KR20200055110A - Epoxy (meth) acrylate resin composition, curable resin composition and cured product - Google Patents
Epoxy (meth) acrylate resin composition, curable resin composition and cured product Download PDFInfo
- Publication number
- KR20200055110A KR20200055110A KR1020207012169A KR20207012169A KR20200055110A KR 20200055110 A KR20200055110 A KR 20200055110A KR 1020207012169 A KR1020207012169 A KR 1020207012169A KR 20207012169 A KR20207012169 A KR 20207012169A KR 20200055110 A KR20200055110 A KR 20200055110A
- Authority
- KR
- South Korea
- Prior art keywords
- meth
- epoxy
- acrylate
- resin composition
- acrylate resin
- Prior art date
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 119
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 92
- 239000000203 mixture Substances 0.000 title claims abstract description 70
- 239000011342 resin composition Substances 0.000 title claims abstract description 19
- 239000003822 epoxy resin Substances 0.000 claims abstract description 100
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 100
- -1 acrylate compound Chemical class 0.000 claims abstract description 61
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 48
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 25
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 23
- 150000007513 acids Chemical class 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000010494 dissociation reaction Methods 0.000 claims abstract description 9
- 230000005593 dissociations Effects 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 21
- 230000008719 thickening Effects 0.000 abstract description 5
- 230000036962 time dependent Effects 0.000 abstract 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 229920005989 resin Polymers 0.000 description 25
- 239000011347 resin Substances 0.000 description 25
- 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 24
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 22
- 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 19
- 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 16
- 229920003986 novolac Polymers 0.000 description 14
- 229930185605 Bisphenol Natural products 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 238000001723 curing Methods 0.000 description 11
- 235000006408 oxalic acid Nutrition 0.000 description 11
- 239000003963 antioxidant agent Substances 0.000 description 10
- 230000003078 antioxidant effect Effects 0.000 description 10
- ICQFAQGXJAVDED-UHFFFAOYSA-N benzene-1,4-diol;4-(methylamino)phenol Chemical compound OC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ICQFAQGXJAVDED-UHFFFAOYSA-N 0.000 description 10
- 238000007664 blowing Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005886 esterification reaction Methods 0.000 description 10
- 239000003112 inhibitor Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 238000012719 thermal polymerization Methods 0.000 description 9
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 125000002723 alicyclic group Chemical group 0.000 description 5
- 229920000193 polymethacrylate Polymers 0.000 description 5
- 229910000679 solder Inorganic materials 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 4
- 239000004210 ether based solvent Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 150000002596 lactones Chemical group 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- 125000006353 oxyethylene group Chemical group 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 3
- 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 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 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
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000005587 carbonate group Chemical group 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 125000005702 oxyalkylene group Chemical group 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 2
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 2
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- HIGURUTWFKYJCH-UHFFFAOYSA-N 2-[[1-(oxiran-2-ylmethoxymethyl)cyclohexyl]methoxymethyl]oxirane Chemical compound C1OC1COCC1(COCC2OC2)CCCCC1 HIGURUTWFKYJCH-UHFFFAOYSA-N 0.000 description 2
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 2
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- GSKNLOOGBYYDHV-UHFFFAOYSA-N 2-methylphenol;naphthalen-1-ol Chemical compound CC1=CC=CC=C1O.C1=CC=C2C(O)=CC=CC2=C1 GSKNLOOGBYYDHV-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- ZFEQSERZJMLTHK-UHFFFAOYSA-N 4-(4-hydroxyphenyl)-2,3,5,6-tetramethylphenol Chemical compound CC1=C(O)C(C)=C(C)C(C=2C=CC(O)=CC=2)=C1C ZFEQSERZJMLTHK-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- 239000003759 ester based solvent Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- VSWALKINGSNVAR-UHFFFAOYSA-N naphthalen-1-ol;phenol Chemical compound OC1=CC=CC=C1.C1=CC=C2C(O)=CC=CC2=C1 VSWALKINGSNVAR-UHFFFAOYSA-N 0.000 description 2
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- CZAZXHQSSWRBHT-UHFFFAOYSA-N 2-(2-hydroxyphenyl)-3,4,5,6-tetramethylphenol Chemical class OC1=C(C)C(C)=C(C)C(C)=C1C1=CC=CC=C1O CZAZXHQSSWRBHT-UHFFFAOYSA-N 0.000 description 1
- FIOCEWASVZHBTK-UHFFFAOYSA-N 2-[2-(2-oxo-2-phenylacetyl)oxyethoxy]ethyl 2-oxo-2-phenylacetate Chemical compound C=1C=CC=CC=1C(=O)C(=O)OCCOCCOC(=O)C(=O)C1=CC=CC=C1 FIOCEWASVZHBTK-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
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 1
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
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- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- LFOXEOLGJPJZAA-UHFFFAOYSA-N [(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphoryl]-(2,6-dimethoxyphenyl)methanone Chemical compound COC1=CC=CC(OC)=C1C(=O)P(=O)(CC(C)CC(C)(C)C)C(=O)C1=C(OC)C=CC=C1OC LFOXEOLGJPJZAA-UHFFFAOYSA-N 0.000 description 1
- 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 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000005325 alkali earth metal hydroxides Chemical class 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000005577 anthracene group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- 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 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- NZNMSOFKMUBTKW-UHFFFAOYSA-M cyclohexanecarboxylate Chemical compound [O-]C(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-M 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- PODOEQVNFJSWIK-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethoxyphenyl)methanone Chemical compound COC1=CC(OC)=CC(OC)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 PODOEQVNFJSWIK-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-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
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000005429 oxyalkyl group Chemical group 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000006187 phenyl benzyl group Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
-
- 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
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- 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
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Macromonomer-Based Addition Polymer (AREA)
- Epoxy Resins (AREA)
Abstract
에폭시 수지(a1)와, 카르복시기 함유 (메타)아크릴레이트 화합물(a2)을 필수의 반응 원료로 하는 에폭시(메타)아크릴레이트 수지(A)와, 산성 화합물(B)을 함유하는 에폭시(메타)아크릴레이트 수지 조성물로서, 상기 에폭시(메타)아크릴레이트 수지(A)가, 에폭시기 및 (메타)아크릴로일기를 갖는 것이며, 상기 산성 화합물(B)의 제1 산해리 상수(pKa1)가, 2.5 이하인 것을 특징으로 하는 에폭시(메타)아크릴레이트 수지 조성물을 제공한다. 이 에폭시(메타)아크릴레이트 수지 조성물은, 경시적(經時的)인 증점(增粘)이 생기기 어려워, 우수한 저장 안정성을 갖는다.Epoxy (meth) acrylate containing epoxy resin (a1), carboxyl group-containing (meth) acrylate compound (a2) as an essential reaction raw material, and epoxy (meth) acrylate resin (A) and acidic compound (B) As the rate resin composition, the epoxy (meth) acrylate resin (A) has an epoxy group and a (meth) acryloyl group, and the first acid dissociation constant (pKa 1 ) of the acidic compound (B) is 2.5 or less. An epoxy (meth) acrylate resin composition is provided. This epoxy (meth) acrylate resin composition is unlikely to develop time-dependent thickening, and has excellent storage stability.
Description
본 발명은, 저장 안정성이 우수한 에폭시(메타)아크릴레이트 수지 조성물, 이것을 함유하는 경화성 수지 조성물, 및 상기 경화성 수지 조성물의 경화물에 관한 것이다.The present invention relates to an epoxy (meth) acrylate resin composition having excellent storage stability, a curable resin composition containing the same, and a cured product of the curable resin composition.
프린트 배선 기판에 있어서의 솔더 레지스트 패턴의 형성에는, 종래 포토 레지스트법이 널리 이용되어 왔다. 당해 포토 레지스트법에서는, 패턴 형성용의 수지 재료로서 (메타)아크릴로일기 등의 광중합성기와, 카르복시기 등의 알칼리 용해성기를 갖는 수지를 사용하고, 노광부의 광경화와 미노광부의 알칼리 현상에 의해 패터닝을 행하는 것을 특징으로 한다. 이에 대하여, 최근에는, 당해 포토 레지스트법과 비교해서 공정수가 적은 잉크젯 방식이, 솔더 레지스트 패턴 형성법으로서 주목받고 있다.For forming a solder resist pattern on a printed wiring board, a conventional photo resist method has been widely used. In the photoresist method, a resin having a photopolymerizable group such as a (meth) acryloyl group and an alkali soluble group such as a carboxy group is used as a resin material for pattern formation, and patterning is performed by photocuring the exposed portion and alkali developing the unexposed portion. Characterized in that to do. On the other hand, in recent years, the inkjet method with fewer steps compared to the photoresist method has attracted attention as a solder resist pattern forming method.
당해 잉크젯 방식으로 사용하는 수지 재료에는, 광경화성이 우수한 것, 경화물의 내열성이 높은 것 등의 일반적인 레지스트 성능 외, 잉크젯 인쇄가 가능한 정도로 저점도인 것이 요구된다. 종래 알려져 있는 저점도이고 잉크젯 인쇄에 적합한 수지 재료로서는, 펜타에리트리톨트리아크릴레이트, 2-메타크릴로일옥시에틸이소시아네이트, N-비닐-2-피롤리돈을 함유하고, 25℃에서의 점도가 79.1mPa·s 이하인 잉크젯용 광경화성·열경화성 조성물 등이 알려져 있지만(예를 들면, 특허문헌 1 참조), 경화물에 있어서의 내열성이 충분하지 않은 등의 문제가 있었다.The resin material used in the inkjet method is required to have low viscosity to the extent that inkjet printing is possible, in addition to general resist performances such as those having excellent photocurability and high heat resistance of cured products. As a conventionally known low viscosity and suitable resin material for inkjet printing, it contains pentaerythritol triacrylate, 2-methacryloyloxyethyl isocyanate, N-vinyl-2-pyrrolidone, and has a viscosity at 25 ° C. Although a photocurable and thermosetting composition for inkjet having a size of 79.1 mPa · s or less is known (for example, see Patent Document 1), there are problems such as insufficient heat resistance in a cured product.
또한, 경화물에 있어서의 내열성을 향상시킨 기술로서는, 비스페놀A형 에폭시 수지의 하프아크릴레이트, 비스페놀A형 에폭시아크릴레이트, 트리에틸렌글리콜디아크릴레이트, 이소보로닐아크릴레이트, 비스페놀A형 에폭시 수지, 및 디시안디아미드를 함유하고, 25℃에서의 점도가 420mPa·s 이하인 잉크젯용 광경화성 조성물 등이 알려져 있지만(예를 들면, 특허문헌 2 참조), 경화물에 있어서의 내열성은 우수하지만, 조성물의 경시적(經時的)인 증점(增粘)이 생기기 쉬워, 저장 안정성이 떨어지는 등의 문제가 있었다.In addition, as a technique for improving the heat resistance in the cured product, bisphenol A-type epoxy resin half acrylate, bisphenol A-type epoxy acrylate, triethylene glycol diacrylate, isoboronil acrylate, bisphenol A-type epoxy resin , And dicyandiamide, and a photocurable composition for inkjet having a viscosity at 25 ° C. of 420 mPa · s or less is known (for example, see Patent Document 2), but the heat resistance of the cured product is excellent, but the composition There was a problem such as easy to occur over time (經 時 的) thickening, poor storage stability.
그래서, 경시적인 증점이 생기기 어려워, 저장 안정성이 우수한 재료가 요구되고 있었다.Therefore, it is difficult to produce thickening over time, and a material having excellent storage stability has been demanded.
본 발명이 해결하고자 하는 과제는, 경시적인 증점이 생기기 어려워, 우수한 저장 안정성을 갖는 에폭시(메타)아크릴레이트 수지 조성물, 이것을 함유하는 경화성 수지 조성물, 및 상기 경화성 수지 조성물의 경화물을 제공하는 것이다.The problem to be solved by the present invention is to provide an epoxy (meth) acrylate resin composition having excellent storage stability, a curable resin composition containing the same, and a cured product of the curable resin composition.
본 발명자들은, 상기 과제를 해결하기 위해 예의 검토를 행한 결과, 에폭시 수지와, 카르복시기 함유 (메타)아크릴레이트 화합물을 필수의 반응 원료로 하는, 에폭시기 및 (메타)아크릴로일기를 갖는 에폭시(메타)아크릴레이트 수지와, 특정한 산해리 상수를 갖는 산성 화합물을 함유하는 에폭시(메타)아크릴레이트 수지 조성물을 사용함으로써, 상기 과제를 해결할 수 있는 것을 찾아내고, 본 발명을 완성시켰다.The present inventors conducted extensive studies to solve the above problems, and as a result, an epoxy resin having an epoxy group and a (meth) acryloyl group containing an epoxy resin and a carboxyl group-containing (meth) acrylate compound as essential reaction raw materials. By using an acrylate resin and an epoxy (meth) acrylate resin composition containing an acidic compound having a specific acid dissociation constant, it was found that the above problems can be solved and the present invention has been completed.
즉, 본 발명은, 에폭시 수지(a1)와, 카르복시기 함유 (메타)아크릴레이트 화합물(a2)을 필수의 반응 원료로 하는 에폭시(메타)아크릴레이트 수지(A)와, 산성 화합물(B)을 함유하는 에폭시(메타)아크릴레이트 수지 조성물로서, 상기 에폭시(메타)아크릴레이트 수지(A)가, 에폭시기 및 (메타)아크릴로일기를 갖는 것이며, 상기 산성 화합물(B)의 제1 산해리 상수(pKa1)가, 2.5 이하인 것을 특징으로 하는 에폭시(메타)아크릴레이트 수지 조성물, 이것을 함유하는 경화성 수지 조성물, 상기 경화성 수지 조성물의 경화물, 및 상기 에폭시(메타)아크릴레이트 수지 조성물의 제조 방법에 관한 것이다.That is, the present invention contains an epoxy resin (a1), an epoxy (meth) acrylate resin (A) containing an carboxyl group-containing (meth) acrylate compound (a2) as an essential reaction raw material, and an acidic compound (B). As an epoxy (meth) acrylate resin composition, the epoxy (meth) acrylate resin (A) has an epoxy group and a (meth) acryloyl group, and the first acid dissociation constant (pKa 1 ) of the acidic compound (B) ) Is 2.5 or less, and relates to an epoxy (meth) acrylate resin composition, a curable resin composition containing the same, a cured product of the curable resin composition, and a method for producing the epoxy (meth) acrylate resin composition.
본 발명의 에폭시(메타)아크릴레이트 수지 조성물은, 경시적인 증점이 생기기 어려워, 우수한 저장 안정성을 가지므로, 상기 에폭시(메타)아크릴레이트 수지 조성물과 광중합개시제를 함유한 경화성 수지 조성물은, 솔더 레지스트용 수지 재료, 및 상기 솔더 레지스트용 수지로 이루어지는 레지스트 부재에 호적(好適)하게 사용할 수 있다.Since the epoxy (meth) acrylate resin composition of the present invention is difficult to generate thickening over time and has excellent storage stability, the curable resin composition containing the epoxy (meth) acrylate resin composition and a photopolymerization initiator is for solder resist. It can be suitably used for a resin material and a resist member made of the resin for the solder resist.
본 발명의 에폭시(메타)아크릴레이트 수지 조성물은, 에폭시(메타)아크릴레이트 수지(A)와, 산성 화합물(B)을 함유하는 것을 특징으로 한다.The epoxy (meth) acrylate resin composition of the present invention is characterized by containing an epoxy (meth) acrylate resin (A) and an acidic compound (B).
또, 본 발명에 있어서, 「(메타)아크릴레이트 수지」란, 분자 중에 아크릴로일기 및 메타크릴로일기의 한쪽 또는 양쪽을 갖는 수지를 말한다. 또한, 「(메타)아크릴로일기」란, 아크릴로일기 및 메타크릴로일기의 한쪽 또는 양쪽을 말하고, 「(메타)아크릴레이트」란, 아크릴레이트 및 메타크릴레이트의 한쪽 또는 양쪽을 말한다.In addition, in this invention, "(meth) acrylate resin" means resin which has one or both of acryloyl group and methacryloyl group in a molecule | numerator. In addition, "(meth) acryloyl group" means one or both of acryloyl group and methacryloyl group, and "(meth) acrylate" refers to one or both of acrylate and methacrylate.
상기 에폭시(메타)아크릴레이트 수지(A)로서는, 에폭시 수지(a1)와 카르복시기 함유 (메타)아크릴레이트 화합물(a2)을 필수의 반응 원료로 하는 것을 사용한다.As said epoxy (meth) acrylate resin (A), what uses an epoxy resin (a1) and a carboxyl group-containing (meth) acrylate compound (a2) as essential reaction raw materials is used.
상기 에폭시 수지(a1)는, 수지 중에 복수의 에폭시기를 갖고, 상기 카르복시기 함유 (메타)아크릴레이트 화합물(a2)과 반응하여, 본 발명의 에폭시(메타)아크릴레이트 수지를 형성할 수 있는 것이면, 그 구체 구조는 특별히 한정되지 않는다. 상기 에폭시 수지(a1)로서는, 예를 들면, 비스페놀형 에폭시 수지, 수첨(水添) 비스페놀형 에폭시 수지, 비페놀형 에폭시 수지, 수첨 비페놀형 에폭시 수지, 페닐렌에테르형 에폭시 수지, 나프틸렌에테르형 에폭시 수지, 페놀노볼락형 에폭시 수지, 크레졸노볼락형 에폭시 수지, 비스페놀노볼락형 에폭시 수지, 나프톨노볼락형 에폭시 수지, 페놀아랄킬형 에폭시 수지, 나프톨아랄킬형 에폭시 수지, 디시클로펜타디엔-페놀 부가 반응형 에폭시 수지 등을 들 수 있다. 또한, 3',4'-에폭시시클로헥실메틸-3,4-에폭시시클로헥산카복실레이트, 비닐시클로헥센디에폭시드, ε-카프로락톤 변성 3',4'-에폭시시클로헥실메틸 3,4-에폭시시클로헥산카복실레이트, 시클로헥산디메탄올디글리시딜에테르 등의 지환식 에폭시 수지도 사용할 수 있다. 이들 에폭시 수지는, 단독으로 사용할 수도 2종 이상을 병용할 수도 있다. 또한, 이들 중에서도, 저장 안정성이 우수한 에폭시(메타)아크릴레이트 수지가 얻어지므로, 비스페놀형 에폭시 수지, 수첨 비스페놀형 에폭시 수지, 비페놀형 에폭시 수지, 수첨 비페놀형 에폭시 수지가 바람직하고, 비스페놀형 에폭시 수지 또는 수첨 비스페놀형 에폭시 수지가 보다 바람직하다.The epoxy resin (a1) has a plurality of epoxy groups in the resin, and reacts with the carboxyl group-containing (meth) acrylate compound (a2) to form the epoxy (meth) acrylate resin of the present invention. The specific structure is not particularly limited. Examples of the epoxy resin (a1) include bisphenol-type epoxy resins, hydrogenated bisphenol-type epoxy resins, biphenol-type epoxy resins, hydrogenated biphenol-type epoxy resins, phenylene ether-type epoxy resins, and naphthylene ether. Type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol novolak type epoxy resin, naphthol novolak type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol And addition-reactive epoxy resins. Also, 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexenediepoxide, ε-caprolactone modified 3', 4'-epoxycyclohexylmethyl 3,4-epoxy Alicyclic epoxy resins, such as cyclohexane carboxylate and cyclohexane dimethanol diglycidyl ether, can also be used. These epoxy resins may be used alone or in combination of two or more. Moreover, among these, since an epoxy (meth) acrylate resin excellent in storage stability is obtained, bisphenol-type epoxy resins, hydrogenated bisphenol-type epoxy resins, biphenol-type epoxy resins, and hydrogenated biphenol-type epoxy resins are preferred, and bisphenol-type epoxy A resin or a hydrogenated bisphenol-type epoxy resin is more preferable.
상기 비스페놀형 에폭시 수지로서는, 예를 들면, 비스페놀A형 에폭시 수지, 비스페놀AP형 에폭시 수지, 비스페놀B형 에폭시 수지, 비스페놀BP형 에폭시 수지, 비스페놀E형 에폭시 수지, 비스페놀F형 에폭시 수지, 비스페놀S형 에폭시 수지 등을 들 수 있다.Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol B type epoxy resin, bisphenol B type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type. And epoxy resins.
상기 수첨 비스페놀형 에폭시 수지로서는, 예를 들면, 수첨 비스페놀A형 에폭시 수지, 수첨 비스페놀B형 에폭시 수지, 수첨 비스페놀E형 에폭시 수지, 수첨 비스페놀F형 에폭시 수지, 수첨 비스페놀S형 에폭시 수지 등을 들 수 있다.Examples of the hydrogenated bisphenol type epoxy resin include hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol B type epoxy resin, hydrogenated bisphenol E type epoxy resin, hydrogenated bisphenol F type epoxy resin, hydrogenated bisphenol S type epoxy resin, and the like. have.
상기 비페놀형 에폭시 수지로서는, 예를 들면, 4,4'-비페놀형 에폭시 수지, 2,2'-비페놀형 에폭시 수지, 테트라메틸-4,4'-비페놀형 에폭시 수지, 테트라메틸-2,2'-비페놀형 에폭시 수지 등을 들 수 있다.Examples of the non-phenol type epoxy resin include 4,4'-biphenol type epoxy resin, 2,2'-biphenol type epoxy resin, tetramethyl-4,4'-biphenol type epoxy resin, and tetramethyl And -2,2'-biphenol-type epoxy resins.
상기 수첨 비페놀형 에폭시 수지로서는, 예를 들면, 수첨 4,4'-비페놀형 에폭시 수지, 수첨 2,2'-비페놀형 에폭시 수지, 수첨 테트라메틸-4,4'-비페놀형 에폭시 수지, 수첨 테트라메틸-2,2'-비페놀형 에폭시 수지 등을 들 수 있다.Examples of the hydrogenated non-phenol type epoxy resin include hydrogenated 4,4'-biphenol type epoxy resin, hydrogenated 2,2'-biphenol type epoxy resin, and hydrogenated tetramethyl-4,4'-biphenol type epoxy. Resin, hydrogenated tetramethyl-2,2'-biphenol type epoxy resin, and the like.
상기 에폭시 수지(a1)가, 상기 비스페놀형 에폭시 수지, 상기 수첨 비스페놀형 에폭시 수지, 상기 비페놀형 에폭시 수지, 상기 수첨 비페놀형 에폭시 수지 중 어느 것일 경우, 우수한 저장 안정성을 갖는 에폭시(메타)아크릴레이트 수지가 얻어지므로, 상기 에폭시 수지(a1)의 에폭시 당량은 110∼400g／당량의 범위인 것이 바람직하다.When the epoxy resin (a1) is any of the bisphenol-type epoxy resin, the hydrogenated bisphenol-type epoxy resin, the biphenol-type epoxy resin, and the hydrogenated non-phenol-type epoxy resin, epoxy (meth) acrylic having excellent storage stability Since the rate resin is obtained, the epoxy equivalent of the epoxy resin (a1) is preferably in the range of 110 to 400 g / equivalent.
상기 카르복시기 함유 (메타)아크릴레이트 화합물(a2)은, 분자 구조 중에 카르복시기와, (메타)아크릴로일기를 갖는 것이면, 그 구체 구조는 특별히 한정되지 않지만, 아크릴산, 메타크릴산 외, 분자량이 100∼500의 범위인 저분자량의 화합물이 바람직하고, 분자량이 150∼400의 범위인 화합물이 보다 바람직하다. 보다 구체적으로는, 예를 들면, 하기 구조식(1)으로 표시되는 화합물 등을 들 수 있다.If the carboxyl group-containing (meth) acrylate compound (a2) has a carboxyl group and a (meth) acryloyl group in the molecular structure, the specific structure is not particularly limited, but other than acrylic acid and methacrylic acid, the molecular weight is 100 to A low molecular weight compound in the range of 500 is preferred, and a compound having a molecular weight in the range of 150 to 400 is more preferred. More specifically, the compound etc. which are represented by following structural formula (1) are mentioned, for example.
[식 중 X는, 탄소수 1∼10의 알킬렌쇄, 폴리옥시알킬렌쇄, (폴리)에스테르쇄, 방향족 탄화수소쇄, 또는 (폴리)카보네이트쇄를 표시하고, 구조 중에 할로겐 원자나 알콕시기 등을 갖고 있어도 된다. Y는, 수소 원자 또는 메틸기이다.][In the formula, X represents an alkylene chain having 1 to 10 carbon atoms, a polyoxyalkylene chain, a (poly) ester chain, an aromatic hydrocarbon chain, or a (poly) carbonate chain, even if it has a halogen atom or an alkoxy group in the structure. do. Y is a hydrogen atom or a methyl group.]
상기 폴리옥시알킬렌쇄로서는, 예를 들면, 폴리옥시에틸렌쇄, 폴리옥시프로필렌쇄 등을 들 수 있다.As said polyoxyalkylene chain, polyoxyethylene chain, polyoxypropylene chain, etc. are mentioned, for example.
상기 (폴리)에스테르쇄로서는, 예를 들면, 하기 구조식(X-1)으로 표시되는 (폴리)에스테르쇄를 들 수 있다.As said (poly) ester chain, the (poly) ester chain represented by the following structural formula (X-1) is mentioned, for example.
(식 중 R1은, 탄소 원자수 1∼10의 알킬렌기이며, n은 1∼5의 정수임)(In the formula, R 1 is an alkylene group having 1 to 10 carbon atoms, and n is an integer from 1 to 5)
상기 방향족 탄화수소쇄로서는, 예를 들면, 페닐렌쇄, 나프틸렌쇄, 비페닐렌쇄, 페닐나프틸렌쇄, 비나프틸렌쇄 등을 들 수 있다. 또한, 부분 구조로서, 벤젠환, 나프탈렌환, 안트라센환, 페난트렌환 등의 방향환을 갖는 탄화수소쇄도 사용할 수 있다.As said aromatic hydrocarbon chain, a phenylene chain, a naphthylene chain, a biphenylene chain, a phenyl naphthylene chain, a binaphthylene chain etc. are mentioned, for example. Further, as the partial structure, a hydrocarbon chain having an aromatic ring such as a benzene ring, a naphthalene ring, anthracene ring, or phenanthrene ring can also be used.
상기 (폴리)카보네이트쇄로서는, 예를 들면, 하기 구조식(X-2)으로 표시되는 (폴리)카보네이트쇄를 들 수 있다.As said (poly) carbonate chain, the (poly) carbonate chain represented by the following structural formula (X-2) is mentioned, for example.
(식 중 R2은, 탄소 원자수 1∼10의 알킬렌기이며, n은 1∼5의 정수임)(In the formula, R 2 is an alkylene group having 1 to 10 carbon atoms, and n is an integer from 1 to 5)
이들 카르복시기 함유 (메타)아크릴레이트 화합물(a2)은, 단독으로 사용할 수도 2종 이상을 병용할 수도 있다.These carboxyl group-containing (meth) acrylate compounds (a2) may be used alone or in combination of two or more.
또한, 상기 카르복시기 함유 (메타)아크릴레이트 화합물(a2)로서는, 상기 카르복시기 함유 (메타)아크릴레이트 화합물의 산무수물도 사용할 수 있다.Further, as the carboxyl group-containing (meth) acrylate compound (a2), an acid anhydride of the carboxyl group-containing (meth) acrylate compound can also be used.
상기 카르복시기 함유 (메타)아크릴레이트 화합물의 산무수물로서는, 예를 들면, 무수 (메타)아크릴산 등을 들 수 있다.As an acid anhydride of the said (carboxy) -containing (meth) acrylate compound, anhydride (meth) acrylic acid etc. are mentioned, for example.
상기 카르복시기 함유 (메타)아크릴레이트 화합물(a2)의 사용량은, 우수한 저장 안정성을 갖는 에폭시(메타)아크릴레이트 수지가 얻어지므로, 상기 에폭시 수지(a1) 1몰에 대하여, 0.2∼0.8몰의 범위가 바람직하고, 0.3∼0.7의 범위가 보다 바람직하다.The amount of the carboxyl group-containing (meth) acrylate compound (a2) is 0.2 to 0.8 moles per 1 mole of the epoxy resin (a1) because an epoxy (meth) acrylate resin having excellent storage stability is obtained. It is preferable, and the range of 0.3 to 0.7 is more preferable.
상기 에폭시(메타)아크릴레이트 수지(A)는, 저장 안정성이 우수하므로, 상기 에폭시(메타)아크릴레이트 수지(A)의 (메타)아크릴로일기 당량은, 200∼800g／당량의 범위가 바람직하다. 또한, 상기 에폭시(메타)아크릴레이트 수지(A)의 에폭시 당량은, 300∼900g／당량의 범위가 바람직하다.Since the epoxy (meth) acrylate resin (A) has excellent storage stability, the (meth) acryloyl group equivalent of the epoxy (meth) acrylate resin (A) is preferably in the range of 200 to 800 g / equivalent. . In addition, the epoxy equivalent of the epoxy (meth) acrylate resin (A) is preferably in the range of 300 to 900 g / equivalent.
상기 에폭시(메타)아크릴레이트 수지(A)는, 저장 안정성이 우수하므로, 산가는, 3㎎KOH／g 이하인 것이 바람직하고, 2㎎KOH／g 이하인 것이 보다 바람직하다. 또한, 수산기가는, 300㎎KOH／g 이하인 것이 바람직하다.Since the epoxy (meth) acrylate resin (A) has excellent storage stability, the acid value is preferably 3 mgKOH / g or less, and more preferably 2 mgKOH / g or less. Moreover, it is preferable that hydroxyl value is 300 mgKOH / g or less.
상기 에폭시 수지(a1)와 상기 카르복시기 함유 (메타)아크릴레이트 화합물(a2)과의 반응은, 염기성 촉매의 존재 하에서 행하는 것이 바람직하다.The reaction between the epoxy resin (a1) and the carboxyl group-containing (meth) acrylate compound (a2) is preferably performed in the presence of a basic catalyst.
상기 염기성 촉매로서는, 예를 들면, 수산화칼슘, 수산화바륨 등의 알칼리 토류 금속 수산화물; 탄산나트륨, 탄산칼륨 등의 알칼리 금속 탄산염; 수산화나트륨, 수산화칼륨 등의 알칼리 금속 수산화물;, 트리메틸포스핀, 트리부틸포스핀, 트리페닐포스핀 등의 인 화합물; 트리에틸아민, 트리부틸아민, 디메틸벤질아민 등의 아민 화합물 등을 들 수 있다. 이들 염기성 촉매는, 단독으로 사용할 수도 2종 이상을 병용할 수도 있다. 또한, 이들 중에서도, 트리페닐포스핀이 바람직하다.Examples of the basic catalyst include alkali earth metal hydroxides such as calcium hydroxide and barium hydroxide; Alkali metal carbonates such as sodium carbonate and potassium carbonate; Alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; phosphorus compounds such as trimethylphosphine, tributylphosphine, and triphenylphosphine; And amine compounds such as triethylamine, tributylamine and dimethylbenzylamine. These basic catalysts may be used alone or in combination of two or more. Moreover, among these, triphenylphosphine is preferable.
상기 염기성 촉매의 사용량은, 저점도이며 또한 우수한 저장 안정성을 갖는 에폭시(메타)아크릴레이트 수지가 얻어지므로, 상기 에폭시 수지(a1)와 상기 카르복시기 함유 (메타)아크릴레이트 화합물(a2)의 합계 100질량부에 대하여, 0.01∼0.5질량부의 범위가 바람직하고, 0.01∼0.4의 범위가 보다 바람직하다.The amount of the basic catalyst used is 100 mass by total of the epoxy resin (a1) and the carboxyl group-containing (meth) acrylate compound (a2) because an epoxy (meth) acrylate resin having low viscosity and excellent storage stability is obtained. With respect to parts, the range of 0.01 to 0.5 parts by mass is preferable, and the range of 0.01 to 0.4 is more preferable.
또한, 상기 에폭시 수지(a1)와 상기 카르복시기 함유 (메타)아크릴레이트 화합물(a2)과의 반응에 있어서 염기성 촉매를 사용했을 경우, 저장 안정성이 우수한 에폭시(메타)아크릴레이트 수지 조성물이 얻어지므로, 상기 염기성 촉매를 분리·제거하지 않고, 상기 산성 화합물(B)로 실활(失活)시키는 것이 바람직하다.In addition, when a basic catalyst is used in the reaction between the epoxy resin (a1) and the carboxyl group-containing (meth) acrylate compound (a2), an epoxy (meth) acrylate resin composition having excellent storage stability is obtained. It is preferable to deactivate and deactivate the basic catalyst with the acidic compound (B) without separating and removing it.
상기 산성 화합물(B)로서는, 우수한 저장 안정성을 갖는 에폭시(메타)아크릴레이트 수지가 얻어지므로, 제1 산해리 상수(pKa1)가, 2.5 이하인 화합물을 사용한다. 또, 본 발명에 있어서, 상기 산성 화합물(B)의 산해리 상수는, 25℃ 수중(水中)에 있어서의 산해리 상수이며, 예를 들면, 「화학 편람(개정 4판) 기초편 Ⅱ」(일본 화학회편) 등에 기재되어 있는 값을 사용할 수 있다.As the acidic compound (B), since an epoxy (meth) acrylate resin having excellent storage stability is obtained, a compound having a first acid dissociation constant (pKa 1 ) of 2.5 or less is used. In addition, in the present invention, the acid dissociation constant of the acidic compound (B) is an acid dissociation constant in water at 25 ° C, for example, "Chemical Handbook (Revised 4th Edition) Basic Edition II" (Japanese Chemical Society) Value), etc. can be used.
상기 산성 화합물(B)로서는, 예를 들면, 염산, 황산, 인산 등의 무기산, 메탄설폰산, 파라톨루엔설폰산, 옥살산 등의 유기산 등을 들 수 있다. 이들 산성 화합물은, 단독으로 사용할 수도 2종 이상을 병용할 수도 있다. 또한, 이들 중에서도, 우수한 저장 안정성을 갖는 에폭시(메타)아크릴레이트 수지가 얻어지므로, 유기산이 바람직하고, 특히, 옥살산이 바람직하다.Examples of the acidic compound (B) include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as methanesulfonic acid, paratoluenesulfonic acid and oxalic acid. These acidic compounds may be used alone or in combination of two or more. Moreover, among these, since an epoxy (meth) acrylate resin having excellent storage stability is obtained, an organic acid is preferable, and oxalic acid is particularly preferable.
상기 산성 화합물(B)의 사용량은, 우수한 저장 안정성을 갖는 에폭시(메타)아크릴레이트 수지가 얻어지므로, 상기 염기성 촉매 100질량부에 대하여 50질량부 이상이 바람직하다.The amount of the acidic compound (B) used is preferably 50 parts by mass or more based on 100 parts by mass of the basic catalyst, because an epoxy (meth) acrylate resin having excellent storage stability is obtained.
본 발명의 에폭시(메타)아크릴레이트 수지 조성물의 제조 방법은, 특별히 한정되지 않고, 어떠한 방법으로 제조해도 된다. 예를 들면, 반응 원료 모두를 일괄로 반응시키는 방법으로 제조해도 되고, 반응 원료를 순차 반응시키는 방법으로 제조해도 된다. 그 중에서도, 반응의 제어가 용이하므로, 먼저 상기 에폭시 수지(a1)와, 상기 카르복시기 함유 (메타)아크릴레이트 화합물(a2)을, 염기성 촉매의 존재 하, 80∼140℃의 온도 범위에서 반응시키고, 그 다음에, 산성 화합물(B)을 첨가하여, 50∼100℃의 온도 범위에서 혼합함으로써, 염기성 촉매를 실활시키는 방법 등에 의해 행할 수 있다.The manufacturing method of the epoxy (meth) acrylate resin composition of this invention is not specifically limited, You may manufacture by any method. For example, it may be produced by a method of reacting all of the reaction raw materials in a batch, or by a method of sequentially reacting the reaction raw materials. Among them, since the reaction is easily controlled, first, the epoxy resin (a1) and the carboxyl group-containing (meth) acrylate compound (a2) are reacted in a temperature range of 80 to 140 ° C. in the presence of a basic catalyst, Then, by adding an acidic compound (B) and mixing in a temperature range of 50 to 100 ° C, it can be carried out by a method such as deactivating the basic catalyst.
본 발명의 에폭시(메타)아크릴레이트 수지 조성물은, 분자 구조 중에 중합성의 (메타)아크릴로일기를 가지므로, 예를 들면, 광중합개시제를 첨가함으로써 경화성 수지 조성물로서 사용할 수 있다.Since the epoxy (meth) acrylate resin composition of the present invention has a polymerizable (meth) acryloyl group in its molecular structure, it can be used as a curable resin composition, for example, by adding a photopolymerization initiator.
상기 광중합개시제는, 예를 들면, 1-히드록시시클로헥실페닐케톤, 2-히드록시-2-메틸-1-페닐프로판-1-온, 1-〔4-(2-히드록시에톡시)페닐〕-2-히드록시-2-메틸-1-프로판-1-온, 티오잔톤 및 티오잔톤 유도체, 2,2'-디메톡시-1,2-디페닐에탄-1-온, 디페닐(2,4,6-트리메톡시벤조일)포스핀옥사이드, 2,4,6-트리메틸벤조일디페닐포스핀옥사이드, 비스(2,4,6-트리메틸벤조일)페닐포스핀옥사이드, 2-메틸-1-(4-메틸티오페닐)-2-모르폴리노프로판-1-온, 2-벤질-2-디메틸아미노-1-(4-모르폴리노페닐)-부탄-1-온 등을 들 수 있다.The photopolymerization initiator is, for example, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethan-1-one, diphenyl (2 , 4,6-trimethoxybenzoyl) phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, and the like.
상기 광중합개시제의 시판품으로서는, 예를 들면, 「이르가큐어-184」, 「이르가큐어-149」, 「이르가큐어-261」, 「이르가큐어-369」, 「이르가큐어-500」, 「이르가큐어-651」, 「이르가큐어-754」, 「이르가큐어-784」, 「이르가큐어-819」, 「이르가큐어-907」, 「이르가큐어-1116」, 「이르가큐어-1664」, 「이르가큐어-1700」, 「이르가큐어-1800」, 「이르가큐어-1850」, 「이르가큐어-2959」, 「이르가큐어-4043」, 「다로큐어-1173」(BASF 재팬 가부시키가이샤제), 「루시린 TPO」(BASF사제), 「카야큐어-DETX」, 「카야큐어-MBP」, 「카야큐어-DMBI」, 「카야큐어-EPA」, 「카야큐어-OA」(니혼가야쿠 가부시키가이샤제), 「바이큐어-10」, 「바이큐어-55」(스토우파·케미컬사제), 「트리고날 P1」(아쿠조사제), 「산도레이 1000」(산도즈사제), 「디프」(아프죤사제), 「쿠온타큐어-PDO」, 「쿠온타큐어-ITX」, 「쿠온타큐어-EPD」(워드브레인킨솝사제) 등을 들 수 있다.As commercial products of the photopolymerization initiator, for example, "Irgacure-184", "Irgacure-149", "Irgacure-261", "Irgacure-369", "Irgacure-500" , "Irgacure-651", "Irgacure-754", "Irgacure-784", "Irgacure-819", "Irgacure-907", "Irgacure-1116", " Irgacure-1664, Irgacure-1700, Irgacure-1800, Irgacure-1850, Irgacure-2959, Irgacure-4043, Darocure -1173 '' (manufactured by BASF Japan Co., Ltd.), `` Lushirin TPO '' (manufactured by BASF), `` Kayacure-DETX '', `` Kayacure-MBP '', `` Kayacure-DMBI '', `` Kayacure-EPA '', `` Kayacure-OA '' (manufactured by Nippon Kayaku Co., Ltd.), `` Bycure-10 '', `` Bycure-55 '' (manufactured by Stupa Chemical), `` Trigonal P1 '' (manufactured by Aku Corporation) Ray 1000 '' (manufactured by Sandoz Corporation), `` Deep '' (manufactured by Afzon Corporation), `` Kuontacure -PDO "," Quantacure-ITX "," Quantacure-EPD "(made by Word Brain Co., Ltd.) and the like.
상기 광중합개시제의 첨가량은, 예를 들면, 상기 경화성 수지 조성물 중에, 1∼20질량％의 범위에서 사용하는 것이 바람직하다.It is preferable to use the addition amount of the said photoinitiator in the range of 1-20 mass% in the said curable resin composition, for example.
본 발명의 경화성 수지 조성물은, 상기 에폭시(메타)아크릴레이트 수지 이외의 그 밖의 수지 성분을 함유해도 된다. 상기 그 밖의 수지 성분으로서는, 예를 들면, 비스페놀형 에폭시 수지, 노볼락형 에폭시 수지 등의 에폭시 수지에, (메타)아크릴산, 디카르복시산무수물, 필요에 따라 불포화 모노카르복시산무수물 등을 반응시켜 얻어지는, 수지 중에 카르복시기와 (메타)아크릴로일기를 갖는 수지, 각종 (메타)아크릴레이트 모노머 등을 들 수 있다.The curable resin composition of this invention may contain other resin components other than the said epoxy (meth) acrylate resin. As said other resin component, resin obtained by making (meth) acrylic acid, dicarboxylic acid anhydride, unsaturated monocarboxylic acid anhydride, etc. react to epoxy resins, such as a bisphenol-type epoxy resin and a novolak-type epoxy resin, if necessary. Among them, resins having a carboxyl group and a (meth) acryloyl group, various (meth) acrylate monomers, and the like can be mentioned.
상기 (메타)아크릴레이트 모노머로서는, 예를 들면, 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 프로필(메타)아크릴레이트, 부틸(메타)아크릴레이트, 펜틸(메타)아크릴레이트, 헥실(메타)아크릴레이트, 2-에틸헥실(메타)아크릴레이트, 옥틸(메타)아크릴레이트 등의 지방족 모노(메타)아크릴레이트 화합물; 시클로헥실(메타)아크릴레이트, 이소보르닐(메타)아크릴레이트, 아다만틸모노(메타)아크릴레이트 등의 지환형 모노(메타)아크릴레이트 화합물; 글리시딜(메타)아크릴레이트, 테트라히드로푸르푸릴아크릴레이트 등의 복소환형 모노(메타)아크릴레이트 화합물; 벤질(메타)아크릴레이트, 페닐(메타)아크릴레이트, 페닐벤질(메타)아크릴레이트, 페녹시(메타)아크릴레이트, 페녹시에틸(메타)아크릴레이트, 페녹시에톡시에틸(메타)아크릴레이트, 2-히드록시-3-페녹시프로필(메타)아크릴레이트, 페녹시벤질(메타)아크릴레이트, 벤질벤질(메타)아크릴레이트, 페닐페녹시에틸(메타)아크릴레이트 등의 방향족 모노(메타)아크릴레이트 화합물 등의 모노(메타)아크릴레이트 화합물: 상기 각종 모노(메타)아크릴레이트 모노머의 분자 구조 중에 (폴리)옥시에틸렌쇄, (폴리)옥시프로필렌쇄, (폴리)옥시테트라메틸렌쇄 등의 폴리옥시알킬렌쇄를 도입한 (폴리)옥시알킬렌 변성 모노(메타)아크릴레이트 화합물; 상기 각종 모노(메타)아크릴레이트 화합물의 분자 구조 중에 (폴리)락톤 구조를 도입한 락톤 변성 모노(메타)아크릴레이트 화합물; 에틸렌글리콜디(메타)아크릴레이트, 프로필렌글리콜디(메타)아크릴레이트, 부탄디올디(메타)아크릴레이트, 헥산디올디(메타)아크릴레이트, 네오펜틸글리콜디(메타)아크릴레이트 등의 지방족 디(메타)아크릴레이트 화합물; 1,4-시클로헥산디메탄올디(메타)아크릴레이트, 노르보르난디(메타)아크릴레이트, 노르보르난디메탄올디(메타)아크릴레이트, 디시클로펜타닐디(메타)아크릴레이트, 트리시클로데칸디메탄올디(메타)아크릴레이트 등의 지환형 디(메타)아크릴레이트 화합물; 비페놀디(메타)아크릴레이트, 비스페놀디(메타)아크릴레이트 등의 방향족 디(메타)아크릴레이트 화합물; 상기 각종 디(메타)아크릴레이트 화합물의 분자 구조 중에 (폴리)옥시에틸렌쇄, (폴리)옥시프로필렌쇄, (폴리)옥시테트라메틸렌쇄 등의 (폴리)옥시알킬렌쇄를 도입한 폴리옥시알킬렌 변성 디(메타)아크릴레이트 화합물; 상기 각종 디(메타)아크릴레이트 화합물의 분자 구조 중에 (폴리)락톤 구조를 도입한 락톤 변성 디(메타)아크릴레이트 화합물; 트리메틸올프로판트리(메타)아크릴레이트, 글리세린트리(메타)아크릴레이트 등의 지방족 트리(메타)아크릴레이트 화합물; 상기 지방족 트리(메타)아크릴레이트 화합물의 분자 구조 중에 (폴리)옥시에틸렌쇄, (폴리)옥시프로필렌쇄, (폴리)옥시테트라메틸렌쇄 등의 (폴리)옥시알킬렌쇄를 도입한 (폴리)옥시알킬렌 변성 트리(메타)아크릴레이트 화합물; 상기 지방족 트리(메타)아크릴레이트 화합물의 분자 구조 중에 (폴리)락톤 구조를 도입한 락톤 변성 트리(메타)아크릴레이트 화합물; 펜타에리트리톨테트라(메타)아크릴레이트, 디트리메틸올프로판테트라(메타)아크릴레이트, 디펜타에리트리톨헥사(메타)아크릴레이트 등의 4관능 이상의 지방족 폴리(메타)아크릴레이트 화합물; 상기 지방족 폴리(메타)아크릴레이트 화합물의 분자 구조 중에 (폴리)옥시에틸렌쇄, (폴리)옥시프로필렌쇄, (폴리)옥시테트라메틸렌쇄 등의 (폴리)옥시알킬렌쇄를 도입한 4관능 이상의 (폴리)옥시알킬렌 변성 폴리(메타)아크릴레이트 화합물; 상기 지방족 폴리(메타)아크릴레이트 화합물의 분자 구조 중에 (폴리)락톤 구조를 도입한 4관능 이상의 락톤 변성 폴리(메타)아크릴레이트 화합물 등을 들 수 있다.Examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and hexyl ( Aliphatic mono (meth) acrylate compounds such as meth) acrylate, 2-ethylhexyl (meth) acrylate, and octyl (meth) acrylate; Alicyclic mono (meth) acrylate compounds such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl mono (meth) acrylate; Heterocyclic mono (meth) acrylate compounds such as glycidyl (meth) acrylate and tetrahydrofurfuryl acrylate; Benzyl (meth) acrylate, phenyl (meth) acrylate, phenylbenzyl (meth) acrylate, phenoxy (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, Aromatic mono (meth) acrylics such as 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenoxybenzyl (meth) acrylate, benzylbenzyl (meth) acrylate, and phenylphenoxyethyl (meth) acrylate Mono (meth) acrylate compounds such as rate compounds: Polyoxy such as (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxytetramethylene chain, etc. in the molecular structure of the above various mono (meth) acrylate monomers (Poly) oxyalkylene-modified mono (meth) acrylate compound having an alkylene chain introduced therein; A lactone-modified mono (meth) acrylate compound in which a (poly) lactone structure is introduced in the molecular structure of the various mono (meth) acrylate compounds; Aliphatic di (meth) such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, and neopentyl glycol di (meth) acrylate ) Acrylate compounds; 1,4-cyclohexanedimethanol di (meth) acrylate, norbornanedi (meth) acrylate, norbornanedimethanoldi (meth) acrylate, dicyclopentanyldi (meth) acrylate, tricyclodecanedimethanol Alicyclic di (meth) acrylate compounds such as di (meth) acrylate; Aromatic di (meth) acrylate compounds such as biphenol di (meth) acrylate and bisphenol di (meth) acrylate; Polyoxyalkylene modification in which (poly) oxyalkylene chains such as (poly) oxyethylene chains, (poly) oxypropylene chains, and (poly) oxytetramethylene chains) are introduced into the molecular structures of the various di (meth) acrylate compounds. Di (meth) acrylate compounds; A lactone-modified di (meth) acrylate compound in which a (poly) lactone structure is introduced into the molecular structure of the various di (meth) acrylate compounds; Aliphatic tri (meth) acrylate compounds such as trimethylolpropane tri (meth) acrylate and glycerin tri (meth) acrylate; (Poly) oxyalkyl in which (poly) oxyalkylene chains such as (poly) oxyethylene chains, (poly) oxypropylene chains, (poly) oxytetramethylene chains) are introduced into the molecular structure of the aliphatic tri (meth) acrylate compound. Ren-modified tri (meth) acrylate compound; A lactone-modified tri (meth) acrylate compound having a (poly) lactone structure introduced into the molecular structure of the aliphatic tri (meth) acrylate compound; Tetrafunctional or higher aliphatic poly (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate; (Polyfunctional) (poly) oxyalkylene chains such as (poly) oxyethylene chains, (poly) oxypropylene chains, (poly) oxytetramethylene chains, etc.) introduced into the molecular structure of the aliphatic poly (meth) acrylate compound ) Oxyalkylene-modified poly (meth) acrylate compound; Among the molecular structures of the aliphatic poly (meth) acrylate compound, a tetrafunctional or higher-functional lactone-modified poly (meth) acrylate compound in which a (poly) lactone structure is introduced can be given.
본 발명의 경화성 수지 조성물은, 도공 점도 조절 등의 목적으로 유기 용제를 함유해도 되고, 그 종류나 첨가량은, 원하는 성능에 따라 적의(適宜) 선택 및 조정된다.The curable resin composition of the present invention may contain an organic solvent for the purpose of adjusting coating viscosity, etc., and the type and the amount of addition are appropriately selected and adjusted according to the desired performance.
상기 유기 용제로서는, 예를 들면, 메틸에틸케톤, 아세톤, 이소부틸케톤 등의 케톤 용제; 테트라히드로퓨란, 디옥솔란 등의 환상(環狀) 에테르 용제; 아세트산메틸, 아세트산에틸, 아세트산부틸 등의 에스테르 용제; 톨루엔, 자일렌, 솔벤트나프타 등의 방향족 용제; 시클로헥산, 메틸시클로헥산 등의 지환족 용제; 카르비톨, 셀로솔브, 메탄올, 이소프로판올, 부탄올, 프로필렌글리콜모노메틸에테르 등의 알코올 용제; 알킬렌글리콜모노알킬에테르, 디알킬렌글리콜모노알킬에테르, 디알킬렌글리콜모노알킬에테르아세테이트 등의 글리콜에테르 용제 등을 들 수 있다. 이들 유기 용제는, 단독으로 사용할 수도 2종 이상을 병용할 수도 있다.As said organic solvent, For example, Ketone solvents, such as methyl ethyl ketone, acetone, and isobutyl ketone; Cyclic ether solvents such as tetrahydrofuran and dioxolane; Ester solvents such as methyl acetate, ethyl acetate and butyl acetate; Aromatic solvents such as toluene, xylene, and solvent naphtha; Alicyclic solvents such as cyclohexane and methylcyclohexane; Alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether; And glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate. These organic solvents may be used alone or in combination of two or more.
또한, 본 발명의 경화성 수지 조성물에는, 필요에 따라, 경화제, 경화 촉진제, 유기 용제, 무기 미립자나 폴리머 미립자, 안료, 소포제, 점도 조정제, 레벨링제, 난연제, 보존 안정화제 등의 각종 첨가제를 함유할 수도 있다.In addition, the curable resin composition of the present invention may contain various additives such as curing agents, curing accelerators, organic solvents, inorganic fine particles or polymer fine particles, pigments, antifoaming agents, viscosity modifiers, leveling agents, flame retardants, and storage stabilizers, if necessary. It might be.
상기 경화제로서는, 상기 에폭시(메타)아크릴레이트 수지 조성물 중의 카르복시기와 반응할 수 있는 관능기를 갖는 것이면 특별히 제한되지 않고, 예를 들면, 에폭시 수지를 들 수 있다. 상기 에폭시 수지로서는, 예를 들면, 비스페놀형 에폭시 수지, 페닐렌에테르형 에폭시 수지, 나프틸렌에테르형 에폭시 수지, 비페닐형 에폭시 수지, 트리페닐메탄형 에폭시 수지, 페놀노볼락형 에폭시 수지, 크레졸노볼락형 에폭시 수지, 비스페놀노볼락형 에폭시 수지, 나프톨노볼락형 에폭시 수지, 나프톨-페놀 공축(共縮) 노볼락형 에폭시 수지, 나프톨-크레졸 공축 노볼락형 에폭시 수지, 페놀아랄킬형 에폭시 수지, 나프톨아랄킬형 에폭시 수지, 디시클로펜타디엔-페놀 부가 반응형 에폭시 수지 등을 들 수 있다. 이들 에폭시 수지는, 단독으로 사용할 수도 2종 이상을 병용할 수도 있다. 또한, 이들 중에서도, 경화물에 있어서의 내열성이 우수하므로, 페놀노볼락형 에폭시 수지, 크레졸노볼락형 에폭시 수지, 비스페놀노볼락형 에폭시 수지, 나프톨노볼락형 에폭시 수지, 나프톨-페놀 공축 노볼락형 에폭시 수지, 나프톨-크레졸 공축 노볼락형 에폭시 수지 등의 노볼락형 에폭시 수지가 바람직하고, 연화점이 50∼120℃의 범위인 것이 특히 바람직하다.The curing agent is not particularly limited as long as it has a functional group capable of reacting with a carboxyl group in the epoxy (meth) acrylate resin composition, and examples thereof include an epoxy resin. Examples of the epoxy resin include bisphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol novolak type epoxy resin, cresolno Bolac type epoxy resin, bisphenol novolak type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol coaxial novolak type epoxy resin, naphthol-cresol coaxial novolak type epoxy resin, phenol aralkyl type epoxy resin, naphthol Aralkyl type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, and the like. These epoxy resins may be used alone or in combination of two or more. Moreover, among these, since it has excellent heat resistance in a cured product, a phenol novolac type epoxy resin, a cresol novolak type epoxy resin, a bisphenol novolak type epoxy resin, a naphthol novolak type epoxy resin, and a naphthol-phenol coaxial novolak type Novolak-type epoxy resins such as epoxy resins and naphthol-cresol co-axial novolac-type epoxy resins are preferred, and the softening point is particularly preferably in the range of 50 to 120 ° C.
상기 경화 촉진제란, 상기 경화제의 경화 반응을 촉진하는 것이며, 상기 경화제로서 에폭시 수지를 사용할 경우에는, 예를 들면, 인계 화합물, 제3급 아민, 이미다졸, 유기산 금속염, 루이스산, 아민착염 등을 들 수 있다. 이들 경화 촉진제는, 단독으로 사용할 수도 2종 이상을 병용할 수도 있다. 또한, 상기 경화 촉진제의 첨가량은, 예를 들면, 상기 경화제 100질량부에 대하여 1∼10질량부의 범위에서 사용하는 것이 바람직하다.The curing accelerator is to accelerate the curing reaction of the curing agent, and when an epoxy resin is used as the curing agent, for example, phosphorus-based compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts, etc. Can be lifted. These curing accelerators may be used alone or in combination of two or more. Moreover, it is preferable to use the addition amount of the said hardening accelerator in 1-10 mass parts with respect to 100 mass parts of said hardening agents, for example.
상기 유기 용제로서는, 상기 에폭시(메타)아크릴레이트 수지 조성물이나 경화제 등의 각종 성분을 용해할 수 있는 것이면 특별히 한정되지 않고, 예를 들면, 메틸에틸케톤, 아세톤, 이소부틸케톤 등의 케톤 용제; 테트라히드로퓨란, 디옥솔란 등의 환상 에테르 용제; 아세트산메틸, 아세트산에틸, 아세트산부틸 등의 에스테르 용제; 톨루엔, 자일렌, 솔벤트나프타 등의 방향족 용제; 시클로헥산, 메틸시클로헥산 등의 지환족 용제; 카르비톨, 셀로솔브, 메탄올, 이소프로판올, 부탄올, 프로필렌글리콜모노메틸에테르 등의 알코올 용제; 알킬렌글리콜모노알킬에테르, 디알킬렌글리콜모노알킬에테르, 디알킬렌글리콜모노알킬에테르아세테이트 등의 글리콜에테르 용제 등을 들 수 있다. 이들 유기 용제는, 단독으로 사용할 수도 2종 이상을 병용할 수도 있다.The organic solvent is not particularly limited as long as it can dissolve various components such as the epoxy (meth) acrylate resin composition and curing agent, and examples thereof include ketone solvents such as methyl ethyl ketone, acetone, and isobutyl ketone; Cyclic ether solvents such as tetrahydrofuran and dioxolane; Ester solvents such as methyl acetate, ethyl acetate and butyl acetate; Aromatic solvents such as toluene, xylene, and solvent naphtha; Alicyclic solvents such as cyclohexane and methylcyclohexane; Alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether; And glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate. These organic solvents may be used alone or in combination of two or more.
본 발명의 경화물은, 상기 경화성 수지 조성물에, 활성 에너지선을 조사(照射)함으로써 얻을 수 있다. 상기 활성 에너지선으로서는, 예를 들면, 자외선, 전자선, α선, β선, γ선 등의 전리 방사선을 들 수 있다. 또한, 상기 활성 에너지선으로서, 자외선을 사용할 경우, 자외선에 의한 경화 반응을 효율적으로 행한 다음에, 질소 가스 등의 불활성 가스 분위기 하에서 조사해도 되고, 공기 분위기 하에서 조사해도 된다.The cured product of the present invention can be obtained by irradiating the curable resin composition with active energy rays. Examples of the active energy ray include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Moreover, when using ultraviolet rays as said active energy ray, after hardening reaction by ultraviolet rays is performed efficiently, you may irradiate under an inert gas atmosphere, such as nitrogen gas, or you may irradiate under air atmosphere.
자외선 발생원으로서는, 실용성, 경제성의 면에서 자외선 램프가 일반적으로 사용되고 있다. 구체적으로는, 저압 수은 램프, 고압 수은 램프, 초고압 수은 램프, 제논 램프, 갈륨 램프, 메탈할라이드 램프, 태양광, LED 등을 들 수 있다.As a UV generating source, an ultraviolet lamp is generally used in terms of practicality and economy. 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, solar light, LED, etc. are mentioned.
또한, 본 발명의 경화성 수지 조성물을 경화시켜 얻어진 경화물은, 예를 들면, 반도체 디바이스 용도에 있어서의, 솔더 레지스트, 층간 절연 재료, 패키지재, 언더필재, 회로 소자 등의 패키지 접착층이나, 집적 회로 소자와 회로 기판의 접착층으로서 호적하게 사용할 수 있다. 또한, LCD, OELD로 대표되는 박형(薄型) 디스플레이 용도에 있어서의, 박막 트랜지스터 보호막, 액정 컬러 필터 보호막, 컬러 필터용 안료 레지스트, 블랙 매트릭스용 레지스트, 스페이서 등에 호적하게 사용할 수 있다.Further, the cured product obtained by curing the curable resin composition of the present invention includes, for example, a package adhesive layer such as a solder resist, an interlayer insulating material, a package material, an underfill material, a circuit element, or an integrated circuit in semiconductor device applications. It can be suitably used as an adhesive layer between an element and a circuit board. Moreover, it can be used suitably for thin film transistor protective films, liquid crystal color filter protective films, color filter pigment resists, black matrix resists, spacers, and the like in thin display applications such as LCD and OELD.
[실시예][Example]
이하, 실시예와 비교예에 의해, 본 발명을 구체적으로 설명한다.Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples.
(실시예 1: 에폭시(메타)아크릴레이트 수지 조성물(1)의 제조)(Example 1: Preparation of epoxy (meth) acrylate resin composition (1))
온도계, 교반기, 및 환류 냉각기를 구비한 플라스크에, 비스페놀A형 에폭시 수지(DIC 가부시키가이샤제 「EPICLON EXA-850CRP」, 에폭시 당량 172g／당량) 344질량부를 투입하고, 산화 방지제로서 디부틸히드록시톨루엔 0.21질량부, 열중합 금지제로서 메토퀴논 0.21질량부를 더한 후, 아크릴산 72질량부, 트리페닐포스핀 0.21질량부를 첨가하고, 공기를 취입(吹入)하면서 100℃에서 10시간 에스테르화 반응을 행했다. 그 다음에, 산가가 1㎎KOH／g 이하인 것을 확인한 후, 옥살산(pKa1; 1.04) 0.42질량부를 첨가하고, 70℃에서 3시간 교반하여 에폭시(메타)아크릴레이트 수지 조성물(1)을 얻었다. 이 에폭시(메타)아크릴레이트 수지 조성물(1) 수지분의 에폭시 당량은 445g／당량, (메타)아크릴로일기 당량은 416g／당량이었다. 또, 옥살산의 pKa1값은, 「화학 편람(개정 4판) 기초편 Ⅱ」(일본 화학회편)에 기재된 값이다. 또한, (메타)아크릴로일기 당량은, 계산값이다.To a flask equipped with a thermometer, stirrer, and reflux cooler, 344 parts by mass of bisphenol A-type epoxy resin ("EPICLON EXA-850CRP" manufactured by DIC Corporation, epoxy equivalent: 172 g / equivalent) was added, and dibutylhydroxy was used as an antioxidant. 0.21 parts by mass of toluene, 0.21 parts by mass of metoquinone as a thermal polymerization inhibitor, 72 parts by mass of acrylic acid and 0.21 parts by mass of triphenylphosphine were added, and the esterification reaction was carried out at 100 ° C for 10 hours while blowing air. Done. Then, after confirming that the acid value was 1 mgKOH / g or less, 0.42 parts by mass of oxalic acid (pKa 1 ; 1.04) was added and stirred at 70 ° C for 3 hours to obtain an epoxy (meth) acrylate resin composition (1). The epoxy equivalent of the epoxy (meth) acrylate resin composition (1) resin powder was 445 g / equivalent, and the (meth) acryloyl group equivalent was 416 g / equivalent. In addition, the pKa 1 value of oxalic acid is a value described in "Chemical Handbook (Revised 4th Edition) Basic Edition II" (Japanese Chemical Society Edition). In addition, (meth) acryloyl group equivalent is a calculated value.
(실시예 2: 에폭시(메타)아크릴레이트 수지 조성물(2)의 제조)(Example 2: Preparation of epoxy (meth) acrylate resin composition (2))
온도계, 교반기, 및 환류 냉각기를 구비한 플라스크에, 비스페놀A형 에폭시 수지(DIC 가부시키가이샤제 「EPICLON EXA-850CRP」, 에폭시 당량 172g／당량) 344질량부를 투입하고, 산화 방지제로서 디부틸히드록시톨루엔 0.21질량부, 열중합 금지제로서 메토퀴논 0.21질량부를 더한 후, 아크릴산 72질량부, 트리페닐포스핀 0.21질량부를 첨가하고, 공기를 취입하면서 100℃에서 10시간 에스테르화 반응을 행했다. 그 다음에, 산가가 1㎎KOH／g 이하인 것을 확인한 후, 옥살산 0.21질량부를 첨가하고, 70℃에서 3시간 교반하여 에폭시(메타)아크릴레이트 수지 조성물(2)을 얻었다. 이 에폭시(메타)아크릴레이트 수지 조성물(2) 수지분의 에폭시 당량은 444g／당량, (메타)아크릴로일기 당량은 416g／당량이었다.To a flask equipped with a thermometer, stirrer, and reflux cooler, 344 parts by mass of bisphenol-A epoxy resin ("EPICLON EXA-850CRP" manufactured by DIC Corporation, epoxy equivalent: 172 g / equivalent) was added, and dibutylhydroxy was used as an antioxidant. After adding 0.21 parts by mass of toluene and 0.21 parts by mass of metoquinone as a thermal polymerization inhibitor, 72 parts by mass of acrylic acid and 0.21 parts by mass of triphenylphosphine were added, and esterification reaction was performed at 100 ° C for 10 hours while blowing air. Next, after confirming that the acid value was 1 mgKOH / g or less, 0.21 parts by mass of oxalic acid was added and stirred at 70 ° C for 3 hours to obtain an epoxy (meth) acrylate resin composition (2). The epoxy equivalent of the epoxy (meth) acrylate resin composition (2) resin powder was 444 g / equivalent, and the (meth) acryloyl group equivalent was 416 g / equivalent.
(실시예 3: 에폭시(메타)아크릴레이트 수지 조성물(3)의 제조)(Example 3: Preparation of epoxy (meth) acrylate resin composition (3))
온도계, 교반기, 및 환류 냉각기를 구비한 플라스크에, 비스페놀A형 에폭시 수지(DIC 가부시키가이샤제 「EPICLON EXA-850CRP」, 에폭시 당량 172g／당량) 344질량부를 투입하고, 산화 방지제로서 디부틸히드록시톨루엔 0.21질량부, 열중합 금지제로서 메토퀴논 0.21질량부를 더한 후, 아크릴산 72질량부, 트리페닐포스핀 0.21질량부를 첨가하고, 공기를 취입하면서 100℃에서 10시간 에스테르화 반응을 행했다. 그 다음에, 산가가 1㎎KOH／g 이하인 것을 확인한 후, 옥살산 0.11질량부를 첨가하고, 70℃에서 3시간 교반하여 에폭시(메타)아크릴레이트 수지 조성물(3)을 얻었다. 이 에폭시(메타)아크릴레이트 수지 조성물(3) 수지분의 에폭시 당량은 446g／당량, (메타)아크릴로일기 당량은 416g／당량이었다.To a flask equipped with a thermometer, stirrer, and reflux cooler, 344 parts by mass of bisphenol-A epoxy resin ("EPICLON EXA-850CRP" manufactured by DIC Corporation, epoxy equivalent: 172 g / equivalent) was added, and dibutylhydroxy was used as an antioxidant. After adding 0.21 parts by mass of toluene and 0.21 parts by mass of metoquinone as a thermal polymerization inhibitor, 72 parts by mass of acrylic acid and 0.21 parts by mass of triphenylphosphine were added, and esterification reaction was performed at 100 ° C for 10 hours while blowing air. Next, after confirming that the acid value was 1 mgKOH / g or less, 0.11 parts by mass of oxalic acid was added and stirred at 70 ° C for 3 hours to obtain an epoxy (meth) acrylate resin composition (3). The epoxy equivalent of the epoxy (meth) acrylate resin composition (3) resin powder was 446 g / equivalent, and the (meth) acryloyl group equivalent was 416 g / equivalent.
(실시예 4: 에폭시(메타)아크릴레이트 수지 조성물(4)의 제조)(Example 4: Preparation of epoxy (meth) acrylate resin composition (4))
온도계, 교반기, 및 환류 냉각기를 구비한 플라스크에, 비스페놀A형 에폭시 수지(DIC 가부시키가이샤제 「EPICLON EXA-850CRP」, 에폭시 당량 172g／당량) 344질량부를 투입하고, 산화 방지제로서 디부틸히드록시톨루엔 0.21질량부, 열중합 금지제로서 메토퀴논 0.21질량부를 더한 후, 아크릴산 72질량부, 트리페닐포스핀 0.21질량부를 첨가하고, 공기를 취입하면서 100℃에서 10시간 에스테르화 반응을 행했다. 그 다음에, 산가가 1㎎KOH／g 이하인 것을 확인한 후, 옥살산 0.04질량부를 첨가하고, 70℃에서 3시간 교반하여 에폭시(메타)아크릴레이트 수지 조성물(4)을 얻었다. 이 에폭시(메타)아크릴레이트 수지 조성물(4) 수지분의 에폭시 당량은 444g／당량, (메타)아크릴로일기 당량은 416g／당량이었다.To a flask equipped with a thermometer, stirrer, and reflux cooler, 344 parts by mass of bisphenol-A epoxy resin ("EPICLON EXA-850CRP" manufactured by DIC Corporation, epoxy equivalent: 172 g / equivalent) was added, and dibutylhydroxy was used as an antioxidant. After adding 0.21 parts by mass of toluene and 0.21 parts by mass of metoquinone as a thermal polymerization inhibitor, 72 parts by mass of acrylic acid and 0.21 parts by mass of triphenylphosphine were added, and esterification reaction was performed at 100 ° C for 10 hours while blowing air. Next, after confirming that the acid value was 1 mgKOH / g or less, 0.04 parts by mass of oxalic acid was added and stirred at 70 ° C for 3 hours to obtain an epoxy (meth) acrylate resin composition (4). The epoxy equivalent of the epoxy (meth) acrylate resin composition (4) resin powder was 444 g / equivalent, and the (meth) acryloyl group equivalent was 416 g / equivalent.
(실시예 5: 에폭시(메타)아크릴레이트 수지 조성물(5)의 제조)(Example 5: Preparation of epoxy (meth) acrylate resin composition (5))
온도계, 교반기, 및 환류 냉각기를 구비한 플라스크에, 비스페놀F형 에폭시 수지(DIC 가부시키가이샤제 「EPICLON EXA-830CRP」, 에폭시 당량 158g／당량) 316질량부를 투입하고, 산화 방지제로서 디부틸히드록시톨루엔 0.19질량부, 열중합 금지제로서 메토퀴논 0.19질량부를 더한 후, 아크릴산 72질량부, 트리페닐포스핀 0.19질량부를 첨가하고, 공기를 취입하면서 100℃에서 10시간 에스테르화 반응을 행했다. 그 다음에, 산가가 1㎎KOH／g 이하인 것을 확인한 후, 옥살산 0.19질량부를 첨가하고, 70℃에서 3시간 교반하여 에폭시(메타)아크릴레이트 수지 조성물(5)을 얻었다. 이 에폭시(메타)아크릴레이트 수지 조성물(5) 수지분의 에폭시 당량은 418g／당량, (메타)아크릴로일기 당량은 388g／당량이었다.To a flask equipped with a thermometer, stirrer, and reflux cooler, 316 parts by mass of bisphenol F-type epoxy resin ("EPICLON EXA-830CRP" manufactured by DIC Corporation, epoxy equivalent: 158 g / equivalent) was added, and dibutylhydroxy was used as an antioxidant. After adding 0.19 parts by mass of toluene and 0.19 parts by mass of metoquinone as a thermal polymerization inhibitor, 72 parts by mass of acrylic acid and 0.19 parts by mass of triphenylphosphine were added, and esterification reaction was performed at 100 ° C for 10 hours while blowing air. Next, after confirming that the acid value was 1 mgKOH / g or less, 0.19 parts by mass of oxalic acid was added and stirred at 70 ° C for 3 hours to obtain an epoxy (meth) acrylate resin composition (5). The epoxy equivalent of the epoxy (meth) acrylate resin composition (5) resin powder was 418 g / equivalent, and the (meth) acryloyl group equivalent was 388 g / equivalent.
(실시예 6: 에폭시(메타)아크릴레이트 수지 조성물(6)의 제조)(Example 6: Preparation of epoxy (meth) acrylate resin composition (6))
온도계, 교반기, 및 환류 냉각기를 구비한 플라스크에, 에폭시 수지(DIC 가부시키가이샤제 「EPICLON HP-820」, 에폭시 당량 209g／당량) 418질량부를 투입하고, 산화 방지제로서 디부틸히드록시톨루엔 0.25질량부, 열중합 금지제로서 메토퀴논 0.25질량부를 더한 후, 아크릴산 72질량부, 트리페닐포스핀 0.25질량부를 첨가하고, 공기를 취입하면서 100℃에서 10시간 에스테르화 반응을 행했다. 그 다음에, 산가가 1㎎KOH／g 이하인 것을 확인한 후, 옥살산 0.25질량부를 첨가하고, 70℃에서 3시간 교반하여 에폭시(메타)아크릴레이트 수지 조성물(6)을 얻었다. 이 에폭시(메타)아크릴레이트 수지 조성물(6) 수지분의 에폭시 당량은 585g／당량, (메타)아크릴로일기 당량은 490g／당량이었다.To a flask equipped with a thermometer, stirrer, and reflux cooler, 418 parts by mass of an epoxy resin ("EPICLON HP-820" manufactured by DIC Corporation, epoxy equivalent: 209 g / equivalent) was added, and 0.25 mass of dibutylhydroxytoluene as an antioxidant. Part, after adding 0.25 parts by mass of metoquinone as a thermal polymerization inhibitor, 72 parts by mass of acrylic acid and 0.25 parts by mass of triphenylphosphine were added, and esterification reaction was performed at 100 ° C for 10 hours while blowing air. Then, after confirming that the acid value was 1 mgKOH / g or less, 0.25 parts by mass of oxalic acid was added and stirred at 70 ° C for 3 hours to obtain an epoxy (meth) acrylate resin composition (6). The epoxy equivalent of the epoxy (meth) acrylate resin composition (6) resin powder was 585 g / equivalent, and the (meth) acryloyl group equivalent was 490 g / equivalent.
(실시예 7: 에폭시(메타)아크릴레이트 수지 조성물(7)의 제조)(Example 7: Preparation of epoxy (meth) acrylate resin composition (7))
온도계, 교반기, 및 환류 냉각기를 구비한 플라스크에, 지환식 에폭시 수지셀록사이드(가부시키가이샤 다이세루제 「2021P」, 에폭시 당량: 131g／당량) 262질량부를 첨가하고, 산화 방지제로서 디부틸히드록시톨루엔 0.15질량부, 열중합 금지제로서 메토퀴논 0.15질량부를 더한 후, 아크릴산 36질량부, 트리페닐포스핀 0.15질량부를 첨가하고, 공기를 취입하면서 80℃에서 10시간 에스테르화 반응을 행했다. 산가 1㎎KOH／g 이하인 것을 확인한 후, 옥살산 0.15질량부를 첨가하고, 70℃에서 3시간 교반하여 에폭시(메타)아크릴레이트 수지 조성물(7)을 얻었다. 이 에폭시(메타)아크릴레이트 수지 조성물(7) 수지분의 에폭시 당량은 286g／당량, (메타)아크릴로일기 당량은 597g／당량이었다.To a flask equipped with a thermometer, stirrer, and reflux cooler, 262 parts by mass of an alicyclic epoxy resin celloxide ("2021P" manufactured by Daiseru Co., Ltd., epoxy equivalent: 131g / equivalent) was added, and dibutylhydroxy was used as an antioxidant. After adding 0.15 parts by mass of toluene and 0.15 parts by mass of metoquinone as a thermal polymerization inhibitor, 36 parts by mass of acrylic acid and 0.15 parts by mass of triphenylphosphine were added, and esterification reaction was performed at 80 ° C for 10 hours while blowing air. After confirming that the acid value was 1 mgKOH / g or less, 0.15 parts by mass of oxalic acid was added and stirred at 70 ° C for 3 hours to obtain an epoxy (meth) acrylate resin composition (7). The epoxy equivalent of the epoxy (meth) acrylate resin composition (7) resin powder was 286 g / equivalent, and the (meth) acryloyl group equivalent was 597 g / equivalent.
(실시예 8: 에폭시(메타)아크릴레이트 수지 조성물(8)의 제조)(Example 8: Preparation of epoxy (meth) acrylate resin composition (8))
온도계, 교반기, 및 환류 냉각기를 구비한 플라스크에, 시클로헥산디메탄올디글리시딜에테르(에폭시 당량: 136g／당량) 272질량부를 첨가하고, 산화 방지제로서 디부틸히드록시톨루엔 0.17질량부, 열중합 금지제로서 메토퀴논 0.17질량부를 더한 후, 아크릴산 72질량부, 트리페닐포스핀 0.17질량부를 첨가하고, 공기를 취입하면서 100℃에서 15시간 에스테르화 반응을 행했다. 산가 1㎎KOH／g 이하인 것을 확인한 후, 옥살산 0.17질량부를 첨가하고, 70℃에서 3시간 교반하여, 에폭시(메타)아크릴레이트 수지 조성물(8)을 얻었다. 이 에폭시(메타)아크릴레이트 수지 조성물(8) 수지분의 에폭시 당량은 399g／당량, (메타)아크릴로일기 당량은 345g／당량이었다.To a flask equipped with a thermometer, stirrer, and reflux cooler, 272 parts by mass of cyclohexane dimethanol diglycidyl ether (epoxy equivalent: 136 g / equivalent) was added, and 0.17 parts by mass of dibutylhydroxytoluene and thermal polymerization as an antioxidant. After adding 0.17 parts by mass of metoquinone as an inhibitor, 72 parts by mass of acrylic acid and 0.17 parts by mass of triphenylphosphine were added, and esterification reaction was performed at 100 ° C for 15 hours while blowing air. After confirming that the acid value was 1 mgKOH / g or less, 0.17 parts by mass of oxalic acid was added and stirred at 70 ° C for 3 hours to obtain an epoxy (meth) acrylate resin composition (8). The epoxy equivalent of the epoxy (meth) acrylate resin composition (8) resin powder was 399 g / equivalent, and the (meth) acryloyl group equivalent was 345 g / equivalent.
(비교예 1: 에폭시(메타)아크릴레이트 수지 조성물(C1)의 제조)(Comparative Example 1: Preparation of epoxy (meth) acrylate resin composition (C1))
온도계, 교반기, 및 환류 냉각기를 구비한 플라스크에, 비스페놀A형 에폭시 수지(DIC 가부시키가이샤제 「EPICLON EXA-850CRP」, 에폭시 당량 172g／당량) 344질량부를 투입하고, 산화 방지제로서 디부틸히드록시톨루엔 0.21질량부, 열중합 금지제로서 메토퀴논 0.21질량부를 더한 후, 아크릴산 72질량부, 트리페닐포스핀 0.21질량부를 첨가하고, 공기를 취입하면서 100℃에서 10시간 에스테르화 반응을 행하여 에폭시(메타)아크릴레이트 수지 조성물(C1)을 얻었다. 이 에폭시(메타)아크릴레이트 수지 조성물(C1) 수지분의 에폭시 당량은 443g／당량, (메타)아크릴로일기 당량은 416g／당량이었다.To a flask equipped with a thermometer, stirrer, and reflux cooler, 344 parts by mass of bisphenol-A epoxy resin ("EPICLON EXA-850CRP" manufactured by DIC Corporation, epoxy equivalent: 172 g / equivalent) was added, and dibutylhydroxy was used as an antioxidant. After adding 0.21 parts by mass of toluene and 0.21 parts by mass of metoquinone as a thermal polymerization inhibitor, 72 parts by mass of acrylic acid and 0.21 parts by mass of triphenylphosphine were added, and esterification was performed at 100 ° C for 10 hours while blowing air to obtain epoxy (meta ) An acrylate resin composition (C1) was obtained. The epoxy equivalent of the epoxy (meth) acrylate resin composition (C1) resin powder was 443 g / equivalent, and the (meth) acryloyl group equivalent was 416 g / equivalent.
(비교예 2: 에폭시(메타)아크릴레이트 수지 조성물(C2)의 제조)(Comparative Example 2: Preparation of epoxy (meth) acrylate resin composition (C2))
온도계, 교반기, 및 환류 냉각기를 구비한 플라스크에, 비스페놀A형 에폭시 수지(DIC 가부시키가이샤제 「EPICLON EXA-850CRP」, 에폭시 당량 172g／당량) 344질량부를 투입하고, 산화 방지제로서 디부틸히드록시톨루엔 0.21질량부, 열중합 금지제로서 메토퀴논 0.21질량부를 더한 후, 아크릴산 72질량부, 트리페닐포스핀 0.21질량부를 첨가하고, 공기를 취입하면서 100℃에서 10시간 에스테르화 반응을 행했다. 그 다음에, 산가가 1㎎KOH／g 이하인 것을 확인한 후, 말론산(pKa1; 2.65) 0.42질량부를 첨가하고, 70℃에서 3시간 교반하여 에폭시(메타)아크릴레이트 수지 조성물(C2)을 얻었다. 이 에폭시(메타)아크릴레이트 수지 조성물(C2) 수지분의 에폭시 당량은 445g／당량, (메타)아크릴로일기 당량은 443g／당량이었다. 또, 말론산의 pKa1값은, 「화학 편람(개정 4판) 기초편 Ⅱ」(일본 화학회편)에 기재된 값이다.To a flask equipped with a thermometer, stirrer, and reflux cooler, 344 parts by mass of bisphenol A-type epoxy resin ("EPICLON EXA-850CRP" manufactured by DIC Corporation, epoxy equivalent: 172 g / equivalent) was added, and dibutylhydroxy was used as an antioxidant. After adding 0.21 parts by mass of toluene and 0.21 parts by mass of metoquinone as a heat polymerization inhibitor, 72 parts by mass of acrylic acid and 0.21 parts by mass of triphenylphosphine were added, and esterification reaction was performed at 100 ° C for 10 hours while blowing air. Next, after confirming that the acid value was 1 mgKOH / g or less, 0.42 parts by mass of malonic acid (pKa 1 ; 2.65) was added and stirred at 70 ° C for 3 hours to obtain an epoxy (meth) acrylate resin composition (C2). . The epoxy equivalent of the epoxy (meth) acrylate resin composition (C2) resin powder was 445 g / equivalent, and the (meth) acryloyl group equivalent was 443 g / equivalent. In addition, the pKa 1 value of malonic acid is a value described in "Basic Manual of Chemical Handbook (Revised 4th Edition) II" (Japanese Chemical Society Edition).
상기의 실시예 및 비교예에서 얻어진 에폭시(메타)아크릴레이트 수지 조성물을 사용하여, 하기의 평가를 행했다.The following evaluation was performed using the epoxy (meth) acrylate resin composition obtained in the said Example and a comparative example.
[저장 안정성의 평가 방법][Evaluation method of storage stability]
실시예 1∼8, 그리고 비교예 1 및 2에서 얻어진 에폭시(메타)아크릴레이트 수지 조성물을 80℃에서 보존했을 경우의 경시적인 점도 변화를 관찰했다.The viscosity changes over time when the epoxy (meth) acrylate resin compositions obtained in Examples 1 to 8 and Comparative Examples 1 and 2 were stored at 80 ° C were observed.
[경화성의 평가 방법][Evaluation method of hardenability]
실시예 1∼8, 그리고 비교예 1 및 2에서 얻어진 에폭시(메타)아크릴레이트 수지 조성물을 유리 기판 상에 두께 50㎛가 되도록 도포했다. 그 다음에, 200mJ／㎠의 자외선을 조사하여, 도막을 얻었다. 얻어진 도막의 표면을 손가락으로 만져, 택(tack)의 유무로 이하의 기준에 따라 경화성을 평가했다.The epoxy (meth) acrylate resin compositions obtained in Examples 1 to 8 and Comparative Examples 1 and 2 were coated on a glass substrate to a thickness of 50 µm. Then, 200 mJ / cm 2 of ultraviolet light was irradiated to obtain a coating film. The surface of the obtained coating film was touched with a finger, and curability was evaluated according to the following criteria with or without a tack.
○: 택이 없고, 완전히 경화했다.○: No tack and completely cured.
×: 택이 있고, 경화가 불충분했다.×: There was a tack, and curing was insufficient.
실시예 1∼8에서 제작한 에폭시(메타)아크릴레이트 수지 조성물(1)∼(8), 그리고 비교예 1 및 2에서 제작한 에폭시(메타)아크릴레이트 수지 조성물(C1) 및 (C2)의 평가 결과를 표 1에 나타낸다.Evaluation of epoxy (meth) acrylate resin compositions (1) to (8) prepared in Examples 1 to 8, and epoxy (meth) acrylate resin compositions (C1) and (C2) produced in Comparative Examples 1 and 2 Table 1 shows the results.
[표 1][Table 1]
표 1 중의 「-」은, 겔화하여, 점도 측정을 할 수 없었던 것을 나타낸다."-" In Table 1 shows that it was gelled and viscosity measurement was not possible.
표 1에 나타낸 실시예 1∼8은, 본 발명의 에폭시(메타)아크릴레이트 수지 조성물의 예이며, 본 발명의 에폭시(메타)아크릴레이트 수지 조성물은, 경시적인 증점이 생기기 어려워, 저장 안정성이 우수한 것을 확인할 수 있었다. 또한, 경화성에 있어서도 우수한 것을 확인할 수 있었다.Examples 1 to 8 shown in Table 1 are examples of the epoxy (meth) acrylate resin composition of the present invention, and the epoxy (meth) acrylate resin composition of the present invention is unlikely to develop thickening over time, and has excellent storage stability. I could confirm that. Moreover, it was confirmed that it was excellent also in curability.
한편, 비교예 1은, 산성 화합물을 사용하지 않는 에폭시(메타)아크릴레이트 수지 조성물의 예이지만, 이 에폭시(메타)아크릴레이트 수지 조성물은, 겔화하여, 저장 안정성이 현저하게 불충분한 것을 확인할 수 있었다.On the other hand, Comparative Example 1 is an example of an epoxy (meth) acrylate resin composition that does not use an acidic compound, but this epoxy (meth) acrylate resin composition was gelled, and it was confirmed that storage stability was remarkably insufficient. .
비교예 2는, 제1 산해리 상수(pKa1)가, 2.5보다도 큰 산성 화합물을 사용한 에폭시(메타)아크릴레이트 수지 조성물의 예이지만, 이 에폭시(메타)아크릴레이트 수지 조성물은, 80℃ 24시간에서 겔화하여, 비교예 1과 마찬가지로 저장 안정성이 불충분한 것을 확인할 수 있었다.Comparative Example 2 is an example of an epoxy (meth) acrylate resin composition using an acidic compound having a first acid dissociation constant (pKa 1 ) greater than 2.5, but this epoxy (meth) acrylate resin composition is at 80 ° C. for 24 hours. By gelling, it was confirmed that storage stability was insufficient, as in Comparative Example 1.
Claims (9)
상기 에폭시(메타)아크릴레이트 수지(A)가, 에폭시기 및 (메타)아크릴로일기를 갖는 것이며,
상기 산성 화합물(B)의 제1 산해리 상수(pKa1)가, 2.5 이하인 것을 특징으로 하는 에폭시(메타)아크릴레이트 수지 조성물.Epoxy (meth) acrylate containing epoxy resin (a1), carboxyl group-containing (meth) acrylate compound (a2) as an essential reaction raw material, and epoxy (meth) acrylate resin (A) and acidic compound (B) As a rate resin composition,
The said epoxy (meth) acrylate resin (A) has an epoxy group and (meth) acryloyl group,
The first acid dissociation constant (pKa 1 ) of the acidic compound (B) is 2.5 or less, characterized in that the epoxy (meth) acrylate resin composition.
상기 에폭시(메타)아크릴레이트 수지(A)의 (메타)아크릴로일기 당량이, 200∼800g／당량의 범위이며, 에폭시 당량이, 300∼900g／당량의 범위인 에폭시(메타)아크릴레이트 수지 조성물.According to claim 1,
The (meth) acryloyl group equivalent of the epoxy (meth) acrylate resin (A) is in the range of 200 to 800 g / equivalent, and the epoxy equivalent is in the range of 300 to 900 g / equivalent epoxy (meth) acrylate resin composition .
상기 카르복시기 함유 (메타)아크릴레이트 화합물(a2)의 사용량이, 상기 에폭시 수지(a1) 1몰에 대하여, 0.2∼0.8몰의 범위인 에폭시(메타)아크릴레이트 수지 조성물.The method according to claim 1 or 2,
The amount of the carboxyl group-containing (meth) acrylate compound (a2) used is an epoxy (meth) acrylate resin composition in the range of 0.2 to 0.8 moles per 1 mole of the epoxy resin (a1).
상기 산성 화합물(B)이, 유기산인 에폭시(메타)아크릴레이트 수지 조성물.The method according to any one of claims 1 to 3,
The acidic compound (B) is an organic acid, an epoxy (meth) acrylate resin composition.
상기 에폭시(메타)아크릴레이트 수지(A)가, 에폭시기 및 (메타)아크릴로일기를 갖는 것이며,
상기 산성 화합물(B)의 제1 산해리 상수(pKa1)가, 2.5 이하인 것을 특징으로 하는 에폭시(메타)아크릴레이트 수지 조성물의 제조 방법.An epoxy (meth) containing an epoxy (meth) acrylate resin (A) and an acidic compound (B) obtained by reacting an epoxy resin (a1) with a carboxyl group-containing (meth) acrylate compound (a2) in the presence of a basic catalyst As a method for producing an acrylate resin composition,
The said epoxy (meth) acrylate resin (A) has an epoxy group and (meth) acryloyl group,
Method for producing an epoxy (meth) acrylate resin composition, characterized in that the first acid dissociation constant (pKa 1 ) of the acidic compound (B) is 2.5 or less.
상기 염기성 촉매의 사용량이, 상기 에폭시 수지(a1)와 상기 카르복시기 함유 (메타)아크릴레이트 화합물(a2)의 합계 100질량부에 대하여, 0.01∼0.5질량부의 범위인 에폭시(메타)아크릴레이트 수지 조성물의 제조 방법.The method of claim 7,
The amount of the basic catalyst used is an epoxy (meth) acrylate resin composition in a range of 0.01 to 0.5 parts by mass based on 100 parts by mass of the epoxy resin (a1) and the carboxyl group-containing (meth) acrylate compound (a2). Manufacturing method.
상기 산성 화합물(B)의 사용량이, 상기 염기성 촉매 100질량부에 대하여 50질량부 이상인 에폭시(메타)아크릴레이트 수지 조성물의 제조 방법.The method of claim 7 or 8,
The method for producing an epoxy (meth) acrylate resin composition in which the amount of the acidic compound (B) used is 50 parts by mass or more based on 100 parts by mass of the basic catalyst.
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| JP2009235114A (en) * | 2008-03-25 | 2009-10-15 | Air Water Inc | Epoxy (meth)acrylate resin, photo-setting or thermosetting resin composition containing the same, and cured product thereof |
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