙酸丁酯等之酯溶劑；甲苯、二甲苯、溶劑油等之芳香族溶劑；環己烷、甲基環己烷等之脂環族溶劑；卡必醇、賽路蘇、甲醇、異丙醇、丁醇、丙二醇單甲基醚等之醇溶劑；烷二醇單烷基醚、二烷二醇單烷基醚、二烷二醇單烷基醚乙酸酯等之二醇醚溶劑等。此等之有機溶劑可單獨使用，也可併用2種以上。 Examples of the organic solvent include ketone solvents such as methyl ethyl ketone, acetone, and isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; methyl acetate, ethyl acetate, and butyl acetate. Ester solvents; aromatic solvents such as toluene, xylene, solvent oil, etc.; cycloaliphatic solvents such as cyclohexane and methylcyclohexane; carbitol, cyclamate, methanol, isopropanol, butanol, Alcohol solvents such as propylene glycol monomethyl ether; glycol ether solvents such as alkylene glycol monoalkyl ether, dialkyl glycol monoalkyl ether, dialkyl glycol monoalkyl ether acetate, etc. These organic solvents may be used alone or in combination of two or more.
又，本發明之硬化性組成物中，亦可因應需要而含有環氧樹脂、無機微粒子或聚合物微粒子、顏料、消泡劑、黏度調整劑、調平劑、阻燃劑、保存安定化劑等之各種添加劑。 In addition, the curable composition of the present invention may contain epoxy resin, inorganic fine particles or polymer fine particles, pigments, defoaming agents, viscosity modifiers, leveling agents, flame retardants, storage stabilizers as needed Etc. various additives.
作為前述環氧樹脂，可使用作為上述之環氧樹脂(d1)而例示者，前述環氧樹脂可單獨使用，也可併用2種以上。 As the epoxy resin, those exemplified as the above-mentioned epoxy resin (d1) may be used, and the epoxy resin may be used alone or in combination of two or more kinds.
本發明之硬化性組成物從為低黏度且具有優異的硬化性來看，可作為塗覆劑或接著劑使用，尤其可適用作為塗覆劑。 The curable composition of the present invention can be used as a coating agent or an adhesive from the viewpoint of having a low viscosity and excellent curability, and is particularly suitable as a coating agent.
本發明之硬化物可藉由對於前述硬化性組成物，照射活性能量線而得。作為前述活性能量線，可舉出例如紫外線、電子線、α線、β線、γ線等之電離輻射線。又，使用紫外線作為前述活性能量線時，在有效率地進行紫外線所致的硬化反應上， 可在氮氣等的惰性氣體環境下照射，也可在空氣環境下照射。 The hardened product of the present invention can be obtained by irradiating the aforementioned curable composition with active energy rays. Examples of the active energy rays include ionizing radiation rays such as ultraviolet rays, electron rays, α rays, β rays, and γ rays. In addition, when ultraviolet rays are used as the active energy rays, the curing reaction due to ultraviolet rays can be efficiently carried out under an inert gas environment such as nitrogen, or under an air environment.
作為紫外線產生源，從實用性、經濟性之面來看，一般使用紫外線燈。具體而言，可舉出低壓水銀燈、高壓水銀燈、超高壓水銀燈、氙燈、鎵燈、金屬鹵化物燈、太陽光、LED等。 As a source of ultraviolet rays, from the viewpoint of practicality and economy, ultraviolet lamps are generally used. Specifically, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a gallium lamp, a metal halide lamp, sunlight, LED, etc. may be mentioned.
前述活性能量線之累計光量係沒有特別的限制，但較佳為50~5000mJ/cm2，更佳為100~1000mJ/cm2。若累計光量為上述範圍，則從可防止或抑制未硬化部分之發生來看為較佳。 The cumulative light amount of the aforementioned active energy rays is not particularly limited, but it is preferably 50 to 5000 mJ/cm 2 , and more preferably 100 to 1000 mJ/cm 2 . If the cumulative light amount is within the above range, it is preferable from the viewpoint of preventing or suppressing the occurrence of unhardened portions.
還有，前述活性能量線之照射係能以一階段進行，也能分成二階段以上進行。 In addition, the irradiation of the aforementioned active energy rays can be performed in one stage, or can be divided into two or more stages.
本發明之物品為具有包含前述硬化物之塗膜者。作為前述物品，可舉出例如行動電話、家電製品、汽車內外裝飾材料、OA機器等的塑膠成形品，或半導體裝置、顯示裝置、攝像裝置等。 The article of the present invention has a coating film containing the aforementioned cured product. Examples of the aforementioned articles include plastic molded articles such as mobile phones, home appliances, automotive interior and exterior decoration materials, OA equipment, etc., semiconductor devices, display devices, and imaging devices.
以下，藉由實施例與比較例，具體地說明本發明。 Hereinafter, the present invention will be specifically described by Examples and Comparative Examples.
還有，於本實施例中，重量平均分子量(Mw)係使用凝膠滲透層析儀(GPC)，依照下述之條件所測定之值。 In this example, the weight average molecular weight (Mw) is a value measured using a gel permeation chromatography (GPC) under the following conditions.
測定裝置：東曹股份有限公司製HLC-8220 Measuring device: HLC-8220 manufactured by Tosoh Corporation
管柱：東曹股份有限公司製保護管柱HXL-H Pipe Column: Tosoh Co., Ltd. protective pipe column H XL -H
+東曹股份有限公司製TSKgel G5000HXL +TSKgel G5000HXL made by Tosoh Corporation
+東曹股份有限公司製TSKgel G4000HXL +TSKgel G4000HXL made by Tosoh Corporation
+東曹股份有限公司製TSKgel G3000HXL +TSKgel G3000HXL made by Tosoh Corporation
+東曹股份有限公司製TSKgel G2000HXL +TSKgel G2000HXL made by Tosoh Corporation
檢測器：RI(示差折射計) Detector: RI (Differential Refractometer)
數據處理：東曹股份有限公司製SC-8010 Data processing: SC-8010 manufactured by Tosoh Corporation
測定條件：管柱溫度40℃ Measurement conditions: column temperature 40℃
溶劑 四氫呋喃 Solvent Tetrahydrofuran
流速1.0ml/分鐘 Flow rate 1.0ml/min
標準：聚苯乙烯 Standard: Polystyrene
試料：將以樹脂固體成分換算為0.4質量%的四氫呋喃溶液用微濾器過濾者(100μl) Sample: A tetrahydrofuran solution converted into 0.4% by mass of the resin solid content is filtered through a microfilter (100 μl)
於具備有溫度計、攪拌器及回流冷卻器的燒瓶中，添加126質量份的五倍子酚、277質量份的碳酸伸乙酯與0.7質量份的50%氫氧化鉀水溶液，於氮氣環境下在170℃使反應進行了20小時。接著，使所得之反應物溶解於333質量份的甲苯之後，加入228質量份的丙烯酸、5.0質量份的對甲苯磺酸、0.2質量份的甲基氫醌，吹入空氣，一邊攪拌，一邊在100℃使反應進行了10小時。然後，冷卻到50℃為止，水洗所得之反應溶液，將甲苯脫溶劑，而得到了(甲基)丙烯酸酯化合物(1)。此(甲基)丙烯酸酯化合物(1)的重量平均分子量(Mw)為620，在25℃的黏度為330mPa．s。還有，黏度係使用E型旋轉黏度計(東機產業股份有限公司製「RE80U」)，在25℃條件下所測定之值。又，相當於含有酚性羥基的化合物(A)與前述環狀碳酸酯化合物(B1)之莫耳比[(B1)/(A)]的五倍子酚與碳酸伸乙酯之莫耳比[(碳酸伸乙酯之莫耳數)/(五倍子酚之莫耳數)]為3.15，相當於環狀碳酸酯化合物(B1)與不飽和羧酸(C)之莫耳比[(C)/(B1)]的碳酸伸乙酯與 丙烯酸之莫耳比[(丙烯酸之莫耳數)/(碳酸伸乙酯之莫耳數)]為1.004。 In a flask equipped with a thermometer, stirrer, and reflux cooler, add 126 parts by mass of gallic acid, 277 parts by mass of ethyl carbonate, and 0.7 parts by mass of 50% potassium hydroxide aqueous solution at 170°C under a nitrogen atmosphere The reaction was allowed to proceed for 20 hours. Next, after dissolving the obtained reactant in 333 parts by mass of toluene, 228 parts by mass of acrylic acid, 5.0 parts by mass of p-toluenesulfonic acid, and 0.2 parts by mass of methylhydroquinone were added, and air was blown in while stirring. The reaction was carried out at 100°C for 10 hours. Then, it cooled to 50 degreeC, the obtained reaction solution was washed with water, and toluene was desolvated, and the (meth)acrylate compound (1) was obtained. The (meth)acrylate compound (1) has a weight average molecular weight (Mw) of 620 and a viscosity of 330 mPa at 25°C. s. The viscosity is a value measured at 25°C using an E-type rotary viscometer ("RE80U" manufactured by Toki Industries Co., Ltd.). In addition, the molar ratio of gallnut phenol to ethylidene carbonate equivalent to the molar ratio of the phenolic hydroxyl group-containing compound (A) to the cyclic carbonate compound (B1) [(B1)/(A)] [( (Molar number of ethylidene carbonate)/(Molar number of gallnut) is 3.15, which is equivalent to the molar ratio of cyclic carbonate compound (B1) to unsaturated carboxylic acid (C) [(C)/( B1)] The molar ratio of ethylidene carbonate to acrylic acid [(number of moles of acrylic acid)/(number of moles of ethylidene carbonate)] is 1.004.
於具備有溫度計、攪拌器及回流冷卻器的燒瓶中，添加126質量份的五倍子酚、337質量份的碳酸伸丙酯與0.7質量份的50%氫氧化鉀水溶液，於氮氣環境下在170℃使反應進行了30小時。接著，使所得之反應物溶解於379質量份的甲苯之後，加入237質量份的丙烯酸、5.7質量份的對甲苯磺酸、0.2質量份的甲基氫醌，吹入空氣，一邊攪拌，一邊在100℃使反應進行了20小時。然後，冷卻到50℃為止，水洗所得之反應溶液，將甲苯脫溶劑，而得到了(甲基)丙烯酸酯化合物(2)。此(甲基)丙烯酸酯化合物(2)的重量平均分子量(Mw)為780，在25℃的黏度為500mPa．s。又，相當於含有酚性羥基的化合物(A)與前述環狀碳酸酯化合物(B1)之莫耳比[(B1)/(A)]的五倍子酚與碳酸伸丙酯之莫耳比[(碳酸伸丙酯之莫耳數)/(五倍子酚之莫耳數)]為3.30，相當於環狀碳酸酯化合物(B1)與不飽和羧酸(C)之莫耳比[(C)/(B1)]的碳酸伸丙酯與丙烯酸之莫耳比[(丙烯酸之莫耳數)/(碳酸伸丙酯之莫耳數)]為0.994。 In a flask equipped with a thermometer, stirrer, and reflux cooler, add 126 parts by mass of gallic acid, 337 parts by mass of propyl carbonate, and 0.7 parts by mass of 50% potassium hydroxide aqueous solution at 170°C under a nitrogen atmosphere The reaction was allowed to proceed for 30 hours. Next, after dissolving the obtained reactant in 379 parts by mass of toluene, 237 parts by mass of acrylic acid, 5.7 parts by mass of p-toluenesulfonic acid, and 0.2 parts by mass of methylhydroquinone were added, and air was blown in while stirring. The reaction was carried out at 100°C for 20 hours. Then, it cooled to 50 degreeC, the obtained reaction solution was washed with water, and toluene was desolvated, and the (meth)acrylate compound (2) was obtained. The (meth)acrylate compound (2) has a weight average molecular weight (Mw) of 780 and a viscosity of 500 mPa at 25°C. s. In addition, the molar ratio of gallnut phenol to propidium carbonate equivalent to the molar ratio of the compound (A) containing a phenolic hydroxyl group (A) and the cyclic carbonate compound (B1) [(B1)/(A)] [( (Mole number of propylene carbonate)/(Mole number of gallnut)) is 3.30, which is equivalent to the mole ratio of cyclic carbonate compound (B1) to unsaturated carboxylic acid (C) [(C)/( B1)] The molar ratio of propylene carbonate to acrylic acid [(number of moles of acrylic acid)/(number of moles of propyl carbonate)] is 0.994.
於具備有溫度計、攪拌器及回流冷卻器的燒瓶中，添加126質量份的五倍子酚、277質量份的碳酸伸乙酯與0.7質量份的50%氫氧化鉀水溶液，於氮氣環境下在170℃使反應進行了20小時。接著，使所得之反應物溶解於282質量份的甲苯中後，加 入152質量份的丙烯酸、4.2質量份的對甲苯磺酸、0.1質量份的甲基氫醌，吹入空氣，一邊攪拌，一邊在100℃使反應進行了10小時。然後，冷卻到50℃為止，水洗所得之反應溶液，將甲苯脫溶劑，而得到了(甲基)丙烯酸酯化合物(3)。此(甲基)丙烯酸酯化合物(3)的重量平均分子量(Mw)為580，在25℃的黏度為520mPa．s。又，相當於含有酚性羥基的化合物(A)與前述環狀碳酸酯化合物(B1)之莫耳比[(B1)/(A)]的五倍子酚與碳酸伸乙酯之莫耳比[(碳酸伸乙酯之莫耳數)/(五倍子酚之莫耳數)]為3.15，相當於環狀碳酸酯化合物(B1)與不飽和羧酸(C)之莫耳比[(C)/(B1)]的碳酸伸乙酯與丙烯酸之莫耳比[(丙烯酸之莫耳數)/(碳酸伸乙酯之莫耳數)]為0.669。 In a flask equipped with a thermometer, stirrer, and reflux cooler, add 126 parts by mass of gallic acid, 277 parts by mass of ethyl carbonate, and 0.7 parts by mass of 50% potassium hydroxide aqueous solution at 170°C under a nitrogen atmosphere The reaction was allowed to proceed for 20 hours. Next, after dissolving the obtained reactant in 282 parts by mass of toluene, 152 parts by mass of acrylic acid, 4.2 parts by mass of p-toluenesulfonic acid, and 0.1 parts by mass of methylhydroquinone were added, and air was blown in while stirring. The reaction was carried out at 100°C for 10 hours. Then, it cooled to 50 degreeC, the obtained reaction solution was washed with water, and toluene was desolvated, and the (meth)acrylate compound (3) was obtained. This (meth)acrylate compound (3) has a weight average molecular weight (Mw) of 580 and a viscosity of 520 mPa at 25°C. s. In addition, the molar ratio of gallnut phenol to ethylidene carbonate equivalent to the molar ratio of the phenolic hydroxyl group-containing compound (A) to the cyclic carbonate compound (B1) [(B1)/(A)] [( (Molar number of ethylidene carbonate)/(Molar number of gallnut) is 3.15, which is equivalent to the molar ratio of cyclic carbonate compound (B1) to unsaturated carboxylic acid (C) [(C)/( B1)] The molar ratio of ethylidene carbonate to acrylic acid [(number of moles of acrylic acid)/(number of moles of ethylidene carbonate)] is 0.669.
於具備有溫度計、攪拌器及回流冷卻器的燒瓶中，添加126質量份的五倍子酚、277質量份的碳酸伸乙酯與0.7質量份的50%氫氧化鉀水溶液，於氮氣環境下在170℃使反應進行了20小時。接著，使所得之反應物溶解於277質量份的甲苯中後，加入144質量份的丙烯酸、4.2質量份的對甲苯磺酸、0.1質量份的甲基氫醌，吹入空氣，一邊攪拌，一邊在100℃使反應進行了10小時。然後，冷卻到50℃為止，水洗所得之反應溶液，將甲苯脫溶劑，而得到了(甲基)丙烯酸酯化合物(4)。此(甲基)丙烯酸酯化合物(4)的重量平均分子量(Mw)為560，在25℃的黏度為600mPa．s。又，相當於含有酚性羥基的化合物(A)與前述環狀碳酸酯化合物(B1)之莫耳比[(B1)/(A)]的五倍子酚與碳酸伸乙酯之莫耳比[(碳酸伸乙酯之莫耳數)/(五倍子酚之莫耳數)]為3.15， 相當於環狀碳酸酯化合物(B1)與不飽和羧酸(C)之莫耳比[(C)/(B1)]的碳酸伸乙酯與丙烯酸之莫耳比[(丙烯酸之莫耳數)/(碳酸伸乙酯之莫耳數)]為0.636。 In a flask equipped with a thermometer, stirrer, and reflux cooler, add 126 parts by mass of gallic acid, 277 parts by mass of ethyl carbonate, and 0.7 parts by mass of 50% potassium hydroxide aqueous solution at 170°C under a nitrogen atmosphere The reaction was allowed to proceed for 20 hours. Next, after dissolving the obtained reactant in 277 parts by mass of toluene, 144 parts by mass of acrylic acid, 4.2 parts by mass of p-toluenesulfonic acid, and 0.1 parts by mass of methylhydroquinone were added, and air was blown in while stirring The reaction was carried out at 100°C for 10 hours. Then, it cooled to 50 degreeC, the obtained reaction solution was washed with water, and toluene was desolvated, and the (meth)acrylate compound (4) was obtained. The weight average molecular weight (Mw) of this (meth)acrylate compound (4) is 560, and the viscosity at 25°C is 600 mPa. s. In addition, the molar ratio of gallnut phenol to ethylidene carbonate equivalent to the molar ratio of the phenolic hydroxyl group-containing compound (A) to the cyclic carbonate compound (B1) [(B1)/(A)] [( (Molar number of ethylidene carbonate)/(Molle number of gallnut)] is 3.15, which is equivalent to the molar ratio of cyclic carbonate compound (B1) to unsaturated carboxylic acid (C) [(C)/( B1)] The molar ratio of ethylidene carbonate to acrylic acid [(number of moles of acrylic acid)/(number of moles of ethylidene carbonate)] is 0.636.
於具備有溫度計、攪拌器及回流冷卻器的燒瓶中，添加126質量份的1,2,4-三羥基苯、277質量份的碳酸伸乙酯與0.7質量份的50%氫氧化鉀水溶液，於氮氣環境下在170℃使反應進行了20小時。接著，使所得之反應物溶解於333質量份的甲苯中後，加入228質量份的丙烯酸、5.0質量份的對甲苯磺酸、0.2質量份的甲基氫醌，吹入空氣，一邊攪拌，一邊在100℃使反應進行了10小時。然後，冷卻到50℃為止，水洗所得之反應溶液，將甲苯脫溶劑，而得到了(甲基)丙烯酸酯化合物(5)。此(甲基)丙烯酸酯化合物(5)的重量平均分子量(Mw)為600，在25℃的黏度為410mPa．s。又，相當於含有酚性羥基的化合物(A)與前述環狀碳酸酯化合物(B1)之莫耳比[(B1)/(A)]的1,2,4-三羥基苯與碳酸伸乙酯之莫耳比[(碳酸伸乙酯之莫耳數)/(1,2,4-三羥基苯之莫耳數)]為3.15，相當於環狀碳酸酯化合物(B1)與不飽和羧酸(C)之莫耳比[(C)/(B1)]的碳酸伸乙酯與丙烯酸之莫耳比[(丙烯酸之莫耳數)/(碳酸伸乙酯之莫耳數)]為1.004。 In a flask equipped with a thermometer, stirrer and reflux cooler, add 126 parts by mass of 1,2,4-trihydroxybenzene, 277 parts by mass of ethyl carbonate and 0.7 parts by mass of 50% potassium hydroxide aqueous solution, The reaction was carried out at 170°C for 20 hours under a nitrogen atmosphere. Next, after dissolving the obtained reactant in 333 parts by mass of toluene, 228 parts by mass of acrylic acid, 5.0 parts by mass of p-toluenesulfonic acid, and 0.2 parts by mass of methylhydroquinone were added, and air was blown in while stirring. The reaction was carried out at 100°C for 10 hours. Then, it cooled to 50 degreeC, the obtained reaction solution was washed with water, and toluene was desolvated, and the (meth)acrylate compound (5) was obtained. The weight average molecular weight (Mw) of this (meth)acrylate compound (5) is 600, and the viscosity at 25°C is 410 mPa. s. Also, equivalent to the molar ratio [(B1)/(A)] of phenolic hydroxyl group-containing compound (A) and the aforementioned cyclic carbonate compound (B1) of 1, 2, 4-trihydroxybenzene and ethylene carbonate The molar ratio of ester [(number of moles of ethyl carbonate)/(number of moles of 1,2,4-trihydroxybenzene)] is 3.15, which is equivalent to cyclic carbonate compound (B1) and unsaturated carboxylic acid The molar ratio of acid (C) [(C)/(B1)] of ethyl carbonate and acrylic acid [(mol number of acrylic acid)/(mol number of ethyl carbonate)] is 1.004 .
於具備有溫度計、攪拌器及回流冷卻器的燒瓶中，添加126質量份的五倍子酚、255質量份的碳酸伸乙酯與0.7質量份的50%氫氧化鉀水溶液，於氮氣環境下在170℃使反應進行了20 小時。接著，使所得之反應物溶解於333質量份的甲苯中後，加入209質量份的丙烯酸、5.0質量份的對甲苯磺酸、0.2質量份的甲基氫醌，吹入空氣，一邊攪拌，一邊在100℃使反應進行了10小時。然後，冷卻到50℃為止，水洗所得之反應溶液，將甲苯脫溶劑，而得到了(甲基)丙烯酸酯化合物(6)。此(甲基)丙烯酸酯化合物(6)的重量平均分子量(Mw)為570，在25℃的黏度為510mPa．s。又，相當於含有酚性羥基的化合物(A)與前述環狀碳酸酯化合物(B1)之莫耳比[(B1)/(A)]的五倍子酚與碳酸伸乙酯之莫耳比[(碳酸伸乙酯之莫耳數)/(五倍子酚之莫耳數)]為2.90，相當於環狀碳酸酯化合物(B1)與不飽和羧酸(C)之莫耳比[(C)/(B1)]的碳酸伸乙酯與丙烯酸之莫耳比[(丙烯酸之莫耳數)/(碳酸伸乙酯之莫耳數)]為1.002。 In a flask equipped with a thermometer, stirrer, and reflux cooler, add 126 parts by mass of gallic acid, 255 parts by mass of ethyl carbonate, and 0.7 parts by mass of 50% potassium hydroxide aqueous solution at 170°C under a nitrogen atmosphere The reaction was allowed to proceed for 20 hours. Next, after dissolving the obtained reactant in 333 parts by mass of toluene, 209 parts by mass of acrylic acid, 5.0 parts by mass of p-toluenesulfonic acid, and 0.2 parts by mass of methylhydroquinone were added, and air was blown in while stirring. The reaction was carried out at 100°C for 10 hours. Then, it cooled to 50 degreeC, the obtained reaction solution was washed with water, and toluene was desolvated, and the (meth)acrylate compound (6) was obtained. This (meth)acrylate compound (6) has a weight average molecular weight (Mw) of 570 and a viscosity of 510 mPa at 25°C. s. In addition, the molar ratio of gallnut phenol to ethylidene carbonate equivalent to the molar ratio of the phenolic hydroxyl group-containing compound (A) to the cyclic carbonate compound (B1) [(B1)/(A)] [( Molar number of ethyl carbonate)/(Molar number of gallnut) is 2.90, which is equivalent to the molar ratio of cyclic carbonate compound (B1) to unsaturated carboxylic acid (C) [(C)/( B1)] The molar ratio of ethyl carbonate to acrylic acid [(moles of acrylic acid)/(moles of ethyl carbonate)] is 1.002.
於具備有溫度計、攪拌器及回流冷卻器的燒瓶中，添加94質量份的苯酚、92質量份的碳酸伸乙酯與0.5質量份的50%氫氧化鉀水溶液，於氮氣環境下在170℃使反應進行了5小時。接著，使所得之反應物溶解於145質量份的甲苯中後，加入75質量份的丙烯酸、2.2質量份的對甲苯磺酸、0.1質量份的甲基氫醌，吹入空氣，一邊攪拌，一邊在100℃使反應進行了10小時。然後，冷卻到50℃為止，水洗所得之反應溶液，將甲苯脫溶劑，而得到了(甲基)丙烯酸酯化合物(7)。此(甲基)丙烯酸酯化合物(7)的重量平均分子量(Mw)為360，在25℃的黏度為110mPa．s。又，相當於含有酚性羥基的化合物(A)與前述環狀碳酸酯化合物(B1)之莫耳比[(B1)/(A)]的苯酚與碳酸伸乙酯之莫耳比[(碳酸伸乙 酯之莫耳數)/(苯酚之莫耳數)]為1.05，相當於環狀碳酸酯化合物(B1)與不飽和羧酸(C)之莫耳比[(C)/(B1)]的碳酸伸乙酯與丙烯酸之莫耳比[(丙烯酸之莫耳數)/(碳酸伸乙酯之莫耳數)]為1.002。 In a flask equipped with a thermometer, stirrer, and reflux cooler, add 94 parts by mass of phenol, 92 parts by mass of ethyl carbonate, and 0.5 parts by mass of 50% potassium hydroxide aqueous solution. The reaction proceeded for 5 hours. Next, after dissolving the obtained reactant in 145 parts by mass of toluene, 75 parts by mass of acrylic acid, 2.2 parts by mass of p-toluenesulfonic acid, and 0.1 parts by mass of methylhydroquinone were added, and air was blown in while stirring. The reaction was carried out at 100°C for 10 hours. Then, it cooled to 50 degreeC, the obtained reaction solution was washed with water, and toluene was desolvated, and the (meth)acrylate compound (7) was obtained. The weight average molecular weight (Mw) of this (meth)acrylate compound (7) is 360, and the viscosity at 25°C is 110 mPa. s. In addition, the molar ratio of phenol and ethylidene carbonate equivalent to the molar ratio [(B1)/(A)] of the phenolic hydroxyl group-containing compound (A) and the aforementioned cyclic carbonate compound (B1) [(carbonic acid Molar number of ethyl ester)/(mole number of phenol)] is 1.05, which is equivalent to the molar ratio of cyclic carbonate compound (B1) and unsaturated carboxylic acid (C) [(C)/(B1) ] The molar ratio of ethylidene carbonate to acrylic acid [(number of moles of acrylic acid)/(number of moles of ethylidene carbonate)] is 1.002.
於具備有溫度計、攪拌器及回流冷卻器的燒瓶中，添加110質量份的兒茶酚、185質量份的碳酸伸乙酯與0.6質量份的50%氫氧化鉀水溶液，於氮氣環境下在170℃使反應進行了7小時。接著，使所得之反應物溶解於240質量份的甲苯中後，加入153質量份的丙烯酸、3.6質量份的對甲苯磺酸及0.1質量份的甲基氫醌，吹入空氣，一邊攪拌，一邊在100℃使反應進行了10小時。然後，冷卻到50℃為止，水洗所得之反應溶液，將甲苯脫溶劑，而得到了(甲基)丙烯酸酯化合物(8)。此(甲基)丙烯酸酯化合物(8)的重量平均分子量(Mw)為470，在25℃的黏度為230mPa．s。又，相當於含有酚性羥基的化合物(A)與前述環狀碳酸酯化合物(B1)之莫耳比[(B1)/(A)]的兒茶酚與碳酸伸乙酯之莫耳比[(碳酸伸乙酯之莫耳數)/(兒茶酚之莫耳數)]為2.10，相當於環狀碳酸酯化合物(B1)與不飽和羧酸(C)之莫耳比[(C)/(B1)]的碳酸伸乙酯與丙烯酸之莫耳比[(丙烯酸之莫耳數)/(碳酸伸乙酯之莫耳數)]為1.008。 In a flask equipped with a thermometer, a stirrer and a reflux cooler, add 110 parts by mass of catechol, 185 parts by mass of ethyl carbonate and 0.6 parts by mass of 50% potassium hydroxide aqueous solution under a nitrogen atmosphere at 170 The reaction was allowed to proceed at 7°C for 7 hours. Next, after dissolving the obtained reactant in 240 parts by mass of toluene, 153 parts by mass of acrylic acid, 3.6 parts by mass of p-toluenesulfonic acid, and 0.1 parts by mass of methylhydroquinone were added, and air was blown in while stirring. The reaction was carried out at 100°C for 10 hours. Then, it cooled to 50 degreeC, the obtained reaction solution was washed with water, and toluene was desolvated, and the (meth)acrylate compound (8) was obtained. The weight average molecular weight (Mw) of this (meth)acrylate compound (8) is 470, and the viscosity at 25°C is 230 mPa. s. In addition, the molar ratio of catechol and ethylidene carbonate equivalent to the molar ratio of the phenolic hydroxyl group-containing compound (A) to the cyclic carbonate compound (B1) [(B1)/(A)] [ (Molar number of ethylidene carbonate)/(Molar number of catechol)] is 2.10, which is equivalent to the molar ratio of cyclic carbonate compound (B1) and unsaturated carboxylic acid (C) [(C) /(B1)] The molar ratio of ethyl carbonate to acrylic acid [(number of moles of acrylic acid)/(number of moles of ethyl carbonate)] is 1.008.
混合100質量份的實施例1所得之(甲基)丙烯酸酯化合物(1)與2質量份的光聚合性起始劑(IGM公司製「Omnirad 184」)，得到了硬化性組成物(1)。 100 parts by mass of the (meth)acrylate compound (1) obtained in Example 1 and 2 parts by mass of a photopolymerizable initiator ("Omnirad 184" manufactured by IGM Corporation) were obtained to obtain a curable composition (1) .
除了取代實施例7所用之(甲基)丙烯酸酯化合物(1)，而以表1所示的摻合量使用了實施例2~6所得之(甲基)丙烯酸酯化合物(2)~(6)以外，係與實施例7同樣地進行，而得到了硬化性組成物(2)~(6)。 In addition to replacing the (meth)acrylate compound (1) used in Example 7, the (meth)acrylate compounds (2) to (6) obtained in Examples 2 to 6 were used at the blending amounts shown in Table 1. Except for ), it was carried out in the same manner as in Example 7 to obtain curable compositions (2) to (6).
混合100質量份的比較例1所得之(甲基)丙烯酸酯化合物(7)與2質量份的光聚合性起始劑(IGM公司製「Omnirad 184」)，得到了硬化性組成物(C1)。 100 parts by mass of the (meth)acrylate compound (7) obtained in Comparative Example 1 and 2 parts by mass of a photopolymerizable initiator ("Omnirad 184" manufactured by IGM Corporation) were obtained to obtain a curable composition (C1) .
除了取代比較例3所用之(甲基)丙烯酸酯化合物(7)，而以表1所示的摻合量使用了比較例2所得之(甲基)丙烯酸酯化合物(8)以外，係與比較例3同樣地進行，而得到了硬化性組成物(C2)。 Except for substituting the (meth)acrylate compound (7) used in Comparative Example 3, and using the (meth)acrylate compound (8) obtained in Comparative Example 2 at the blending amount shown in Table 1, it is comparable to Example 3 was carried out in the same manner to obtain a curable composition (C2).
除了取代比較例3所用之(甲基)丙烯酸酯化合物(7)，而以表1所示的摻合量使用了三羥甲基丙烷EO改質三丙烯酸酯(Miwon公司製「Miramer M-3130」)以外，係與比較例3同樣地進行，而得到了硬化性組成物(C3)。 Instead of replacing the (meth)acrylate compound (7) used in Comparative Example 3, trimethylolpropane EO modified triacrylate ("Miramer M-3130" manufactured by Miwon Corporation) was used at the blending amount shown in Table 1. ”) except that it was carried out in the same manner as in Comparative Example 3 to obtain a curable composition (C3).
使用上述之實施例及比較例所得之硬化性組成物， 而進行了下述之評價。 Using the curable compositions obtained in the above examples and comparative examples, the following evaluations were carried out.
將實施例所得之硬化性組成物(1)~(6)及比較例所得之硬化性組成物(C1)~(C3)，使用塗布器而以成為膜厚10μm之方式，塗布於玻璃基材上。接著，使用高壓水銀燈而照射紫外線，得到了硬化塗膜。用手指觸摸所得之硬化塗膜的表面，以變成不沾黏時的累計光量之最小值，依照以下之基準進行了評價。 The curable compositions (1) to (6) obtained in the examples and the curable compositions (C1) to (C3) obtained in the comparative examples were applied to a glass substrate with a film thickness of 10 μm using an applicator on. Next, ultraviolet light was irradiated using a high-pressure mercury lamp to obtain a cured coating film. The surface of the resulting hardened coating film was touched with a finger to evaluate the minimum value of the accumulated light amount at the time of non-sticking, according to the following criteria.
A：於累計光量為500mJ/cm2以下硬化了。 A: It hardened when the accumulated light amount was 500 mJ/cm 2 or less.
B：於累計光量超過500mJ/cm2且為700mJ/cm2以下硬化了。 B: The cumulative light intensity exceeds 500 mJ/cm 2 and hardens at 700 mJ/cm 2 or less.
C：於累計光量超過700mJ/cm2且為900mJ/cm2以下硬化了。 C: It is hardened when the cumulative light amount exceeds 700 mJ/cm 2 and is 900 mJ/cm 2 or less.
D：於累計光量超過900mJ/cm2且為1100mJ/cm2以下硬化了。 D: Hardened when the accumulated light amount exceeds 900 mJ/cm 2 and is 1100 mJ/cm 2 or less.
E：即使累計光量超過1100mJ/cm2也未硬化。 E: Even if the accumulated light amount exceeds 1100 mJ/cm 2, it is not hardened.
將實施例所得之硬化性組成物(1)~(6)及比較例所得之硬化性組成物(C1)~(C3)，使用塗布器而以成為膜厚50μm之方式，塗布於玻璃基材上，在80℃乾燥了30分鐘。接著，使用金屬鹵化物燈而照射1000mJ/cm2的紫外線之後，從玻璃基材剝離硬化物，得到了硬化物。從前述硬化物切出6mm×35mm的試驗片，使用黏彈性測定裝置(DMA：RHEOMETRIC公司製固體黏彈性測定裝置「RSAII」，拉伸法：頻率1Hz、升溫速度3℃/分 鐘)，而將彈性模數變成最大的溫度當作玻璃轉移溫度(以下簡稱「Tg」)，進行了評價。還有，Tg愈高就表示耐熱性愈優異。 The curable compositions (1) to (6) obtained in the examples and the curable compositions (C1) to (C3) obtained in the comparative examples were applied to a glass substrate so as to have a film thickness of 50 μm using an applicator It was dried at 80°C for 30 minutes. Next, after irradiating 1000 mJ/cm 2 of ultraviolet rays using a metal halide lamp, the cured product was peeled from the glass substrate to obtain a cured product. A 6 mm×35 mm test piece was cut out from the aforementioned hardened material, and a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device “RSAII” manufactured by RHEOMETRIC Corporation, stretching method: frequency 1 Hz, heating rate 3° C./min) was used The temperature at which the elastic modulus became the maximum was regarded as the glass transition temperature (hereinafter referred to as "Tg") and evaluated. Also, the higher the Tg, the better the heat resistance.
於表1呈示實施例7~12所得之硬化性組成物(1)~(6)及比較例3~5所得之硬化性組成物(C1)~(C3)的組成及評價結果。 Table 1 shows the compositions and evaluation results of the curable compositions (1) to (6) obtained in Examples 7 to 12 and the curable compositions (C1) to (C3) obtained in Comparative Examples 3 to 5.
表1中的「-」表示無法評價。這是因硬化性不充分而無法得到硬化塗膜，因此記為無法評價。 "-" in Table 1 indicates that evaluation is impossible. This is because a hard coating film cannot be obtained due to insufficient curability, and therefore, it is regarded as not evaluated.
於具備有溫度計、攪拌器及回流冷卻器的燒瓶中，添加344質量份的雙酚A型環氧樹脂(DIC股份有限公司製 「EPICLONEXA-850CRP」，環氧當量：172g/當量)，且加入了作為抗氧化劑的二丁基羥基甲苯0.21質量份、作為熱聚合抑制劑的氫醌單甲醚0.21質量份之後，添加72質量份的丙烯酸、0.21質量份的三苯基膦，一邊吹入空氣，一邊在100℃進行了10小時酯化反應。確認酸價為1mgKOH/g以下後，添加0.42質量份的草酸，在70℃攪拌3小時，得到了環氧(甲基)丙烯酸酯樹脂。此環氧(甲基)丙烯酸酯樹脂之環氧當量為445g/當量。 In a flask equipped with a thermometer, stirrer and reflux cooler, add 344 parts by mass of bisphenol A epoxy resin ("EPICLONEXA-850CRP" manufactured by DIC Corporation, epoxy equivalent: 172g/equivalent) and add After 0.21 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.21 parts by mass of hydroquinone monomethyl ether as a thermal polymerization inhibitor, 72 parts by mass of acrylic acid and 0.21 parts by mass of triphenylphosphine were added while blowing in air At the same time, the esterification reaction was performed at 100°C for 10 hours. After confirming that the acid value was 1 mgKOH/g or less, 0.42 parts by mass of oxalic acid was added and stirred at 70° C. for 3 hours to obtain an epoxy (meth)acrylate resin. The epoxy equivalent of this epoxy (meth)acrylate resin is 445 g/equivalent.
混合20質量份的實施例1所得之(甲基)丙烯酸酯化合物(1)、80質量份的合成例1所得之環氧(甲基)丙烯酸酯樹脂、1.6質量份的2-乙基-4-甲基咪唑與2質量份的光聚合性起始劑(IGM公司製「Omnirad 184」)，得到了硬化性組成物(7)。 20 parts by mass of the (meth)acrylate compound (1) obtained in Example 1, 80 parts by mass of the epoxy (meth)acrylate resin obtained in Synthesis Example 1, and 1.6 parts by mass of 2-ethyl-4 -Methylimidazole and 2 parts by mass of a photopolymerizable initiator ("Omnirad 184" manufactured by IGM Corporation) to obtain a curable composition (7).
除了取代實施例13所用之(甲基)丙烯酸酯化合物(1)，而以表2所示的摻合量使用了實施例2~6所得之(甲基)丙烯酸酯化合物(2)~(6)以外，係與實施例13同樣地進行，而得到了硬化性組成物(8)~(16)。 In addition to replacing the (meth)acrylate compound (1) used in Example 13, the (meth)acrylate compounds (2) to (6) obtained in Examples 2 to 6 were used at the blending amounts shown in Table 2. Except for ), it was carried out in the same manner as in Example 13 to obtain curable compositions (8) to (16).
混合20質量份的比較例1所得之(甲基)丙烯酸酯化合物(7)、80質量份的合成例1所得之環氧(甲基)丙烯酸酯樹脂、1.6質量份的的2-乙基-4-甲基咪唑與2質量份的光聚合性起始劑(IGM公司製「Omnirad 184」)，得到了硬化性組成物(C4)。 20 parts by mass of the (meth)acrylate compound (7) obtained in Comparative Example 1, 80 parts by mass of the epoxy (meth)acrylate resin obtained in Synthesis Example 1, and 1.6 parts by mass of 2-ethyl- 4-Methylimidazole and 2 parts by mass of a photopolymerizable initiator ("Omnirad 184" manufactured by IGM Corporation) yielded a curable composition (C4).
除了取代比較例6所用之(甲基)丙烯酸酯化合物(7)，而以表2所示的摻合量使用了比較例2所得之(甲基)丙烯酸酯化合物(8)以外，係與比較例6同樣地進行，而得到了硬化性組成物(C5)。 Except for substituting the (meth)acrylate compound (7) used in Comparative Example 6, and using the (meth)acrylate compound (8) obtained in Comparative Example 2 at the blending amount shown in Table 2, it is comparable to Example 6 was carried out in the same manner to obtain a curable composition (C5).
除了取代比較例6所用之(甲基)丙烯酸酯化合物(7)，而以表2所示的摻合量使用了三羥甲基丙烷EO改質三丙烯酸酯以外，係與比較例6同樣地進行，而得到了硬化性組成物(C6)。 It is the same as Comparative Example 6 except that instead of the (meth)acrylate compound (7) used in Comparative Example 6, trimethylolpropane EO-modified triacrylate was used at the blending amount shown in Table 2. This was carried out to obtain a curable composition (C6).
使用上述之實施例及比較例所得之硬化性組成物，而進行了下述之評價。 Using the curable compositions obtained in the above examples and comparative examples, the following evaluations were carried out.
將實施例所得之硬化性組成物(7)~(16)及比較例所得之硬化性組成物(C4)~(C6)，使用塗布器而以成為膜厚10μm之方式，塗布於玻璃基材上。接著，使用高壓水銀燈而照射紫外線，得到了硬化塗膜。用手指觸摸所得之硬化塗膜的表面，以變成不沾黏時的累計光量之最小值，依照以下之基準進行了評價。 The curable compositions (7) to (16) obtained in the examples and the curable compositions (C4) to (C6) obtained in the comparative examples were applied to a glass substrate so as to have a film thickness of 10 μm using an applicator on. Next, ultraviolet light was irradiated using a high-pressure mercury lamp to obtain a cured coating film. The surface of the resulting hardened coating film was touched with a finger to evaluate the minimum value of the accumulated light amount at the time of non-sticking, according to the following criteria.
A：於累計光量為200mJ/cm2以下硬化了。 A: It hardened when the accumulated light amount was 200 mJ/cm 2 or less.
B：於累計光量超過200mJ/cm2且為300mJ/cm2以下硬化了。 B: It is hardened when the cumulative light amount exceeds 200 mJ/cm 2 and is 300 mJ/cm 2 or less.
C：於累計光量超過300mJ/cm2且為400mJ/cm2以下硬化了。 C: It is hardened when the cumulative light amount exceeds 300 mJ/cm 2 and is 400 mJ/cm 2 or less.
D：於累計光量超過500mJ/cm2且為600mJ/cm2以下硬化了。 D: It is hardened when the cumulative light amount exceeds 500 mJ/cm 2 and is 600 mJ/cm 2 or less.
E：即使累計光量超過600mJ/cm2也未硬化。 E: Even if the accumulated light amount exceeds 600 mJ/cm 2, it is not hardened.
將實施例所得之硬化性組成物(7)~(16)及比較例所得之硬化性組成物(C4)~(C6)，使用塗布器而以成為膜厚50μm之方式，塗布於玻璃基材上，在80℃乾燥30分鐘。接著，使用金屬鹵化物燈而照射了1000mJ/cm2的紫外線之後，在160℃加熱1小時，將硬化物從玻璃基材剝離，得到了硬化物。從前述硬化物切出6mm×35mm的試驗片，使用黏彈性測定裝置(DMA：RHEOMETRIC公司製固體黏彈性測定裝置「RSAII」，拉伸法：頻率1Hz、升溫速度3℃/分鐘)，而將彈性模數變成最大的溫度當作Tg，進行了評價。還有，Tg愈高就表示耐熱性愈優異。 The curable compositions (7) to (16) obtained in the examples and the curable compositions (C4) to (C6) obtained in the comparative examples were applied to a glass substrate with a coating thickness of 50 μm using an applicator Above, dry at 80°C for 30 minutes. Next, after irradiating 1000 mJ/cm 2 of ultraviolet rays using a metal halide lamp, it was heated at 160° C. for 1 hour, and the cured product was peeled from the glass substrate to obtain a cured product. A 6 mm×35 mm test piece was cut out from the aforementioned hardened material, and a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device “RSAII” manufactured by RHEOMETRIC Corporation, stretching method: frequency 1 Hz, heating rate 3° C./min) was used The temperature at which the elastic modulus became the maximum was regarded as Tg and evaluated. Also, the higher the Tg, the better the heat resistance.
於表2呈示實施例13~22所得之硬化性組成物(7)~(16)及比較例6~8所得之硬化性組成物(C4)~(C6)的組成及評價結果。 Table 2 shows the compositions and evaluation results of the curable compositions (7) to (16) obtained in Examples 13 to 22 and the curable compositions (C4) to (C6) obtained in Comparative Examples 6 to 8.
表1中的「環氧樹脂」表示雙酚A型環氧樹脂(DIC股份有限公司製「EPICLON EXA-850CRP」，環氧當量：172g/當量)。 "Epoxy resin" in Table 1 represents a bisphenol A type epoxy resin ("EPICLON EXA-850CRP" manufactured by DIC Corporation, epoxy equivalent: 172g/equivalent).
表1及2所示的實施例7~22係使用了本發明之(甲基)丙烯酸酯化合物之例。可確認：含有本發明之(甲基)丙烯酸酯化合物的硬化性組成物具有優異的硬化性，而且，含有本發明之(甲基)丙烯酸酯化合物的硬化性組成物之硬化物具有優異的耐熱性。 Examples 7 to 22 shown in Tables 1 and 2 are examples using the (meth)acrylate compound of the present invention. It can be confirmed that the curable composition containing the (meth)acrylate compound of the present invention has excellent curability, and the cured product containing the (meth)acrylate compound of the present invention has excellent heat resistance Sex.
另一方面，比較例3及6係使用了具有1個羥基的酚化合物來作為是(甲基)丙烯酸酯化合物的反應原料之含有酚性羥基的化合物之例。可確認：含有此(甲基)丙烯酸酯化合物 之硬化性組成物硬化性明顯不充分，而且，含有該(甲基)丙烯酸酯化合物之硬化性組成物的硬化物係Tg低為98℃，在耐熱性上亦明顯不充分。再者，於比較例3之硬化性組成物中，因硬化性不充分而無法形成硬化塗膜，無法供耐熱性之評價。 On the other hand, Comparative Examples 3 and 6 are examples of using a phenol compound having one hydroxyl group as a phenolic hydroxyl group-containing compound that is a reaction raw material of a (meth)acrylate compound. It can be confirmed that the curability of the curable composition containing the (meth)acrylate compound is obviously insufficient, and the curing system of the curable composition containing the (meth)acrylate compound has a low Tg of 98°C. The heat resistance is also obviously insufficient. In addition, in the curable composition of Comparative Example 3, the curable coating film could not be formed due to insufficient curability, and the heat resistance could not be evaluated.
比較例4及7係使用了具有2個羥基的酚化合物作為是(甲基)丙烯酸酯化合物的反應原料之含有酚性羥基的化合物之例。可確認：含有此(甲基)丙烯酸酯化合物之硬化性組成物硬化性不充分，而且，含有該(甲基)丙烯酸酯化合物之硬化性組成物的硬化物係Tg低為121℃，在耐熱性上亦明顯不充分。再者，於比較例4之硬化性組成物中，因硬化性不充分而無法形成硬化塗膜，無法供耐熱性之評價。 Comparative Examples 4 and 7 are examples in which a phenolic compound having two hydroxy groups is used as a phenolic hydroxyl group-containing compound that is a reaction raw material of a (meth)acrylate compound. It can be confirmed that the curable composition containing the (meth)acrylate compound has insufficient curability, and the cured system of the curable composition containing the (meth)acrylate compound has a low Tg of 121°C and is heat-resistant Sexually it is also clearly insufficient. In addition, in the curable composition of Comparative Example 4, since the curability was insufficient, a cured coating film could not be formed, and the heat resistance could not be evaluated.
比較例5及8係使用了三羥甲基丙烷EO改質三丙烯酸酯之例。可確認：含有前述三羥甲基丙烷EO改質三丙烯酸酯之硬化性組成物硬化性明顯不充分，而且，含有該硬化性組成物之硬化物係Tg低為92℃，在耐熱性亦明顯不充分。再者，於比較例5之硬化性組成物中，因硬化性不充分而無法形成硬化塗膜，無法供耐熱性之評價。 Comparative Examples 5 and 8 are examples in which trimethylolpropane EO modified triacrylate was used. It can be confirmed that the curable composition containing the above-mentioned trimethylolpropane EO modified triacrylate is obviously insufficient in curability, and the cured system containing the curable composition has a low Tg of 92°C and is also obvious in heat resistance insufficient. In addition, in the curable composition of Comparative Example 5, since the curability was insufficient, a cured coating film could not be formed, and the heat resistance could not be evaluated.
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