KR20210113064A - Curable resin composition, dry film, cured product, and electronic component - Google Patents
Curable resin composition, dry film, cured product, and electronic component Download PDFInfo
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- KR20210113064A KR20210113064A KR1020210027967A KR20210027967A KR20210113064A KR 20210113064 A KR20210113064 A KR 20210113064A KR 1020210027967 A KR1020210027967 A KR 1020210027967A KR 20210027967 A KR20210027967 A KR 20210027967A KR 20210113064 A KR20210113064 A KR 20210113064A
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- South Korea
- Prior art keywords
- resin composition
- curable resin
- meth
- carboxyl group
- compound
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- 239000011342 resin composition Substances 0.000 title claims abstract description 71
- 150000001875 compounds Chemical class 0.000 claims abstract description 53
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000003822 epoxy resin Substances 0.000 claims abstract description 33
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 33
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 106
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 72
- 229920005989 resin Polymers 0.000 claims description 52
- 239000011347 resin Substances 0.000 claims description 52
- 239000000377 silicon dioxide Substances 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 18
- 229910052731 fluorine Inorganic materials 0.000 claims description 17
- 239000003963 antioxidant agent Substances 0.000 claims description 16
- 125000001153 fluoro group Chemical group F* 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 230000003078 antioxidant effect Effects 0.000 claims description 14
- 239000003086 colorant Substances 0.000 claims description 9
- 238000002845 discoloration Methods 0.000 abstract description 17
- 239000010408 film Substances 0.000 description 55
- -1 2,4,6-trimethylbenzoylphenylphosphine methyl ester Chemical class 0.000 description 35
- 239000000047 product Substances 0.000 description 31
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 30
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 29
- 238000000576 coating method Methods 0.000 description 27
- 239000011248 coating agent Substances 0.000 description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 16
- 239000010410 layer Substances 0.000 description 16
- 229920005862 polyol Polymers 0.000 description 16
- 229910002012 Aerosil® Inorganic materials 0.000 description 15
- 150000008065 acid anhydrides Chemical class 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 13
- 150000003077 polyols Chemical class 0.000 description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 11
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 11
- 125000002947 alkylene group Chemical group 0.000 description 11
- 239000007795 chemical reaction product Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 10
- 230000001588 bifunctional effect Effects 0.000 description 10
- 230000002349 favourable effect Effects 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- 238000005476 soldering Methods 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 238000013329 compounding Methods 0.000 description 8
- 238000003682 fluorination reaction Methods 0.000 description 8
- 230000001476 alcoholic effect Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000013039 cover film Substances 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 125000005442 diisocyanate group Chemical group 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 150000007519 polyprotic acids Polymers 0.000 description 6
- 229910000679 solder Inorganic materials 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 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 4
- YCCILVSKPBXVIP-UHFFFAOYSA-N 2-(4-hydroxyphenyl)ethanol Chemical compound OCCC1=CC=C(O)C=C1 YCCILVSKPBXVIP-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229920006026 co-polymeric resin Polymers 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 229920005906 polyester polyol Polymers 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 244000028419 Styrax benzoin Species 0.000 description 3
- 235000000126 Styrax benzoin Nutrition 0.000 description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 150000007973 cyanuric acids Chemical class 0.000 description 3
- 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 3
- 239000004744 fabric Substances 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 235000019382 gum benzoic Nutrition 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 230000007774 longterm Effects 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
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000008646 thermal stress Effects 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 2
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 description 2
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- RHNJVKIVSXGYBD-UHFFFAOYSA-N 10-prop-2-enoyloxydecyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCCCCCOC(=O)C=C RHNJVKIVSXGYBD-UHFFFAOYSA-N 0.000 description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 2
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-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
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
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- 239000004115 Sodium Silicate Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
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- 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 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000000654 additive Substances 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- UMLWXYJZDNNBTD-UHFFFAOYSA-N alpha-dimethylaminoacetophenone Natural products CN(C)CC(=O)C1=CC=CC=C1 UMLWXYJZDNNBTD-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
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- 239000012965 benzophenone Substances 0.000 description 2
- 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 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
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- 229910052799 carbon Inorganic materials 0.000 description 2
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- 238000007334 copolymerization reaction Methods 0.000 description 2
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- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 2
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- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 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 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
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- 239000003999 initiator Substances 0.000 description 2
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 230000000670 limiting effect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 235000012054 meals Nutrition 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
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- 238000002156 mixing Methods 0.000 description 2
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
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- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 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
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- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 1
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 1
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- 238000007766 curtain coating Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- HZWAUDKTZOUQPD-UHFFFAOYSA-N diphenylphosphoryl-(2-methylphenyl)methanone Chemical compound CC1=CC=CC=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 HZWAUDKTZOUQPD-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SSTAXLJQSRFHMB-UHFFFAOYSA-N ethyl 1,4-dimethylcyclohexa-2,4-diene-1-carboxylate Chemical compound CCOC(=O)C1(C)CC=C(C)C=C1 SSTAXLJQSRFHMB-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- HIFJCPQKFCZDDL-ACWOEMLNSA-N iloprost Chemical compound C1\C(=C/CCCC(O)=O)C[C@@H]2[C@@H](/C=C/[C@@H](O)C(C)CC#CC)[C@H](O)C[C@@H]21 HIFJCPQKFCZDDL-ACWOEMLNSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- MBAUOPQYSQVYJV-UHFFFAOYSA-N octyl 3-[4-hydroxy-3,5-di(propan-2-yl)phenyl]propanoate Chemical compound OC1=C(C=C(C=C1C(C)C)CCC(=O)OCCCCCCCC)C(C)C MBAUOPQYSQVYJV-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 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
- 239000012071 phase Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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- 238000010992 reflux Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000004291 sulphur dioxide Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
- C08G59/3263—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/508—Amines heterocyclic containing only nitrogen as a heteroatom having three nitrogen atoms in the ring
- C08G59/5086—Triazines; Melamines; Guanamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/04—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Materials For Photolithography (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
본 발명은 경화성 수지 조성물, 당해 경화성 수지 조성물을 수지층으로서 갖는 드라이 필름, 당해 드라이 필름의 수지층의 경화물, 및 당해 경화물을 갖는 전자 부품에 관한 것이다.Curable resin composition, the dry film which has the said curable resin composition as a resin layer, the hardened|cured material of the resin layer of the said dry film, and the electronic component which has the said hardened|cured material.
프린트 배선판의 제조에 있어서는, 통상, 기재 상의 도체 회로를 땜납의 부착으로부터 보호하기 위해 솔더 레지스트가 사용되고 있으며, 그리고 그러한 솔더 레지스트를 형성하기 위해서, 종래부터 각종 구조를 갖는 각종 성분을 함유하는 경화성 수지 조성물이 제안되어 있다.In manufacture of a printed wiring board, in order to protect the conductor circuit on a base material from adhesion of solder normally, a soldering resist is used, And in order to form such a soldering resist, curable resin composition containing various components which have conventionally various structures conventionally. This is proposed.
예를 들어 특허문헌 1은, (메타)아크릴로일기를 갖는 특정한 구조의 (메타)아크릴 공중합체와, 에틸렌성 불포화 결합을 갖는 모노머와, 광개시제를 함유하는 감광성 수지 조성물을 개시하고 있다.For example, patent document 1 is disclosing the photosensitive resin composition containing the (meth)acryl copolymer of the specific structure which has a (meth)acryloyl group, the monomer which has an ethylenically unsaturated bond, and a photoinitiator.
그런데 솔더 레지스트에는, 사용되는 프린트 배선판의 용도에 따라서 각종 특성이 필요하지만, 그 중 하나로서 내열성을 들 수 있다. 솔더 레지스트의 내열성이 충분하지 않으면, 솔더 레지스트 그 자체가 변색될 우려가 있기 때문이다. 예를 들어, 발광 다이오드(LED) 등의 발광 소자가 실장되는 배선판에 사용되는 솔더 레지스트에는, LED로부터의 광선의 반사 효율을 높여서 그 이용의 효율화를 도모하기 위해서 백색 착색제가 함유되어 있기 때문에, 솔더 레지스트가 백색으로부터 황색으로 변색(황변)되었을 때에는 LED 광선의 반사 효율이 매우 저하되어버린다.By the way, although various characteristics are required for a soldering resist according to the use of the printed wiring board used, heat resistance is mentioned as one of them. It is because there exists a possibility that soldering resist itself may discolor when the heat resistance of a soldering resist is not enough. For example, a solder resist used for a wiring board on which a light emitting element such as a light emitting diode (LED) is mounted contains a white colorant in order to increase the reflection efficiency of the light from the LED and to increase the efficiency of its use. When the resist changes color from white to yellow (yellowing), the reflective efficiency of the LED light is greatly reduced.
솔더 레지스트는 그의 형성 후에 있어서, 특히 기재에 대한 전자 부품의 실장 시에 있어서의 땜납 열이나, 실장 후에 있어서의 전자 부품으로부터의 발열, 및 기타 열 스트레스를 받기 쉽기 때문에, 그러한 열 스트레스에 대한 변색의 내성은 중요한 특성이라고 할 수 있다.After the solder resist is formed, in particular, since it is easy to receive solder heat at the time of mounting an electronic component to a base material, heat generation from an electronic component after mounting, and other thermal stress, the color change with respect to such thermal stress Tolerance is an important characteristic.
그러나 이 점에 대하여, 특허문헌 1에 기재된 감광성 수지 조성물과 같은 종래의 경화성 수지 조성물에 대하여는 솔더 레지스트의 내열성, 특히 열 변색 내성까지 충분히 고려된 것이라고는 할 수 없었다.However, about this point, about the conventional curable resin composition like the photosensitive resin composition of patent document 1, it cannot be said that it was fully taken into consideration even to the heat resistance of a soldering resist, especially thermal discoloration tolerance.
상기 과제를 해결하기 위해 본 발명자들은 예의 검토를 거듭한 결과, 이소시아누레이트 구조와 2개 이상의 (메타)아크릴로일기를 갖는 화합물과 이소시아누레이트 구조를 갖는 에폭시 수지를 경화성 수지 조성물 중에 병용함으로써, 열 변색 내성이 높여진 경화 도막(예를 들어 솔더 레지스트)을 형성할 수 있음을 발견하고, 본 발명을 완성하였다.In order to solve the said subject, the present inventors repeated earnest examination, As a result, the compound which has an isocyanurate structure and two or more (meth)acryloyl groups, and the epoxy resin which has an isocyanurate structure are used together in curable resin composition By doing so, it discovered that the cured coating film (for example, soldering resist) by which thermal discoloration tolerance was improved could be formed, and this invention was completed.
즉, 본 발명에 있어서의 과제는,That is, the subject in the present invention is
적어도, 하기 성분 (A) 내지 (C):At least, the following components (A) to (C):
(A) 이소시아누레이트 구조와 2개 이상의 (메타)아크릴로일기를 갖는 화합물,(A) a compound having an isocyanurate structure and two or more (meth)acryloyl groups,
(B) 이소시아누레이트 구조를 갖는 에폭시 수지, 및(B) an epoxy resin having an isocyanurate structure, and
(C) 광중합 개시제를 함유하는 경화성 수지 조성물에 의해 해결될 수 있는 것이 발견되었다.(C) It was discovered that it can be solved by the curable resin composition containing a photoinitiator.
이 중 본 발명의 바람직한 양태는, (D) 이소시아누레이트 구조를 갖는 산화 방지제를 더 함유하는 상기 경화성 수지 조성물에 관한 것이다.Among these, the preferable aspect of this invention relates to the said curable resin composition which further contains the antioxidant which has (D) isocyanurate structure.
더욱 바람직한 양태는, (E) 백색 착색제를 더 함유하는 상기 경화성 수지 조성물에 관한 것이다.A more preferable aspect relates to the said curable resin composition which further contains (E) a white coloring agent.
또 다른 바람직한 형태는, 카르복실기 함유 불소 수지 및 불소 원자를 함유하지 않는 카르복실기 함유 공중합 수지 중 적어도 1종을 더 함유하는 상기 경화성 수지 조성물에 관한 것이다.Another preferable aspect relates to the said curable resin composition which further contains at least 1 sort(s) of a carboxyl group-containing fluororesin and a carboxyl group-containing copolymer resin which does not contain a fluorine atom.
또 다른 바람직한 형태는, 비표면적이 10m2/g 이상 100m2/g 미만인 실리카, 및 비표면적이 100m2/g 이상 300m2/g 미만인 실리카 중 적어도 1종을 더 함유하는 상기 경화성 수지 조성물에 관한 것이다.Another preferred aspect relates to the curable resin composition further comprising at least one of silica having a specific surface area of 10 m 2 /g or more and less than 100 m 2 /g, and silica having a specific surface area of 100 m 2 /g or more and less than 300 m 2 /g will be.
또한 본 발명의 다른 양태는, 상기 경화성 수지 조성물을 수지층으로서 갖는 드라이 필름, 및 상기 경화성 수지 조성물, 또는 상기 드라이 필름의 수지층의 경화물, 그리고 상기 경화물을 갖는 전자 부품에도 관한 것이다.Another aspect of the present invention also relates to a dry film having the curable resin composition as a resin layer, a cured product of the curable resin composition or a resin layer of the dry film, and an electronic component having the cured product.
본 발명에 따르면, 더 높은 내열성을 갖는 경화물(경화 도막), 및 당해 경화물을 형성할 수 있는 경화성 수지 조성물이 제공된다. 따라서, 당해 경화물은 열에 의한 변색에 대하여 높은 내성을 갖는 점에서, 솔더 레지스트층으로서, 특히 LED가 실장되는 배선판에 대한 백색의 솔더 레지스트층으로서 보다 적합하게 사용될 수 있다.ADVANTAGE OF THE INVENTION According to this invention, the hardened|cured material (cured coating film) which has higher heat resistance, and the curable resin composition which can form the said hardened|cured material are provided. Accordingly, since the cured product has high resistance to discoloration due to heat, it can be more suitably used as a solder resist layer, particularly as a white solder resist layer for a wiring board on which an LED is mounted.
본 발명의 경화성 수지 조성물로부터 얻어지는 경화물의 높은 열 변색 내성은, 기본적으로, (A) 이소시아누레이트 구조와 2개 이상의 (메타)아크릴로일기를 갖는 화합물과 (B) 이소시아누레이트 구조를 갖는 에폭시 수지를 병용함으로써 달성될 수 있다.The high heat discoloration resistance of the hardened|cured material obtained from the curable resin composition of this invention is basically (A) a compound which has an isocyanurate structure and two or more (meth)acryloyl groups, and (B) an isocyanurate structure. It can be achieved by using together an epoxy resin having
본 발명에 있어서 열 변색 내성이란, 경화성 수지 조성물로 형성한 경화 도막에 대하여, 열 스트레스를 부여한 전후의 당해 경화 도막의 색조 변화의 정도(색차: ΔE)로서도 나타날 수 있다. ΔE가 작을수록 열 변색 내성이 높고, ΔE가 클수록 열 변색 내성이 낮다고 할 수 있다.Heat discoloration resistance in the present invention can also be expressed as the degree of change in color tone (color difference: ΔE) of the cured coating film before and after applying thermal stress to the cured coating film formed from the curable resin composition. It can be said that the thermal discoloration resistance is high, so that ΔE is small, and the thermal discoloration resistance is so large that ΔE is large.
예를 들어, ΔE는 경화성 수지 조성물의 도포, 건조, 노광, 현상 및 경화 처리를 행한 경화물에 대하여, 피크 톱 온도를 285℃로 하여 10초의 열처리를 행하고, 초기값으로부터의 색의 변화량으로서 산출될 수 있다.For example, ΔE is calculated as the amount of change in color from the initial value by performing heat treatment for 10 seconds at a peak top temperature of 285° C. for a cured product subjected to coating, drying, exposure, development and curing of the curable resin composition. can be
또한, 본 발명의 경화성 수지 조성물은 그 자체가 양호한 장기 보존 안정성도 갖는다. 그 때문에, 예를 들어 선박에 의한 해외로의 운반 등, 경화성 수지 조성물의 수송이 장기에 걸친 후라도, 사용 시에 있어서의 품질이 유지될 수 있다는 이점도 갖는다.Moreover, curable resin composition of this invention also has favorable long-term storage stability itself. Therefore, it also has the advantage that the quality at the time of use can be maintained, even after transportation of curable resin composition, such as transportation to foreign countries by a ship for a long term, for example.
이하, 이러한 본 발명의 경화성 수지 조성물을 구성하는 각 성분에 대하여 설명한다.Hereinafter, each component which comprises this curable resin composition of this invention is demonstrated.
[(A) 이소시아누레이트 구조와 2개 이상의 (메타)아크릴로일기를 갖는 화합물][(A) a compound having an isocyanurate structure and two or more (meth)acryloyl groups]
(A) 이소시아누레이트 구조와 2개 이상의 (메타)아크릴로일기를 갖는 화합물은, 그의 단위 구조 중에, 이소시아누레이트환 및 2개 이상의 (메타)아크릴로일기를 갖는다.(A) The compound which has an isocyanurate structure and a 2 or more (meth)acryloyl group has an isocyanurate ring and a 2 or more (meth)acryloyl group in the unit structure.
(A) 화합물로서는, 예를 들어 2관능 또는 3관능 (메타)아크릴레이트를 들 수 있다.(A) As a compound, bifunctional or trifunctional (meth)acrylate is mentioned, for example.
이 중, 2관능 (메타)아크릴레이트를 갖는 것으로서는, 에톡시화이소시아누르산디(메타)아크릴레이트 또는 프로폭시화이소시아누르산디(메타)아크릴레이트가 바람직하다.Among these, as what has a bifunctional (meth)acrylate, ethoxylated isocyanuric-acid di(meth)acrylate or propoxylated isocyanuric-acid di(meth)acrylate is preferable.
또한, 3관능 (메타)아크릴레이트를 갖는 것으로서는, 에톡시화이소시아누르산트리(메타)아크릴레이트 또는 프로폭시화이소시아누르산트리(메타)아크릴레이트가 바람직하다.Moreover, as what has trifunctional (meth)acrylate, ethoxylated isocyanuric-acid tri(meth)acrylate or propoxylated isocyanuric-acid tri(meth)acrylate is preferable.
나아가, 이들의 카프로락톤 변성체도 바람직하게 들 수 있다.Furthermore, these caprolactone-modified substances are also mentioned preferably.
상기 (A) 이소시아누레이트 구조와 2개 이상의 (메타)아크릴로일기를 갖는 화합물로서 더욱 바람직한 것은, 에톡시화이소시아누르산트리(메타)아크릴레이트이다. (A) 이소시아누레이트 구조와 2개 이상의 (메타)아크릴로일기를 갖는 화합물의 시판품으로서는, 도아 고세사제의 M-215, M-313, M-315, 신나카무라 가가쿠사제의 A-9300, A-9300-1CL, A-9300YN, IGM Resins사제의 Photomer4356, 히따찌 가세이사제의 FA-731A가 있다.As a compound which has the said (A) isocyanurate structure and two or more (meth)acryloyl groups, an ethoxylated isocyanuric acid tri(meth)acrylate is more preferable. (A) As a commercial item of the compound which has an isocyanurate structure and two or more (meth)acryloyl groups, M-215, M-313, M-315 by Toagosei Co., Ltd., A-9300 by Shin-Nakamura Chemical Co., Ltd. , A-9300-1CL, A-9300YN, Photomer4356 manufactured by IGM Resins, and FA-731A manufactured by Hitachi Chemical.
본 발명에 있어서는, (A) 이소시아누레이트 구조와 2개 이상의 (메타)아크릴로일기를 갖는 화합물의 함유량은, 전체 조성물의 고형분 전체량에 대하여 3 내지 25질량%인 것이 바람직하다. 특히, 본 발명의 경화성 수지 조성물이 백색 착색제를 함유하는 경우, (A) 이소시아누레이트 구조와 2개 이상의 (메타)아크릴로일기를 갖는 화합물의 함유량은 3 내지 10질량%가 바람직하고, 5 내지 7 질량%가 보다 바람직하다. 3 내지 25질량%의 경우, 얻어지는 경화물의 열 변색 내성이 양호할 뿐만 아니라, 경화 도막 강도가 양호하고, 조성물의 점성이 적당하여 도포성 등을 향상시킬 수 있다.In this invention, it is preferable that content of the compound which has (A) an isocyanurate structure and two or more (meth)acryloyl groups is 3-25 mass % with respect to solid content whole amount of all the compositions. In particular, when curable resin composition of this invention contains a white coloring agent, 3-10 mass % is preferable, as for content of the compound which has (A) an isocyanurate structure and two or more (meth)acryloyl groups, 5 -7 mass % is more preferable. In the case of 3-25 mass %, not only the heat discoloration resistance of the hardened|cured material obtained is favorable, but also cured coating-film intensity|strength is favorable, the viscosity of a composition is moderate, and applicability|paintability etc. can be improved.
[(B) 이소시아누레이트 구조를 갖는 에폭시 수지][(B) Epoxy resin having an isocyanurate structure]
본 발명의 경화성 수지 조성물에 있어서는, 이소시아누레이트 구조를 갖는 에폭시 수지이며, 그 이소시아누레이트 구조 중의 질소 원자와 에폭시기 사이가 알킬렌쇄에 의해 결합된 구조의 에폭시 수지가 함유된다. 특히, 알킬렌쇄의 탄소수가 2개 이상인 구조를 갖는 에폭시 수지의 것이 바람직하다. 당해 알킬렌쇄의 탄소수가 2 내지 5의 범위 내이면, 얻어지는 경화물에 있어서 양호한 열 변색 내성이 얻어진다.In the curable resin composition of this invention, it is an epoxy resin which has an isocyanurate structure, The epoxy resin of the structure couple|bonded by the alkylene chain between the nitrogen atom in the isocyanurate structure and the epoxy group is contained. In particular, the thing of the epoxy resin which has a structure in which carbon number of an alkylene chain is 2 or more is preferable. When carbon number of the said alkylene chain is in the range of 2-5, favorable heat discoloration resistance is acquired in the hardened|cured material obtained.
이러한, 본 발명에 있어서 사용되는 (B) 이소시아누레이트 구조를 갖는 에폭시 수지로서는, 하기 식 (I)로 표시되는 구조를 갖는 것이 바람직하다.As an epoxy resin which has such an isocyanurate structure (B) used in this invention, it is preferable to have a structure represented by following formula (I).
(식 중,(During the meal,
R1, R2 및 R3은 각각 독립적으로 탄소수 2 내지 5의 알킬렌기를 나타내고,R 1 , R 2 and R 3 each independently represents an alkylene group having 2 to 5 carbon atoms,
n은 0 또는 1이지만, 단, 모든 n이 동시에 0을 나타내지 않는다)n is 0 or 1, provided that not all n represent 0 at the same time)
이 중 특히 바람직한 것은, 식 중, R1, R2 및 R3이 동시에 탄소수 3의 알킬렌기를 나타내며, 또한 n이 동시에 1을 나타내는 구조의 것이다.Of these, particularly preferred is a structure in which R 1 , R 2 and R 3 simultaneously represent an alkylene group having 3 carbon atoms, and n simultaneously represents 1.
본 발명에 있어서 바람직하게 사용되는 (B) 이소시아누레이트 구조를 갖는 에폭시 수지의 구체적인 제품으로서는, 예를 들어 TEPIC(등록 상표)-VL, TEPIC(등록 상표)-FL(모두 닛산 가가쿠사제)을 들 수 있다.As a specific product of the epoxy resin which has the (B) isocyanurate structure used suitably in this invention, For example, TEPIC (trademark)-VL, TEPIC (trademark)-FL (all are made by Nissan Chemical Corporation) can be heard
이러한 (B) 이소시아누레이트 구조를 갖는 에폭시 수지의 함유량은, (A) 이소시아누레이트 구조와 2개 이상의 (메타)아크릴로일기를 갖는 화합물 100질량부에 대하여 30 내지 70질량%인 것이 바람직하다. 특히, 본 발명의 경화성 수지 조성물이 (E) 백색 착색제를 함유하는 경우, (A) 이소시아누레이트 구조와 2개 이상의 (메타)아크릴로일기를 갖는 화합물의 함유량은 48 내지 68질량부인 것이 바람직하다. 30 내지 70질량%의 범위 내이면, 얻어지는 경화물의 열 변색 내성이 양호해지고, 또한 경화성 수지 조성물의 보존 안정성도 향상된다.It is that content of the epoxy resin which has such (B) isocyanurate structure is 30-70 mass % with respect to 100 mass parts of compounds which have (A) isocyanurate structure and two or more (meth)acryloyl groups desirable. In particular, when curable resin composition of this invention contains (E) a white coloring agent, it is preferable that content of the compound which has (A) an isocyanurate structure and two or more (meth)acryloyl groups is 48-68 mass parts. do. If it exists in the range of 30-70 mass %, the heat discoloration tolerance of the hardened|cured material obtained will become favorable, and the storage stability of curable resin composition also improves.
[(C) 광중합 개시제][(C) Photoinitiator]
(C) 광중합 개시제로서는, 광중합 개시제나 광라디칼 발생제로서 공지된 광중합 개시제라면 어느 것을 사용할 수도 있고, 예를 들어 비스-(2,6-디클로로벤조일)페닐포스핀옥사이드, 비스-(2,6-디클로로벤조일)-2,5-디메틸페닐포스핀옥사이드, 비스-(2,6-디클로로벤조일)-4-프로필페닐포스핀옥사이드, 비스-(2,6-디클로로벤조일)-1-나프틸포스핀옥사이드, 비스-(2,6-디메톡시벤조일)페닐포스핀옥사이드, 비스-(2,6-디메톡시벤조일)-2,4,4-트리메틸펜틸포스핀옥사이드, 비스-(2,6-디메톡시벤조일)-2,5-디메틸페닐포스핀옥사이드, 비스-(2,4,6-트리메틸벤조일)-페닐포스핀옥사이드 등의 비스아실포스핀옥사이드류; 2,6-디메톡시벤조일디페닐포스핀옥사이드, 2,6-디클로로벤조일디페닐포스핀옥사이드, 2,4,6-트리메틸벤조일페닐포스핀산메틸에스테르, 2-메틸벤조일디페닐포스핀옥사이드, 피발로일페닐포스핀산이소프로필에스테르, 2,4,6-트리메틸벤조일디페닐포스핀옥사이드 등의 모노아실포스핀옥사이드류; 1-히드록시-시클로헥실페닐케톤, 1-[4-(2-히드록시에톡시)-페닐]-2-히드록시-2-메틸-1-프로판-1-온, 2-히드록시-1-{4-[4-(2-히드록시-2-메틸-프로피오닐)-벤질]페닐}-2-메틸-프로판-1-온, 2-히드록시-2-메틸-1-페닐프로판-1-온 등의 히드록시아세토페논류; 벤조인, 벤질, 벤조인메틸에테르, 벤조인에틸에테르, 벤조인n-프로필에테르, 벤조인이소프로필에테르, 벤조인n-부틸에테르 등의 벤조인류; 벤조인알킬에테르류; 벤조페논, p-메틸벤조페논, 미힐러 케톤, 메틸벤조페논, 4,4'-디클로로벤조페논, 4,4'-비스디에틸아미노벤조페논 등의 벤조페논류; 아세토페논, 2,2-디메톡시-2-페닐아세토페논, 2,2-디에톡시-2-페닐아세토페논, 1,1-디클로로아세토페논, 1-히드록시시클로헥실페닐케톤, 2-메틸-1-[4-(메틸티오)페닐]-2-모르폴리노-1-프로파논, 2-벤질-2-디메틸아미노-1-(4-모르폴리노페닐)-부타논-1,2-(디메틸아미노)-2-[(4-메틸페닐)메틸]-1-[4-(4-모르폴리닐)페닐]-1-부타논, N,N-디메틸아미노아세토페논 등의 아세토페논류; 티옥산톤, 2-에틸티옥산톤, 2-이소프로필티옥산톤, 2,4-디메틸티옥산톤, 2,4-디에틸티옥산톤, 2-클로로티옥산톤, 2,4-디이소프로필티옥산톤 등의 티옥산톤류; 안트라퀴논, 클로로안트라퀴논, 2-메틸안트라퀴논, 2-에틸안트라퀴논, 2-tert-부틸안트라퀴논, 1-클로로안트라퀴논, 2-아밀안트라퀴논, 2-아미노안트라퀴논 등의 안트라퀴논류; 아세토페논디메틸케탈, 벤질디메틸케탈 등의 케탈류; 에틸-4-디메틸아미노벤조에이트, 2-(디메틸아미노)에틸벤조에이트, p-디메틸벤조산에틸에스테르 등의 벤조산에스테르류; 1,2-옥탄디온,1-[4-(페닐티오)-,2-(O-벤조일옥심)], 에타논,1-[9-에틸-6-(2-메틸벤조일)-9H-카르바졸-3-일]-,1-(O-아세틸옥심) 등의 옥심에스테르류; 비스(η5-2,4-시클로펜타디엔-1-일)-비스(2,6-디플루오로-3-(1H-피롤-1-일)페닐)티타늄, 비스(시클로펜타디에닐)-비스[2,6-디플루오로-3-(2-(1-필-1-일)에틸)페닐]티타늄 등의 티타노센류; 페닐디술피드2-니트로플루오렌, 부틸로인, 아니소인에틸에테르, 아조비스이소부티로니트릴, 테트라메틸티우람디술피드 등을 들 수 있다. 광중합 개시제는 1종을 단독으로 사용해도 되고, 2종 이상을 조합하여 사용해도 된다.(C) As the photopolymerization initiator, any photoinitiator known as a photopolymerization initiator or a photoradical generator may be used. For example, bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6) -Dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-1-naphthylphos Pinoxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis-(2,6- bisacylphosphine oxides such as dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide and bis-(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphine methyl ester, 2-methylbenzoyldiphenylphosphine oxide, P monoacylphosphine oxides such as valoylphenylphosphinic acid isopropyl ester and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 1-Hydroxy-cyclohexylphenylketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1 -{4-[4-(2-Hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-hydroxy-2-methyl-1-phenylpropane- hydroxyacetophenones such as 1-one; benzoins such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, and benzoin n-butyl ether; benzoin alkyl ethers; benzophenones such as benzophenone, p-methylbenzophenone, Michler ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, and 4,4'-bisdiethylaminobenzophenone; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl- 1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2- acetophenones such as (dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone and N,N-dimethylaminoacetophenone; Thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-di thioxanthone such as isopropyl thioxanthone; anthraquinones such as anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethylbenzoate, and p-dimethylbenzoic acid ethyl ester; 1,2-Octanedione,1-[4-(phenylthio)-,2-(O-benzoyloxime)], ethanone,1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbox oxime esters such as bazol-3-yl]-,1-(O-acetyloxime); Bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, bis(cyclopentadienyl)- titanocenes such as bis[2,6-difluoro-3-(2-(1-phyll-1-yl)ethyl)phenyl]titanium; phenyldisulfide 2-nitrofluorene, butyroin, anisoinethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, etc. are mentioned. A photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more type.
(C) 광중합 개시제의 함유량은, (A) 이소시아누레이트 구조와 2개 이상의 (메타)아크릴로일기를 갖는 화합물 100질량부에 대하여 5 내지 20질량부인 것이 바람직하고, 10 내지 20질량부인 것이 보다 바람직하다. 5 내지 20질량부의 범위 내이면, 표면 경화성이 양호해지고, 또한 헐레이션이 발생하기 어려워 양호한 해상성이 얻어진다.(C) It is preferable that content of a photoinitiator is 5-20 mass parts with respect to 100 mass parts of compounds which have (A) an isocyanurate structure and two or more (meth)acryloyl groups, and it is 10-20 mass parts more preferably. When it exists in the range of 5-20 mass parts, surface hardenability becomes favorable, and halation is hard to generate|occur|produce and favorable resolution is acquired.
[(D) 이소시아누레이트 구조를 갖는 산화 방지제][(D) antioxidant having an isocyanurate structure]
본 발명의 경화성 수지 조성물에는, (D) 이소시아누레이트 구조를 갖는 산화 방지제를 더 함유시킬 수도 있다. 이에 의해, 경화 도막의 열 변색 내성이 보다 높아진다는 효과가 발휘될 수 있다.The curable resin composition of this invention can also be made to contain the antioxidant which has (D) isocyanurate structure further. Thereby, the effect that the heat discoloration resistance of a cured coating film becomes higher can be exhibited.
이러한 (D) 이소시아누레이트 구조를 갖는 산화 방지제는, 바람직하게는 하기 식 (II)로 표시되는 것을 들 수 있다.As for the antioxidant which has such (D) isocyanurate structure, Preferably what is represented by following formula (II) is mentioned.
(식 중,(During the meal,
기 R4, R5 및 R6은 각각 독립적으로 수소 원자를 나타내거나, 또는 수산기 및 탄소 원자수 1 내지 10의 탄화수소기로 이루어지는 군에서 선택되는 적어도 1종의 치환기에 의해 치환되어 있어도 되는 지방족 탄화수소기 혹은 방향족 탄화수소기를 나타내며, 또한The groups R 4 , R 5 and R 6 each independently represent a hydrogen atom or an aliphatic hydrocarbon group which may be substituted with at least one substituent selected from the group consisting of a hydroxyl group and a hydrocarbon group having 1 to 10 carbon atoms. Or an aromatic hydrocarbon group, and
식 중의 질소 원자와, 기 R4, R5 또는 R6은 직접 결합되어 있어도 되고, 또는 탄소 원자수 1 내지 10의 알킬렌기를 통해 결합되어 있어도 된다)The nitrogen atom in the formula and the group R 4 , R 5 or R 6 may be directly bonded or may be bonded via an alkylene group having 1 to 10 carbon atoms)
보다 바람직한 (D) 이소시아누레이트 구조를 갖는 산화 방지제는, 식 (II) 중, 기 R4, R5 및 R6이 각각 1개의 수산기 및 1 내지 3개의 탄소 원자수 1 내지 4의 탄화수소기로 치환된 페닐기를 나타내며, 또한 각각의 질소 원자와, 기 R4, R5 또는 R6이 탄소 원자수 1 내지 3의 알킬렌기를 통해 결합된 구조의 것이다.More preferable (D) antioxidant having an isocyanurate structure, in formula (II), groups R 4 , R 5 and R 6 are each a hydroxyl group and a hydrocarbon group having 1 to 3 carbon atoms. It represents a substituted phenyl group, and has a structure in which each nitrogen atom and the group R 4 , R 5 or R 6 are bonded via an alkylene group having 1 to 3 carbon atoms.
특히 바람직한 (D) 이소시아누레이트 구조를 갖는 산화 방지제는, 하기 식 (II')로 표시되는 1,3,5-트리스(3,5-디-tert-부틸)-4-히드록시벤질)-1,3,5-트리아진-2,4,6(1H,3H,5H)-트리온(상품명: Irganox3114; BASF 재팬사제)이다. 그 밖에도 (D) 이소시아누레이트 구조를 갖는 산화 방지제의 시판품으로서는, 닛본 사이텍 인더스트리즈사제의 사이아녹스 1790, 아데카사제의 아데카스탭 AO-20이 있다.Particularly preferable (D) antioxidant having an isocyanurate structure is 1,3,5-tris(3,5-di-tert-butyl)-4-hydroxybenzyl) -1,3,5-triazine-2,4,6(1H,3H,5H)-trion (trade name: Irganox3114; manufactured by BASF Japan). In addition, (D) As a commercial item of the antioxidant which has an isocyanurate structure, there exist Cyanox 1790 by Nippon Cytec Industries, Inc. and Adekastab AO-20 by Adeka.
(D) 이소시아누레이트 구조를 갖는 산화 방지제의 함유량은, (A) 이소시아누레이트 구조와 2개 이상의 (메타)아크릴로일기를 갖는 화합물 100질량부에 대하여 1 내지 8질량%인 것이 바람직하다. 1 내지 8질량%의 범위이면 경화 도막의 열 변색 내성을 더 높일 수 있다.(D) It is preferable that content of the antioxidant which has an isocyanurate structure is 1-8 mass % with respect to 100 mass parts of compounds which have (A) an isocyanurate structure and two or more (meth)acryloyl groups. do. If it is 1-8 mass %, the heat discoloration tolerance of a cured coating film can be improved further.
[(E) 백색 착색제][(E) white colorant]
본 발명의 경화성 수지 조성물을, 예를 들어 LED용의 프린트 배선 기판의 솔더 레지스트에 사용하는 경우에는, 백색 착색제가 함유되어 있어도 된다. 그것에 의해, 경화 도막의 반사율을 높여서 LED의 광선의 이용 효율화를 도모할 수 있다.When using the curable resin composition of this invention for the soldering resist of the printed wiring board for LEDs, the white coloring agent may contain. Thereby, the reflectance of a cured coating film can be raised and utilization efficiency improvement of the light ray of LED can be aimed at.
(E) 백색 착색제로서는, 예를 들어 산화티타늄, 산화아연, 티타늄산칼륨, 산화지르코늄, 산화안티몬, 연백, 황화아연, 티타늄산납 등을 들 수 있지만, 열에 의한 변색의 억제 효과가 높은 점에서, 산화티타늄을 사용하는 것이 바람직하다.(E) Examples of the white colorant include titanium oxide, zinc oxide, potassium titanate, zirconium oxide, antimony oxide, lead white, zinc sulfide, and lead titanate. It is preferable to use titanium oxide.
산화티타늄으로서는, 루틸형, 아나타제형, 람스델라이트형 중 어느 구조의 산화티타늄이어도 되고, 1종을 단독으로 사용해도 되고 2종 이상을 조합하여 사용해도 된다. 이 중 람스델라이트형 산화티타늄은, 람스델라이트형 Li0.5TiO2에 화학 산화에 의한 리튬 탈리 처리를 실시함으로써 얻을 수 있다.As titanium oxide, the titanium oxide of any structure among a rutile type, an anatase type, and a Ramsdelite type may be sufficient, and may be used individually by 1 type, or may be used in combination of 2 or more type. Among them, Ramsdelite-type titanium oxide can be obtained by subjecting Ramsdelite-type Li0.5TiO2 to lithium desorption treatment by chemical oxidation.
상기 중 루틸형 산화티타늄을 사용하면, 경화 도막의 내열성을 보다 향상시킬 수 있기 때문에 바람직하다. 특히, 알루미나 등의 알루미늄 산화물이나 실리카에 의해 표면 처리된 루틸형 산화티타늄을 사용함으로써, 경화 도막의 반사율이나 내열성을 더욱 향상시킬 수 있다.Among the above, use of rutile-type titanium oxide is preferable because the heat resistance of the cured coating film can be further improved. In particular, by using aluminum oxide such as alumina or rutile-type titanium oxide surface-treated with silica, the reflectance and heat resistance of the cured coating film can be further improved.
또한, 표면 처리한 후에 추가로 다른 표면 처리를 할 수도 있다. 특히, 알루미나로 표면 처리한 후에 지르코니아로 추가로 표면 처리함으로써, 반사율을 한층 더 향상시킬 수 있다.In addition, after surface treatment, other surface treatment may be further performed. In particular, the reflectance can be further improved by further surface treatment with zirconia after surface treatment with alumina.
상기 알루미늄 산화물에 의해 표면 처리된 루틸형 산화티타늄으로서는, 예를 들어 루틸형 염소법 산화티타늄인 이시하라 산교(주)제의 CR-58이나, 루틸형 황산법 산화티타늄인 동사제의 R-630 등을 들 수 있다. 또한, 규소 산화물에 의해 표면 처리된 루틸형 산화티타늄을 사용하는 것도 바람직하고, 이 경우에도 내열성을 더욱 향상시킬 수 있다. 또한, 알루미늄 산화물과 규소 산화물의 양쪽으로 표면 처리된 루틸형 산화티타늄을 사용하는 것도 바람직하고, 예를 들어 루틸형 염소법 산화티타늄인 이시하라 산교(주)제의 CR-90 등을 들 수 있다.As the rutile-type titanium oxide surface-treated with the aluminum oxide, for example, CR-58 manufactured by Ishihara Sangyo Co., Ltd. which is rutile-type chlorine method titanium oxide, R-630 manufactured by the company which is rutile type sulfuric acid method titanium oxide, etc. can be heard In addition, it is also preferable to use a rutile-type titanium oxide surface-treated with silicon oxide, and even in this case, heat resistance can be further improved. Moreover, it is also preferable to use the rutile-type titanium oxide surface-treated by both aluminum oxide and silicon oxide, For example, CR-90 etc. made from Ishihara Sangyo Co., Ltd. which are rutile-type chlorine method titanium oxide are mentioned.
이러한 (E) 백색 착색제의 배합량은, (A) 이소시아누레이트 구조와 2개 이상의 (메타)아크릴로일기를 갖는 화합물 100질량부에 대하여, 바람직하게는 750 내지 950질량부의 범위, 보다 바람직하게는 800 내지 900질량부의 범위이다.The compounding amount of such (E) white colorant is preferably in the range of 750 to 950 parts by mass, more preferably in the range of (A) 100 parts by mass of the compound having an isocyanurate structure and two or more (meth)acryloyl groups. is in the range of 800 to 900 parts by mass.
[카르복실기 함유 수지][Carboxyl group-containing resin]
본 발명의 경화성 수지 조성물에는, 카르복실기 함유 불소 수지 또는 불소 원자를 함유하지 않는 카르복실기 함유 수지 중 적어도 1종이 더 함유되는 것이 바람직하다.It is preferable that curable resin composition of this invention contains at least 1 sort(s) of a carboxyl group-containing fluororesin or carboxyl group-containing resin which does not contain a fluorine atom further.
카르복실기 함유 불소 수지로서는, 공지된 카르복실기를 포함하는 불소 수지를 사용할 수 있다. 불소 수지란, 적어도 하나의 불소 원자를 갖는 폴리머 또는 올리고머를 말한다. 카르복실기의 존재에 의해, 경화성 수지 조성물을 알칼리 현상성으로 할 수 있음과 함께, 불소 원자의 존재에 의해, 열 변색 내성을 향상시킬 수 있다.As a carboxyl group containing fluororesin, the fluororesin containing a well-known carboxyl group can be used. The fluororesin refers to a polymer or oligomer having at least one fluorine atom. While curable resin composition can be made alkali developable by presence of a carboxyl group, thermal discoloration resistance can be improved by presence of a fluorine atom.
또한, 본 발명의 경화성 수지 조성물을 광경화성으로 하는 것이나 내현상성의 관점에서, 카르복실기 및 불소 원자 이외에도, 분자 내에 에틸렌성 불포화 결합을 가져도 된다. 에틸렌성 불포화 이중 결합으로서는, 아크릴산 혹은 메타크릴산 또는 그들의 유도체 유래의 것이어도 된다.Moreover, you may have an ethylenically unsaturated bond in a molecule|numerator other than a carboxyl group and a fluorine atom from a viewpoint of making curable resin composition of this invention photocurable and developing resistance. As an ethylenically unsaturated double bond, the thing derived from acrylic acid, methacrylic acid, or those derivatives may be sufficient.
본 발명의 경화성 수지 조성물에 사용할 수 있는 카르복실기 함유 불소 수지의 구체예로서는, 이하에 열거하는 화합물(올리고머 및 폴리머 중 어느 것이어도 됨)을 들 수 있다. 또한, 이하에 기술되는 「불소 치환물」이란, 소정 화합물의 관능기를 구성하는 수소 원자 이외의 수소 원자의 하나 이상이 불소로 치환된 화합물을 말한다.As a specific example of the carboxyl group-containing fluororesin which can be used for the curable resin composition of this invention, the compound (any of an oligomer and a polymer may be sufficient) is mentioned below. In addition, the "fluorine-substituted product" described below refers to a compound in which at least one hydrogen atom other than a hydrogen atom constituting a functional group of a given compound is substituted with fluorine.
(1) (메타)아크릴산 등의 불포화 카르복실산과, 스티렌, α-메틸스티렌, 알킬(메타)아크릴레이트(알킬은, 예를 들어 탄소 원자수가 2 내지 15, 바람직하게는 2 내지 8인 알킬임), 이소부틸렌 등의 불포화기 함유 화합물의 불소 치환물의 공중합에 의해 얻어지는 카르복실기 함유 불소 수지.(1) unsaturated carboxylic acids such as (meth)acrylic acid and styrene, α-methylstyrene, and alkyl (meth)acrylate (alkyl is, for example, an alkyl having 2 to 15 carbon atoms, preferably 2 to 8 carbon atoms) ), a carboxyl group-containing fluororesin obtained by copolymerization of a fluorine-substituted compound of an unsaturated group-containing compound such as isobutylene.
(2) 지방족 디이소시아네이트, 분지 지방족 디이소시아네이트, 지환식 디이소시아네이트, 방향족 디이소시아네이트 등의 디이소시아네이트와, 디메틸올프로피온산, 디메틸올부탄산 등의 카르복실기 함유 디알코올 화합물 및 폴리카보네이트계 폴리올, 폴리에테르계 폴리올, 폴리에스테르계 폴리올, 폴리올레핀계 폴리올, 아크릴계 폴리올, 비스페놀 A계 알킬렌옥사이드 부가체 디올, 페놀성 수산기 및 알코올성 수산기를 갖는 화합물 등의 디올 화합물의 중부가 반응에 의한 카르복실기 함유 우레탄 수지이며, 기술한 원료의 적어도 하나가 불소 치환물인, 카르복실기 및 우레탄 결합을 함유하는 불소 수지.(2) Diisocyanates such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate and aromatic diisocyanate, carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate-based polyols, and polyether-based polyols , polyester polyol, polyolefin polyol, acrylic polyol, bisphenol A alkylene oxide adduct diol, a carboxyl group-containing urethane resin by polyaddition reaction of a diol compound such as a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group, A fluororesin containing a carboxyl group and a urethane bond, wherein at least one of the raw materials is a fluorine-substituted product.
(3) 지방족 디이소시아네이트, 분지 지방족 디이소시아네이트, 지환식 디이소시아네이트, 방향족 디이소시아네이트 등의 디이소시아네이트 화합물과, 폴리카보네이트계 폴리올, 폴리에테르계 폴리올, 폴리에스테르계 폴리올, 폴리올레핀계 폴리올, 아크릴계 폴리올, 비스페놀 A계 알킬렌옥사이드 부가체 디올, 페놀성 수산기 및 알코올성 수산기를 갖는 화합물 등의 디올 화합물의 중부가 반응에 의한 우레탄 수지의 말단에 산 무수물을 반응시켜 이루어지는 말단 카르복실기 함유 우레탄 수지이며, 기술한 원료의 적어도 하나가 불소 치환물인, 카르복실기 및 우레탄 결합을 함유하는 불소 수지.(3) Diisocyanate compounds such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate and aromatic diisocyanate, polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol A-type alkylene oxide adduct is a terminal carboxyl group-containing urethane resin formed by reacting an acid anhydride with the terminal of a urethane resin by polyaddition reaction of a diol compound such as diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group, A fluororesin containing a carboxyl group and a urethane bond, at least one of which is a fluorine-substituted product.
(4) 디이소시아네이트와, 비스페놀 A형 에폭시 수지, 수소 첨가 비스페놀 A형 에폭시 수지, 비스페놀 F형 에폭시 수지, 비스페놀 S형 에폭시 수지, 비크실레놀형 에폭시 수지, 비페놀형 에폭시 수지 등의 2관능 에폭시 수지의 (메타)아크릴레이트 혹은 그의 부분 산 무수물 변성물, 카르복실기 함유 디알코올 화합물 및 디올 화합물의 중부가 반응에 의한 감광성 카르복실기 함유 우레탄 수지이며, 기술한 원료의 적어도 하나가 불소 치환물인, 카르복실기 및 우레탄 결합을 함유하는 불소 수지.(4) Diisocyanate and bifunctional epoxy resins such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, and biphenol type epoxy resin of (meth)acrylate or a partial acid anhydride-modified product thereof, a photosensitive carboxyl group-containing urethane resin by polyaddition reaction of a carboxyl group-containing dialcohol compound and a diol compound, wherein at least one of the raw materials described is a fluorine-substituted carboxyl group and a urethane bond Fluorine resin containing.
(5) 상기 (2) 또는 (4)의 수지의 합성 중에, 히드록시알킬(메타)아크릴레이트 등의 분자 중에 하나의 수산기와 하나 이상의 (메타)아크릴로일기를 갖는 화합물을 첨가하여, 말단 (메타)아크릴화한 카르복실기 및 우레탄 결합을 함유하는 불소 수지.(5) During the synthesis of the resin of (2) or (4) above, a compound having one hydroxyl group and one or more (meth)acryloyl group is added to a molecule such as hydroxyalkyl (meth)acrylate, and the terminal ( A fluororesin containing a meth)acrylated carboxyl group and a urethane bond.
(6) 상기 (2) 또는 (4)의 수지의 합성 중에, 이소포론디이소시아네이트와 펜타에리트리톨트리아크릴레이트의 등몰 반응물 등, 분자 중에 하나의 이소시아네이트기와 하나 이상의 (메타)아크릴로일기를 갖는 화합물을 첨가하여, 말단 (메타)아크릴화한 카르복실기 및 우레탄 결합을 함유하는 불소 수지.(6) Compounds having one isocyanate group and one or more (meth)acryloyl groups in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate during the synthesis of the resin of (2) or (4) A fluororesin containing a carboxyl group and a urethane bond obtained by adding a (meth)acrylated terminal.
(7) 후술하는 바와 같은 다관능 에폭시 수지의 불소 치환물에 (메타)아크릴산을 반응시켜, 측쇄에 존재하는 수산기에 무수 프탈산, 테트라히드로 무수 프탈산, 헥사히드로 무수 프탈산 등의 2염기산 무수물을 부가시킨 감광성 카르복실기 함유 불소 수지.(7) (meth)acrylic acid is reacted with a fluorine-substituted product of a polyfunctional epoxy resin as described below, and dibasic acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride are added to the hydroxyl group present in the side chain A photosensitive carboxyl group-containing fluororesin.
(8) 2관능 에폭시 수지의 수산기를 추가로 에피클로로히드린으로 에폭시화한 다관능 에폭시 수지의 불소 치환물에 (메타)아크릴산을 반응시키고, 발생한 수산기에 2염기산 무수물을 부가시킨 감광성 카르복실기 함유 불소 수지.(8) containing a photosensitive carboxyl group obtained by reacting (meth)acrylic acid with a fluorine-substituted product of a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of the bifunctional epoxy resin with epichlorohydrin, and adding a dibasic acid anhydride to the generated hydroxyl group fluorine resin.
(9) 후술하는 바와 같은 다관능 옥세탄 수지의 불소 치환물에 디카르복실산을 반응시키고, 발생한 1급의 수산기에 2염기산 무수물을 부가시킨 카르복실기 및 에스테르 결합을 함유하는 불소 수지.(9) A fluororesin containing a carboxyl group and an ester bond obtained by adding a dibasic acid anhydride to a primary hydroxyl group generated by reacting a fluorine-substituted product of a polyfunctional oxetane resin as described later with dicarboxylic acid.
(10) 1 분자 중에 복수의 페놀성 수산기를 갖는 화합물의 불소 치환물과 에틸렌옥사이드, 프로필렌옥사이드 등의 알킬렌옥사이드를 반응시켜 얻어지는 반응 생성물에 불포화기 함유 모노카르복실산을 반응시키고, 얻어지는 반응 생성물에 다염기산 무수물을 반응시켜 얻어지는 카르복실기 함유 감광성 불소 수지.(10) A reaction product obtained by reacting a monocarboxylic acid containing an unsaturated group with a reaction product obtained by reacting a fluorine-substituted product of a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide A carboxyl group-containing photosensitive fluororesin obtained by reacting a polybasic acid anhydride with
(11) 1 분자 중에 복수의 페놀성 수산기를 갖는 화합물의 불소 치환물과 에틸렌카보네이트, 프로필렌카보네이트 등의 환상 카보네이트 화합물을 반응시켜 얻어지는 반응 생성물에 불포화기 함유 모노카르복실산을 반응시키고, 얻어지는 반응 생성물에 다염기산 무수물을 반응시켜 얻어지는 카르복실기 함유 감광성 불소 수지.(11) A reaction product obtained by reacting a monocarboxylic acid containing an unsaturated group with a reaction product obtained by reacting a fluorine-substituted product of a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate A carboxyl group-containing photosensitive fluororesin obtained by reacting a polybasic acid anhydride with
(12) 1 분자 중에 복수의 에폭시기를 갖는 에폭시 화합물의 불소 치환물에, p-히드록시페네틸알코올 등의 1 분자 중에 적어도 1개의 알코올성 수산기와 1개의 페놀성 수산기를 갖는 화합물과, (메타)아크릴산 등의 불포화기 함유 모노카르복실산을 반응시키고, 얻어진 반응 생성물의 알코올성 수산기에 대하여, 무수 말레산, 테트라히드로 무수 프탈산, 무수 트리멜리트산, 무수 피로멜리트산, 아디프산 등의 다염기산 무수물을 반응시켜 얻어지는 카르복실기 함유 감광성 불소 수지.(12) a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol, as a fluorine-substituted product of an epoxy compound having a plurality of epoxy groups in one molecule, (meth) Polybasic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride and adipic acid A carboxyl group-containing photosensitive fluororesin obtained by making it react.
(13) 상기 (1) 내지 (12) 중 어느 수지에 글리시딜(메타)아크릴레이트, α-메틸글리시딜(메타)아크릴레이트 등의 분자 중에 하나의 에폭시기와 하나 이상의 (메타)아크릴로일기를 갖는 화합물을 더 부가하여 이루어지는 감광성 카르복실기 함유 불소 수지.(13) In any of the above (1) to (12) resins, one epoxy group and one or more (meth)acryloyl in molecules such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate A photosensitive carboxyl group-containing fluororesin formed by further adding a compound having a diyl group.
상술한 불소 치환물은 소정의 화합물을 불소화함으로써 얻을 수 있다. 불소화 방법으로서는 공지된 방법이면 되고, 예를 들어 저온 불소화, 접촉 불소화, 수용액 불소화, 액상 불소화, 고상 불소화, 기상 불소화 등을 채용할 수 있다.The fluorine-substituted product described above can be obtained by fluorination of a given compound. The fluorination method may be a known method, and for example, low-temperature fluorination, contact fluorination, aqueous solution fluorination, liquid phase fluorination, solid phase fluorination, gas phase fluorination, or the like can be employed.
카르복실기 함유 불소 수지로서, 구체적으로는 신나카무라 가가쿠제의 카르복실기 함유 불소 수지(제품명: TIF-1, TIF-2, TIF-3)를 사용할 수 있다.As the carboxyl group-containing fluororesin, specifically, a carboxyl group-containing fluororesin manufactured by Shin-Nakamura Chemical (product names: TIF-1, TIF-2, TIF-3) can be used.
상기한 바와 같은 카르복실기 함유 불소 수지의 배합량은, (A) 이소시아누레이트 구조와 2개 이상의 (메타)아크릴로일기를 갖는 화합물 100질량부에 대하여, 바람직하게는 135 내지 360질량부, 보다 바람직하게는 150 내지 300질량부이다. 135 내지 300질량부의 경우, 도막 강도가 양호하고, 조성물의 점성이 적당하여 도포성 등을 향상시킬 수 있다.The compounding amount of the carboxyl group-containing fluororesin as described above is preferably 135 to 360 parts by mass, more preferably from 100 parts by mass of the compound (A) having an isocyanurate structure and two or more (meth)acryloyl groups. It is preferably 150 to 300 parts by mass. In the case of 135-300 parts by mass, the coating film strength is good, the viscosity of the composition is moderate, and the coating property and the like can be improved.
본 발명의 경화성 수지 조성물에는, 상기 카르복실기 함유 불소 수지 이외의 카르복실기 함유 수지, 즉 불소 원자를 함유하지 않는 카르복실기 함유 수지가 더 함유되는 것이 바람직하다. 불소 원자를 함유하지 않는 카르복실기 함유 수지가 함유됨으로써, 현상성이 더욱 향상된다.It is preferable that carboxyl group-containing resin other than the said carboxyl group-containing fluororesin, ie, carboxyl group-containing resin which does not contain a fluorine atom, further contains in curable resin composition of this invention. By containing carboxyl group-containing resin which does not contain a fluorine atom, developability improves further.
불소 원자를 함유하지 않는 카르복실기 함유 수지로서는, 공지된 카르복실기를 포함하는 수지를 사용할 수 있다. 본 발명의 경화성 수지 조성물을 광경화성으로 하는 것이나 내현상성의 관점에서, 카르복실기 이외에도 분자 내에 에틸렌성 불포화 결합을 갖는 것이 바람직하지만, 에틸렌성 불포화 이중 결합을 갖지 않는 카르복실기 함유 수지만을 사용할 수도 있다. 에틸렌성 불포화 이중 결합으로서는, 아크릴산 혹은 메타크릴산 또는 그들의 유도체 유래의 것이 바람직하다.As carboxyl group-containing resin which does not contain a fluorine atom, resin containing a well-known carboxyl group can be used. From the viewpoint of making the curable resin composition of the present invention photocurable and developing resistance, it is preferable to have an ethylenically unsaturated bond in the molecule in addition to the carboxyl group, but only a carboxyl group-containing resin having no ethylenically unsaturated double bond may be used. As an ethylenically unsaturated double bond, the thing derived from acrylic acid, methacrylic acid, or those derivatives is preferable.
본 발명의 경화성 수지 조성물에 사용할 수 있는 카르복실기 함유 수지의 구체예로서는, 이하에 열거하는 화합물(올리고머 및 폴리머 중 어느 것이어도 됨)을 들 수 있다.As a specific example of the carboxyl group-containing resin which can be used for the curable resin composition of this invention, the compound (any of an oligomer and a polymer may be sufficient) is mentioned below.
(1) (메타)아크릴산 등의 불포화 카르복실산과, 스티렌, α-메틸스티렌, 저급 알킬(메타)아크릴레이트, 이소부틸렌 등의 불포화기 함유 화합물의 공중합에 의해 얻어지는 카르복실기 함유 공중합 수지.(1) A carboxyl group-containing copolymer resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth)acrylic acid with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth)acrylate or isobutylene.
(2) 지방족 디이소시아네이트, 분지 지방족 디이소시아네이트, 지환식 디이소시아네이트, 방향족 디이소시아네이트 등의 디이소시아네이트와, 디메틸올프로피온산, 디메틸올부탄산 등의 카르복실기 함유 디알코올 화합물 및 폴리카보네이트계 폴리올, 폴리에테르계 폴리올, 폴리에스테르계 폴리올, 폴리올레핀계 폴리올, 아크릴계 폴리올, 비스페놀 A계 알킬렌옥사이드 부가체 디올, 페놀성 수산기 및 알코올성 수산기를 갖는 화합물 등의 디올 화합물의 중부가 반응에 의한 카르복실기 함유 우레탄 수지.(2) Diisocyanates such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate and aromatic diisocyanate, carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate-based polyols, and polyether-based polyols , polyester polyol, polyolefin polyol, acrylic polyol, bisphenol A alkylene oxide adduct diol, carboxyl group-containing urethane resin by polyaddition reaction of a diol compound such as a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
(3) 지방족 디이소시아네이트, 분지 지방족 디이소시아네이트, 지환식 디이소시아네이트, 방향족 디이소시아네이트 등의 디이소시아네이트 화합물과, 폴리카보네이트계 폴리올, 폴리에테르계 폴리올, 폴리에스테르계 폴리올, 폴리올레핀계 폴리올, 아크릴계 폴리올, 비스페놀 A계 알킬렌옥사이드 부가체 디올, 페놀성 수산기 및 알코올성 수산기를 갖는 화합물 등의 디올 화합물의 중부가 반응에 의한 우레탄 수지의 말단에 산 무수물을 반응시켜 이루어지는 말단 카르복실기 함유 우레탄 수지.(3) Diisocyanate compounds such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate and aromatic diisocyanate, polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with the terminal of a urethane resin by polyaddition reaction of a diol compound such as A-type alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
(4) 디이소시아네이트와, 비스페놀 A형 에폭시 수지, 수소 첨가 비스페놀 A형 에폭시 수지, 비스페놀 F형 에폭시 수지, 비스페놀 S형 에폭시 수지, 비크실레놀형 에폭시 수지, 비페놀형 에폭시 수지 등의 2관능 에폭시 수지의 (메타)아크릴레이트 혹은 그의 부분 산 무수물 변성물, 카르복실기 함유 디알코올 화합물 및 디올 화합물의 중부가 반응에 의한 감광성 카르복실기 함유 우레탄 수지.(4) Diisocyanate and bifunctional epoxy resins such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, and biphenol type epoxy resin A photosensitive carboxyl group-containing urethane resin by polyaddition reaction of (meth)acrylate or a partial acid anhydride-modified product thereof, a carboxyl group-containing dialcohol compound and a diol compound.
(5) 상기 (2) 또는 (4)의 수지의 합성 중에, 히드록시알킬(메타)아크릴레이트 등의 분자 중에 하나의 수산기와 하나 이상의 (메타)아크릴로일기를 갖는 화합물을 첨가하여, 말단 (메타)아크릴화한 카르복실기 함유 우레탄 수지.(5) During the synthesis of the resin of (2) or (4) above, a compound having one hydroxyl group and one or more (meth)acryloyl group is added to a molecule such as hydroxyalkyl (meth)acrylate, and the terminal ( Meth) acrylated carboxyl group-containing urethane resin.
(6) 상기 (2) 또는 (4)의 수지의 합성 중에, 이소포론디이소시아네이트와 펜타에리트리톨트리아크릴레이트의 등몰 반응물 등, 분자 중에 하나의 이소시아네이트기와 하나 이상의 (메타)아크릴로일기를 갖는 화합물을 첨가하여, 말단 (메타)아크릴화한 카르복실기 함유 우레탄 수지.(6) Compounds having one isocyanate group and one or more (meth)acryloyl groups in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate during the synthesis of the resin of (2) or (4) A carboxyl group-containing urethane resin obtained by adding a (meth)acrylated terminal.
(7) 후술하는 바와 같은 다관능 에폭시 수지에 (메타)아크릴산을 반응시켜, 측쇄에 존재하는 수산기에 무수 프탈산, 테트라히드로 무수 프탈산, 헥사히드로 무수 프탈산 등의 2염기산 무수물을 부가시킨 감광성 카르복실기 함유 수지.(7) A photosensitive carboxyl group containing a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is added to a hydroxyl group present in a side chain by reacting (meth)acrylic acid with a polyfunctional epoxy resin as described below profit.
(8) 2관능 에폭시 수지의 수산기를 추가로 에피클로로히드린으로 에폭시화한 다관능 에폭시 수지에 (메타)아크릴산을 반응시키고, 발생한 수산기에 2염기산 무수물을 부가시킨 감광성 카르복실기 함유 수지.(8) A photosensitive carboxyl group-containing resin in which (meth)acrylic acid is reacted with a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of the bifunctional epoxy resin with epichlorohydrin, and dibasic acid anhydride is added to the generated hydroxyl group.
(9) 후술하는 바와 같은 다관능 옥세탄 수지에 디카르복실산을 반응시키고, 발생한 1급의 수산기에 2염기산 무수물을 부가시킨 카르복실기 함유 폴리에스테르 수지.(9) A polyester resin containing a carboxyl group in which dicarboxylic acid is reacted with polyfunctional oxetane resin as described below, and dibasic acid anhydride is added to the primary hydroxyl group generated.
(10) 1 분자 중에 복수의 페놀성 수산기를 갖는 화합물과 에틸렌옥사이드, 프로필렌옥사이드 등의 알킬렌옥사이드를 반응시켜 얻어지는 반응 생성물에 불포화기 함유 모노카르복실산을 반응시키고, 얻어지는 반응 생성물에 다염기산 무수물을 반응시켜 얻어지는 카르복실기 함유 감광성 수지.(10) A reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide is reacted with an unsaturated group-containing monocarboxylic acid, and a polybasic acid anhydride is added to the obtained reaction product Carboxyl group-containing photosensitive resin obtained by making it react.
(11) 1 분자 중에 복수의 페놀성 수산기를 갖는 화합물과 에틸렌카보네이트, 프로필렌카보네이트 등의 환상 카보네이트 화합물을 반응시켜 얻어지는 반응 생성물에 불포화기 함유 모노카르복실산을 반응시키고, 얻어지는 반응 생성물에 다염기산 무수물을 반응시켜 얻어지는 감광성 카르복실기 함유 수지.(11) An unsaturated group-containing monocarboxylic acid is reacted with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, and a polybasic acid anhydride is added to the obtained reaction product Photosensitive carboxyl group-containing resin obtained by making it react.
(12) 1 분자 중에 복수의 에폭시기를 갖는 에폭시 화합물에, p-히드록시페네틸알코올 등의 1 분자 중에 적어도 1개의 알코올성 수산기와 1개의 페놀성 수산기를 갖는 화합물과, (메타)아크릴산 등의 불포화기 함유 모노카르복실산을 반응시키고, 얻어진 반응 생성물의 알코올성 수산기에 대하여, 무수 말레산, 테트라히드로 무수 프탈산, 무수 트리멜리트산, 무수 피로멜리트산, 아디프산 등의 다염기산 무수물을 반응시켜 얻어지는 감광성 카르복실기 함유 수지.(12) In an epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol, and unsaturation such as (meth)acrylic acid Photosensitivity obtained by reacting a group-containing monocarboxylic acid and reacting a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and adipic acid with the alcoholic hydroxyl group of the obtained reaction product Carboxyl group-containing resin.
(13) 상기 (1) 내지 (12) 중 어느 수지에 글리시딜(메타)아크릴레이트, α-메틸글리시딜(메타)아크릴레이트 등의 분자 중에 하나의 에폭시기와 하나 이상의 (메타)아크릴로일기를 갖는 화합물을 더 부가하여 이루어지는 감광성 카르복실기 함유 수지.(13) In any of the above (1) to (12) resins, one epoxy group and one or more (meth)acryloyl in molecules such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate The photosensitive carboxyl group-containing resin which further adds the compound which has a diary.
상기 카르복실기 함유 불소 수지 및 불소 원자를 함유하지 않는 카르복실기 함유 수지는, 각각 백본·폴리머의 측쇄에 다수의 카르복실기를 갖기 때문에 희알칼리 수용액에 의한 현상이 가능해진다.Since the said carboxyl group-containing fluororesin and the carboxyl group-containing resin not containing a fluorine atom each have a large number of carboxyl groups in the side chain of the backbone polymer, development with a diluted aqueous alkali solution becomes possible.
또한, 상기 카르복실기 함유 불소 수지 및 불소 원자를 함유하지 않는 카르복실기 함유 수지의 산가는, 각각 20 내지 200mgKOH/g의 범위가 바람직하고, 보다 바람직하게는 40 내지 150mgKOH/g의 범위이다. 카르복실기 함유 수지의 산가가 20mgKOH/g 이상인 경우, 도막의 밀착성이 양호해지고, 알칼리 현상이 양호해진다. 한편, 산가가 200mgKOH/g 이하인 경우에는, 현상액에 의한 노광부의 용해를 억제할 수 있기 때문에, 필요 이상으로 라인이 여위거나, 경우에 따라서는 노광부와 미노광부의 구별없이 현상액으로 용해 박리되거나 하는 것을 억제하여, 양호하게 경화막의 패턴을 묘화할 수 있다.The acid value of the carboxyl group-containing fluororesin and the carboxyl group-containing resin not containing a fluorine atom is preferably in the range of 20 to 200 mgKOH/g, more preferably in the range of 40 to 150 mgKOH/g. When the acid value of carboxyl group-containing resin is 20 mgKOH/g or more, the adhesiveness of a coating film becomes favorable and alkali image development becomes favorable. On the other hand, when the acid value is 200 mgKOH/g or less, since the dissolution of the exposed part by the developer can be suppressed, the line becomes thinner than necessary, or in some cases, the exposed part and the unexposed part are dissolved and peeled off with the developer without distinction. thing can be suppressed and the pattern of a cured film can be drawn favorably.
또한, 상기 카르복실기 함유 불소 수지 및 불소 원자를 함유하지 않는 카르복실기 함유 수지의 질량 평균 분자량은, 수지 골격에 따라서 다르지만, 각각 2,000 내지 150,000, 나아가 5,000 내지 100,000의 범위가 바람직하다. 질량 평균 분자량이 2,000 이상인 경우, 지촉 건조 성능이 양호하고, 노광 후의 도막의 내습성이 양호하고, 현상 시에 막 감소를 억제하여, 해상도의 저하를 억제할 수 있다. 한편, 질량 평균 분자량이 150,000 이하인 경우, 현상성이 양호하고, 저장 안정성도 우수하다.In addition, although the mass average molecular weight of the said carboxyl group-containing fluororesin and the carboxyl group-containing resin not containing a fluorine atom varies depending on the resin skeleton, it is preferably in the range of 2,000 to 150,000, and further preferably 5,000 to 100,000. When the mass average molecular weight is 2,000 or more, the dry to touch performance is good, the moisture resistance of the coating film after exposure is good, the film reduction can be suppressed at the time of image development, and the fall of resolution can be suppressed. On the other hand, when a mass average molecular weight is 150,000 or less, developability is favorable and it is excellent also in storage stability.
또한, 본 명세서에 있어서 (메타)아크릴레이트란, 아크릴레이트, 메타크릴레이트 및 그들의 혼합물을 총칭하는 용어이며, 다른 유사한 표현에 대해서도 마찬가지이다.In addition, in this specification, (meth)acrylate is a general term for an acrylate, a methacrylate, and a mixture thereof, and it is the same also about other similar expression.
불소 원자를 포함하지 않는 카르복실기 함유 수지가 함유되는 경우, 그 배합량은 바람직하게는 카르복실기 함유 불소 수지와 동량 또는 그 이하의 양이다. 구체적으로는, (A) 이소시아누레이트 구조와 2개 이상의 (메타)아크릴로일기를 갖는 화합물 100질량부에 대하여, 바람직하게는 100 내지 250질량부, 보다 바람직하게는 100 내지 200질량부이다. 100 내지 250질량부의 경우, 도막 강도가 양호하고, 조성물의 점성이 적당하여 도포성 등을 향상시킬 수 있다.When the carboxyl group-containing resin not containing a fluorine atom is contained, the compounding amount is preferably the same amount or less than that of the carboxyl group-containing fluororesin. Specifically, (A) With respect to 100 mass parts of compounds which have an isocyanurate structure and two or more (meth)acryloyl groups, Preferably it is 100-250 mass parts, More preferably, it is 100-200 mass parts. . In the case of 100 to 250 parts by mass, the coating film strength is good, the viscosity of the composition is moderate, and the applicability and the like can be improved.
또한, 카르복실기 함유 불소 수지와, 불소 원자를 포함하지 않는 카르복실기 함유 수지의 질량비는 예를 들어 95:5 내지 50:50, 바람직하게는 90:10 내지 60:40이다.The mass ratio of the carboxyl group-containing fluororesin to the carboxyl group-containing resin not containing a fluorine atom is, for example, 95:5 to 50:50, preferably 90:10 to 60:40.
[실리카][Silica]
본 발명의 경화성 수지 조성물에는, 당해 경화성 수지 조성물 중의 배합 성분의 분리를 억제하여, 그의 장기 보존 안정성을 더욱 향상시키는 효과를 부여하기 위해서 실리카가 더 함유되는 것이 바람직하다. 이 경우, 비표면적이 비교적 큰 실리카 및 그것보다 비표면적이 작은 실리카 중 적어도 1종이 사용될 수 있다. 또는, 이들 2종의 실리카를 병용하는 것이 상기 효과를 높이기 때문에 바람직하다.It is preferable that the curable resin composition of this invention contains silica further in order to provide the effect of suppressing separation|separation of the compounding component in the said curable resin composition and improving the long-term storage stability further. In this case, at least one of silica having a relatively large specific surface area and silica having a smaller specific surface area than that may be used. Or it is preferable to use these two types of silica together in order to improve the said effect.
본 발명에 있어서, 비표면적이 비교적 큰 실리카는 100m2/g 이상 300m2/g 미만의 비표면적을 갖는 것이 바람직하다. 비표면적이 비교적 큰 실리카의 배합량은, (A) 이소시아누레이트 구조와 2개 이상의 (메타)아크릴로일기를 갖는 화합물 100질량부에 대하여, 바람직하게는 1 내지 20질량부가 바람직하다. 한편, 비표면적이 비교적 작은 실리카는 10m2/g 이상 100m2/g 미만의 비표면적을 갖는 것이 바람직하다. 비표면적이 비교적 작은 실리카의 배합량은, (A) 이소시아누레이트 구조와 2개 이상의 (메타)아크릴로일기를 갖는 화합물 100질량부에 대하여, 바람직하게는 5 내지 20질량부가 바람직하다.In the present invention, the silica having a relatively large specific surface area preferably has a specific surface area of 100 m 2 /g or more and less than 300 m 2 /g. To [ the compounding quantity of the silica with a comparatively large specific surface area / 100 mass parts of compounds which has (A) an isocyanurate structure and two or more (meth)acryloyl groups), Preferably 1-20 mass parts is preferable. On the other hand, the silica having a relatively small specific surface area preferably has a specific surface area of 10 m 2 /g or more and less than 100 m 2 /g. To [ the compounding quantity of the silica with a comparatively small specific surface area / 100 mass parts of compounds which has (A) an isocyanurate structure and two or more (meth)acryloyl groups), Preferably 5-20 mass parts is preferable.
또한, 비표면적이 비교적 큰 실리카와 비표면적이 비교적 작은 실리카의 배합비는, 질량부 기준으로 1:3 내지 1:6인 것이 바람직하다. 이 범위 내이면 조성물의 보존 안정성이 향상된다.Further, the mixing ratio of silica having a relatively large specific surface area and silica having a relatively small specific surface area is preferably 1:3 to 1:6 based on parts by mass. The storage stability of a composition improves as it exists in this range.
또한, 비표면적은 「BET법」에 의해 측정될 수 있다. 보다 상세하게는, 예를 들어 (주)마운테크제의 전자동 BET 비표면적 측정 장치 MassorbHM-1201을 사용하여, BET 1점법 측정으로 실측하는 방법이 채용될 수 있다.In addition, the specific surface area can be measured by "BET method". In more detail, for example, using a fully automatic BET specific surface area measuring apparatus MassorbHM-1201 manufactured by Muntech Co., Ltd., a method of measuring by BET one-point measurement may be employed.
본 발명에 있어서 사용되는 실리카로서는, 합성 또는 천연의 결정성 실리카의 분쇄품, 용융 실리카의 분쇄품 또는 용융 실리카의 구형 가공품, 또는 합성 구형 실리카, 합성 미분 실리카 등을 사용할 수 있다.As the silica used in the present invention, a pulverized product of synthetic or natural crystalline silica, a pulverized product of fused silica or a spherical processed product of fused silica, or synthetic spherical silica, synthetic finely divided silica, or the like can be used.
합성 실리카, 즉 함수 비정질 이산화규소(SiO2·nH2O)는 반응조에서 규산나트륨 용액(물 유리)과 황산을 반응시킴으로써 제조되고, 반응 조건에 따라서 형상이나 입경을 관리하여, 합성 구형 실리카 또는 합성 미분 실리카로 할 수 있다.Synthetic silica, that is, hydrous amorphous silicon dioxide (SiO 2 ·nH 2 O) is prepared by reacting a sodium silicate solution (water glass) with sulfuric acid in a reaction tank, and controlling the shape or particle size according to the reaction conditions, synthetic spherical silica or synthetic It can be set as finely divided silica.
본 발명에서 바람직하게 사용되는 실리카로서는, 예를 들어 Aerosil 90, Aerosil 130, Aerosil 150, Aerosil 200, Aerosil 225, Aerosil 300, Aerosil 380, Aerosil OX50, Aerosil TT600, Aerosil R104, Aerosil R106, Aerosil R202, Aerosil R711, Aerosil R805, Aerosil R812, Aerosil R816, Aerosil R972, Aerosil R974, Aerosil R7200, Aerosil R8200, Aerosil R9200(닛본 에어로실 가부시키가이샤제), ACEMATT 82, ACEMATT HK125, ACEMATT HK400, ACEMATT HK460, ACEMATT TS100, ACEMATT 82(EVONIK DEGUSSA사제) E-200A, E-220A, K-500, E-1009, E-1011, E-1030, E-150J, E-170, E-200, E-220, E-743, E-974, E-75, HD, HD-2, L-250, L-300, G-300, SS-10, SS-50, SS-30P, SS-30V, SS-30X, SS-50, SS-70(도소·실리카 가부시키가이샤제) 등의 합성 미분 실리카, FUSELEX RD-8, FUSELEX RD-8AL, FUSELEX RD-120, FUSELEX MCF-200C, FUSELEXGP-200TC, FUSELEX TZ-20, FUSELEX ZA-30C, FUSELEX E-1, FUSELEX E-2, FUSELEX AS-1, FUSELEX X(가부시키가이샤 다쯔모리제), FS-3DC, FS-5DC(덴카 가부시키가이샤제) 등의 용융 분쇄 실리카, FB-5D, FB-12D, FB-20D, FB-105, FB-940, FB-9454, FB-950, FB-105FC, FB-870FC, FB-875FC, FB-9454FC, FB-950FC, FB-300FC, FB-105FD, FB-970FD, FB-975FD, FB-950FD, FB-300FD, FB-400FD, FB-7SDC, FB-5SDC, FB-3SDC, FB-74X, FB-25SX, FB-35X, FB-302X, FB-105X, FB-940X, FB-950X, FB-105XFC, FB-950XFC, FB-100XFD, FB-950XFD, FB-7SDX, FB-5SDX, FB-3SDX(덴카 가부시키가이샤제), MSR-2212, MSR-25, MSR-3512, MSR-2212M4, MSV-2212N, MSV-2212NH, MSV-2507NH, MSV-3512N, MSV-3512NH, MSS-7, MSS-6, EXR-4, EXR-3, AC-5VLD, B-21, A-21, MP-15EF, AC-5V, MP-8FS(가부시키가이샤 다쯔모리제) 등의 용융 구상 실리카, SO-E1, SO-E2, SO-E3, SO-E5, SO-E6, SO-C1, SO-C2, SO-C3, SO-C5, SO-C6(가부시키가이샤 애드마텍스) 등의 합성 구상 실리카, CRYSTALITE 3K, CRYSTALITE 3K-S, CRYSTALITE C, CRYSTALITE TNC-1, CRYSTALITE NX-7, CRYSTALITE SMT-10, CRYSTALITE CMC-12S, CRYSTALITE XJ-7, CRYSTALITE C-BASE-1, CRYSTALITE A-1, CRYSTALITE A-A, CRYSTALITE VX-S2(가부시키가이샤 다쯔모리제) 등의 결정성 파쇄 실리카를 들 수 있다.As the silica preferably used in the present invention, for example, Aerosil 90, Aerosil 130, Aerosil 150, Aerosil 200, Aerosil 225, Aerosil 300, Aerosil 380, Aerosil OX50, Aerosil TT600, Aerosil R104, Aerosil R106, Aerosil R202, Aerosil R711, Aerosil R805, Aerosil R812, Aerosil R816, Aerosil R972, Aerosil R974, Aerosil R7200, Aerosil R8200, Aerosil R9200 (manufactured by Nippon Aerosil Co., Ltd.), ACEMATT 82, ACEMATT HK125, ACEMATT HK400, ACEMATT HK460, ACEMATT TS100 ACEMATT 82 (manufactured by EVONIK DEGUSSA) E-200A, E-220A, K-500, E-1009, E-1011, E-1030, E-150J, E-170, E-200, E-220, E-743 , E-974, E-75, HD, HD-2, L-250, L-300, G-300, SS-10, SS-50, SS-30P, SS-30V, SS-30X, SS-50 , SS-70 (manufactured by Tosoh Silica Co., Ltd.) synthetic finely divided silica, FUSELEX RD-8, FUSELEX RD-8AL, FUSELEX RD-120, FUSELEX MCF-200C, FUSELEXGP-200TC, FUSELEX TZ-20, FUSELEX ZA Fused pulverized silica, FB, such as -30C, FUSELEX E-1, FUSELEX E-2, FUSELEX AS-1, FUSELEX X (manufactured by Tatsumori, Ltd.), FS-3DC, FS-5DC (manufactured by Denka Corporation) -5D, FB-12D, FB-20D, FB-105, FB-940, FB-9454, FB-950, FB-105FC, FB-870FC, FB-875FC, FB-9454FC, FB-950FC, FB-300FC , FB-105FD, FB- 970FD, FB-975FD, FB-950FD, FB-300FD, FB-400FD, FB-7SDC, FB-5SDC, FB-3SDC, FB-74X, FB-25SX, FB-35X, FB-302X, FB-105X, FB-940X, FB-950X, FB-105XFC, FB-950XFC, FB-100XFD, FB-950XFD, FB-7SDX, FB-5SDX, FB-3SDX (made by Denka Corporation), MSR-2212, MSR-25 , MSR-3512, MSR-2212M4, MSV-2212N, MSV-2212NH, MSV-2507NH, MSV-3512N, MSV-3512NH, MSS-7, MSS-6, EXR-4, EXR-3, AC-5VLD, B Fused spherical silica such as -21, A-21, MP-15EF, AC-5V, MP-8FS (manufactured by Tatsumori Corporation), SO-E1, SO-E2, SO-E3, SO-E5, SO- Synthetic spherical silica such as E6, SO-C1, SO-C2, SO-C3, SO-C5, SO-C6 (Admatex, Inc.), CRYSTALITE 3K, CRYSTALITE 3K-S, CRYSTALITE C, CRYSTALITE TNC-1 , CRYSTALITE NX-7, CRYSTALITE SMT-10, CRYSTALITE CMC-12S, CRYSTALITE XJ-7, CRYSTALITE C-BASE-1, CRYSTALITE A-1, CRYSTALITE AA, CRYSTALITE VX-S2 (manufactured by Tatsumori Corporation), etc. and crystalline crushed silica.
[2관능 (메타)아크릴레이트 모노머][Bifunctional (meth)acrylate monomer]
본 발명의 경화성 수지 조성물에는, 경화 도막의 열 변색 내성을 더 높이기 위해서, 2관능 (메타)아크릴레이트 모노머가 더 함유되는 것이 바람직하다.In order to further improve the heat discoloration resistance of a cured coating film, it is preferable that the curable resin composition of this invention contains a bifunctional (meth)acrylate monomer further.
그러한 2관능 (메타)아크릴레이트 모노머로서는, 예를 들어 1,3-부틸렌글리콜디(메타)아크릴레이트, 1,4-부탄디올디(메타)아크릴레이트, 1,6-헥산디올디(메타)아크릴레이트, 1,9-노난디올아크릴레이트, 1,10-데칸디올디아크릴레이트, 1,16-헥사데칸디올디아크릴레이트 등을 들 수 있다.Examples of such a bifunctional (meth)acrylate monomer include 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, and 1,6-hexanedioldi(meth)acrylate. acrylate, 1,9-nonanediol acrylate, 1,10-decanediol diacrylate, 1,16-hexadecanediol diacrylate, and the like.
시판품으로서는, 예를 들어 HDDA(다이이찌 고교 세야꾸 가부시키가이샤제), A-NOD-N(신나까무라 가가쿠 고교사제), B1065(도꾜 가세이 고교 가부시키가이샤제), 비스코트 #195(오사까 유끼 가가쿠 고교 가부시키가이샤제), A-DOD-N(신나까무라 가가쿠 고교사제) 등을 들 수 있다.As a commercial item, For example, HDDA (made by Daiichi Kogyo Seyaku Co., Ltd.), A-NOD-N (made by Shin-Nakamura Chemical Co., Ltd.), B1065 (made by Tokyo Kasei Kogyo Co., Ltd.), Viscote #195 (Osaka) Yuki Chemical Co., Ltd. make), A-DOD-N (made by Shin-Nakamura Chemical Co., Ltd.), etc. are mentioned.
상기 2관능 (메타)아크릴레이트 모노머의 배합량은, (A) 이소시아누레이트 구조와 2개 이상의 (메타)아크릴로일기를 갖는 화합물 100질량부에 대하여, 바람직하게는 5 내지 65질량부이다. 본 발명의 경화성 수지 조성물에는, 필요에 따라서 단관능 (메타)아크릴레이트 모노머 또는 3관능 이상의 (메타)아크릴레이트 모노머가 함유되어 있어도 된다.To [ the compounding quantity of the said bifunctional (meth)acrylate monomer / 100 mass parts of compounds which has (A) an isocyanurate structure and two or more (meth)acryloyl groups), Preferably it is 5-65 mass parts. The curable resin composition of this invention may contain the monofunctional (meth)acrylate monomer or the (meth)acrylate monomer more than trifunctional as needed.
[기타 산화 방지제][Other antioxidants]
본 발명의 경화성 수지 조성물에는, 경화물의 열 변색 내성을 더 높이기 위해서, (D) 이소시아누레이트 구조를 갖는 산화 방지제에 더하여, 그 이외의 산화 방지제가 더 함유되어 있어도 물론 된다.In addition to the antioxidant which has (D) isocyanurate structure, in curable resin composition of this invention, in order to raise the heat discoloration resistance of hardened|cured material further, it is of course possible even if antioxidant other than that is contained further.
그러한 산화 방지제로서, 예를 들어 히드로퀴논, 4-tert-부틸카테콜, 2-t-부틸히드로퀴논, 히드로퀴논모노메틸에테르, 2,6-디-t-부틸-p-크레졸, 2,2-메틸렌-비스-(4-메틸-6-t-부틸페놀), 1,1,3-트리스(2-메틸-4-히드록시-5-t-부틸페닐)부탄, 1,3,5-트리메틸-2,4,6-트리스(3,5-디-t-부틸-4-히드록시벤질)벤젠 등의 페놀계, 메타퀴논, 벤조퀴논 등의 퀴논계 화합물, 비스(2,2,6,6-테트라메틸-4-피페리딜)-세바케이트, 페노티아진 등의 아민계 화합물 등, 트리페닐포스파이트 등의 인계 화합물, 펜타에리트리톨테트라라우릴티오프로피오네이트, 디라우릴티오디프로피오네이트, 디스테아릴3,3'-티오디프로피오네이트 등의 황계 화합물 등을 들 수 있다.As such antioxidants, for example, hydroquinone, 4-tert-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-p-cresol, 2,2-methylene- Bis-(4-methyl-6-t-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2 Phenolic compounds such as ,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, quinone compounds such as metaquinone and benzoquinone, bis(2,2,6,6- Amine compounds such as tetramethyl-4-piperidyl)-sebacate and phenothiazine, phosphorus compounds such as triphenylphosphite, pentaerythritol tetralauryl thiopropionate, and dilauryl thiodipropionate and sulfur-based compounds such as distearyl 3,3'-thiodipropionate.
시판품으로서는, 예를 들어 아데카스탭 AO-30, 아데카스탭 AO-330, 아데카스탭 AO-20, 아데카스탭 LA-77, 아데카스탭 LA-57, 아데카스탭 LA-67, 아데카스탭 LA-68, 아데카스탭 LA-87(이상, ADEKA사제, 상품명), IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100(이상, BASF 재팬사제, 상품명), 아데카스탭TPP(ADEKA사제, 상품명), 마크 AO-412S(ADEKA사제, 상품명), 스밀라이저 TPS(스미토모 가가쿠사제, 상품명) 등을 들 수 있다.As a commercial item, For example, Adecastap AO-30, Adecastap AO-330, Adekastab AO-20, Adecastab LA-77, Adekastab LA-57, Adekastab LA-67, Adekastab are, for example. Staff LA-68, ADEKA STAB LA-87 (above, made by ADEKA, brand name), IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (above, TINUVIN 5100) The company make, brand name), ADEKA STAP TPP (made by ADEKA, brand name), Mark AO-412S (made by ADEKA, brand name), Smilizer TPS (made by Sumitomo Chemical, brand name), etc. are mentioned.
이러한 산화 방지제는, (D) 이소시아누레이트 구조를 갖는 산화 방지제와 병용하는 경우에는, (D) 이소시아누레이트 구조를 갖는 산화 방지제 1질량부에 대하여 0.5 내지 3의 질량비로 배합되는 것이 바람직하고, 보다 바람직하게는 0.5 내지 2의 질량비이다.When using together with the antioxidant which has (D) isocyanurate structure, it is preferable that such antioxidant is mix|blended in the mass ratio of 0.5-3 with respect to 1 mass part of antioxidant which has (D) isocyanurate structure. and, more preferably, a mass ratio of 0.5 to 2.
[유기 용제][Organic solvent]
또한, 본 발명의 경화성 수지 조성물에는, 조성물의 조제나, 기판이나 캐리어 필름에 도포할 때의 점도 조정 등의 목적으로, 유기 용제를 함유시킬 수 있다. 유기 용제로서는, 메틸에틸케톤, 시클로헥사논 등의 케톤류; 톨루엔, 크실렌, 테트라메틸벤젠 등의 방향족 탄화수소류; 셀로솔브, 메틸셀로솔브, 부틸셀로솔브, 카르비톨, 메틸카르비톨, 부틸카르비톨, 프로필렌글리콜모노메틸에테르, 디프로필렌글리콜모노메틸에테르, 디프로필렌글리콜디에틸에테르, 디에틸렌글리콜모노메틸에테르아세테이트, 트리프로필렌글리콜모노메틸에테르 등의 글리콜에테르류; 아세트산에틸, 아세트산부틸, 락트산부틸, 셀로솔브아세테이트, 부틸셀로솔브아세테이트, 카르비톨아세테이트, 부틸카르비톨아세테이트, 프로필렌글리콜모노메틸에테르아세테이트, 디프로필렌글리콜모노메틸에테르아세테이트, 탄산프로필렌 등의 에스테르류; 옥탄, 데칸 등의 지방족 탄화수소류; 석유 에테르, 석유 나프타, 솔벤트 나프타 등의 석유계 용제 등, 공지 관용의 유기 용제를 사용할 수 있다. 이들 유기 용제는 단독으로 또는 2종류 이상 조합하여 사용할 수 있다.Moreover, the curable resin composition of this invention can be made to contain the organic solvent for the purpose of preparation of a composition, viscosity adjustment at the time of apply|coating to a board|substrate or a carrier film, etc. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether glycol ethers such as acetate and tripropylene glycol monomethyl ether; esters such as ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butylcarbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and propylene carbonate; aliphatic hydrocarbons such as octane and decane; A well-known and usual organic solvent, such as petroleum solvents, such as petroleum ether, petroleum naphtha, and solvent naphtha, can be used. These organic solvents can be used individually or in combination of 2 or more types.
[그 밖의 성분][Other Ingredients]
본 발명의 경화성 수지 조성물에는, 필요에 따라서, 전자 재료의 분야에 있어서 공지 관용의 다른 첨가제가 더 함유되어 있어도 된다. 그러한 첨가제로서는, 열중합 금지제, 자외선 흡수제, 실란 커플링제, 가소제, 난연제, 대전 방지제, 노화 방지제, 항균·방미제, 소포제, 레벨링제, 증점제, 밀착성 부여제, 광개시 보조제, 증감제, 열가소성 수지, 유기 필러, 이형제, 표면 처리제, 분산제, 분산 보조제, 표면 개질제, 안정제, 형광체 등을 들 수 있다.The curable resin composition of this invention may further contain other well-known and usual additives in the field|area of an electronic material as needed. Examples of such additives include a thermal polymerization inhibitor, a UV absorber, a silane coupling agent, a plasticizer, a flame retardant, an antistatic agent, an anti-aging agent, an antibacterial/mildew inhibitor, an antifoaming agent, a leveling agent, a thickener, an adhesion imparting agent, a photoinitiation aid, a sensitizer, and a thermoplastic. A resin, an organic filler, a mold release agent, a surface treatment agent, a dispersing agent, a dispersion auxiliary agent, a surface modifier, a stabilizer, a fluorescent substance, etc. are mentioned.
[드라이 필름][Dry Film]
본 발명의 경화성 수지 조성물은 드라이 필름화하여 사용해도 되고 혹은 액상으로서 사용해도 된다. 액상으로서 사용하는 경우에는, 1액성이어도 되고 2액성 이상이어도 된다.The curable resin composition of the present invention may be used as a dry film, or may be used as a liquid. When using as a liquid phase, one-component type may be sufficient, and two or more components may be sufficient.
본 발명의 드라이 필름은 캐리어 필름 상에, 본 발명의 경화성 수지 조성물을 도포, 건조시킴으로써 얻어지는 수지층을 갖는다. 드라이 필름을 형성할 때에는, 먼저, 본 발명의 경화성 수지 조성물을 상기 유기 용제로 희석하여 적절한 점도로 조정한 다음에, 콤마 코터, 블레이드 코터, 립 코터, 로드 코터, 스퀴즈 코터, 리버스 코터, 트랜스퍼 롤 코터, 그라비아 코터, 스프레이 코터 등에 의해, 캐리어 필름 상에 균일한 두께로 도포한다. 그 후, 도포된 조성물을 통상 50 내지 130℃의 온도에서 1 내지 30분간 건조시킴으로써, 수지층을 형성할 수 있다. 도포 막 두께에 대하여는 특별히 제한은 없지만, 일반적으로 건조 후의 막 두께로 10 내지 150㎛, 바람직하게는 20 내지 60㎛의 범위에서 적절히 선택된다.The dry film of this invention has a resin layer obtained by apply|coating and drying the curable resin composition of this invention on a carrier film. When forming a dry film, first, the curable resin composition of the present invention is diluted with the organic solvent and adjusted to an appropriate viscosity, and then a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, a transfer roll It is apply|coated to a uniform thickness on a carrier film with a coater, a gravure coater, a spray coater, etc. Thereafter, the resin layer can be formed by drying the applied composition at a temperature of 50 to 130° C. for 1 to 30 minutes. Although there is no restriction|limiting in particular about the coating film thickness, Usually, it is 10-150 micrometers as a film thickness after drying, Preferably it selects suitably in the range of 20-60 micrometers.
캐리어 필름으로서는 플라스틱 필름이 사용되고, 예를 들어 폴리에틸렌테레프탈레이트(PET) 등의 폴리에스테르 필름, 폴리이미드 필름, 폴리아미드이미드 필름, 폴리프로필렌 필름, 폴리스티렌 필름 등을 사용할 수 있다. 캐리어 필름의 두께에 대하여는 특별히 제한은 없지만, 일반적으로 10 내지 150㎛의 범위에서 적절히 선택된다.A plastic film is used as a carrier film, For example, polyester films, such as a polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, etc. can be used. Although there is no restriction|limiting in particular about the thickness of a carrier film, Generally, it selects suitably in the range of 10-150 micrometers.
캐리어 필름 상에 본 발명의 경화성 수지 조성물을 포함하는 수지층을 형성한 후, 막의 표면에 티끌이 부착되는 것을 방지하는 등의 목적으로, 막의 표면에, 박리 가능한 커버 필름을 더 적층하는 것이 바람직하다. 박리 가능한 커버 필름으로서는, 예를 들어 폴리에틸렌 필름이나 폴리테트라플루오로에틸렌 필름, 폴리프로필렌 필름, 표면 처리한 종이 등을 사용할 수 있다. 커버 필름으로서는, 커버 필름을 박리할 때, 수지층과 캐리어 필름의 접착력보다 작은 것이면 된다.After forming the resin layer containing the curable resin composition of the present invention on the carrier film, it is preferable to further laminate a peelable cover film on the surface of the film for the purpose of preventing dust from adhering to the surface of the film. . As a peelable cover film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, the surface-treated paper etc. can be used, for example. As a cover film, when peeling a cover film, what is necessary is just what is smaller than the adhesive force of a resin layer and a carrier film.
또한, 본 발명에 있어서는, 상기 커버 필름 상에 본 발명의 경화성 수지 조성물을 도포, 건조시킴으로써 수지층을 형성하고, 그 표면에 캐리어 필름을 적층하는 것이어도 된다. 즉, 본 발명에 있어서 드라이 필름을 제조할 때에 본 발명의 경화성 수지 조성물을 도포하는 필름으로서는, 캐리어 필름 및 커버 필름 중 어느 것을 사용해도 된다.Moreover, in this invention, a resin layer is formed by apply|coating and drying the curable resin composition of this invention on the said cover film, and you may laminate|stack a carrier film on the surface. That is, when manufacturing a dry film in this invention, you may use any of a carrier film and a cover film as a film which apply|coats curable resin composition of this invention.
[경화물][Cured material]
본 발명의 경화성 수지 조성물을 사용하여 경화물을 형성하기 위해서는, 그 조성물을 기재 상에 도포하고, 용제를 휘발 건조시킨 후에 얻어진 수지층에 대하여 노광(광 조사)을 행함으로써, 노광부(광 조사된 부분)가 경화된다. 구체적으로는 접촉식 또는 비접촉 방식에 의해, 패턴을 형성한 포토마스크를 통하여 선택적으로 활성 에너지선에 의해 노광, 혹은 레이저 다이렉트 노광기에 의해 직접 패턴 노광하고, 미노광부를 알칼리 수용액(예를 들어, 0.3 내지 3질량% 탄산소다 수용액)에 의해 현상함으로써, 레지스트 패턴이 형성된다. 또한 약 100 내지 180℃의 온도에서 가열하여 열경화(후경화)시킴으로써, 내열성, 내약품성, 내흡습성, 밀착성, 전기 특성 등의 여러 특성이 우수한 경화 도막(경화물)을 형성할 수 있다.In order to form a cured product using the curable resin composition of the present invention, the composition is applied on a base material, and the resin layer obtained after the solvent is volatilized and dried is exposed (light irradiation) to an exposed portion (light irradiation). part) is hardened. Specifically, by a contact or non-contact method, through a photomask on which a pattern is formed, selectively exposed to an active energy ray, or directly pattern exposed by a laser direct exposure machine, and the unexposed portion is exposed to an aqueous alkali solution (for example, 0.3 thru|or 3 mass % sodium carbonate aqueous solution), a resist pattern is formed. In addition, by heating at a temperature of about 100 to 180° C. and thermosetting (post-curing), a cured coating film (cured product) excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties can be formed.
본 발명의 경화성 수지 조성물은, 예를 들어 상기 유기 용제를 사용하여 도포 방법에 적합한 점도로 조정하여, 기재 상에, 딥 코팅법, 플로우 코팅법, 롤 코팅법, 바 코터법, 스크린 인쇄법, 커튼 코팅법 등의 방법에 의해 도포한 후, 약 60 내지 100℃의 온도에서 조성물 중에 포함되는 유기 용제를 휘발 건조(가건조)시킴으로써, 지촉 건조성의 수지층을 형성할 수 있다. 또한, 상기 경화성 수지 조성물을 캐리어 필름 또는 커버 필름 상에 도포하고, 건조시켜 필름으로서 권취한 드라이 필름의 경우, 라미네이터 등에 의해 수지층이 기재와 접촉하도록 접합한 후, 캐리어 필름을 박리함으로써, 기재 상에 수지층을 전사할 수 있다.The curable resin composition of the present invention is, for example, adjusted to a viscosity suitable for a coating method using the above organic solvent, and applied onto a substrate by a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method, After coating by a method such as a curtain coating method, a dry to touch resin layer can be formed by volatilizing and drying the organic solvent contained in the composition at a temperature of about 60 to 100°C (temporary drying). In addition, in the case of a dry film in which the curable resin composition is applied on a carrier film or cover film, dried and wound as a film, the resin layer is bonded to the substrate by a laminator or the like, and then the carrier film is peeled off to form the substrate on the substrate. A resin layer can be transcribe|transferred.
기재로서는, 미리 구리 등에 의해 회로 형성된 프린트 배선판이나 플렉시블 프린트 배선판 외에도, 종이 페놀, 종이 에폭시, 유리천 에폭시, 유리 폴리이미드, 유리천/부직포 에폭시, 유리천/종이 에폭시, 합성 섬유 에폭시, 불소 수지·폴리에틸렌·폴리페닐렌에테르, 폴리페닐렌옥사이드·시아네이트 등을 사용한 고주파 회로용 동장 적층판 등의 재질을 사용한 것이며, 모든 그레이드(FR-4 등)의 동장 적층판, 그 밖에도 금속 기판, 폴리이미드 필름, PET 필름, 폴리에틸렌나프탈레이트(PEN) 필름, 유리 기판, 세라믹 기판, 웨이퍼판 등을 들 수 있다.As the substrate, in addition to printed wiring boards and flexible printed wiring boards in which circuits are formed in advance with copper or the like, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/nonwoven epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, fluororesin Materials such as copper-clad laminates for high-frequency circuits using polyethylene/polyphenylene ether, polyphenylene oxide/cyanate, etc. are used, and copper-clad laminates of all grades (FR-4, etc.) A PET film, a polyethylene naphthalate (PEN) film, a glass substrate, a ceramic substrate, a wafer plate, etc. are mentioned.
상기 휘발 건조 또는 열경화는 열풍 순환식 건조로, IR로, 핫 플레이트, 컨벡션 오븐 등(증기에 의한 공기 가열 방식의 열원을 구비한 것을 사용하여 건조기 내의 열풍을 향류 접촉시키는 방법 및 노즐로부터 지지체에 분사하는 방식)을 사용하여 행할 수 있다.The volatilization drying or thermal curing is a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven, etc. spraying method) can be used.
상기 활성 에너지선 조사에 사용되는 노광기로서는, 고압 수은등 램프, 초고압 수은등 램프, 메탈 할라이드 램프, 수은 쇼트 아크램프 등을 탑재하고, 350 내지 450nm의 범위에서 활성 에너지선을 조사하는 장치이면 되고, 또한 직접 묘화 장치(예를 들어, 컴퓨터로부터의 CAD 데이터에 의해 직접 레이저로 화상을 그리는 레이저 다이렉트 이미징 장치)도 사용할 수 있다. 직묘기의 램프 광원 또는 레이저 광원으로서는, 최대 파장이 350 내지 410nm의 범위에 있는 것이면 된다. 화상 형성을 위한 노광량은 막 두께 등에 따라서 다르지만, 일반적으로는 20 내지 1000mJ/cm2, 바람직하게는 20 내지 800mJ/cm2의 범위 내로 할 수 있다.As an exposure machine used for the active energy ray irradiation, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, etc. is mounted, and any device irradiating active energy rays in the range of 350 to 450 nm may be used, and also directly A drawing apparatus (for example, a laser direct imaging apparatus which draws an image with a laser directly by CAD data from a computer) can also be used. As a lamp light source or a laser light source of a straight drawing machine, what is necessary is just to exist in the range of 350-410 nm of maximum wavelength. Light exposure for image formation is different depending on the thickness, in general, it may be within the 20 to 1000mJ / cm 2, preferably in the range of 20 to a range of 800mJ / cm 2.
상기 현상 방법으로서는 디핑법, 샤워법, 스프레이법, 브러시법 등에 의할 수 있고, 현상액으로서는 수산화칼륨, 수산화나트륨, 탄산나트륨, 탄산칼륨, 인산나트륨, 규산나트륨, 암모니아, 아민류 등의 알칼리 수용액을 사용할 수 있다.As the developing method, a dipping method, showering method, spraying method, brush method, etc. can be used. As the developer, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines can be used. have.
본 발명의 경화성 수지 조성물은 프린트 배선판 상에, 솔더 레지스트 등의 표면 보호막을 형성하기 위해 적합하게 사용된다. 또한, 본 발명의 경화성 수지 조성물은 다층 프린트 배선판의 층간 절연층으로서 사용되어도 된다.Curable resin composition of this invention is used suitably in order to form surface protective films, such as a soldering resist, on a printed wiring board. Moreover, the curable resin composition of this invention may be used as an interlayer insulating layer of a multilayer printed wiring board.
[전자 부품][Electronic parts]
또한, 본 발명은, 본 발명의 경화성 수지 조성물을 경화하여 이루어지는 경화물을 갖는 전자 부품도 제공한다. 본 발명의 경화성 수지 조성물을 사용함으로써, 품질 및 신뢰성이 높은 전자 부품이 제공된다.Moreover, this invention also provides the electronic component which has a hardened|cured material formed by hardening|curing curable resin composition of this invention. By using the curable resin composition of this invention, an electronic component with high quality and reliability is provided.
또한, 본 발명에 있어서 전자 부품이란 전자 회로에 사용하는 부품을 의미하고, 프린트 배선판, 트랜지스터, 발광 다이오드, 레이저 다이오드 등의 능동 부품 외에, 저항, 콘덴서, 인덕터, 커넥터 등의 수동 부품도 포함되고, 본 발명의 경화물이 이들의 절연성 경화 도막으로서 본 발명의 효과를 발휘하는 것이다.In addition, in the present invention, electronic components refer to components used in electronic circuits, and in addition to active components such as printed wiring boards, transistors, light emitting diodes, and laser diodes, passive components such as resistors, capacitors, inductors, and connectors are also included. The hardened|cured material of this invention exhibits the effect of this invention as these insulating cured coating films.
[본 발명의 경화성 수지 조성물의 제조][Preparation of curable resin composition of the present invention]
본 발명의 경화성 수지 조성물은, (A) 이소시아누레이트 구조와 2개 이상의 (메타)아크릴로일기를 갖는 화합물, (B) 이소시아누레이트 구조를 갖는 에폭시 수지, 및 (C) 광중합 개시제, 그리고 원한다면 그 밖의 성분을 소정의 양으로, 예를 들어 3개 롤 밀 등으로 혼합 분산함으로써 조제될 수 있다.The curable resin composition of the present invention comprises (A) an isocyanurate structure and a compound having two or more (meth)acryloyl groups, (B) an epoxy resin having an isocyanurate structure, and (C) a photoinitiator; And if desired, it can be prepared by mixing and dispersing other components in a predetermined amount, for example, with a three-roll mill or the like.
이하, 실시예에 의해 본 발명의 일 양태를 구체적으로 나타내지만, 물론 본원 청구항에 관한 발명의 범위를 한정하는 것을 목적으로 하지 않는다.Hereinafter, one aspect of the present invention will be specifically illustrated by way of examples, but, of course, it is not intended to limit the scope of the invention according to the claims of the present application.
[실시예][Example]
이하, 실시예 및 비교예를 나타내어 본 발명에 대하여 구체적으로 설명하지만, 본 발명이 이하의 실시예에 한정되는 것이 아님은 물론이다.Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but it is needless to say that the present invention is not limited to the following Examples.
또한, 달리 단서가 없는 한, 나타나는 「부」 및 「%」는 질량에 기초하는 것으로 한다.In addition, unless otherwise indicated, "part" and "%" appearing shall be based on mass.
[실시예 1 내지 7 및 비교예 1 내지 3][Examples 1 to 7 and Comparative Examples 1 to 3]
하기 표 1에 나타내는 바와 같은 각 성분을, 각 배합량으로 교반기에서 예비 혼합한 후, 3개 롤 밀에서 혼련하여, 실시예 1 내지 7 및 비교예 1 내지 3의 경화성 수지 조성물을 각각 조제하였다. 교반기의 교반 조건은, 예비 교반을 회전수가 500rpm, 교반 시간이 10min으로 실시하고, 본 교반은 회전수 800rpm, 교반 시간 15min으로 실시하였다. 어느 교반에 사용한 교반기 날개는 12cm이다. 또한, 표 중의 수치는 유기 용제를 제외한 고형분의 수치이다.Each component as shown in Table 1 below was pre-mixed with a stirrer at each compounding amount, and then kneaded in a three-roll mill to prepare curable resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3, respectively. As for the stirring conditions of the stirrer, preliminary stirring was performed at a rotation speed of 500 rpm and a stirring time of 10 min, and the main stirring was performed at a rotation speed of 800 rpm and a stirring time of 15 min. The stirrer blade used for any stirring was 12 cm. In addition, the numerical value in a table|surface is the numerical value of solid content except the organic solvent.
(합성예 1)(Synthesis Example 1)
교반기, 온도계, 환류 냉각기, 적하 깔때기 및 질소 도입관을 구비한 2리터 세퍼러블 플라스크에, 용매로서 디에틸렌글리콜디메틸에테르 900g 및 중합 개시제로서 t-부틸퍼옥시2-에틸헥사노에이트(니혼 유시(주)제 퍼부틸 O) 21.4g을 첨가하여 90℃에서 가열하였다. 가열 후, 여기에 메타크릴산 309.9g, 메타크릴산메틸 116.4g 및 락톤 변성 2-히드록시에틸메타크릴레이트(다이셀 가가쿠 고교(주)제 플락셀FM1) 109.8g을, 중합 개시제인 비스(4-t-부틸시클로헥실)퍼옥시디카보네이트(니혼 유시(주)제 퍼로일 TCP) 21.4g과 함께 3시간에 걸쳐 적하하여 첨가하고, 추가로 6시간 숙성함으로써, 카르복실기 함유 공중합 수지를 얻었다. 또한, 반응은 질소 분위기 하에서 행하였다.In a 2-liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube, 900 g of diethylene glycol dimethyl ether as a solvent and t-butylperoxy 2-ethylhexanoate (Nippon Oil Corporation) as a polymerization initiator 21.4 g of Perbutyl O) manufactured by Note) was added and heated at 90°C. After heating, 309.9 g of methacrylic acid, 116.4 g of methyl methacrylate, and 109.8 g of lactone-modified 2-hydroxyethyl methacrylate (Flaxel FM1 manufactured by Daicel Chemical Industry Co., Ltd.) were mixed with bis as a polymerization initiator. (4-t-butylcyclohexyl)peroxydicarbonate (Nippon Yushi Co., Ltd. Peroyl TCP) 21.4 g was added dropwise over 3 hours, and further aged for 6 hours to obtain a carboxyl group-containing copolymer resin. In addition, the reaction was performed under nitrogen atmosphere.
이어서, 얻어진 카르복실기 함유 공중합 수지에, 3,4-에폭시시클로헥실메틸아크릴레이트(다이셀 가가쿠(주)제 사이클로머 A200) 363.9g, 개환 촉매로서 디메틸벤질아민 3.6g, 중합 억제제로서 히드로퀴논모노메틸에테르 1.80g을 첨가하고, 100℃에서 가열하고, 교반함으로써 에폭시의 개환 부가 반응을 행하였다. 16시간 후, 고형분의 산가가 108.9mgKOH/g, 중량 평균 분자량이 25,000인, 방향환을 갖지 않는 카르복실기 함유 수지를 포함하는 용액을 얻었다.Next, to the obtained carboxyl group-containing copolymer resin, 363.9 g of 3,4-epoxycyclohexylmethyl acrylate (Cyclomer A200 manufactured by Daicel Chemical Co., Ltd.), 3.6 g of dimethylbenzylamine as a ring-opening catalyst, and hydroquinone monomethyl as a polymerization inhibitor A ring-opening addition reaction of the epoxy was performed by adding 1.80 g of ether, heating at 100°C, and stirring. After 16 hours, an acid value of 108.9 mgKOH/g of solid content and a weight average molecular weight of 25,000 obtained a solution containing carboxyl group-containing resin having no aromatic ring.
*1 A-9300YN; 에톡시화이소시아누르산트리아크릴레이트, 신나카무라 가가쿠사제 *1 A-9300YN; Ethoxysulfide isocyanuric acid triacrylate, Shin-Nakamura Chemical Co., Ltd.
*2 A-DOD-N; 1,10-데칸디올디아크릴레이트, 신나카무라 가가쿠사제 *2 A-DOD-N; 1,10-decanediol diacrylate, manufactured by Shin-Nakamura Chemical
*3 A-DPH; 신나카무라 가가쿠사제 *3 A-DPH; Made by Shin-Nakamura Chemical
*4 Laromer LR8863; BASF사제 *4 Laromer LR8863; Product made in BASF company
*5 TEPIC(등록 상표)-VL; 닛산 가가쿠사제 *5 TEPIC (registered trademark)-VL; Made by Nissan Chemicals
*6 jER828; 미쓰비시 케미컬사제 *6 jER828; Mitsubishi Chemical Co., Ltd.
*7 합성예 1 *7 Synthesis Example 1
*8 TIF-3(산가 130mgKOH/g); 신나카무라 가가쿠사제 *8 TIF-3 (acid value 130 mgKOH/g); Made by Shin-Nakamura Chemical
*9 Omnirad TPO; 2,4,6-트리메틸벤조일-디페닐포스핀옥사이드; IGM Resins사제 *9 Omnirad TPO; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide; Product made by IGM Resins
*10 Omnirad 819; 비스(2,4,6-트리메틸벤조일)페닐포스핀옥사이드; IGM Resins사제 *10 Omnirad 819; bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide; Product made by IGM Resins
*11 Irganox3114; BASF 재팬사제 *11 Irganox3114; Product made in BASF Japan company
*12 Irganox1010; BASF 재팬사제 *12 Irganox1010; Product made in BASF Japan company
*13 Irganox1330; BASF 재팬사제 *13 Irganox1330; Product made in BASF Japan company
*14 PX-3788; 사까이 가가쿠 고교(주)사제 *14 PX-3788; Product made by Sakai Chemical High School Co., Ltd.
*15 Nipsil E-743(평균 입경 1.5 내지 2.2㎛; 비표면적: 45m2/g); 도소·실리카사제 *15 Nipsil E-743 (average particle diameter 1.5 to 2.2 μm; specific surface area: 45 m 2 /g); Tosoh Silica Co., Ltd.
*16 AEROSIL R974(1차 입경 12nm; 비표면적: 150 내지 190m2/g); 닛본 에어로실사제 *16 AEROSIL R974 (primary particle size 12 nm; specific surface area: 150 to 190 m 2 /g); Product made by Nippon Aerosil Co., Ltd.
얻어진 실시예 1 내지 7 및 비교예 1 내지 3의 경화성 수지 조성물에 대하여, 하기와 같이 색차 ΔE 및 보존 안정성에 관한 시험을 행하였다.About the obtained curable resin composition of Examples 1-7 and Comparative Examples 1-3, the test regarding color difference (DELTA)E and storage stability was done as follows.
[색차 ΔE(열 변색 내성)에 관한 시험][Test on color difference ΔE (thermal discoloration resistance)]
상기에서 제작한 실시예 1 내지 7 및 비교예 3의 경화성 수지 조성물을 각각, 애플리케이터를 사용하여 유리 기판에 도포하고, 80℃×30분의 건조 처리를 행하여, 막 두께 20㎛의 건조 도막을 얻었다. 그 후, 패터닝을 갖는 네가티브를 통해 메탈 할라이드 램프 광원을 사용하여 노광량 600mJ/cm2를 조사한 후에, 1질량%의 탄산나트륨 수용액에 침지하여 현상하고, 이어서 150℃에서 60분간 가열하여 경화 처리를 행하였다.Each of the curable resin compositions of Examples 1 to 7 and Comparative Example 3 prepared above were applied to a glass substrate using an applicator, dried at 80°C for 30 minutes, and a dry coating film having a thickness of 20 µm was obtained. . Then, after irradiating an exposure amount of 600 mJ/cm 2 using a metal halide lamp light source through a negative having patterning, it was developed by immersion in a 1 mass % sodium carbonate aqueous solution, followed by heating at 150° C. for 60 minutes to perform a curing treatment. .
얻어진 기판에 대하여, 피크 톱 온도를 285℃로 하여 10초간의 열처리를 1회 행하였다. 초기값으로부터의 색의 변화량 ΔE(색차)를 산출하였다.With respect to the obtained board|substrate, the peak top temperature was 285 degreeC, and the heat processing for 10 second was performed once. The amount of color change ΔE (color difference) from the initial value was calculated.
ΔE가 2.0 이하였던 것을 ◎로 하고, ΔE가 2.1 이상 4.0 미만이었던 것을 ○로 하고, ΔE가 4.0 이상이었던 것을 ×로 하였다.Those having ΔE of 2.0 or less were denoted by (double-circle), those having ΔE of 2.1 or more and less than 4.0 were denoted by ○, and those having ΔE of 4.0 or more were denoted by ×.
[보존 안정성에 관한 시험][Test on storage stability]
실시예 1 내지 7 및 비교예 1 내지 3의 각각의 경화성 수지 조성물을 20℃에서 정치하고, 정치하였을 때부터, 그들 경화성 수지 조성물의 표면에 분리가 발생할 때까지의 일수를 기록하였다.Each of the curable resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 was left still at 20°C, and the number of days from standing still until separation occurred on the surface of these curable resin compositions was recorded.
Claims (8)
(A) 이소시아누레이트 구조와 2개 이상의 (메타)아크릴로일기를 갖는 화합물,
(B) 이소시아누레이트 구조를 갖는 에폭시 수지, 및
(C) 광중합 개시제
를 함유하는 경화성 수지 조성물.At least, the following components (A) to (C):
(A) a compound having an isocyanurate structure and two or more (meth)acryloyl groups,
(B) an epoxy resin having an isocyanurate structure, and
(C) photoinitiator
A curable resin composition containing
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