CN111315794B - 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
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- CN111315794B CN111315794B CN201880072421.1A CN201880072421A CN111315794B CN 111315794 B CN111315794 B CN 111315794B CN 201880072421 A CN201880072421 A CN 201880072421A CN 111315794 B CN111315794 B CN 111315794B
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- Prior art keywords
- meth
- epoxy
- acrylate
- resin composition
- resin
- Prior art date
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 113
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 90
- 239000000203 mixture Substances 0.000 title claims abstract description 72
- 239000011342 resin composition Substances 0.000 title claims description 18
- 239000003822 epoxy resin Substances 0.000 claims abstract description 96
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 96
- -1 acrylate compound Chemical class 0.000 claims abstract description 57
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 26
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 21
- 150000007513 acids Chemical class 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000010494 dissociation reaction Methods 0.000 claims abstract description 9
- 230000005593 dissociations Effects 0.000 claims abstract description 9
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 43
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 33
- 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
- 229920005989 resin Polymers 0.000 description 23
- 239000011347 resin Substances 0.000 description 23
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 18
- 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 18
- 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
- 238000001723 curing Methods 0.000 description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 11
- 229930185605 Bisphenol Natural products 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 235000006408 oxalic acid Nutrition 0.000 description 11
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 10
- 239000003963 antioxidant agent Substances 0.000 description 10
- 230000003078 antioxidant effect Effects 0.000 description 10
- 238000007664 blowing Methods 0.000 description 10
- 235000010354 butylated hydroxytoluene Nutrition 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
- 229920003986 novolac Polymers 0.000 description 10
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 238000012719 thermal polymerization Methods 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 125000001931 aliphatic group Chemical group 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 7
- 239000004841 bisphenol A epoxy resin 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000002723 alicyclic group Chemical group 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
- 150000002148 esters Chemical class 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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-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
- 239000004210 ether based solvent Substances 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
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-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
- 125000002947 alkylene group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000004842 bisphenol F epoxy resin Substances 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
- 229930003836 cresol Natural products 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- ARNKHYQYAZLEEP-UHFFFAOYSA-N 1-naphthalen-1-yloxynaphthalene Chemical compound C1=CC=C2C(OC=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ARNKHYQYAZLEEP-UHFFFAOYSA-N 0.000 description 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
- 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
- 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
- OXQXGKNECHBVMO-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptane-4-carboxylic acid Chemical compound C1C(C(=O)O)CCC2OC21 OXQXGKNECHBVMO-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 2
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 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
- 238000007259 addition reaction Methods 0.000 description 2
- 239000005456 alcohol based solvent 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
- 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
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000003759 ester based solvent Substances 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
- 235000005985 organic acids Nutrition 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
- 230000007261 regionalization Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 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
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-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
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-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
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 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
- 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 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- 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
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- BATCUENAARTUKW-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-diphenylmethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BATCUENAARTUKW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- RDCRVCNPGSYUCY-UHFFFAOYSA-N [4-(hydroxymethyl)-3-bicyclo[2.2.1]heptanyl]methanol Chemical compound C1CC2(CO)C(CO)CC1C2 RDCRVCNPGSYUCY-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
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000003513 alkali Substances 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
- 229910001860 alkaline earth metal hydroxide Inorganic materials 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
- 239000002585 base Substances 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
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical class C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-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
- 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
- 230000018109 developmental process Effects 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
- 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 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 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
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 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
- 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
- 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
- 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
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- 125000006187 phenyl benzyl group Chemical group 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000012945 sealing adhesive Substances 0.000 description 1
- 239000003566 sealing material Substances 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
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000010409 thin film Substances 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
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
-
- 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
-
- 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
-
- 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
Abstract
The present invention provides an epoxy (meth) acrylate resin composition comprising an epoxy (meth) acrylate resin (A) and an acidic compound (B), wherein the epoxy (meth) acrylate resin (A) comprises an epoxy resin (a 1) and a carboxyl group-containing (meth) acrylate compound (a 2) as essential reaction raw materials, the epoxy (meth) acrylate resin (A) has an epoxy group and a (meth) acryloyl group, and the acidic compound (B) has a first acid dissociation constant (pKa) 1 ) Is 2.5 or less. The epoxy (meth) acrylate resin composition is less likely to be thickened with time and has excellent storage stability.
Description
Technical Field
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.
Background
In order to form a solder resist pattern on a printed circuit board, a photoresist method has been widely used. The photoresist method is characterized in that a resin having a photopolymerizable group such as a (meth) acryloyl group and an alkali-soluble group such as a carboxyl group is used as a resin material for pattern formation, and patterning is performed by photocuring in exposed portions and alkali development in unexposed portions. In contrast, in recent years, an ink jet method, which requires a smaller number of steps than the photoresist method, has attracted attention as a solder resist pattern formation method.
The resin material used in the inkjet system is required to have general resist performance such as excellent photocurability and high heat resistance of a cured product, and low viscosity to the extent that inkjet printing can be performed. As a conventionally known resin material having a low viscosity and suitable for inkjet printing, there has been known a photocurable/thermosetting composition for inkjet containing pentaerythritol triacrylate, 2-methacryloyloxyethyl isocyanate, and N-vinyl-2-pyrrolidone, and having a viscosity of 79.1mPa · s or less at 25 ℃ (see, for example, patent document 1), but there has been a problem that the heat resistance of a cured product is insufficient.
As a technique for improving the heat resistance of a cured product, there has been known an inkjet photocurable composition containing a half-acrylate of a bisphenol a type epoxy resin, a bisphenol a type epoxy acrylate, triethylene glycol diacrylate, isobornyl acrylate, a bisphenol a type epoxy resin, and dicyandiamide and having a viscosity of 420mPa · s or less at 25 ℃ (see, for example, patent document 2).
Therefore, a material which is less likely to be thickened with time and has excellent storage stability has been desired.
Documents of the prior art
Patent document
Patent document 1: international publication No. 2004/099272
Patent document 2: international publication No. 2012/039379
Disclosure of Invention
Problems to be solved by the invention
The problem to be solved by the present invention is to provide an epoxy (meth) acrylate resin composition which is less likely to undergo thickening over time and has excellent storage stability, a curable resin composition containing the same, and a cured product of the curable resin composition.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that: the present invention has been accomplished by solving the above problems by using an epoxy (meth) acrylate resin composition containing an epoxy (meth) acrylate resin having an epoxy group and a (meth) acryloyl group, which are essential reaction raw materials of an epoxy resin and a carboxyl group-containing (meth) acrylate compound, and an acidic compound having a specific acid dissociation constant.
That is, the present invention relates to an epoxy (meth) acrylate resin composition comprising an epoxy (meth) acrylate resin (a) containing an epoxy resin (a 1) and a carboxyl group-containing (meth) acrylate compound (a 2) as essential reaction raw materials, the epoxy (meth) acrylate resin (a) having an epoxy group and a (meth) acryloyl group, and an acid compound (B) having a first acid dissociation constant (pKa) of the acid compound (B), a curable resin composition comprising the same, a cured product of the curable resin composition, and a method for producing the epoxy (meth) acrylate resin composition 1 ) Is 2.5 or less.
ADVANTAGEOUS EFFECTS OF INVENTION
The epoxy (meth) acrylate resin composition of the present invention is less likely to be thickened with time and has excellent storage stability, and therefore, a curable resin composition containing the epoxy (meth) acrylate resin composition and a photopolymerization initiator can be suitably used for a resin material for a solder resist and a resist member containing the resin for a solder resist.
Detailed Description
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).
In the present invention, the "(meth) acrylate resin" means a resin having one or both of an acryloyl group and a methacryloyl group in a molecule. Further, "(meth) acryloyl group" means one or both of an acryloyl group and a methacryloyl group, and "(meth) acrylate" means one or both of acrylate and methacrylate.
As the epoxy (meth) acrylate resin (a), a resin in which an epoxy resin (a 1) and a carboxyl group-containing (meth) acrylate compound (a 2) are used as essential reaction raw materials is used.
The specific structure of the epoxy resin (a 1) is not particularly limited as long as it has a plurality of epoxy groups in the resin and can react with the carboxyl group-containing (meth) acrylate compound (a 2) to form the epoxy (meth) acrylate resin of the present invention. Examples of the epoxy resin (a 1) include a bisphenol type epoxy resin, a hydrogenated bisphenol type epoxy resin, a biphenol type epoxy resin, a hydrogenated biphenol type epoxy resin, a phenyl ether type epoxy resin, a naphthyl ether type epoxy resin, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a bisphenol novolac type epoxy resin, a naphthol novolac type epoxy resin, a phenol aralkyl type epoxy resin, a naphthol aralkyl type epoxy resin, a dicyclopentadiene-phenol addition reaction type epoxy resin, and the like. In addition, alicyclic epoxy resins such as 3, 4-epoxycyclohexanecarboxylic acid 3',4' -epoxycyclohexylmethyl ester, diepoxvinylcyclohexene, 3, 4-epoxycyclohexanecarboxylic acid epsilon-caprolactone-modified 3',4' -epoxycyclohexylmethyl ester, and cyclohexanedimethanol diglycidyl ether can also be used. These epoxy resins may be used alone or in combination of two or more. Among these, from the viewpoint of obtaining an epoxy (meth) acrylate resin having excellent storage stability, a bisphenol epoxy resin, a hydrogenated bisphenol epoxy resin, a diphenol epoxy resin, and a hydrogenated diphenol epoxy resin are preferable, and a bisphenol epoxy resin or a hydrogenated diphenol epoxy resin is more preferable.
Examples of the bisphenol epoxy resin include bisphenol a epoxy resin, bisphenol AP epoxy resin, bisphenol B epoxy resin, bisphenol BP epoxy resin, bisphenol E epoxy resin, bisphenol F epoxy resin, and bisphenol S epoxy resin.
Examples of the hydrogenated bisphenol epoxy resin include hydrogenated bisphenol a epoxy resin, hydrogenated bisphenol B epoxy resin, hydrogenated bisphenol E epoxy resin, hydrogenated bisphenol F epoxy resin, and hydrogenated bisphenol S epoxy resin.
Examples of the diphenol type epoxy resin include 4,4 '-diphenol type epoxy resin, 2' -diphenol type epoxy resin, tetramethyl-4, 4 '-diphenol type epoxy resin, tetramethyl-2, 2' -diphenol type epoxy resin, and the like.
Examples of the hydrogenated diphenol type epoxy resin include hydrogenated 4,4 '-diphenol type epoxy resin, hydrogenated 2,2' -diphenol type epoxy resin, hydrogenated tetramethyl-4, 4 '-diphenol type epoxy resin, hydrogenated tetramethyl-2, 2' -diphenol type epoxy resin, and the like.
When the epoxy resin (a 1) is any one of the bisphenol epoxy resin, the hydrogenated bisphenol epoxy resin, the diphenol epoxy resin and the hydrogenated diphenol epoxy resin, the epoxy equivalent of the epoxy resin (a 1) is preferably in the range of 110 to 400 g/equivalent in view of obtaining an epoxy (meth) acrylate resin having excellent storage stability.
The specific structure of the carboxyl group-containing (meth) acrylate compound (a 2) is not particularly limited as long as it has a carboxyl group and a (meth) acryloyl group in the molecular structure, and a low-molecular-weight compound having a molecular weight in the range of 100 to 500 is preferable, and a compound having a molecular weight in the range of 150 to 400 is more preferable, in addition to acrylic acid and methacrylic acid. More specifically, for example, a compound represented by the following structural formula (1) and the like can be cited.
[ in the formula, X represents an alkylene chain, a polyoxyalkylene chain, a (poly) ester chain, an aromatic hydrocarbon chain or a (poly) carbonate chain having 1 to 10 carbon atoms, and optionally has a halogen atom, an alkoxy group or the like in the structure. Y is a hydrogen atom or a methyl group. ]
Examples of the polyoxyalkylene chain include a polyoxyethylene chain and a polyoxypropylene chain.
Examples of the (poly) ester chain include a (poly) ester chain represented by the following structural formula (X-1).
(in the formula, R 1 Is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5. )
Examples of the aromatic hydrocarbon chain include a phenylene chain, a naphthylene chain, a biphenylene chain, a phenylnaphthylene chain, and a binaphthylene chain. Further, as a partial structure, a hydrocarbon chain having an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring may be used.
Examples of the (poly) carbonate chain include a (poly) carbonate chain represented by the following structural formula (X-2).
(in the formula, R 2 Is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5. )
These carboxyl group-containing (meth) acrylate compounds (a 2) may be used alone or in combination of two or more.
Further, as the carboxyl group-containing (meth) acrylate compound (a 2), an acid anhydride of the carboxyl group-containing (meth) acrylate compound may also be used.
Examples of the acid anhydride of the carboxyl group-containing (meth) acrylate compound include (meth) acrylic anhydride and the like.
The amount of the carboxyl group-containing (meth) acrylate compound (a 2) used is preferably in the range of 0.2 to 0.8 mol, more preferably in the range of 0.3 to 0.7 mol, based on 1 mol of the epoxy resin (a 1), from the viewpoint of obtaining an epoxy (meth) acrylate resin having excellent storage stability.
The epoxy (meth) acrylate resin (a) preferably has a (meth) acryloyl equivalent weight in the range of 200 to 800 g/equivalent in view of excellent storage stability of the epoxy (meth) acrylate resin (a). The epoxy equivalent of the epoxy (meth) acrylate resin (a) is preferably in the range of 300 to 900 g/equivalent.
The acid value is preferably 3mgKOH/g or less, more preferably 2mgKOH/g or less, from the viewpoint of excellent storage stability of the epoxy (meth) acrylate resin (A). Further, the hydroxyl value is preferably 300mgKOH/g or less.
The reaction of the epoxy resin (a 1) with the carboxyl group-containing (meth) acrylate compound (a 2) is preferably carried out in the presence of a basic catalyst.
Examples of the basic catalyst include alkaline 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, triphenylphosphine, etc.; amine compounds such as triethylamine, tributylamine, and dimethylbenzylamine. These basic catalysts may be used alone or in combination of two or more. Among these, triphenylphosphine is preferable.
The amount of the basic catalyst used is preferably in the range of 0.01 to 0.5 parts by mass, more preferably in the range of 0.01 to 0.4 parts by mass, based on 100 parts by mass of the total of the epoxy resin (a 1) and the carboxyl group-containing (meth) acrylate compound (a 2), from the viewpoint of obtaining an epoxy (meth) acrylate resin having a low viscosity and excellent storage stability.
In addition, when a basic catalyst is used in the reaction of the epoxy resin (a 1) and the carboxyl group-containing (meth) acrylate compound (a 2), it is preferable that the acidic compound (B) is deactivated so as not to separate and remove the basic catalyst, from the viewpoint of obtaining an epoxy (meth) acrylate resin composition having excellent storage stability.
The acidic compound (B) is an epoxy (meth) acrylate resin having excellent storage stability, and is obtained by using a first acid dissociation constant (pKa) 1 ) The content of the compound is 2.5 or less. In the present invention, the acid dissociation constant of the acidic compound (B) is an acid dissociation constant in water at 25 ℃ and, for example, "chemistry overview (revision 4 th edition) basic reference II (chemistry)One described in (i.e., \ 35239 (version 4) \ 30990) ("Nippon chemical Association"), and the like.
Examples of the acidic compound (B) include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; and organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid. These acidic compounds may be used alone, or two or more of them may be used in combination. Among these, organic acids are preferable, and oxalic acid is particularly preferable, from the viewpoint of obtaining an epoxy (meth) acrylate resin having excellent storage stability.
The amount of the acidic compound (B) used is preferably 50 parts by mass or more per 100 parts by mass of the basic catalyst, from the viewpoint of obtaining an epoxy (meth) acrylate resin having excellent storage stability.
The method for producing the epoxy (meth) acrylate resin composition of the present invention is not particularly limited, and the epoxy (meth) acrylate resin composition can be produced by any method. For example, the following method can be used: the catalyst may be produced by a method of reacting all the reaction materials at once, or may be produced by a method of reacting the reaction materials sequentially. Among them, from the viewpoint of easy control of the reaction, the epoxy resin (a 1) and the carboxyl group-containing (meth) acrylate compound (a 2) are reacted in the presence of a basic catalyst at a temperature ranging from 80 to 140 ℃, and then the acidic compound (B) is added and mixed at a temperature ranging from 50 to 100 ℃ to deactivate the basic catalyst.
The epoxy (meth) acrylate resin composition of the present invention has a polymerizable (meth) acryloyl group in the molecular structure, and therefore can be used as a curable resin composition by adding, for example, a photopolymerization initiator.
Examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl propane-1-one, 1- [ 4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propane-1-one, thioxanthone and thioxanthone derivatives, 2' -dimethoxy-1, 2-diphenylethane-1-one, diphenyl (2, 4, 6-trimethoxybenzoyl) phosphine oxide, 2,4, 6-trimethylbenzoyl diphenylphosphine oxide, bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one.
Examples of commercially available photopolymerization initiators include 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, irgacure-1173, BASF Ltd, lucirin TPO, KAYACURE-DETX, KAYARE-MBP, KAYACURE-DMCURE-EPA, KAYASUITRE-OB, JYA, SANKAGEN-1000, and so on.
The amount of the photopolymerization initiator added is preferably in the range of 1 to 20% by mass in the curable resin composition, for example.
The curable resin composition of the present invention may contain other resin components than the epoxy (meth) acrylate resin. Examples of the other resin component include resins having a carboxyl group and a (meth) acryloyl group in the resin obtained by reacting an epoxy resin such as a bisphenol epoxy resin or a novolak epoxy resin with (meth) acrylic acid, a dicarboxylic anhydride, and if necessary, an unsaturated monocarboxylic acid anhydride, and various (meth) acrylate monomers.
Examples of the (meth) acrylate monomer include aliphatic mono (meth) acrylate compounds such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (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; mono (meth) acrylate compounds such as aromatic mono (meth) acrylate compounds including benzyl (meth) acrylate, phenyl (meth) acrylate, phenylbenzyl (meth) acrylate, phenoxy ester (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenoxybenzyl (meth) acrylate, benzylbenzyl (meth) acrylate, and phenylphenoxyethyl (meth) acrylate: (poly) oxyalkylene-modified mono (meth) acrylate compounds in which polyoxyalkylene chains such as (poly) oxyethylene chains, (poly) oxypropylene chains, and (poly) oxytetramethylene chains are introduced into the molecular structures of the above-mentioned various mono (meth) acrylate monomers; lactone-modified mono (meth) acrylate compounds having a (poly) lactone structure introduced into the molecular structure of each of the above mono (meth) acrylate compounds; aliphatic di (meth) acrylate compounds such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, and neopentyl glycol di (meth) acrylate; alicyclic di (meth) acrylate compounds such as 1, 4-cyclohexanedimethanol di (meth) acrylate, norbornanedimethanol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, and tricyclodecanedimethanol di (meth) acrylate; aromatic di (meth) acrylate compounds such as biphenol di (meth) acrylate and bisphenol di (meth) acrylate; polyoxyalkylene-modified di (meth) acrylate compounds in which a (poly) oxyalkylene chain such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, or a (poly) oxytetramethylene chain is introduced into the molecular structure of each of the above di (meth) acrylate compounds; lactone-modified di (meth) acrylate compounds having a (poly) lactone structure introduced into the molecular structure of each of the above di (meth) acrylate compounds; aliphatic tri (meth) acrylate compounds such as trimethylolpropane tri (meth) acrylate and glycerol tri (meth) acrylate; a (poly) oxyalkylene-modified tri (meth) acrylate compound in which a (poly) oxyalkylene chain such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, or a (poly) oxytetramethylene chain is introduced into the molecular structure of the aliphatic 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, ditrimethylolpropane tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate; a (poly) oxyalkylene-modified poly (meth) acrylate compound having a tetrafunctional or higher (poly) oxyalkylene group such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, or a (poly) oxytetramethylene chain introduced into the molecular structure of the aliphatic poly (meth) acrylate compound; and a tetrafunctional or higher lactone-modified poly (meth) acrylate compound having a (poly) lactone structure introduced into the molecular structure of the aliphatic poly (meth) acrylate compound.
The curable resin composition of the present invention may contain an organic solvent for the purpose of adjusting the coating viscosity, etc., and the kind and the addition amount thereof may be appropriately selected and adjusted according to the desired performance.
Examples of the organic solvent include ketone solvents such as methyl ethyl ketone, acetone, and isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, solvent naphtha and the like; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether, and the like; 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 two or more of them may be used in combination.
The curable resin composition of the present invention may further contain various additives such as a curing agent, a curing accelerator, an organic solvent, inorganic fine particles, polymer fine particles, a pigment, an antifoaming agent, a viscosity modifier, a leveling agent, a flame retardant, and a storage stabilizer, if necessary.
The curing agent is not particularly limited as long as it has a functional group capable of reacting with the carboxyl group in the epoxy (meth) acrylate resin composition, and examples thereof include epoxy resins. Examples of the epoxy resin include bisphenol type epoxy resins, phenyl ether type epoxy resins, naphthyl ether type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol novolac type epoxy resins, naphthol-phenol condensed novolac type epoxy resins, naphthol-cresol condensed novolac type epoxy resins, phenol aralkyl type epoxy resins, naphthol aralkyl type epoxy resins, dicyclopentadiene-phenol addition reaction type epoxy resins, and the like. These epoxy resins may be used alone or in combination of two or more. Among these, from the viewpoint of excellent heat resistance of the cured product, novolac-type epoxy resins such as phenol novolac-type epoxy resin, cresol novolac-type epoxy resin, bisphenol novolac-type epoxy resin, naphthol-phenol co-condensed novolac-type epoxy resin, and naphthol-cresol co-condensed novolac-type epoxy resin are preferable, and a resin having a softening point in the range of 50 to 120 ℃ is particularly preferable.
The curing accelerator is a curing agent for accelerating a curing reaction of the curing agent, and when an epoxy resin is used as the curing agent, examples thereof include a phosphorus compound, a tertiary amine, imidazole, an organic acid metal salt, a lewis acid, and an amine complex salt. These curing accelerators may be used alone or in combination of two or more. The amount of the curing accelerator added is preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the curing agent, for example.
The organic solvent is not particularly limited as long as it can dissolve various components such as the epoxy (meth) acrylate resin composition and the 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, solvent naphtha and the like; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether, and the like; 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 two or more of them may be used in combination.
The cured product of the present invention can be obtained by irradiating the curable resin composition with an active energy ray. Examples of the active energy ray include ionizing radiation rays such as ultraviolet rays, electron beams, alpha rays, beta rays, and gamma rays. When ultraviolet rays are used as the active energy rays, irradiation may be performed in an inert gas atmosphere such as nitrogen gas or in an air atmosphere in order to efficiently perform the curing reaction by the ultraviolet rays.
As the ultraviolet light generating source, an ultraviolet lamp is generally used from the viewpoint of practicality and economy. Specific examples thereof include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a gallium lamp, a metal halide lamp, sunlight, and an LED.
The cured product obtained by curing the curable resin composition of the present invention can be suitably used as, for example, a solder resist, an interlayer insulating material, a sealing material, an underfill material, a sealing adhesive layer for a circuit element or the like, and an adhesive layer for an integrated circuit element and a circuit board in applications to semiconductor devices. Further, the present invention can be suitably used for a protective film of a thin film transistor, a protective film of a liquid crystal color filter, a pigment resist layer for a color filter, a resist layer for a black matrix, a spacer, and the like in applications of thin displays represented by LCDs and OELDs.
Examples
The present invention will be specifically described below with reference to examples and comparative examples.
( Example 1: production of epoxy (meth) acrylate resin composition (1) )
344 parts by mass of a bisphenol A epoxy resin ("EPICLONEXA-850 CRP" manufactured by DIC corporation, epoxy equivalent of 172 g/equivalent) was charged into a flask equipped with a thermometer, a stirrer and a reflux condenser, 0.21 part by mass of dibutylhydroxytoluene as an antioxidant and 0.21 part by mass of p-methoxyphenol as a thermal polymerization inhibitor were added, and then 72 parts by mass of acrylic acid and 0.21 part by mass of triphenylphosphine were added to conduct an esterification reaction at 100 ℃ for 10 hours while blowing air. Then, after confirming that the acid value is 1mgKOH/g or less, oxalic acid (pKa) is added 1 (ii) a 1.04 0.42 parts by mass and stirred at 70 ℃ for 3 hours to obtain an epoxy (meth) acrylate resin composition (1). The epoxy (meth) acrylate resin composition (1) has an epoxy equivalent of 445 g/eq and a (meth) acryloyl equivalent of 416 g/eq as resin components. Note that pKa of oxalic acid 1 The values are those described in the "chemistry overview (revision 4 th edition) base II" (codification by the Japanese society of chemistry). Further, the (meth) acryloyl equivalent is a calculated value.
( Example 2: production of epoxy (meth) acrylate resin composition (2) )
344 parts by mass of a bisphenol A epoxy resin ("EPICLONEXA-850 CRP" manufactured by DIC corporation, epoxy equivalent of 172 g/equivalent) was charged into a flask equipped with a thermometer, a stirrer and a reflux condenser, 0.21 part by mass of dibutylhydroxytoluene as an antioxidant and 0.21 part by mass of p-methoxyphenol as a thermal polymerization inhibitor were added, and then 72 parts by mass of acrylic acid and 0.21 part by mass of triphenylphosphine were added to conduct an esterification reaction at 100 ℃ for 10 hours while blowing air. Then, after confirming that the acid value was 1mgKOH/g or less, 0.21 part by mass of oxalic acid was added thereto and the mixture was stirred at 70 ℃ for 3 hours to obtain an epoxy (meth) acrylate resin composition (2). The epoxy equivalent of the resin component of the epoxy (meth) acrylate resin composition (2) is 444 g/eq and the equivalent of the (meth) acryloyl group is 416 g/eq.
( Example 3: production of epoxy (meth) acrylate resin composition (3) )
344 parts by mass of a bisphenol A epoxy resin ("EPICLONEXA-850 CRP" manufactured by DIC corporation, epoxy equivalent of 172 g/equivalent) was charged into a flask equipped with a thermometer, a stirrer and a reflux condenser, 0.21 part by mass of dibutylhydroxytoluene as an antioxidant and 0.21 part by mass of p-methoxyphenol as a thermal polymerization inhibitor were added, and then 72 parts by mass of acrylic acid and 0.21 part by mass of triphenylphosphine were added to conduct an esterification reaction at 100 ℃ for 10 hours while blowing air. Then, after confirming that the acid value was 1mgKOH/g or less, 0.11 part by mass of oxalic acid was added thereto and the mixture was stirred at 70 ℃ for 3 hours to obtain an epoxy (meth) acrylate resin composition (3). The epoxy equivalent of the resin component of the epoxy (meth) acrylate resin composition (3) is 446 g/eq and the equivalent of the (meth) acryloyl group is 416 g/eq.
( Example 4: production of epoxy (meth) acrylate resin composition (4) )
344 parts by mass of a bisphenol A epoxy resin ("EPICLONEXA-850 CRP" manufactured by DIC corporation, epoxy equivalent of 172 g/eq) was charged in a flask equipped with a thermometer, a stirrer and a reflux condenser, 0.21 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.21 parts by mass of p-methoxyphenol as a thermal polymerization inhibitor were added, and then 72 parts by mass of acrylic acid and 0.21 parts by mass of triphenylphosphine were added to carry out an esterification reaction at 100 ℃ for 10 hours while blowing air. Then, after confirming that the acid value was 1mgKOH/g or less, 0.04 parts by mass of oxalic acid was added thereto and the mixture was stirred at 70 ℃ for 3 hours to obtain an epoxy (meth) acrylate resin composition (4). The epoxy equivalent of the resin component of the epoxy (meth) acrylate resin composition (4) is 444 g/equivalent, and the equivalent of the (meth) acryloyl group is 416 g/equivalent.
( Example 5: production of epoxy (meth) acrylate resin composition (5) )
316 parts by mass of bisphenol F epoxy resin ("EPICLONEXA-830 CRP" manufactured by DIC corporation and having an epoxy equivalent of 158 g/equivalent) was charged into a flask equipped with a thermometer, a stirrer and a reflux condenser, 0.19 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.19 parts by mass of p-methoxyphenol as a thermal polymerization inhibitor were added, and then 72 parts by mass of acrylic acid and 0.19 parts by mass of triphenylphosphine were added to conduct an esterification reaction at 100 ℃ for 10 hours while blowing air. Then, after confirming that the acid value was 1mgKOH/g or less, 0.19 part by mass of oxalic acid was added thereto and the mixture was stirred at 70 ℃ for 3 hours to obtain an epoxy (meth) acrylate resin composition (5). The epoxy (meth) acrylate resin composition (5) had an epoxy equivalent of 418 g/eq and an acryl equivalent of 388 g/eq.
( Example 6: production of epoxy (meth) acrylate resin composition (6) )
418 parts by mass of an epoxy resin ("EPICLONHP-820" manufactured by DIC corporation, epoxy equivalent of 209 g/eq) was charged in a flask equipped with a thermometer, a stirrer and a reflux condenser, 0.25 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.25 parts by mass of p-methoxyphenol as a thermal polymerization inhibitor were added, and then 72 parts by mass of acrylic acid and 0.25 parts by mass of triphenylphosphine were added to conduct an esterification reaction at 100 ℃ for 10 hours while blowing air. Then, after confirming that the acid value was 1mgKOH/g or less, 0.25 part by mass of oxalic acid was added thereto and the mixture was stirred at 70 ℃ for 3 hours to obtain an epoxy (meth) acrylate resin composition (6). The epoxy equivalent of the resin component of the epoxy (meth) acrylate resin composition (6) was 585 g/equivalent, and the (meth) acryloyl equivalent was 490 g/equivalent.
( Example 7: production of epoxy (meth) acrylate resin composition (7) )
262 parts by mass of alicyclic epoxy resin COLLOXIDE ("2021P" manufactured by Dacellosolve, epoxy equivalent: 131 g/equivalent), 0.15 part by mass of dibutylhydroxytoluene as an antioxidant and 0.15 part by mass of P-methoxyphenol as a thermal polymerization inhibitor were added to a flask equipped with a thermometer, a stirrer and a reflux condenser, and then 36 parts by mass of acrylic acid and 0.15 part by mass of triphenylphosphine were added to conduct an esterification reaction at 80 ℃ for 10 hours while blowing air. After confirming that the acid value was 1mgKOH/g or less, 0.15 part by mass of oxalic acid was added thereto and the mixture was stirred at 70 ℃ for 3 hours to obtain an epoxy (meth) acrylate resin composition (7). The epoxy equivalent of the resin component of the epoxy (meth) acrylate resin composition (7) was 286 g/eq and the equivalent of the (meth) acryloyl group was 597 g/eq.
( Example 8: production of epoxy (meth) acrylate resin composition (8) )
272 parts by mass of cyclohexanedimethanol diglycidyl ether (epoxy equivalent: 136 g/eq) was added to a flask equipped with a thermometer, a stirrer and a reflux condenser, 0.17 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.17 parts by mass of p-methoxyphenol as a thermal polymerization inhibitor were added, and then 72 parts by mass of acrylic acid and 0.17 parts by mass of triphenylphosphine were added, and esterification reaction was carried out at 100 ℃ for 15 hours while blowing air. After confirming that the acid value was 1mgKOH/g or less, 0.17 part by mass of oxalic acid was added thereto and the mixture was stirred at 70 ℃ for 3 hours to obtain an epoxy (meth) acrylate resin composition (8). The epoxy equivalent of the resin component of the epoxy (meth) acrylate resin composition (8) was 399 g/eq, and the equivalent of the (meth) acryloyl group was 345 g/eq.
( Comparative example 1: production of epoxy (meth) acrylate resin composition (C1) )
In a flask equipped with a thermometer, a stirrer and a reflux condenser, 344 parts by mass of a bisphenol a type epoxy resin ("EPICLONEXA-850 CRP" manufactured by DIC corporation, epoxy equivalent of 172 g/eq) was charged, 0.21 part by mass of dibutylhydroxytoluene as an antioxidant and 0.21 part by mass of p-methoxyphenol as a thermal polymerization inhibitor were added, and then 72 parts by mass of acrylic acid and 0.21 part by mass of triphenylphosphine were added, and esterification reaction was carried out at 100 ℃ for 10 hours while blowing air, to obtain an epoxy (meth) acrylate resin composition (C1). The epoxy equivalent of the resin component of the epoxy (meth) acrylate resin composition (C1) is 443 g/equivalent, and the equivalent of the (meth) acryloyl group is 416 g/equivalent.
( Comparative example 2: production of epoxy (meth) acrylate resin composition (C2) )
344 parts by mass of a bisphenol A epoxy resin ("EPICLONEXA-850 CRP" manufactured by DIC corporation, epoxy equivalent of 172 g/eq) was charged in a flask equipped with a thermometer, a stirrer and a reflux condenser, 0.21 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.21 parts by mass of p-methoxyphenol as a thermal polymerization inhibitor were added, and then 72 parts by mass of acrylic acid and 0.21 parts by mass of triphenylphosphine were added to carry out an esterification reaction at 100 ℃ for 10 hours while blowing air. Then, after confirming that the acid value is 1mgKOH/g or less, malonic acid (pKa) was added 1 (ii) a 2.65 0.42 part by mass and stirred at 70 ℃ for 3 hours to obtain epoxy resinA (meth) acrylate resin composition (C2). The epoxy equivalent of the resin component of the epoxy (meth) acrylate resin composition (C2) is 445 g/eq, and the equivalent of the (meth) acryloyl group is 443 g/eq. Note that pKa of malonic acid is 1 The values are those described in "chemistry review (revision 4 th edition) foundation II" (Japan chemical Association).
The following evaluations were carried out using the epoxy (meth) acrylate resin compositions obtained in the above examples and comparative examples.
[ evaluation method of storage stability ]
The changes in viscosity 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 ℃ were observed.
[ method for evaluating curability ]
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, 200mJ/cm of irradiation was carried out 2 The ultraviolet ray of (3) to obtain a coating film. The surface of the obtained coating film was touched with a finger to determine the presence or absence of tackiness, and the curability was evaluated according to the following criteria.
O: it is not sticky and completely cured.
X: sticky and insufficiently cured.
The evaluation results of the epoxy (meth) acrylate resin compositions (1) to (8) prepared in examples 1 to 8 and the epoxy (meth) acrylate resin compositions (C1) and (C2) prepared in comparative examples 1 and 2 are shown in table 1.
[ Table 1]
In Table 1, "-" indicates that gelation occurred and that the viscosity could not be measured.
Examples 1 to 8 shown in table 1 are examples of the epoxy (meth) acrylate resin composition of the present invention, and it was confirmed that the epoxy (meth) acrylate resin composition of the present invention is less likely to be thickened with time and has excellent storage stability. Further, it was confirmed that the curability was also excellent.
On the other hand, comparative example 1 is an example of an epoxy (meth) acrylate resin composition not using an acidic compound, and it was confirmed that the epoxy (meth) acrylate resin composition was gelled and had significantly insufficient storage stability.
Comparative example 2 was conducted using the first acid dissociation constant (pKa) 1 ) In the case of the epoxy (meth) acrylate resin composition containing an acidic compound of more than 2.5, it was confirmed that the epoxy (meth) acrylate resin composition gelled at 80 ℃ for 24 hours and had insufficient storage stability as in comparative example 1.
Claims (5)
1. An epoxy (meth) acrylate resin composition comprising an epoxy (meth) acrylate resin (A) and an acidic compound (B), wherein the epoxy (meth) acrylate resin (A) comprises an epoxy resin (a 1) and a carboxyl group-containing (meth) acrylate compound (a 2) as essential reaction raw materials, the reaction of the epoxy resin (a 1) with the carboxyl group-containing (meth) acrylate compound (a 2) is carried out in the presence of a basic catalyst comprising a phosphorus compound,
the epoxy (meth) acrylate resin (A) has an epoxy group and a (meth) acryloyl group, and has a (meth) acryloyl equivalent weight in the range of 200 to 800 g/equivalent and an epoxy equivalent weight in the range of 300 to 900 g/equivalent,
the amount of the carboxyl group-containing (meth) acrylate compound (a 2) used is in the range of 0.2 to 0.8 mol per 1 mol of the epoxy resin (a 1),
the acidic compound (B) is an organic acid, and the amount of the acidic compound (B) to be used is 50 parts by mass or more per 100 parts by mass of the basic catalyst,
a first acid dissociation constant (pKa) of the acidic compound (B) 1 ) Is 2.5 or less.
2. A curable resin composition comprising the epoxy (meth) acrylate resin composition according to claim 1 and a photopolymerization initiator.
3. A cured product of the curable resin composition according to claim 2.
4. A process for producing an epoxy (meth) acrylate resin composition comprising an epoxy (meth) acrylate resin (A) obtained by reacting an epoxy resin (a 1) with a carboxyl group-containing (meth) acrylate compound (a 2) in the presence of a basic catalyst, wherein the reaction of the epoxy resin (a 1) with the carboxyl group-containing (meth) acrylate compound (a 2) is carried out in the presence of a basic catalyst, and an acidic compound (B),
the epoxy (meth) acrylate resin (A) has an epoxy group and a (meth) acryloyl group, and has a (meth) acryloyl equivalent weight in the range of 200 to 800 g/equivalent and an epoxy equivalent weight in the range of 300 to 900 g/equivalent,
the amount of the carboxyl group-containing (meth) acrylate compound (a 2) used is in the range of 0.2 to 0.8 mol per 1 mol of the epoxy resin (a 1),
the acidic compound (B) is an organic acid, and the amount of the acidic compound (B) to be used is 50 parts by mass or more per 100 parts by mass of the basic catalyst,
a first acid dissociation constant (pKa) of the acidic compound (B) 1 ) Is 2.5 or less.
5. The method for producing an epoxy (meth) acrylate resin composition according to claim 4 wherein the amount of the basic catalyst used is in the range of 0.01 to 0.5 parts by mass relative to 100 parts by mass of the total of the epoxy resin (a 1) and the carboxyl group-containing (meth) acrylate compound (a 2).
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| KR101521362B1 (en) | 2010-09-22 | 2015-05-18 | 세키스이가가쿠 고교가부시키가이샤 | Curable composition for inkjet, and method for producing electronic component |
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| JP6620923B2 (en) * | 2015-06-05 | 2019-12-18 | Dic株式会社 | (Meth) acrylate resin and resist member |
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| JP2006030449A (en) * | 2004-07-14 | 2006-02-02 | Dainippon Ink & Chem Inc | Active energy ray-curing epoxy (meth)acrylate resin composition and cured product thereof |
| 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 |
| CN106489098A (en) * | 2014-10-30 | 2017-03-08 | 三井化学株式会社 | The manufacture method of display panels, display panels and liquid crystal sealing agent composition |
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| JP6690791B2 (en) | 2020-04-28 |
| JPWO2019098114A1 (en) | 2020-05-28 |
| KR102286872B1 (en) | 2021-08-09 |
| TWI784077B (en) | 2022-11-21 |
| WO2019098114A1 (en) | 2019-05-23 |
| CN111315794A (en) | 2020-06-19 |
| KR20200055110A (en) | 2020-05-20 |
| TW201930388A (en) | 2019-08-01 |
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