TWI782991B - (Meth)acrylate resins containing acid groups and resin materials for solder resist - Google Patents
(Meth)acrylate resins containing acid groups and resin materials for solder resist Download PDFInfo
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- TWI782991B TWI782991B TW107119605A TW107119605A TWI782991B TW I782991 B TWI782991 B TW I782991B TW 107119605 A TW107119605 A TW 107119605A TW 107119605 A TW107119605 A TW 107119605A TW I782991 B TWI782991 B TW I782991B
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- Taiwan
- Prior art keywords
- meth
- acrylate
- acid
- resin
- group
- Prior art date
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- 239000002253 acid Substances 0.000 title claims abstract description 124
- 229920005989 resin Polymers 0.000 title claims abstract description 62
- 239000011347 resin Substances 0.000 title claims abstract description 62
- 229910000679 solder Inorganic materials 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 title claims abstract description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title description 54
- -1 acrylate compound Chemical class 0.000 claims abstract description 71
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 150000001875 compounds Chemical class 0.000 claims abstract description 46
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 31
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 26
- 239000011342 resin composition Substances 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 239000004593 Epoxy Substances 0.000 claims abstract description 14
- 239000011810 insulating material Substances 0.000 claims abstract description 6
- 150000008064 anhydrides Chemical group 0.000 claims description 33
- 125000001931 aliphatic group Chemical group 0.000 claims description 13
- 125000002723 alicyclic group Chemical group 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 11
- 239000005056 polyisocyanate Substances 0.000 claims description 10
- 229920001228 polyisocyanate Polymers 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000003607 modifier Substances 0.000 claims description 3
- 125000004018 acid anhydride group Chemical group 0.000 abstract description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 37
- 239000003822 epoxy resin Substances 0.000 description 28
- 229920000647 polyepoxide Polymers 0.000 description 28
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 23
- 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 18
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 15
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 10
- 229920003986 novolac Polymers 0.000 description 10
- BJINVQNEBGOMCR-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethyl acetate Chemical compound COCCOCCOC(C)=O BJINVQNEBGOMCR-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 8
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 8
- 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 8
- 125000005702 oxyalkylene group Chemical group 0.000 description 8
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 238000007664 blowing Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 230000032050 esterification Effects 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 6
- 150000002596 lactones Chemical class 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 229920000058 polyacrylate Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 239000004843 novolac epoxy resin Substances 0.000 description 5
- 125000006353 oxyethylene group Chemical group 0.000 description 5
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 229920000193 polymethacrylate Polymers 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 3
- 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 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- 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 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
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-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
- UHMARZNHEMRXQH-UHFFFAOYSA-N 3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical class C1=CCCC2C(=O)OC(=O)C21 UHMARZNHEMRXQH-UHFFFAOYSA-N 0.000 description 2
- 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 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- JMMSLMMJRMCXPW-UHFFFAOYSA-N OC.OC.C1CC2CCC1C2 Chemical compound OC.OC.C1CC2CCC1C2 JMMSLMMJRMCXPW-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 2
- XFSBVAOIAHNAPC-WSORPINJSA-N acetylbenzoylaconine Chemical compound O([C@H]1[C@]2(O)C[C@H]3C45[C@@H]6[C@@H]([C@@]([C@H]31)(OC(C)=O)[C@@H](O)[C@@H]2OC)[C@H](OC)C4[C@]([C@@H](C[C@H]5OC)O)(COC)CN6CC)C(=O)C1=CC=CC=C1 XFSBVAOIAHNAPC-WSORPINJSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000005641 methacryl group Chemical group 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 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
- 238000006386 neutralization reaction Methods 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 150000003018 phosphorus compounds Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- 229940116269 uric acid Drugs 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 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
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-N 0.000 description 1
- FDYWJVHETVDSRA-UHFFFAOYSA-N 1,1-diisocyanatobutane Chemical compound CCCC(N=C=O)N=C=O FDYWJVHETVDSRA-UHFFFAOYSA-N 0.000 description 1
- IWTINSUNRUQBBO-UHFFFAOYSA-N 1,2-diphenylethyl 2-methylprop-2-enoate Chemical compound C=1C=CC=CC=1C(OC(=O)C(=C)C)CC1=CC=CC=C1 IWTINSUNRUQBBO-UHFFFAOYSA-N 0.000 description 1
- FWHUTKPMCKSUCV-UHFFFAOYSA-N 1,3-dioxo-3a,4,5,6,7,7a-hexahydro-2-benzofuran-5-carboxylic acid Chemical compound C1C(C(=O)O)CCC2C(=O)OC(=O)C12 FWHUTKPMCKSUCV-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- ATOUXIOKEJWULN-UHFFFAOYSA-N 1,6-diisocyanato-2,2,4-trimethylhexane Chemical compound O=C=NCCC(C)CC(C)(C)CN=C=O ATOUXIOKEJWULN-UHFFFAOYSA-N 0.000 description 1
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 description 1
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- PMUPSYZVABJEKC-UHFFFAOYSA-N 1-methylcyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)CCCCC1C(O)=O PMUPSYZVABJEKC-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-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
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- LESMLVDJJCWZAJ-UHFFFAOYSA-N 2-(diphenylphosphorylmethyl)-1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 LESMLVDJJCWZAJ-UHFFFAOYSA-N 0.000 description 1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
本發明提供一種含有酸基之(甲基)丙烯酸酯樹脂,其特徵為以具有酸基或酸酐基之醯胺醯亞胺樹脂(A)、羥基(甲基)丙烯酸酯化合物(B)、含有(甲基)丙烯醯基之環氧化合物(C)及多羧酸酐(D)作為必須之反應原料;並提供含有該含有酸基之(甲基)丙烯酸酯樹脂的硬化性樹脂組成物、包含前述硬化性樹脂組成物之絕緣材料、阻焊用樹脂材料及阻焊構件。該含有酸基之(甲基)丙烯酸酯樹脂可形成耐熱性及伸長率優良的硬化物。 The present invention provides a kind of (meth)acrylic acid ester resin that contains acid group, it is characterized in that having acid group or acid anhydride group amidoimide resin (A), hydroxyl (meth)acrylate compound (B), containing (Meth) acrylic epoxy compound (C) and polycarboxylic acid anhydride (D) are used as necessary reaction raw materials; and a curable resin composition containing the (meth) acrylate resin containing acid groups is provided, including The insulating material of the curable resin composition, the resin material for solder resist, and the solder resist member. This acid group-containing (meth)acrylate resin can form a cured product excellent in heat resistance and elongation.
Description
本發明係關於硬化物之耐熱性及伸長率高的含有酸基之(甲基)丙烯酸酯樹脂、含有其之硬化性樹脂組成物、包含前述硬化性樹脂組成物之絕緣材料、阻焊用樹脂材料及阻焊構件。 The present invention relates to an acid group-containing (meth)acrylate resin with high heat resistance and elongation of the cured product, a curable resin composition containing the same, an insulating material containing the curable resin composition, and a solder resist resin materials and solder mask components.
在印刷配線基板用之阻焊用樹脂材料中,廣泛使用將環氧樹脂以丙烯酸進行丙烯酸酯化後,並與酸酐反應所得到的含有酸基之環氧丙烯酸酯樹脂。對於阻焊用樹脂材料之性能要求,可列舉下列各種性能:以少許曝光量即可硬化、鹼顯影性優良、硬化物之耐熱性、強度、柔軟性、伸長率、介電特性、基材密著性等優良。 Among solder resist resin materials for printed wiring boards, acid group-containing epoxy acrylate resins obtained by acrylated epoxy resins with acrylic acid and reacted with acid anhydrides are widely used. For the performance requirements of resin materials for solder resist, the following properties can be listed: hardening with a small amount of exposure, excellent alkali developability, heat resistance of hardened products, strength, flexibility, elongation, dielectric properties, substrate density, etc. Good adhesion and so on.
就先前所知之阻焊用樹脂材料而言,已知有酚醛清漆型環氧樹脂與丙烯酸及四氫酞酸酐反應所得到的含有酸基之環氧丙烯酸酯樹脂(參照下述專利文獻1)。專利文獻1記載之含有酸基之環氧丙烯酸酯樹脂,起因於為反應原料之酚醛清漆型環氧樹脂,具有硬化物之耐熱性高等特徴,然而要應對最近的市場要求仍嫌不夠充分。又,由於硬化物之伸長率非常低,有硬化物容易產生龜裂,可靠性差的問題。 Among the conventionally known resin materials for solder resist, there is known an acid group-containing epoxy acrylate resin obtained by reacting a novolak-type epoxy resin with acrylic acid and tetrahydrophthalic anhydride (see
專利文獻1 日本特開昭61-243869號公報
因此,本發明所欲解決之課題,為提供一種硬化物之耐熱性及伸長率高的含有酸基之(甲基)丙烯酸酯樹脂、含有其之硬化性樹脂組成物、包含前述硬化性樹脂組成物之絕緣材料、阻焊用樹脂材料及阻焊構件。 Therefore, the problem to be solved by the present invention is to provide an acid group-containing (meth)acrylate resin with high heat resistance and elongation of the cured product, a curable resin composition containing the same, and a composition comprising the aforementioned curable resin. Insulation materials for objects, resin materials for solder resist and solder resist components.
本發明人等為解決上述課題而進行專心檢討之結果,發現使醯胺醯亞胺樹脂與羥基(甲基)丙烯酸酯及含有(甲基)丙烯醯基之環氧化合物反應,導入(甲基)丙烯醯基,進一步與多羧酸酐反應所得到的含有酸基之(甲基)丙烯酸酯樹脂,硬化物之耐熱性及伸長率非常高,於是完成本發明。 As a result of earnest investigations by the present inventors in order to solve the above-mentioned problems, it was found that by reacting an amidoimide resin with a hydroxy (meth)acrylate and an epoxy compound containing a (meth)acryl group, the introduction of (methyl) ) acryl group, further reaction with polycarboxylic acid anhydride to obtain (meth)acrylate resin containing acid groups, the heat resistance and elongation of the hardened product are very high, so the present invention has been completed.
亦即,本發明係關於以具有酸基或酸酐基之醯胺醯亞胺樹脂(A)、羥基(甲基)丙烯酸酯化合物(B)、含有(甲基)丙烯醯基之環氧化合物(C)及多羧酸酐(D)作為必需之反應原料的含有酸基之(甲基)丙烯酸酯樹脂。 That is, the present invention relates to the amidoimide resin (A) having an acid group or an acid anhydride group, a hydroxyl (meth)acrylate compound (B), an epoxy compound containing a (meth)acryl group ( C) and polycarboxylic acid anhydride (D) as an acid group-containing (meth)acrylate resin as necessary reaction raw materials.
再者,本發明係關於一種硬化性樹脂組成物,其含有前述含有酸基之(甲基)丙烯酸酯樹脂及光聚合起始劑。 Furthermore, the present invention relates to a curable resin composition comprising the above-mentioned acid group-containing (meth)acrylate resin and a photopolymerization initiator.
再者,本發明係關於前述硬化性樹脂組成物之硬化物。 Furthermore, the present invention relates to a cured product of the aforementioned curable resin composition.
再者,本發明係關於包含前述硬化性樹脂組成物之絕緣材料。 Furthermore, the present invention relates to an insulating material comprising the aforementioned curable resin composition.
再者,本發明係關於包含前述硬化性樹脂組成物之阻焊用樹脂材料。 Furthermore, this invention relates to the resin material for solder resists containing the said curable resin composition.
再者,本發明係關於包含前述阻焊用樹脂材料之阻焊構件。 Furthermore, this invention relates to the solder resist member containing the said resin material for solder resists.
若依據本發明,可提供硬化物之耐熱性及伸長率高的含有酸基之(甲基)丙烯酸酯樹脂、含有其之硬化性樹脂組成物、包含前述硬化性樹脂組成物之絕緣材料、阻焊用樹脂材料及阻焊構件。 According to the present invention, it is possible to provide an acid group-containing (meth)acrylate resin having high heat resistance and elongation of the cured product, a curable resin composition containing the same, an insulating material including the curable resin composition, and a barrier material. Soldering resin materials and solder resist components.
圖1為實施例1所得到的含有酸基之(甲基)丙烯酸酯樹脂(1)的GPC圖。 Fig. 1 is the GPC graph of the (meth)acrylate resin (1) containing acid groups obtained in Example 1.
以下,詳細說明本發明。 Hereinafter, the present invention will be described in detail.
本發明的含有酸基之(甲基)丙烯酸酯樹脂,係以具有酸基或酸酐基之醯胺醯亞胺樹脂(A)、羥基(甲基)丙烯酸酯化合物(B)、含有(甲基)丙烯醯基之環氧化合物(C)及多羧酸酐(D)作為必需的反應原料。 The acid group-containing (meth)acrylate resin of the present invention is based on the amidoimide resin (A) with acid group or acid anhydride group, hydroxyl (meth)acrylate compound (B), containing (methyl) ) acryl-based epoxy compound (C) and polycarboxylic acid anhydride (D) as necessary reaction raw materials.
在本發明中,(甲基)丙烯酸酯樹脂意指分子中具有丙烯醯基、甲基丙烯醯基、或此兩者之樹脂。又,(甲基)丙烯醯基意指丙烯醯基、甲基丙烯醯基之一者或兩者,(甲基)丙烯酸酯為丙烯酸酯及甲基丙烯酸酯之總稱。 In the present invention, a (meth)acrylate resin means a resin having an acryl group, a methacryl group, or both in a molecule. In addition, (meth)acryl group means one or both of acryl group and methacryl group, and (meth)acrylate is a generic term for acrylate and methacrylate.
前述具有酸基或酸酐基之醯胺醯亞胺樹脂(A),可為只具有酸基或酸酐基任一者,亦可兼具兩者。其中,從與前述羥基(甲基)丙烯酸酯化合物(B)或前述含有(甲基)丙烯醯基之環氧化合物(C)之反應性或反應控制的觀點而言,以具有酸酐基為較佳,以具有酸基及酸酐基兩者為較佳。前述醯胺醯亞胺樹脂(A)之酸值,以中性條件下,亦即,於不使酸酐基開環之條件下的測定值係在60~350mgKOH/g之範圍為較佳。另一方面,於水存在下等使酸酐基開環之條件下的測定值係在61~360mgKOH/g之範圍為較佳。 The aforementioned amidoimide resin (A) having an acid group or an acid anhydride group may have either only an acid group or an acid anhydride group, or may have both. Among them, from the viewpoint of reactivity or reaction control with the aforementioned hydroxy (meth)acrylate compound (B) or the aforementioned (meth)acryl group-containing epoxy compound (C), it is preferable to have an acid anhydride group. Preferably, it is more preferred to have both acid groups and acid anhydride groups. The acid value of the aforementioned amidoimide resin (A) is preferably in the range of 60 to 350 mgKOH/g under neutral conditions, that is, under the condition that the acid anhydride group is not ring-opened. On the other hand, it is preferable that the measured value is in the range of 61 to 360 mgKOH/g under conditions such as the presence of water to open the acid anhydride group.
前述醯胺醯亞胺樹脂(A)之具體結構或製法無特別限定,可廣泛地使用一般之醯胺醯亞胺樹脂等。具體而言,可列舉以多異氰酸酯化合物(a1)及多羧酸或其酸酐(a2)作為反應原料者。 The specific structure or production method of the aforementioned amidoimide resin (A) is not particularly limited, and general amidoimide resins and the like can be widely used. Specifically, what uses a polyisocyanate compound (a1), a polycarboxylic acid, or its anhydride (a2) as a reaction raw material is mentioned.
前述多異氰酸酯化合物(a1),例如,可列舉丁烷二異氰酸酯、六亞甲基二異氰酸酯、2,2,4-三甲基六亞甲基二異氰酸酯、2,4,4-三甲基六亞甲基二異氰酸酯等脂肪族二異氰酸酯化合物;降莰烷二異氰酸酯、異佛爾酮二異氰酸酯、氫化二甲苯二異氰酸酯、氫化二苯基甲烷二異氰酸酯等脂環式二異氰酸酯化合物;甲伸苯基 二異氰酸酯、二甲苯二異氰酸酯、四甲基二甲苯二異氰酸酯、二苯基甲烷二異氰酸酯、1,5-萘二異氰酸酯、4,4’-二異氰酸基-3,3’-二甲基聯苯、聯鄰甲苯胺二異氰酸酯等芳香族二異氰酸酯化合物;具有下述結構式(1)所示之重覆結構的多亞甲基多苯基多異氰酸酯;此等之三聚異氰酸酯改質體、縮二脲改質體、脲甲酸酯改質體等。此等可個別單獨使用,亦可將2種以上併用。 The aforementioned polyisocyanate compound (a1) includes, for example, butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, Aliphatic diisocyanate compounds such as methylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate; methylene diisocyanate Diisocyanate, xylene diisocyanate, tetramethylxylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanato-3,3'-dimethyl Aromatic diisocyanate compounds such as biphenyl and bi-o-toluidine diisocyanate; polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following structural formula (1); modified isocyanates of these , biuret modified body, alloformate modified body, etc. These may be used individually or in combination of 2 or more types.
[式中,R1各自獨立,為氫原子、碳原子數1~6之烴基之任一者;R2各自獨立,為碳原子數1~4之烷基、或經由附加*記號之亞甲基與結構式(1)所示之結構部位連結之結合點的任一者;l為0或1~3之整數,m為1以上之整數]。 [In the formula, R 1 are each independently a hydrogen atom or any one of a hydrocarbon group with 1 to 6 carbon atoms; R 2 are each independently an alkyl group with 1 to 4 carbon atoms, or a methylene group marked with * Any of the bonding points where the group is connected to the structural site represented by the structural formula (1); l is 0 or an integer of 1 to 3, and m is an integer of 1 or more].
此等之中,從成為具有高溶劑溶解性的含有酸基之(甲基)丙烯酸酯樹脂的觀點而言,以前述脂環式二異氰酸酯化合物或其改質體為較佳,以脂環式二異氰酸酯或其三聚異氰酸酯改質體為較佳。又,就成為硬化物之伸長率非常高的含有酸基之(甲基)丙烯酸酯樹脂的觀點而言,以前述脂肪族二異氰酸酯化合物或其改質體為較佳,以脂肪族二異氰酸酯或其三聚異氰酸酯改質體為較佳。再者,相對於前述多異氰酸酯化合物(a1)之 總質量,前述脂環式二異氰酸酯化合物或其改質體與前述脂肪族二異氰酸酯化合物或其改質體之合計質量的比率,以70質量%以上為較佳,以90質量%以上為較佳。又,在將前述脂環式二異氰酸酯化合物或其改質體與前述脂肪族二異氰酸酯化合物或其改質體併用的情況,兩者之質量比以30/70~70/30之範圍為較佳。 Among them, from the viewpoint of being an acid group-containing (meth)acrylate resin having high solvent solubility, the aforementioned alicyclic diisocyanate compound or a modified product thereof is preferable, and the alicyclic diisocyanate compound or its modified form is preferable. Diisocyanate or its modified form of isocyanate is preferable. Also, from the viewpoint of an acid group-containing (meth)acrylate resin having a very high elongation rate of the cured product, the aforementioned aliphatic diisocyanate compound or a modified product thereof is preferable, and the aliphatic diisocyanate or Its modified isocyanate is preferred. In addition, the ratio of the total mass of the aforementioned alicyclic diisocyanate compound or a modified product thereof to the aforementioned aliphatic diisocyanate compound or a modified product thereof relative to the total mass of the aforementioned polyisocyanate compound (a1) is 70% by mass. The above is more preferable, and more than 90 mass % is more preferable. Also, when the alicyclic diisocyanate compound or its modified product is used in combination with the aliphatic diisocyanate compound or its modified product, the mass ratio of the two is preferably in the range of 30/70 to 70/30. .
前述多羧酸或其酸酐(a2),只要為分子結構中具有複數個羧基之化合物或其酸酐即可,具體結構則不在意,可使用各式各樣的化合物。又,多羧酸或其酸酐(a2)可分別單獨使用,亦可將2種以上併用。再者,由於醯胺醯亞胺樹脂(A)具有醯胺基及醯亞胺基兩者,必須在系統中存在羧基及酸酐基兩者,而在本發明中,可使用分子中具有羧基及酸酐基兩者之化合物,亦可將具有羧基之化合物與具有酸酐基之化合物併用。 The aforementioned polycarboxylic acid or its anhydride (a2) does not matter the specific structure as long as it has a plurality of carboxyl groups in its molecular structure or its anhydride, and various compounds can be used. Moreover, polycarboxylic acid or its acid anhydride (a2) may be used individually, respectively, and may use 2 or more types together. Furthermore, since amidoimide resin (A) has both amido and imide groups, there must be both carboxyl and acid anhydride groups in the system, and in the present invention, it is possible to use molecules with carboxyl and acid anhydride groups. As for the compound of both acid anhydride groups, the compound which has a carboxyl group and the compound which has an acid anhydride group can also be used together.
就前述多羧酸或其酸酐(a2)之一例而言,例如,可列舉脂肪族多羧酸化合物或其酸酐、脂環式多羧酸化合物或其酸酐、芳香族多羧酸化合物或其酸酐等。關於前述脂肪族多羧酸化合物或其酸酐,脂肪族烴基可為直鏈型及分枝型的任一種,結構中亦可具有不飽和鍵。就前述脂肪族多羧酸化合物或其酸酐的一例而言,例如,可列舉草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、馬來酸、富馬酸、檸康酸、衣康酸、戊烯二酸、1,2,3,4-丁烷四羧酸、及此等之酸酐等。 Examples of the aforementioned polycarboxylic acid or its anhydride (a2) include, for example, an aliphatic polycarboxylic acid compound or an anhydride thereof, an alicyclic polycarboxylic acid compound or an anhydride thereof, an aromatic polycarboxylic acid compound or an anhydride thereof Wait. Regarding the above-mentioned aliphatic polycarboxylic acid compound or its anhydride, the aliphatic hydrocarbon group may be any of a straight-chain type and a branched type, and may have an unsaturated bond in the structure. As an example of the aforementioned aliphatic polycarboxylic acid compound or its anhydride, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, Diacid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, and their anhydrides.
關於前述脂環式多羧酸化合物或其酸酐,本發明中,以羧基或酸酐基與脂環結構結合者當作脂環式多羧酸化合物或其酸酐,不管其以外之結構部位有無芳香環。就前述脂環式多羧酸化合物或其酸酐之一例而言,例如,可列舉四氫酞酸、六氫酞酸、甲基六氫酞酸、環己烷三羧酸、環己烷四羧酸、雙環[2.2.1]庚烷-2,3-二羧酸、雙環[2.2.1]庚烷-2,3-二羧酸甲酯、4-(2,5-二側氧基四氫呋喃-3-基)-1,2,3,4-四氫萘-1,2-二羧酸、及此等之酸酐等。 Regarding the aforementioned alicyclic polycarboxylic acid compounds or their anhydrides, in the present invention, those with carboxyl or acid anhydride groups combined with an alicyclic structure are regarded as alicyclic polycarboxylic acid compounds or their anhydrides, regardless of whether there are aromatic rings in other structural parts. . As an example of the aforementioned alicyclic polycarboxylic acid compound or an anhydride thereof, for example, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylate methyl ester, 4-(2,5-dioxo-tetrahydrofuran -3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, and their anhydrides.
就前述芳香族多羧酸化合物或其酸酐之一例而言,例如,可列舉酞酸、偏苯三酸、焦蜜石酸、萘二羧酸、萘三羧酸、萘四羧酸、聯苯二羧酸、聯苯三羧酸、聯苯四羧酸、二苯基酮四羧酸等。 As an example of the aforementioned aromatic polycarboxylic acid compound or its anhydride, for example, phthalic acid, trimellitic acid, pyromelite, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl Dicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, diphenylketonetetracarboxylic acid, and the like.
其中,從成為耐熱性特高的含有酸基之(甲基)丙烯酸酯樹脂而言,以前述脂環式多羧酸化合物或其酸酐、或前述芳香族多羧酸化合物或其酸酐為較佳。又,從能有效率地製造前述醯胺醯亞胺樹脂(A)而言,以使用分子結構中具有羧基及酸酐基兩者的三羧酸酐為較佳,以使用環己烷三羧酸酐或偏苯三酸酐為特佳。再者,相對於前述多羧酸或其酸酐(a2)之總質量,脂環式三羧酸酐與芳香族三羧酸酐之合計量的比率以70質量%以上為較佳,以90質量%以上為較佳。 Among them, the above-mentioned alicyclic polycarboxylic acid compound or its anhydride, or the above-mentioned aromatic polycarboxylic acid compound or its anhydride are preferable in terms of being an acid group-containing (meth)acrylate resin having particularly high heat resistance. . Also, from the viewpoint of efficiently producing the aforementioned amidoimide resin (A), it is preferable to use tricarboxylic anhydrides having both carboxyl and acid anhydride groups in the molecular structure, and to use cyclohexanetricarboxylic anhydride or Trimellitic anhydride is particularly preferred. Furthermore, the ratio of the total amount of the alicyclic tricarboxylic anhydride to the aromatic tricarboxylic anhydride is preferably 70% by mass or more, and 90% by mass or more with respect to the total mass of the polycarboxylic acid or its anhydride (a2). is better.
在前述醯胺醯亞胺樹脂(A)以前述多異氰酸酯化合物(a1)及前述多羧酸或其酸酐(a2)做為反應原料之情況,依據期望之樹脂性能等,可將此等以外之反應 原料併用。在此情況,從本發明達到之效果可充分發揮而言,相對於醯胺醯亞胺樹脂(A)之反應原料總質量,前述多異氰酸酯化合物(a1)與前述多羧酸或其酸酐(a2)之合計質量的比率以90質量%以上為較佳,以95質量%以上為較佳。 In the case where the aforementioned amidoimide resin (A) uses the aforementioned polyisocyanate compound (a1) and the aforementioned polycarboxylic acid or its anhydride (a2) as reaction raw materials, depending on desired resin properties, etc., other than these may be used. The reaction raw materials are used together. In this case, the effect achieved from the present invention can be fully brought into play, relative to the total mass of the reaction raw materials of the amidoimide resin (A), the aforementioned polyisocyanate compound (a1) and the aforementioned polycarboxylic acid or its anhydride (a2 ) is preferably at least 90% by mass, more preferably at least 95% by mass.
在前述醯胺醯亞胺樹脂(A)以多異氰酸酯化合物(a1)及多羧酸或其酸酐(a2)做為反應原料之情況,其製造方法無特別限定,可藉由任何方法製造。例如,可藉由與一般醯胺醯亞胺樹脂同樣之方法製造。具體而言,可列舉相對於1莫耳之前述多異氰酸酯化合物(a1)所具有的異氰酸基,使用0.8~1.2莫耳之前述多羧酸或其酸酐(a2),於約120~180℃之溫度條件下攪拌混合,使其反應的方法。 When the aforementioned amidoimide resin (A) uses polyisocyanate compound (a1) and polycarboxylic acid or its anhydride (a2) as reaction raw materials, its production method is not particularly limited, and can be produced by any method. For example, it can be manufactured by the same method as general amidoimide resin. Specifically, 0.8 to 1.2 mol of the aforementioned polycarboxylic acid or its anhydride (a2) is used with respect to 1 mol of the isocyanate group contained in the aforementioned polyisocyanate compound (a1), at about 120 to 180 The method of stirring and mixing at a temperature of ℃ to make it react.
反應可視需要於有機溶劑中進行。所用之有機溶劑之選擇,可依據反應原料及為生成物的含有酸基之(甲基)丙烯酸酯樹脂之溶解性或反應溫度條件等而適宜選擇,例如,可列舉甲基乙基酮、丙酮、二甲基甲醯胺、甲基異丁基酮、甲氧基丙醇、環己酮、甲基賽路蘇、二伸烷基二醇單烷基醚乙酸酯、二伸烷基二醇乙酸酯等。此等可個別單獨使用,亦可形成2種以上之混合溶劑。有機溶劑之使用量,從反應效率變得良好而言,相對於反應原料之合計質量,以於約0.1~5倍量之範圍使用為較佳。 The reaction may be carried out in an organic solvent if necessary. The selection of the organic solvent used can be appropriately selected according to the solubility of the reaction raw materials and the acid group-containing (meth)acrylate resin or the reaction temperature conditions of the product, for example, methyl ethyl ketone, acetone, etc. , Dimethylformamide, Methyl Isobutyl Ketone, Methoxypropanol, Cyclohexanone, Methyl Cellusu, Dialkylene Glycol Monoalkyl Ether Acetate, Dialkylene Di alcohol acetate etc. These may be used individually, or may form the mixed solvent of 2 or more types. The amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction raw materials in order to improve the reaction efficiency.
前述羥基(甲基)丙烯酸酯化合物(B),只要為分子結構中具有羥基及(甲基)丙烯醯基之化合物即 可,其他之具體結構無特別限定,可使用各式各樣之化合物。又,前述羥基(甲基)丙烯酸酯化合物(B)可分別單獨使用,亦可將2種以上併用。其中,從反應之控制變得容易而言,以單羥基(甲基)丙烯酸酯化合物為較佳。就其一例而言,例如,可列舉(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸羥基丙酯、三羥甲基丙烷二(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、二-三羥甲基丙烷三(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯等羥基(甲基)丙烯酸酯化合物;在前述各種羥基(甲基)丙烯酸酯化合物之分子結構中導入(聚)氧伸乙基鏈、(聚)氧伸丙基鏈、(聚)氧四亞甲基鏈等(聚)氧伸烷基鏈的(聚)氧伸烷基改質體;在前述各種羥基(甲基)丙烯酸酯化合物之分子結構中導入(聚)內酯結構的內酯改質體等。此等可分別單獨使用,亦可將2種以上併用。其中,從成為硬化物之耐熱性與伸長率之平衡優良的含有酸基之(甲基)丙烯酸酯樹脂而言,以分子量為1,000以下者為較佳。又,在前述羥基(甲基)丙烯酸酯化合物(B)為前述氧伸烷基改質體或內酯改質體之情況,重量平均分子量(Mw)以1,000以下為較佳。 The above-mentioned hydroxy (meth)acrylate compound (B) is not particularly limited as long as it has a hydroxyl group and a (meth)acryl group in its molecular structure, and other specific structures can be used. Various compounds can be used. Moreover, the said hydroxy (meth)acrylate compound (B) may be used individually, respectively, and may use 2 or more types together. Among them, monohydroxy (meth)acrylate compounds are preferred in terms of easy control of the reaction. As an example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane di(meth)acrylate, neopentylthritol tri(methyl) Hydroxy (meth)acrylate compounds such as acrylates, di-trimethylolpropane tri(meth)acrylate, dipenteoerythritol penta(meth)acrylate; in the aforementioned various hydroxy(meth)acrylates A (poly)oxyalkylene group that introduces (poly)oxyethylene chains, (poly)oxypropylene chains, (poly)oxytetramethylene chains, etc. (poly)oxyalkylene chains into the molecular structure of a compound Modifiers; lactone modifiers that introduce (poly)lactone structures into the molecular structures of the aforementioned various hydroxy (meth)acrylate compounds, etc. These may be used individually, respectively, and may use 2 or more types together. Among them, the acid group-containing (meth)acrylate resin having a good balance between heat resistance and elongation as a cured product preferably has a molecular weight of 1,000 or less. Moreover, when the said hydroxy (meth)acrylate compound (B) is the said oxyalkylene modified body or lactone modified body, it is preferable that a weight average molecular weight (Mw) is 1,000 or less.
前述含有(甲基)丙烯醯基之環氧化合物(C),只要分子結構中具有(甲基)丙烯醯基及環氧基,其他之具體結構無特別限定,可使用各式各樣之化合物。又,前述含有(甲基)丙烯醯基之環氧化合物(C)可分別單獨使用,亦可將2種以上併用。其中,從反應之控制變得容易而言,以單環氧化合物為較佳。就其一例而言, 例如,可列舉(甲基)丙烯酸環氧丙酯、(甲基)丙烯酸4-羥基丁酯環氧丙基醚、(甲基)丙烯酸環氧環己基甲酯等含有環氧丙基的(甲基)丙烯酸酯單體;二羥基苯二環氧丙基醚、二羥基萘二環氧丙基醚、聯苯酚二環氧丙基醚、雙酚二環氧丙基醚等二環氧丙基醚化合物之單(甲基)丙烯酸酯化物等。其中,從成為硬化物之耐熱性與伸長率之平衡優良的含有酸基之(甲基)丙烯酸酯樹脂而言,以前述含有環氧丙基的(甲基)丙烯酸酯單體為較佳。又,其分子量以500以下為較佳。再者,相對於前述含有(甲基)丙烯醯基之環氧化合物(C)之總質量,前述含有環氧丙基的(甲基)丙烯酸酯單體之比率以70質量%以上為較佳,以90質量%以上為較佳。 The aforementioned epoxy compound (C) containing a (meth)acryl group, as long as it has a (meth)acryl group and an epoxy group in the molecular structure, other specific structures are not particularly limited, and various compounds can be used . Moreover, the said (meth)acryl group containing epoxy compound (C) may be used individually, respectively, and may use 2 or more types together. Among these, monoepoxides are preferred in terms of ease of reaction control. As an example, for example, glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, epoxycyclohexylmethyl (meth)acrylate, etc. containing ring Oxypropyl (meth)acrylate monomers; Dihydroxybenzene Diglycidyl Ether, Dihydroxynaphthalene Diglycidyl Ether, Biphenol Diglycidyl Ether, Bisphenol Diglycidyl Ether Diglycidyl ether compounds such as mono(meth)acrylate compounds, etc. Among them, the above-mentioned glycidyl group-containing (meth)acrylate monomer is preferable from the viewpoint of an acid group-containing (meth)acrylate resin having an excellent balance between heat resistance and elongation as a cured product. Also, its molecular weight is preferably 500 or less. Furthermore, with respect to the total mass of the epoxy compound (C) containing the (meth)acryl group, the ratio of the (meth)acrylate monomer containing the glycidyl group is preferably 70% by mass or more , preferably more than 90% by mass.
前述多羧酸酐(D),例如,可列舉就前述多羧酸或其酸酐(a2)而言所例示之各化合物中的酸酐等。又,前述多羧酸酐(D)可分別單獨使用,亦可將2種以上併用。其中,從成為除硬化物之耐熱性或伸長率外,顯影性亦優良的含有酸基之(甲基)丙烯酸酯化合物而言,以前述脂肪族多羧酸酐或前述脂環式多羧酸酐為較佳,以脂肪族二羧酸酐或脂環式二羧酸酐為更佳。 As said polycarboxylic acid anhydride (D), the acid anhydride etc. in each compound which were illustrated about the said polycarboxylic acid or its anhydride (a2) are mentioned, for example. Moreover, said polycarboxylic acid anhydride (D) may be used individually, respectively, and may use 2 or more types together. Among them, the aforementioned aliphatic polycarboxylic acid anhydride or the aforementioned alicyclic polycarboxylic acid anhydride is used as an acid group-containing (meth)acrylate compound having excellent developability in addition to the heat resistance and elongation of the cured product. Preferably, aliphatic dicarboxylic acid anhydride or alicyclic dicarboxylic acid anhydride is more preferred.
本發明之含有酸基之(甲基)丙烯酸酯樹脂,依據期望之樹脂性能等,除前述具有酸基或酸酐基之醯胺醯亞胺樹脂(A)、羥基(甲基)丙烯酸酯化合物(B)、含有(甲基)丙烯醯基之環氧化合物(C)及多羧酸酐(D)之外,亦可併用其他之反應原料。在此情況,從本發明所達到之效果可充分地發揮而言,相對於含有酸基之(甲基) 丙烯酸酯樹脂之反應原料總質量,前述(A)~(D)成分之合計質量的比率以80質量%以上為較佳,以90質量%以上為較佳。 The acid group-containing (meth)acrylate resin of the present invention, according to desired resin properties, etc., except the aforementioned amidoimide resin (A) with acid group or acid anhydride group, hydroxyl (meth)acrylate compound ( B), besides (meth)acryl group-containing epoxy compound (C) and polycarboxylic acid anhydride (D), other reaction raw materials can also be used in combination. In this case, from the effect achieved by the present invention can be fully brought into play, relative to the total mass of the reaction raw materials of the acid group-containing (meth)acrylate resin, the total mass of the aforementioned (A) ~ (D) components The ratio is preferably at least 80% by mass, more preferably at least 90% by mass.
前述含有酸基之(甲基)丙烯酸酯樹脂之製造方法無特別限定,可藉由任何方法製造。例如,可藉由使反應原料全部一併反應之方法製造,亦可藉由使反應原料依序反應之方法製造。其中,從反應之控制容易的觀點而言,以藉由包含下述步驟之方法製造為較佳,此等步驟為:使前述醯胺醯亞胺樹脂(A)與前述羥基(甲基)丙烯酸酯化合物(B)反應(步驟1)、使步驟1之生成物與前述含有(甲基)丙烯醯基之環氧化合物(C)反應(步驟2)、使步驟2之生成物與前述多羧酸酐(D)反應。 The manufacturing method of the said acid group containing (meth)acrylate resin is not specifically limited, It can manufacture by any method. For example, it may be produced by a method of reacting all the reaction raw materials at once, or may be produced by a method of sequentially reacting the reaction raw materials. Among them, from the viewpoint of easy control of the reaction, it is preferable to produce by a method including the steps of: making the aforementioned amidoimide resin (A) and the aforementioned hydroxy (meth)acrylic acid Reaction of ester compound (B) (step 1), reaction of the product of
關於前述步驟1,於前述醯胺醯亞胺樹脂(A)與前述羥基(甲基)丙烯酸酯化合物(B)之反應中,主要係使前述醯胺醯亞胺樹脂(A)中之酸基或酸酐基與羥基(甲基)丙烯酸酯化合物(B)中之羥基反應。由於前述羥基(甲基)丙烯酸酯化合物(B)與酸酐基之反應性特別優良,如前述,前述醯胺醯亞胺樹脂(A)以具有酸酐基為較佳。前述醯胺醯亞胺樹脂(A)與前述羥基(甲基)丙烯酸酯化合物(B)之反應比率,相對於前述醯胺醯亞胺樹脂(A)中之酸基及酸酐基之合計,以使用0.9~1.1莫耳之範圍的前述羥基(甲基)丙烯酸酯化合物(B)為較佳。尤其,相對於前述醯胺醯亞胺樹脂(A)中之酸酐基之合計,以使用0.9~1.1莫耳之範圍的前述羥基(甲基)丙烯酸酯化合物(B)為較佳。前述醯胺醯亞胺樹脂(A)中之酸酐基之含量,可 從如前述2之酸值之測定值的差異,亦即,使酸酐基開環之條件之酸值,及不使酸酐基開環之條件之酸值的差異算出。 Regarding the
前述醯胺醯亞胺樹脂(A)與前述羥基(甲基)丙烯酸酯化合物(B)之反應,例如,可於適當之酯化觸媒存在下,在約90~140℃之溫度條件下加熱攪拌而進行。前述酯化觸媒,例如,可列舉三甲基膦、三丁基膦、三苯基膦等磷化合物;三乙基胺、三丁基胺、二甲基苄基胺等胺化合物;2-甲基咪唑、2-十七基咪唑、2-乙基-4-甲基咪唑、1-苄基-2-甲基咪唑、1-異丁基-2-甲基咪唑等咪唑化合物等。此等可分別單獨使用,亦可將2種以上併用。觸媒之添加量,相對於反應原料之合計質量,以0.001~5質量份之範圍使用為較佳。 The reaction between the aforementioned amidoimide resin (A) and the aforementioned hydroxy (meth)acrylate compound (B) can be, for example, heated at a temperature of about 90~140°C in the presence of an appropriate esterification catalyst While stirring. The aforementioned esterification catalysts, for example, phosphorus compounds such as trimethylphosphine, tributylphosphine, and triphenylphosphine; amine compounds such as triethylamine, tributylamine, and dimethylbenzylamine; 2- imidazole compounds such as methylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-isobutyl-2-methylimidazole, and the like. These may be used individually, respectively, and may use 2 or more types together. The amount of catalyst added is preferably within the range of 0.001 to 5 parts by mass relative to the total mass of the reaction raw materials.
反應可視需要於有機溶劑中進行。所用的有機溶劑之選擇,可依據反應原料及為生成物之含有酸基之(甲基)丙烯酸酯樹脂的溶解性或反應溫度條件等而適宜選擇,例如,可列舉甲基乙基酮、丙酮、二甲基甲醯胺、甲基異丁基酮、甲氧基丙醇、環己酮、甲基賽路蘇、二伸烷基二醇單烷基醚乙酸酯、二伸烷基二醇乙酸酯等。此等可分別單獨使用,亦可形成2種以上之混合溶劑。在前述醯胺醯亞胺樹脂(A)之製造與步驟1連續地進行的情況,亦可於前述醯胺醯亞胺樹脂(A)之製造所用的有機溶劑中原樣繼續反應。 The reaction may be carried out in an organic solvent if necessary. The selection of the organic solvent used can be appropriately selected according to the reaction raw materials and the solubility or reaction temperature conditions of the acid group-containing (meth)acrylate resin as the product, for example, methyl ethyl ketone, acetone, etc. , Dimethylformamide, Methyl Isobutyl Ketone, Methoxypropanol, Cyclohexanone, Methyl Cellusu, Dialkylene Glycol Monoalkyl Ether Acetate, Dialkylene Di alcohol acetate etc. These may be used individually, respectively, and may form the mixed solvent of 2 or more types. When the production of the aforementioned amidoimide resin (A) is performed continuously with
關於前述步驟2,前述含有(甲基)丙烯醯基之環氧化合物(C)主要與前述步驟1之生成物中的羧基反 應。其反應比率,相對於步驟1之生成物中之羧基,以使用0.5~1.2莫耳之範圍的前述含有(甲基)丙烯醯基之環氧化合物(C)為較佳,以使用0.9~1.1莫耳之範圍為更佳。步驟2之反應,例如,可於適當之酯化觸媒存在下,在約90~140℃之溫度條件下加熱攪拌而進行。在將步驟1及步驟2連續進行之情況,酯化觸媒可不追加,亦可適宜追加。又,反應可視需要於有機溶劑中進行。 Regarding the aforementioned step 2, the aforementioned (meth)acryl group-containing epoxy compound (C) mainly reacts with the carboxyl group in the product of the
關於前述步驟3,前述多羧酸酐(D)主要與前述步驟2之生成物中的羥基反應。前述步驟2之生成物中,例如,存在藉由前述含有(甲基)丙烯醯基之環氧化合物(C)中的環氧基之開環而產生的羥基等。前述多羧酸酐(D)之反應比率,以調整至最終生成物的含有酸基之(甲基)丙烯酸酯樹脂之酸值成為約50~100mgKOH/g為較佳。步驟3之反應,例如,可於適當之酯化觸媒存在下,在約90~140℃之溫度條件下加熱攪拌而進行。在將步驟2及步驟3連續地進行之情況,酯化觸媒可不追加,亦可適宜追加。又,反應亦可視需要於有機溶劑中進行。 Regarding the aforementioned step 3, the aforementioned polycarboxylic acid anhydride (D) mainly reacts with the hydroxyl group in the product of the aforementioned step 2. In the product of the aforementioned step 2, for example, there are hydroxyl groups generated by ring-opening of the epoxy group in the aforementioned (meth)acryl group-containing epoxy compound (C), and the like. It is preferable to adjust the reaction ratio of the said polycarboxylic acid anhydride (D) so that the acid value of the acid group containing (meth)acrylate resin of the final product may become about 50-100 mgKOH/g. The reaction in step 3 can be carried out, for example, by heating and stirring at a temperature of about 90-140° C. in the presence of an appropriate esterification catalyst. When performing step 2 and step 3 continuously, the esterification catalyst may not be added, but may be added appropriately. In addition, the reaction may also be performed in an organic solvent if necessary.
此種方法所得到的含有酸基之(甲基)丙烯酸酯樹脂之酸值,從成為硬化物之耐熱性或伸長率優良之外,顯影性等亦優良的含有酸基之(甲基)丙烯酸酯樹脂而言,以50~100mgKOH/g之範圍為較佳,以60~90mgKOH/g之範圍為更佳。再者,本發明中,含有酸基之(甲基)丙烯酸酯樹脂之酸值為依照JIS K 0070(1992)之中和滴定法所測定的值。又,前述含有酸基之(甲基)丙烯酸酯樹脂之(甲基)丙烯醯基當量,以 250~750g/當量之範圍為較佳,以300~700g/當量之範圍為更佳。前述含有酸基之(甲基)丙烯酸酯樹脂之質量平均分子量(Mw)以1,000~10,000之範圍為較佳。 The acid value of the acid group-containing (meth)acrylate resin obtained by this method becomes an acid group-containing (meth)acrylic acid that is excellent in heat resistance and elongation of the cured product, and is also excellent in developability, etc. For ester resin, the range of 50~100mgKOH/g is better, and the range of 60~90mgKOH/g is more preferable. In addition, in this invention, the acid value of the (meth)acrylate resin containing an acid group is the value measured based on the neutralization titration method of JISK0070 (1992). In addition, the (meth)acryl group equivalent weight of the (meth)acrylate resin containing acid groups is preferably in the range of 250-750 g/equivalent, more preferably in the range of 300-700 g/equivalent. The mass average molecular weight (Mw) of the aforementioned acid group-containing (meth)acrylate resin is preferably in the range of 1,000 to 10,000.
前述含有酸基之(甲基)丙烯酸酯樹脂之分子量,係於下述條件下藉由GPC所測定之值。 The molecular weight of the aforementioned acid group-containing (meth)acrylate resin is a value measured by GPC under the following conditions.
測定裝置:東曹股份有限公司製「HLC-8220 GPC」、管柱:東曹股份有限公司製保護管柱「HXL-L」 Measuring device: Tosoh Co., Ltd. "HLC-8220 GPC", column: Tosoh Co., Ltd. guard column "HXL-L"
+東曹股份有限公司製「TSK-GEL G2000HXL」 + "TSK-GEL G2000HXL" manufactured by Tosoh Co., Ltd.
+東曹股份有限公司製「TSK-GEL G2000HXL」 + "TSK-GEL G2000HXL" manufactured by Tosoh Co., Ltd.
+東曹股份有限公司製「TSK-GEL G3000HXL」 + "TSK-GEL G3000HXL" manufactured by Tosoh Co., Ltd.
+東曹股份有限公司製「TSK-GEL G4000HXL」 + "TSK-GEL G4000HXL" manufactured by Tosoh Co., Ltd.
檢測器:RI(示差折射計) Detector: RI (Differential Refractometer)
數據處理:東曹股份有限公司製「GPC-8020機型II版本4.10」 Data processing: "GPC-8020 Model II Version 4.10" manufactured by Tosoh Co., Ltd.
測定條件:管柱溫度40℃ Measuring conditions: column temperature 40°C
展開溶劑 四氫呋喃 Developing solvent Tetrahydrofuran
流速1.0ml/分鐘 Flow rate 1.0ml/min
標準:依據前述「GPC-8020機型II版本4.10」之測定操作手冊,使用分子量已知之下述單分散聚苯乙烯。 Standard: According to the measurement operation manual of the aforementioned "GPC-8020 Model II Version 4.10", use the following monodisperse polystyrene with known molecular weight.
東曹股份有限公司製「A-500」 "A-500" manufactured by Tosoh Co., Ltd.
東曹股份有限公司製「A-1000」 "A-1000" manufactured by Tosoh Co., Ltd.
東曹股份有限公司製「A-2500」 "A-2500" manufactured by Tosoh Co., Ltd.
東曹股份有限公司製「A-5000」 "A-5000" manufactured by Tosoh Co., Ltd.
東曹股份有限公司製「F-1」 "F-1" manufactured by Tosoh Co., Ltd.
東曹股份有限公司製「F-2」 "F-2" manufactured by Tosoh Co., Ltd.
東曹股份有限公司製「F-4」 "F-4" manufactured by Tosoh Co., Ltd.
東曹股份有限公司製「F-10」 "F-10" manufactured by Tosoh Co., Ltd.
東曹股份有限公司製「F-20」 "F-20" manufactured by Tosoh Co., Ltd.
東曹股份有限公司製「F-40」 "F-40" manufactured by Tosoh Co., Ltd.
東曹股份有限公司製「F-80」 "F-80" manufactured by Tosoh Co., Ltd.
東曹股份有限公司製「F-128」 "F-128" manufactured by Tosoh Co., Ltd.
試料:將1.0質量%(以樹脂固體成分換算)之四氫呋喃溶液藉由微濾器過濾者(50μl) Sample: 1.0% by mass (resin solid content conversion) tetrahydrofuran solution filtered through a microfilter (50 μl)
本發明之含有酸基之(甲基)丙烯酸酯樹脂,由於分子結構中具有聚合性之(甲基)丙烯醯基,例如,可藉由添加光聚合起始劑,形成硬化性樹脂組成物而利用。 The acid group-containing (meth)acrylate resin of the present invention has a polymerizable (meth)acryl group in the molecular structure, for example, can be formed by adding a photopolymerization initiator to form a curable resin composition. use.
前述光聚合起始劑,只要依據照射之活性能量射線的種類等而選擇適當者使用即可。又,亦可與胺化合物、尿素化合物、含硫化合物、含磷化合物、含氯化合物、腈化合物等光增感劑併用。就光聚合起始劑之具體例而言,例如,可列舉1-羥基-環己基-苯基-酮、2-苄基-2-二甲基胺基-1-(4-啉基苯基)-丁酮-1,2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-啉基)苯基]-1-丁酮等烷基苯基酮系光聚合起始劑;2,4,6-三甲基苄醯基-二苯基-膦氧化物等醯基膦氧化物系光聚合起始劑;二苯基酮化合物等分子內奪氫型光聚合起始劑等。此等可分別單獨使用,亦可將2種以上併用。 The aforementioned photopolymerization initiator may be used by selecting an appropriate one according to the type of active energy rays to be irradiated, and the like. In addition, it can also be used in combination with photosensitizers such as amine compounds, urea compounds, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, and nitrile compounds. Specific examples of photopolymerization initiators include, for example, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1-(4- Linylphenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- Alkyl phenyl ketone photopolymerization initiators such as linyl)phenyl]-1-butanone; acylphosphine oxides such as 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide It is a photopolymerization initiator; intramolecular hydrogen abstraction photopolymerization initiators such as diphenyl ketone compounds, etc. These may be used individually, respectively, and may use 2 or more types together.
前述光聚合起始劑之市售品,例如,可列舉BASF公司製「IRGACURE127」、「IRGACURE184」、「IRGACURE250」、「IRGACURE270」、「IRGACURE290」、「IRGACURE369E」、「IRGACURE379EG」、「IRGACURE500」、「IRGACURE651」、「IRGACURE754」、「IRGACURE819」、「IRGACURE907」、「IRGACURE1173」、「IRGACURE2959」、「IRGACURE MBF」、「IRGACURE TPO」、「IRGACURE OXE 01」、「IRGACURE OXE 02」、IGM RESINS公司製「OMNIRAD184」、「OMNIRAD250」、「OMNIRAD369」、「OMNIRAD369E」、「OMNIRAD651」、「OMNIRAD907FF」、「OMNIRAD1173」等。 Commercially available products of the aforementioned photopolymerization initiator include, for example, "IRGACURE 127", "IRGACURE 184", "IRGACURE 250", "IRGACURE 270", "IRGACURE 290", "IRGACURE 369E", "IRGACURE 379EG", "IRGACURE 500" manufactured by BASF Corporation. "IRGACURE651", "IRGACURE754", "IRGACURE819", "IRGACURE907", "IRGACURE1173", "IRGACURE2959", "IRGACURE MBF", "IRGACURE TPO", "IRGACURE OXE 01", "IRGACURE OXE 02", manufactured by IGM RESINS "OMNIRAD184", "OMNIRAD250", "OMNIRAD369", "OMNIRAD369E", "OMNIRAD651", "OMNIRAD907FF", "OMNIRAD1173", etc.
前述光聚合起始劑之添加量,例如,相對於硬化性樹脂組成物之溶劑以外之成分的合計,以0.05~15質量%之範圍為較佳,以0.1~10質量%之範圍為更佳。 The amount of the above-mentioned photopolymerization initiator to be added is, for example, preferably in the range of 0.05 to 15% by mass, and more preferably in the range of 0.1 to 10% by mass, based on the total of components other than the solvent of the curable resin composition. .
本發明之硬化性樹脂組成物,可含有前述本發明的含有酸基之(甲基)丙烯酸酯樹脂以外的樹脂成分。該樹脂成分,例如,可列舉如使雙酚型環氧樹脂或酚醛清漆型環氧樹脂等之環氧樹脂,與(甲基)丙烯酸、二羧酸酐、視需要不飽和單羧酸酐等反應所得到的樹脂中具有羧基及(甲基)丙烯醯基之樹脂,或各種(甲基)丙烯酸酯單體等。 The curable resin composition of the present invention may contain resin components other than the aforementioned acid group-containing (meth)acrylate resin of the present invention. The resin component is, for example, one obtained by reacting an epoxy resin such as a bisphenol-type epoxy resin or a novolak-type epoxy resin with (meth)acrylic acid, a dicarboxylic acid anhydride, an unsaturated monocarboxylic acid anhydride, or the like if necessary. Among the obtained resins, there are resins having carboxyl groups and (meth)acryl groups, or various (meth)acrylate monomers.
前述(甲基)丙烯酸酯單體,例如,可列舉(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸辛酯等脂肪族單(甲基)丙烯酸酯化合物;(甲基)丙烯酸環己酯、(甲基)丙烯酸異莰酯、單(甲基)丙烯酸金剛烷酯等脂環型單(甲基)丙烯酸酯化合物;(甲基)丙烯酸環氧丙酯、丙烯酸四氫糠酯等雜環型單(甲基)丙烯酸酯化合物;(甲基)丙烯酸苄酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸苯基苄酯、(甲基)丙烯酸苯氧酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸苯氧基乙氧基乙酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯、(甲基)丙烯酸苯氧基苄酯、(甲基)丙烯酸苄基苄酯、(甲基)丙烯酸苯基苯氧基乙酯等芳香族單(甲基)丙烯酸酯化合物等單(甲基)丙烯酸酯化合物;在前述各種單(甲基)丙烯酸酯單體之分子結構中導入(聚)氧伸乙基鏈、(聚)氧伸丙基鏈、(聚)氧四亞甲基鏈等聚氧伸烷基鏈的(聚)氧伸烷基改質單(甲基)丙烯酸酯化合物;在前述各種單(甲基)丙烯酸酯化合物之分子結構中導入(聚)內酯結構的內酯改質單(甲基)丙烯酸酯化合物; The aforementioned (meth)acrylate monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylate Aliphatic mono(meth)acrylate compounds such as amyl acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, etc.; cyclohexyl (meth)acrylate alicyclic mono(meth)acrylate compounds such as ester, isocamphoryl (meth)acrylate, adamantyl mono(meth)acrylate; Cyclic mono(meth)acrylate compounds; benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate, (meth) Phenoxyethyl acrylate, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate, ( Mono(meth)acrylate compounds such as benzylbenzyl methacrylate, phenylphenoxyethyl (meth)acrylate and other aromatic mono(meth)acrylate compounds; (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, (poly)oxytetramethylene chains and other polyoxyalkylene chains introduced into the molecular structure of acrylate monomers Modified mono(meth)acrylate compounds; lactone-modified mono(meth)acrylate compounds that introduce (poly)lactone structures into the molecular structures of the aforementioned various mono(meth)acrylate compounds;
乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯等脂肪族二(甲基)丙烯酸酯化合物;1,4-環己烷二甲醇二(甲基)丙烯酸酯、降莰烷二(甲基)丙烯酸酯、降莰烷二甲醇二(甲基)丙烯酸酯、二環戊基二(甲基)丙烯酸酯、三環癸烷二甲醇二(甲 基)丙烯酸酯等脂環型二(甲基)丙烯酸酯化合物;聯苯酚二(甲基)丙烯酸酯、雙酚二(甲基)丙烯酸酯等芳香族二(甲基)丙烯酸酯化合物;在前述各種二(甲基)丙烯酸酯化合物之分子結構中導入(聚)氧伸乙基鏈、(聚)氧伸丙基鏈、(聚)氧四亞甲基鏈等(聚)氧伸烷基鏈的聚氧伸烷基改質二(甲基)丙烯酸酯化合物;在前述各種二(甲基)丙烯酸酯化合物之分子結構中導入(聚)內酯結構的內酯改質二(甲基)丙烯酸酯化合物; Ethylene glycol di(meth)acrylate, Propylene glycol di(meth)acrylate, Butylene glycol di(meth)acrylate, Hexylene glycol di(meth)acrylate, Neopentyl glycol di(meth)acrylate ) acrylate and other aliphatic di(meth)acrylate compounds; 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane dimethanol di(meth)acrylate, norbornane dimethanol di( Alicyclic di(meth)acrylate compounds such as meth)acrylate, dicyclopentyl di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate; biphenol di(meth)acrylate ) acrylate, bisphenol di(meth)acrylate and other aromatic di(meth)acrylate compounds; introducing (poly)oxyethylene chains, Polyoxyalkylene modified di(meth)acrylate compounds of (poly)oxypropylene chains, (poly)oxytetramethylene chains and other (poly)oxyalkylene chains; A lactone-modified di(meth)acrylate compound with a (poly)lactone structure introduced into the molecular structure of the acrylate compound;
三羥甲基丙烷三(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯等脂肪族三(甲基)丙烯酸酯化合物;在前述脂肪族三(甲基)丙烯酸酯化合物之分子結構中導入(聚)氧伸乙基鏈、(聚)氧伸丙基鏈、(聚)氧四亞甲基鏈等(聚)氧伸烷基鏈的(聚)氧伸烷基改質三(甲基)丙烯酸酯化合物;在前述脂肪族三(甲基)丙烯酸酯化合物之分子結構中導入(聚)內酯結構的內酯改質三(甲基)丙烯酸酯化合物; Aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerin tri(meth)acrylate; introduced into the molecular structure of the aforementioned aliphatic tri(meth)acrylate compounds (Poly)oxyethylene chain, (poly)oxypropylene chain, (poly)oxytetramethylene chain, etc. (poly)oxyalkylene modified tri(methyl) ) acrylate compound; a lactone-modified tri(meth)acrylate compound in which a (poly)lactone structure is introduced into the molecular structure of the aforementioned aliphatic tri(meth)acrylate compound;
新戊四醇四(甲基)丙烯酸酯、二-三羥甲基丙烷四(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯等4官能以上之脂肪族聚(甲基)丙烯酸酯化合物;在前述脂肪族聚(甲基)丙烯酸酯化合物之分子結構中導入(聚)氧伸乙基鏈、(聚)氧伸丙基鏈、(聚)氧四亞甲基鏈等(聚)氧伸烷基鏈的4官能以上之(聚)氧伸烷基改質聚(甲基)丙烯酸酯化合物;在前述脂肪族聚(甲基)丙烯酸酯化合物之分子結構中導入(聚)內酯結構的4官能以上之內酯改質聚(甲基)丙烯酸酯化合物等。 Aliphatic poly(meth)acrylates with more than 4 functionalities such as neopentylthritol tetra(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, and dipentynerythritol hexa(meth)acrylate ) acrylate compounds; introducing (poly)oxyethylene chains, (poly)oxypropylene chains, (poly)oxytetramethylene chains, etc. into the molecular structure of the aforementioned aliphatic poly(meth)acrylate compounds The (poly)oxyalkylene modified poly(meth)acrylate compound with more than 4 functional groups in the (poly)oxyalkylene chain; ) lactone-structured tetrafunctional or higher lactone-modified poly(meth)acrylate compounds, etc.
本發明之硬化性樹脂組成物,為了調節塗布黏度等之目的,可含有有機溶劑。其種類、添加量,可依據所期望之性能而適宜調整。一般而言,以相對於硬化性樹脂組成物之合計為10~90質量%之範圍使用。就前述溶劑之具體例而言,例如,可列舉丙酮、甲基乙基酮、甲基異丁基酮等酮溶劑;四氫呋喃、二氧環戊烷等環狀醚溶劑;乙酸甲酯、乙酸乙酯、乙酸丁酯等酯;甲苯、二甲苯等芳香族溶劑;環己烷、甲基環己烷等脂環族溶劑;卡必醇、賽路蘇、甲醇、異丙醇、丁醇、丙二醇單甲基醚等醇溶劑;伸烷基二醇單烷基醚、二伸烷基二醇單烷基醚、二伸烷基二醇單烷基醚乙酸酯等二醇醚系溶劑。此等可分別單獨使用,亦可將2種以上併用。 The curable resin composition of the present invention may contain an organic solvent for the purpose of adjusting coating viscosity and the like. Its type and dosage can be adjusted appropriately according to the expected performance. Generally, it is used in the range of 10 to 90% by mass relative to the total of the curable resin composition. Specific examples of the aforementioned solvents include, for example, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; methyl acetate, ethyl acetate, and the like; Esters such as esters and butyl acetate; aromatic solvents such as toluene and xylene; alicyclic solvents such as cyclohexane and methylcyclohexane; carbitol, celuso, methanol, isopropanol, butanol, propylene glycol Alcohol solvents such as monomethyl ether; glycol ether-based solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate. These may be used individually, respectively, and may use 2 or more types together.
本發明之硬化性樹脂組成物,除此之外,亦可含有無機微粒子或聚合物微粒子、顏料、消泡劑、黏度調整劑、調平劑、阻燃劑、保存安定化劑等各種添加劑。 The curable resin composition of the present invention may also contain various additives such as inorganic fine particles or polymer fine particles, pigments, defoamers, viscosity regulators, leveling agents, flame retardants, storage stabilizers and the like.
本發明之含有酸基之(甲基)丙烯酸酯樹脂,具有硬化物之耐熱性、伸長率高的特徴。再者,具有藉由光感度或乾燥管理幅度等所評價的顯影性、硬化物之基材密著性、暫時乾燥後之非黏著性等亦優良的特徵。就活用本發明之含有酸基之(甲基)丙烯酸酯樹脂之各種性能優良的特徴之用途而言,例如,在與半導體裝置相關之用途方面,可作為阻焊、層間絕緣材料、包裝材料、底部填充材料、電路元件等包裝接著層或積體電路元件與電路基板之接著層使用。又,就以LCD、OELD 為代表之薄型顯示器相關的用途而言,適合使用於薄膜電晶體保護膜、液晶彩色濾光片保護膜、彩色濾光片用顏料抗蝕劑、黑矩陣用抗蝕劑、間隔層等。此等之中,特別可適合用於阻焊用途。本發明之阻焊用樹脂材料,例如,除前述含有酸基之(甲基)丙烯酸酯樹脂、光聚合起始劑及各種添加劑外,尚包含硬化劑、硬化促進劑、有機溶劑等各成分。 The acid group-containing (meth)acrylate resin of the present invention has the characteristics of heat resistance and high elongation of the cured product. In addition, it has the characteristics of being excellent in developability evaluated by photosensitivity, drying control range, etc., substrate adhesion of cured products, and non-adhesiveness after temporary drying. In terms of applications utilizing the various excellent properties of the acid group-containing (meth)acrylate resin of the present invention, for example, in applications related to semiconductor devices, it can be used as solder resist, interlayer insulating materials, packaging materials, Underfill materials, circuit components, etc. are used as packaging adhesive layers or as adhesive layers between integrated circuit components and circuit substrates. In addition, for applications related to thin displays represented by LCDs and OELDs, it is suitable for thin film transistor protective films, liquid crystal color filter protective films, pigment resists for color filters, and resists for black matrices. agents, spacers, etc. Among these, it can be used especially suitably for a solder resist application. The resin material for soldering resist of the present invention, for example, includes various components such as a hardener, a hardening accelerator, and an organic solvent in addition to the above-mentioned acid group-containing (meth)acrylate resin, photopolymerization initiator, and various additives.
前述硬化劑只要具有能與前述含有酸基之(甲基)丙烯酸酯樹脂中之羧基反應的官能基者,無特別限制,例如,可列舉環氧樹脂。此處所用之環氧樹脂,例如,可列舉雙酚型環氧樹脂、伸苯基醚型環氧樹脂、伸萘基醚型環氧樹脂、聯苯型環氧樹脂、三苯基甲烷型環氧樹脂、酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、雙酚酚醛清漆型環氧樹脂、萘酚酚醛清漆型環氧樹脂、萘酚-酚共縮酚醛清漆型環氧樹脂、萘酚-甲酚共縮酚醛清漆型環氧樹脂、酚芳烷基型環氧樹脂、萘酚芳烷基型環氧樹脂、二環戊二烯-酚加成反應型環氧樹脂等。此等可分別單獨使用,亦可將2種以上併用。此等環氧樹脂之中,從硬化物之耐熱性優良而言,以酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、雙酚酚醛清漆型環氧樹脂、萘酚酚醛清漆型環氧樹脂、萘酚-苯酚共縮酚醛清漆型環氧樹脂、萘酚-甲酚共縮酚醛清漆型環氧樹脂等酚醛清漆型環氧樹脂為較佳,以軟化點為50~120℃之範圍者為特佳。 The curing agent is not particularly limited as long as it has a functional group capable of reacting with the carboxyl group in the acid group-containing (meth)acrylate resin, for example, an epoxy resin is mentioned. The epoxy resins used here include, for example, bisphenol-type epoxy resins, phenylene ether-type epoxy resins, naphthyl ether-type epoxy resins, biphenyl-type epoxy resins, and triphenylmethane-type epoxy resins. Oxygen resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol novolac epoxy resin, naphthol novolac epoxy resin, naphthol-phenol novolak epoxy resin , Naphthol-cresol co-condensed novolak type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, etc. These may be used individually, respectively, and may use 2 or more types together. Among these epoxy resins, phenol novolak type epoxy resin, cresol novolac type epoxy resin, bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin are used in view of the excellent heat resistance of the cured product. Epoxy resin, naphthol-phenol novolac type epoxy resin, naphthol-cresol novolac type epoxy resin and other novolac epoxy resins are preferred, with a softening point of 50~120°C The range is especially good.
前述硬化促進劑為促進前述硬化劑之硬化反應者,在使用環氧樹脂作為前述硬化劑之情況,可列舉磷系化合物、三級胺、咪唑、有機酸金屬鹽、路易斯酸、胺錯鹽等。此等可分別單獨使用,亦可將2種以上併用。硬化促進劑之添加量,例如,相對於100質量份之前述硬化劑,以1~10質量份之範圍使用。 The aforementioned hardening accelerator is one that accelerates the hardening reaction of the aforementioned hardening agent. In the case of using an epoxy resin as the aforementioned hardening agent, examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine zirconium salts, etc. . These may be used individually, respectively, and may use 2 or more types together. The addition amount of a hardening accelerator is used in the range of 1-10 mass parts with respect to 100 mass parts of said hardening agents, for example.
前述有機溶劑,只要能溶解前述含有酸基之(甲基)丙烯酸酯樹脂或硬化劑等各種成分者,無特別限定,例如,可列舉甲基乙基酮、丙酮、二甲基甲醯胺、甲基異丁基酮、甲氧基丙醇、環己酮、甲基賽路蘇、二乙二醇單乙基醚乙酸酯、丙二醇單甲基醚乙酸酯等。 The above-mentioned organic solvent is not particularly limited as long as it can dissolve various components such as the above-mentioned acid group-containing (meth)acrylate resin or hardener, for example, methyl ethyl ketone, acetone, dimethylformamide, Methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl celuso, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, etc.
使用本發明之阻焊用樹脂材料以得到阻焊構件的方法,例如,可列舉將前述阻焊用樹脂材料塗布於基材上,在約60~100℃之溫度範圍使有機溶劑揮發乾燥後,通過形成所期望之圖案的光罩,藉由紫外線或電子射線等曝光,並藉由鹼水溶液將未曝光部分顯影,進一步於約140~180℃之溫度範圍使其加熱硬化的方法。 The method of using the solder resist resin material of the present invention to obtain a solder resist member includes, for example, coating the aforementioned solder resist resin material on a base material, and drying the organic solvent at a temperature range of about 60 to 100°C. A method in which a photomask with a desired pattern is formed, exposed to ultraviolet rays or electron rays, and the unexposed part is developed with an aqueous alkali solution, and then heated and hardened at a temperature range of about 140 to 180°C.
以下,以實施例及比較例更詳細地說明本發明。 Hereinafter, the present invention will be described in more detail with examples and comparative examples.
在本實施例中,含有酸基之(甲基)丙烯酸酯樹脂之酸值係依照JIS K 0070(1992)之中和滴定法測定。 In this example, the acid value of the (meth)acrylate resin containing acid groups was measured according to the neutralization titration method of JIS K 0070 (1992).
在本實施例中,含有酸基之(甲基)丙烯酸酯樹脂之分子量係藉由下述條件之GPC測定。 In this example, the molecular weight of the (meth)acrylate resin containing acid groups was measured by GPC under the following conditions.
測定裝置:東曹股份有限公司製「HLC-8220GPC」、管柱:東曹股份有限公司製保護管柱「HXL-L」 Measuring device: Tosoh Co., Ltd. "HLC-8220GPC", column: Tosoh Co., Ltd. guard column "HXL-L"
+東曹股份有限公司製「TSK-GEL G2000HXL」 + "TSK-GEL G2000HXL" manufactured by Tosoh Co., Ltd.
+東曹股份有限公司製「TSK-GEL G2000HXL」 + "TSK-GEL G2000HXL" manufactured by Tosoh Co., Ltd.
+東曹股份有限公司製「TSK-GEL G3000HXL」 + "TSK-GEL G3000HXL" manufactured by Tosoh Co., Ltd.
+東曹股份有限公司製「TSK-GEL G4000HXL」 + "TSK-GEL G4000HXL" manufactured by Tosoh Co., Ltd.
檢測器:RI(示差折射計) Detector: RI (Differential Refractometer)
數據處理:東曹股份有限公司製「GPC-8020機型II版本4.10」 Data processing: "GPC-8020 Model II Version 4.10" manufactured by Tosoh Co., Ltd.
測定條件:管柱溫度40℃ Measuring conditions: column temperature 40°C
展開溶劑 四氫呋喃 Developing solvent Tetrahydrofuran
流速1.0ml/分鐘 Flow rate 1.0ml/min
標準:依據前述「GPC-8020機型II版本4.10」之測定操作手冊,使用分子量已知之下述單分散聚苯乙烯。 Standard: According to the measurement operation manual of the aforementioned "GPC-8020 Model II Version 4.10", use the following monodisperse polystyrene with known molecular weight.
東曹股份有限公司製「A-500」 "A-500" manufactured by Tosoh Co., Ltd.
東曹股份有限公司製「A-1000」 "A-1000" manufactured by Tosoh Co., Ltd.
東曹股份有限公司製「A-2500」 "A-2500" manufactured by Tosoh Co., Ltd.
東曹股份有限公司製「A-5000」 "A-5000" manufactured by Tosoh Co., Ltd.
東曹股份有限公司製「F-1」 "F-1" manufactured by Tosoh Co., Ltd.
東曹股份有限公司製「F-2」 "F-2" manufactured by Tosoh Co., Ltd.
東曹股份有限公司製「F-4」 "F-4" manufactured by Tosoh Co., Ltd.
東曹股份有限公司製「F-10」 "F-10" manufactured by Tosoh Co., Ltd.
東曹股份有限公司製「F-20」 "F-20" manufactured by Tosoh Co., Ltd.
東曹股份有限公司製「F-40」 "F-40" manufactured by Tosoh Co., Ltd.
東曹股份有限公司製「F-80」 "F-80" manufactured by Tosoh Co., Ltd.
東曹股份有限公司製「F-128」 "F-128" manufactured by Tosoh Co., Ltd.
試料:將以樹脂固體成分換算為1.0質量%之四氫呋喃溶液藉由微濾器過濾者(50μl) Sample: A tetrahydrofuran solution of 1.0% by mass in terms of resin solids was filtered through a microfilter (50 μl)
在具備溫度計、攪拌器、及回流冷卻器的燒瓶中,添加449.7質量份之二乙二醇單甲基醚乙酸酯、175.5質量份之異佛爾酮二異氰酸酯之三聚異氰酸酯改質體(EVONIK公司製「VESTANAT T-1890/100」,異氰酸基含量17.2質量%)、142.6質量份之偏苯三酸酐、1.4質量份之二丁基羥基甲苯,使其溶解。在氮氣環境下,於160℃反應5小時,確認異氰酸基含量成為0.1質量%以下。添加0.3質量份之對羥基苯甲醚(Methoquinone)、31.1質量份之新戊四醇聚丙烯酸酯混合物(東亞合成股份有限公司製「Aronix M-306」,新戊四醇三丙烯酸酯含量約67%,羥基值159.7mgKOH/g)及2.8質量份之三苯基膦,吹入空氣,同時於110℃反應5小時。繼而,添加116.5質量份之甲基丙烯酸環氧丙酯,並於120℃反應10小時。再者,添加116.3質量份之四氫酞酸酐,於110℃反應5小時,得到含有酸基之(甲基)丙烯酸酯樹脂(1)。含有酸基之(甲基)丙烯酸酯樹脂(1)之固體成分酸值為80mgKOH/g,丙烯醯基當量為485g/當量,重量平均分子量(Mw)為5,200。將含有酸基之(甲基)丙烯酸酯樹脂(1)之GPC圖表示於圖1。 In a flask equipped with a thermometer, a stirrer, and a reflux cooler, add 449.7 parts by mass of diethylene glycol monomethyl ether acetate and 175.5 parts by mass of isophorone diisocyanate ( "VESTANAT T-1890/100" manufactured by EVONIK Co., Ltd., isocyanate group content 17.2% by mass), 142.6 parts by mass of trimellitic anhydride, and 1.4 parts by mass of dibutylhydroxytoluene were dissolved. Under a nitrogen atmosphere, the reaction was carried out at 160° C. for 5 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Add 0.3 parts by mass of p-hydroxyanisole (Methoquinone), 31.1 parts by mass of neopentylthritol polyacrylate mixture ("Aronix M-306" manufactured by Dong Ya Gosei Co., Ltd., the content of neopentylthritol triacrylate is about 67 %, hydroxyl value 159.7mgKOH/g) and 2.8 parts by mass of triphenylphosphine, while blowing in air, react at 110°C for 5 hours. Then, 116.5 parts by mass of glycidyl methacrylate was added, and it was made to react at 120 degreeC for 10 hours. Furthermore, 116.3 mass parts of tetrahydrophthalic anhydrides were added, and it was made to react at 110 degreeC for 5 hours, and the (meth)acrylate resin (1) containing an acid group was obtained. The acid group-containing (meth)acrylate resin (1) had a solid content acid value of 80 mgKOH/g, an acryl group equivalent of 485 g/equivalent, and a weight average molecular weight (Mw) of 5,200. The GPC chart of the acid group-containing (meth)acrylate resin (1) is shown in FIG. 1 .
在具備溫度計、攪拌器、及回流冷卻器的燒瓶中,添加449.9質量份之二乙二醇單甲基醚乙酸酯、191.4質量份之異佛爾酮二異氰酸酯之三聚異氰酸酯改質體(EVONIK公司製「VESTANAT T-1890/100」,異氰酸基含量17.2質量%)、155.5質量份之偏苯三酸酐、1.4質量份之二丁基羥基甲苯,使其溶解。在氮氣環境下,於160℃反應5小時,確認異氰酸基含量成為0.1質量%以下。添加0.3質量份之對羥基苯甲醚、34.0質量份之新戊四醇聚丙烯酸酯混合物(東亞合成股份有限公司製「Aronix M-306」,新戊四醇三丙烯酸酯含量約67%,羥基值159.7mgKOH/g)及2.8質量份之三苯基膦,吹入空氣,同時於110℃反應5小時。繼而,添加127.1質量份之甲基丙烯酸環氧丙酯,並於120℃反應10小時。再者,添加76.6質量份之琥珀酸酐,於110℃反應5小時,得到含有酸基之(甲基)丙烯酸酯樹脂(2)。含有酸基之(甲基)丙烯酸酯樹脂(2)之固體成分酸值為80mgKOH/g,丙烯醯基當量為445g/當量,重量平均分子量(Mw)為4,700。 In a flask equipped with a thermometer, a stirrer, and a reflux cooler, add 449.9 parts by mass of diethylene glycol monomethyl ether acetate and 191.4 parts by mass of isophorone diisocyanate ( "VESTANAT T-1890/100" manufactured by EVONIK Co., Ltd., isocyanate group content 17.2% by mass), 155.5 parts by mass of trimellitic anhydride, and 1.4 parts by mass of dibutylhydroxytoluene were dissolved. Under a nitrogen atmosphere, the reaction was carried out at 160° C. for 5 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Add 0.3 parts by mass of p-hydroxyanisole, 34.0 parts by mass of neopentylthritol polyacrylate mixture ("Aronix M-306" manufactured by Dong Yasei Co., Ltd., the content of neopentylthritol triacrylate is about 67%, and the hydroxyl group Value 159.7 mgKOH/g) and 2.8 parts by mass of triphenylphosphine were reacted at 110° C. for 5 hours while blowing in air. Then, 127.1 parts by mass of glycidyl methacrylate was added, and it was made to react at 120 degreeC for 10 hours. Furthermore, 76.6 mass parts of succinic anhydrides were added, it was made to react at 110 degreeC for 5 hours, and the (meth)acrylate resin (2) containing an acid group was obtained. The acid group-containing (meth)acrylate resin (2) had a solid content acid value of 80 mgKOH/g, an acryl group equivalent of 445 g/equivalent, and a weight average molecular weight (Mw) of 4,700.
在具備溫度計、攪拌器、及回流冷卻器的燒瓶中,添加350.4質量份之二乙二醇單甲基醚乙酸酯、85.8質量份之異佛爾酮二異氰酸酯之三聚異氰酸酯改質體(EVONIK公司製「VESTANAT T-1890/100」,異氰酸基含 量17.2質量%)、85.8質量份之六亞甲基二異氰酸酯之尿酸酯改質體(DIC股份有限公司製「Burnock DN901S」、異氰酸基含量23.5質量%)、209.4質量份之偏苯三酸酐、1.6質量份之二丁基羥基甲苯,使其溶解。在氮氣環境下,於160℃反應5小時,確認異氰酸基含量成為0.1質量%以下。添加0.3質量份之對羥基苯甲醚、16.9質量份之新戊四醇聚丙烯酸酯混合物(東亞合成股份有限公司製「Aronix M-306」,新戊四醇三丙烯酸酯含量約67%,羥基值159.7mgKOH/g)及3.3質量份之三苯基膦,吹入空氣,同時於110℃反應5小時。繼而,添加197.9質量份之甲基丙烯酸環氧丙酯,於120℃反應10小時。再者,添加90.4質量份之琥珀酸酐並於110℃反應5小時,得到含有酸基之(甲基)丙烯酸酯樹脂(3)。含有酸基之(甲基)丙烯酸酯樹脂(3)之固體成分酸值為80mgKOH/g,丙烯醯基當量為415g/當量,重量平均分子量(Mw)為4,980。 In a flask equipped with a thermometer, a stirrer, and a reflux cooler, add 350.4 parts by mass of diethylene glycol monomethyl ether acetate and 85.8 parts by mass of isophorone diisocyanate ( "VESTANAT T-1890/100" manufactured by EVONIK, the isocyanate group content is 17.2% by mass), 85.8 parts by mass of uric acid ester modified product of hexamethylene diisocyanate ("Burnock DN901S" manufactured by DIC Co., Ltd., The content of isocyanate group is 23.5% by mass), 209.4 parts by mass of trimellitic anhydride, and 1.6 parts by mass of dibutylhydroxytoluene are dissolved. Under a nitrogen atmosphere, the reaction was carried out at 160° C. for 5 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Add 0.3 parts by mass of p-hydroxyanisole and 16.9 parts by mass of neopentylthritol polyacrylate mixture ("Aronix M-306" manufactured by Dong Yasei Co., Ltd., the content of neopentylthritol triacrylate is about 67%, and the hydroxyl value 159.7 mgKOH/g) and 3.3 parts by mass of triphenylphosphine were reacted at 110° C. for 5 hours while blowing in air. Then, 197.9 parts by mass of glycidyl methacrylate was added, and it was made to react at 120 degreeC for 10 hours. Furthermore, 90.4 mass parts of succinic anhydrides were added, and it was made to react at 110 degreeC for 5 hours, and the (meth)acrylate resin (3) containing an acid group was obtained. The acid group-containing (meth)acrylate resin (3) had a solid content acid value of 80 mgKOH/g, an acryl group equivalent of 415 g/equivalent, and a weight average molecular weight (Mw) of 4,980.
在具備溫度計、攪拌器、及回流冷卻器的燒瓶中,添加300.2質量份之二乙二醇單甲基醚乙酸酯、197.9質量份之六亞甲基二異氰酸酯之尿酸酯改質體(DIC股份有限公司製「Burnock DN901S」,異氰酸基含量23.5質量%)、219.7質量份之偏苯三酸酐、1.8質量份之二丁基羥基甲苯,使其溶解。在氮氣環境下,於160℃反應5小時,確認異氰酸基含量成為0.1質量%以下。添加0.4質量份之對羥基苯甲醚、11.9質量份之新戊四醇聚丙烯酸酯混 合物(東亞合成股份有限公司製「Aronix M-306」,新戊四醇三丙烯酸酯含量約67%,羥基值159.7mgKOH/g)及3.5質量份之三苯基膦,吹入空氣,同時於110℃反應5小時。繼而,添加221.7質量份之甲基丙烯酸環氧丙酯,於120℃反應10小時。再者,添加97.3質量份之琥珀酸酐,並於110℃反應5小時,得到含有酸基之(甲基)丙烯酸酯樹脂(4)。含有酸基之(甲基)丙烯酸酯樹脂(4)之固體成分酸值為80mgKOH/g,丙烯醯基當量為416g/當量,重量平均分子量(Mw)為4,350。 In a flask equipped with a thermometer, a stirrer, and a reflux cooler, add uric acid ester modified body ( "Burnock DN901S" manufactured by DIC Co., Ltd., isocyanate group content 23.5% by mass), 219.7 parts by mass of trimellitic anhydride, and 1.8 parts by mass of dibutylhydroxytoluene were dissolved. Under a nitrogen atmosphere, the reaction was carried out at 160° C. for 5 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Add 0.4 parts by mass of p-hydroxyanisole and 11.9 parts by mass of neopentylthritol polyacrylate mixture ("Aronix M-306" manufactured by Dong Yasei Co., Ltd., the content of neopentylthritol triacrylate is about 67%, and the hydroxyl group Value 159.7 mgKOH/g) and 3.5 parts by mass of triphenylphosphine were reacted at 110° C. for 5 hours while blowing in air. Then, 221.7 parts by mass of glycidyl methacrylate was added, and it was made to react at 120 degreeC for 10 hours. Furthermore, 97.3 mass parts of succinic anhydrides were added, and it was made to react at 110 degreeC for 5 hours, and the (meth)acrylate resin (4) containing an acid group was obtained. The acid group-containing (meth)acrylate resin (4) had a solid content acid value of 80 mgKOH/g, an acryl group equivalent of 416 g/equivalent, and a weight average molecular weight (Mw) of 4,350.
在具備溫度計、攪拌器、及回流冷卻器的燒瓶中,添加299.8質量份之二乙二醇單甲基醚乙酸酯、232.8質量份之異佛爾酮二異氰酸酯、302.0質量份之偏苯三酸酐、1.8質量份之二丁基羥基甲苯,使其溶解。在氮氣環境下,於160℃反應5小時,確認異氰酸基含量成為0.1質量%以下。添加0.4質量份之對羥基苯甲醚、11.1質量份之新戊四醇聚丙烯酸酯混合物(東亞合成股份有限公司製「Aronix M-306」,新戊四醇三丙烯酸酯含量約67%,羥基值159.7mgKOH/g)及3.5質量份之三苯基膦,吹入空氣,同時於110℃反應5小時。繼而,添加149.2質量份之甲基丙烯酸環氧丙酯,於120℃反應10小時。再者,添加97.4質量份之琥珀酸酐,並於110℃反應5小時,得到含有酸基之(甲基)丙烯酸酯樹脂(5)。含有酸基之(甲基)丙烯酸酯樹脂(5)之固體成分酸值為80mgKOH/g,丙烯醯基當量為603g/當量,重量平均分子量(Mw)為1,780。 In a flask equipped with a thermometer, a stirrer, and a reflux cooler, add 299.8 parts by mass of diethylene glycol monomethyl ether acetate, 232.8 parts by mass of isophorone diisocyanate, 302.0 parts by mass of trimellitic anhydride, 1.8 Parts by mass of dibutylhydroxytoluene to dissolve it. Under a nitrogen atmosphere, the reaction was carried out at 160° C. for 5 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Add 0.4 parts by mass of p-hydroxyanisole and 11.1 parts by mass of neopentylthritol polyacrylate mixture ("Aronix M-306" manufactured by Dong Ya Gosei Co., Ltd., the content of neopentylthritol triacrylate is about 67%, and the hydroxyl Value 159.7 mgKOH/g) and 3.5 parts by mass of triphenylphosphine were reacted at 110° C. for 5 hours while blowing in air. Then, 149.2 mass parts of glycidyl methacrylates were added, and it was made to react at 120 degreeC for 10 hours. Furthermore, 97.4 mass parts of succinic anhydrides were added, and it was made to react at 110 degreeC for 5 hours, and the (meth)acrylate resin (5) containing an acid group was obtained. The acid group-containing (meth)acrylate resin (5) had a solid content acid value of 80 mgKOH/g, an acryl group equivalent of 603 g/equivalent, and a weight average molecular weight (Mw) of 1,780.
在具備溫度計、攪拌器、及回流冷卻器的燒瓶中,添加1422.7質量份之二乙二醇單甲基醚乙酸酯、753.2質量份之異佛爾酮二異氰酸酯之三聚異氰酸酯改質體(EVONIK公司製「VESTANAT T-1890/100」,異氰酸基含量17.2質量%)及644.2質量份之環己烷-1,3,4-三羧酸-3,4-酐、6.5質量份之二丁基羥基甲苯,使其溶解。在氮氣環境下,於160℃反應5小時,確認異氰酸基含量成為0.1質量%以下。添加1.3質量份之對羥基苯甲醚、189.2質量份之新戊四醇聚丙烯酸酯混合物(東亞合成股份有限公司製「Aronix M-306」,新戊四醇三丙烯酸酯含量約67%,羥基值159.7mgKOH/g)、12.9質量份之三苯基膦,吹入空氣,同時於110℃反應5小時。繼而,添加617.1質量份之甲基丙烯酸環氧丙酯,於120℃反應10小時。再者,添加546質量份之四氫酞酸酐,並於110℃反應5小時,得到含有酸基之(甲基)丙烯酸酯樹脂(6)。含有酸基之(甲基)丙烯酸酯樹脂(6)之固體成分酸值為80mgKOH/g,丙烯醯基當量為434g/當量,重量平均分子量(Mw)為5,600。 In a flask equipped with a thermometer, a stirrer, and a reflux cooler, add 1422.7 parts by mass of diethylene glycol monomethyl ether acetate and 753.2 parts by mass of isophorone diisocyanate ( "VESTANAT T-1890/100" manufactured by EVONIK, the content of isocyanate group is 17.2% by mass), 644.2 parts by mass of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, 6.5 parts by mass dibutylhydroxytoluene to dissolve it. Under a nitrogen atmosphere, the reaction was carried out at 160° C. for 5 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Add 1.3 parts by mass of p-hydroxyanisole and 189.2 parts by mass of neopentylthritol polyacrylate mixture ("Aronix M-306" manufactured by Dong Ya Gosei Co., Ltd., the content of neopentylthritol triacrylate is about 67%, and the hydroxyl value 159.7 mgKOH/g), 12.9 parts by mass of triphenylphosphine, and reacted at 110° C. for 5 hours while blowing in air. Then, 617.1 parts by mass of glycidyl methacrylate was added, and it was made to react at 120 degreeC for 10 hours. Furthermore, 546 mass parts of tetrahydrophthalic anhydrides were added, and it was made to react at 110 degreeC for 5 hours, and the (meth)acrylate resin (6) containing an acid group was obtained. The acid group-containing (meth)acrylate resin (6) had a solid content acid value of 80 mgKOH/g, an acryl group equivalent of 434 g/equivalent, and a weight average molecular weight (Mw) of 5,600.
在具備溫度計、攪拌機、及回流冷卻器之燒瓶中,添加449.7質量份之二乙二醇單甲基醚乙酸酯、170.5質量份之異佛爾酮二異氰酸酯之三聚異氰酸酯改質體 (EVONIK公司製「VESTANAT T-1890/100」,異氰酸基含量17.2質量%)、138.5質量份之偏苯三酸酐、1.4質量份之二丁基羥基甲苯,使其溶解。在氮氣環境下,於160℃反應5小時,確認異氰酸基含量成為0.1質量%以下。添加0.3質量份之對羥基苯甲醚、30.3質量份之新戊四醇三丙烯酸酯混合物(東亞合成股份有限公司製「Aronix M-306」,新戊四醇三丙烯酸酯含量約67%,羥基值159.7mgKOH/g)及2.8質量份之三苯基膦,吹入空氣,同時於110℃反應5小時。繼而,添加165質量份之甲基丙烯酸3,4-環氧環己基甲酯(Daicel股份有限公司製「Cyclomer M100」,環氧基當量207g/當量),於120℃反應10小時。再者,添加76.7質量份之琥珀酸酐,並於110℃反應5小時,得到含有酸基之(甲基)丙烯酸酯樹脂(7)。含有酸基之(甲基)丙烯酸酯樹脂(7)之固體成分酸值為80mgKOH/g,丙烯醯基當量為500g/當量,重量平均分子量(Mw)為4,040。 In a flask equipped with a thermometer, a stirrer, and a reflux cooler, add 449.7 parts by mass of diethylene glycol monomethyl ether acetate and 170.5 parts by mass of isophorone diisocyanate (EVONIK "VESTANAT T-1890/100" produced by the company, the content of isocyanate group is 17.2% by mass), 138.5 parts by mass of trimellitic anhydride, and 1.4 parts by mass of dibutylhydroxytoluene are dissolved. Under a nitrogen atmosphere, the reaction was carried out at 160° C. for 5 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Add 0.3 parts by mass of p-hydroxyanisole and 30.3 parts by mass of neopentylitol triacrylate mixture ("Aronix M-306" manufactured by Dong Yasei Co., Ltd., the content of neopentylthritol triacrylate is about 67%, and the hydroxyl Value 159.7 mgKOH/g) and 2.8 parts by mass of triphenylphosphine were reacted at 110° C. for 5 hours while blowing in air. Then, 165 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate ("Cyclomer M100" manufactured by Daicel Co., Ltd., 207 g/equivalent of epoxy group) was added, and it was made to react at 120 degreeC for 10 hours. Furthermore, 76.7 mass parts of succinic anhydrides were added, and it was made to react at 110 degreeC for 5 hours, and the (meth)acrylate resin (7) containing an acid group was obtained. The acid group-containing (meth)acrylate resin (7) had a solid content acid value of 80 mgKOH/g, an acryl group equivalent of 500 g/equivalent, and a weight average molecular weight (Mw) of 4,040.
在具備溫度計、攪拌器、及回流冷卻器的燒瓶中,加入101質量份之二乙二醇單甲基醚乙酸酯,使428質量份之鄰甲酚酚醛清漆型環氧樹脂(DIC股份有限公司製「EPICLON N-680」,軟化點85℃,環氧基當量214g/當量)溶解。再者,加入4質量份之二丁基羥基甲苯、0.4質量份之對羥基苯甲醚後,添加144質量份之丙烯酸、1.6質量份之三苯基膦,吹入空氣同時於120℃反應10 小時。接著,添加311質量份之二乙二醇單甲基醚乙酸酯、160質量份之四氫酞酸酐,並於110℃反應2.5小時,得到含有酸基之(甲基)丙烯酸酯樹脂(1’)。含有酸基之(甲基)丙烯酸酯樹脂(1’)之固體成分酸值為85mgKOH/g。 In the flask equipped with thermometer, stirrer, and reflux cooler, add 101 mass parts of diethylene glycol monomethyl ether acetate to make 428 mass parts of o-cresol novolak type epoxy resin (DIC Co., Ltd. "EPICLON N-680" manufactured by the company, softening point 85°C, epoxy group equivalent weight 214g/equivalent) was dissolved. Furthermore, after adding 4 parts by mass of dibutylhydroxytoluene and 0.4 parts by mass of p-hydroxyanisole, 144 parts by mass of acrylic acid and 1.6 parts by mass of triphenylphosphine were added, and air was blown in while reacting at 120°C for 10 Hour. Then, add 311 parts by mass of diethylene glycol monomethyl ether acetate, 160 parts by mass of tetrahydrophthalic anhydride, and react at 110° C. for 2.5 hours to obtain the (meth)acrylate resin containing acid groups (1 '). The solid content acid value of the acid group-containing (meth)acrylate resin (1') was 85 mgKOH/g.
以下述要領調製硬化性樹脂組成物,進行各種評價試驗。將結果示於表1。 Curable resin compositions were prepared in the following manner, and various evaluation tests were performed. The results are shown in Table 1.
摻合100質量份之先前所得到的含有酸基之(甲基)丙烯酸酯樹脂(以固體成分換算)、24質量份之DIC股份有限公司製「EPICLON N-680」(甲酚酚醛清漆型環氧樹脂)、5質量份之BASF公司製「IRGACURE 907」[2-甲基-1-(4-甲基硫基苯基)-2-啉基丙-1-酮]、13質量份之二乙二醇單甲基醚乙酸酯,得到硬化性樹脂組成物。 100 parts by mass of the previously obtained acid group-containing (meth)acrylate resin (in terms of solid content), 24 parts by mass of "EPICLON N-680" (cresol novolak type ring) manufactured by DIC Co., Ltd. oxygen resin), 5 parts by mass of "IRGACURE 907" [2-methyl-1-(4-methylthiophenyl)-2- Linyl propan-1-one], 13 parts by mass of diethylene glycol monomethyl ether acetate to obtain a curable resin composition.
在玻璃上,將硬化性樹脂組成物以50μm之塗布器塗布,並於80℃乾燥30分鐘。使用金屬鹵素燈,照射1000mJ/cm2之紫外線後,於160℃加熱1小時。將硬化物從玻璃剝離。 On the glass, the curable resin composition was coated with a 50 μm applicator, and dried at 80° C. for 30 minutes. After irradiating 1000mJ/cm 2 of ultraviolet rays using a metal halide lamp, it was heated at 160°C for 1 hour. Peel hardened material from glass.
從硬化物切出6mm×40mm之試驗片,使用黏彈性測定裝置(DMA:Rheometric公司製固體黏彈性測定裝置「RSAII」,拉伸法:頻率1Hz,升溫速度3℃/分鐘),以彈性率變化成為最大(tanδ變化率最大)的溫度,當作玻璃轉移溫度(Tg),進行評價。 Cut out a test piece of 6 mm x 40 mm from the cured product, and use a viscoelasticity measuring device (DMA: Rheometric Solid Viscoelasticity Measuring Device "RSAII", tensile method:
從硬化物切出10mm×80mm之試驗片,使用拉伸試驗裝置(島津製作所公司製「機密萬能試驗器Autograph AG-IS」),以下述條件測定試驗片之伸長率,並評價。 A test piece of 10 mm x 80 mm was cut out from the cured product, and the elongation of the test piece was measured and evaluated under the following conditions using a tensile tester ("Secret Universal Tester Autograph AG-IS" manufactured by Shimadzu Corporation).
溫度23℃,濕度50%,標線間距離20mm,支點間距離20mm,拉伸速度10mm/分鐘 Temperature 23°C, humidity 50%, distance between marking lines 20mm, distance between fulcrums 20mm, tensile speed 10mm/min
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