CN101464632A - Light solidifying/heat solidifying resin composition and dry film and printed circuit board using the same - Google Patents
Light solidifying/heat solidifying resin composition and dry film and printed circuit board using the same Download PDFInfo
- Publication number
- CN101464632A CN101464632A CNA2008101864585A CN200810186458A CN101464632A CN 101464632 A CN101464632 A CN 101464632A CN A2008101864585 A CNA2008101864585 A CN A2008101864585A CN 200810186458 A CN200810186458 A CN 200810186458A CN 101464632 A CN101464632 A CN 101464632A
- Authority
- CN
- China
- Prior art keywords
- solidifying
- resin composition
- dry film
- film
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000011342 resin composition Substances 0.000 title claims abstract description 58
- 239000000203 mixture Substances 0.000 claims description 37
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 21
- 230000015572 biosynthetic process Effects 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 13
- 229910000679 solder Inorganic materials 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 239000003112 inhibitor Substances 0.000 claims description 7
- 238000001723 curing Methods 0.000 abstract description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- 239000011574 phosphorus Substances 0.000 abstract description 4
- 238000000016 photochemical curing Methods 0.000 abstract 5
- 239000010408 film Substances 0.000 description 76
- 229920000647 polyepoxide Polymers 0.000 description 59
- 239000003822 epoxy resin Substances 0.000 description 58
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 55
- -1 (methyl) acryloyl group Chemical group 0.000 description 48
- 229920005989 resin Polymers 0.000 description 42
- 239000011347 resin Substances 0.000 description 42
- 239000010409 thin film Substances 0.000 description 40
- 229920002120 photoresistant polymer Polymers 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 27
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 24
- 239000013039 cover film Substances 0.000 description 20
- 238000001000 micrograph Methods 0.000 description 18
- 239000004593 Epoxy Chemical group 0.000 description 16
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 16
- 239000002585 base Substances 0.000 description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 16
- 239000002966 varnish Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- 229940106691 bisphenol a Drugs 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 238000007792 addition Methods 0.000 description 9
- 235000013824 polyphenols Nutrition 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 8
- 229930185605 Bisphenol Natural products 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- 239000005864 Sulphur Substances 0.000 description 8
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 150000002148 esters Chemical group 0.000 description 7
- 238000003475 lamination Methods 0.000 description 7
- 229920001568 phenolic resin Polymers 0.000 description 7
- 239000005011 phenolic resin Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 7
- WEHZNZTWKUYVIY-UHFFFAOYSA-N 3-oxabicyclo[3.2.2]nona-1(7),5,8-triene-2,4-dione Chemical compound O=C1OC(=O)C2=CC=C1C=C2 WEHZNZTWKUYVIY-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000008602 contraction Effects 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 125000005442 diisocyanate group Chemical group 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical class CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 230000002650 habitual effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 150000002924 oxiranes Chemical class 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- HEQOJEGTZCTHCF-UHFFFAOYSA-N 2-amino-1-phenylethanone Chemical compound NCC(=O)C1=CC=CC=C1 HEQOJEGTZCTHCF-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 150000004294 cyclic thioethers Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005538 encapsulation Methods 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 150000002168 ethanoic acid esters Chemical class 0.000 description 4
- TVKRSHXXACIRAW-UHFFFAOYSA-N ethoxycarbonylcarbamic acid Chemical compound CCOC(=O)NC(O)=O TVKRSHXXACIRAW-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 4
- 125000003566 oxetanyl group Chemical group 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229960003742 phenol Drugs 0.000 description 4
- 238000001029 thermal curing Methods 0.000 description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 4
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- 230000006978 adaptation Effects 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 150000001896 cresols Chemical class 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 238000013007 heat curing Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- ZJTLZYDQJHKRMQ-UHFFFAOYSA-N menadiol Chemical compound C1=CC=CC2=C(O)C(C)=CC(O)=C21 ZJTLZYDQJHKRMQ-UHFFFAOYSA-N 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 150000002921 oxetanes Chemical class 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000011182 sodium carbonates Nutrition 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- 150000003739 xylenols Chemical group 0.000 description 3
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 3
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical class CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 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
- 238000000862 absorption spectrum Methods 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 239000012675 alcoholic extract Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- NEPKLUNSRVEBIX-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,4-dicarboxylate Chemical compound C=1C=C(C(=O)OCC2OC2)C=CC=1C(=O)OCC1CO1 NEPKLUNSRVEBIX-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 description 2
- 229940035423 ethyl ether Drugs 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 229940015043 glyoxal Drugs 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-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
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 229950000688 phenothiazine Drugs 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000000101 thioether group Chemical group 0.000 description 2
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/08—Epoxidised polymerised polyenes
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
- H05K3/287—Photosensitive compositions
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Abstract
The invention provides a photo-curing and hot-curing resin composition and a dry film and a printing circuit board by using the same. The photo-curing and hot-curing resin composition does not has the problems of residual burr form section around a hole or the hole smaller than a stated aperture, and forms an anticorrosion pattern as a stated exposing pattern, thereby providing the printing circuit board with good productivity and high reliability. The invention provides the photo-curing and hot-curing resin composition and the dry film characterized in that the photo-curing and hot-curing resin composition and the dry film are used for forming the anticorrosion pattern with the hole, wherein a photoplymerization simultaneously containing a photo-curing component and a hot-curing component uses a phosphorus-containing photoplymerization, adaptively, the phosphorus-containing photoplymerization is an acylphosphine oxide photoplymerization.
Description
Technical field
The present invention relates to the manufacturing of circuit substrate, the installation of electronic unit etc. used the dry film of the light solidifying/heat solidifying resin composition that is fit to, and then in more detail, relate to the solder mask etc. that to be provided with hole portion and be formed at the people's livelihood with to industrial printed-wiring board (PWB), light solidifying/heat solidifying resin composition and dry film that particularly flexibility printed circuit board was fit to.The invention still further relates to by this light solidifying/heat solidifying resin composition and dry film and form the printed-wiring board (PWB) that the solder mask that is provided with hole portion forms.
Background technology
Along with improving rapidly of nearest semiconductor device, e-machine has the tendency of miniaturization and, high performance, multifunction, follows therewith, and printed-wiring board (PWB) is densification more and more.Carry out the high-density installation etc. of the mounted on surface of the pathization of the graph thinning of conductor circuit for example, high multiple stratification, via (through via hole), blind hole (blind via hole) etc. and small chip parts all the more.In addition, densification corresponding to such printed-wiring board (PWB), replace being called as the IC encapsulation of flat encapsulation (QFP, QuadFlat Pockage), little outline packages (SOP, Small Outline Package) etc., the IC encapsulation of ball grid array (BGA, Ball Grid Array), wafer-level package (C SP, Chip Scale Package) etc. occurred being called as.In the such base plate for packaging and the printed-wiring board (PWB) of vehicle mounted, in order to implement to be used to improve the gold-plated etc. of reliability, the pad peristomes such as (pad) that is used for being connected with semiconductor device on base plate for packaging uses solder resist.
As solder resist, in the manufacturing of high density printed circuit board, adopt photoresist usually, in addition,, require the dry filmization of solder resist from viewpoints such as operability, thickness precision, cured film smoothness of the surface.In addition, recently, coil type fit automatically (TAB, Tape Auto Bonding), tape ball grid array (T-BGA, Tape-BallGrid Array), carrier band wafer-level package (T-CSP, Tape-Chip ScalePackage), ultra-thin chip level encapsulation (UT-CSP, Ultra Thin-Chip ScalePackage) etc. have for example appearred in the core that is used for printed-wiring board (PWB) and the base plate for packaging thin plateization that becomes.When using the core of such carrier band shape, be necessary to produce the solder resist of (roll-to-roll) method laminating film type by whole volume.
The photoresist of dry film type usually be called as on the supporter of carrier thin film the dry epithelium that forms light solidifying/heat solidifying resin composition or and then cover its surface with cover film, supply with laminar or roller shape, the limit peel off carrier thin film or cover film one, boundary layer is pressed onto on the printed-wiring board (PWB), carry out the selectivity exposure then, thereafter, stripping film (carrier thin film or cover film) afterwards, develops, thereby forms the corrosion-resisting pattern of regulation.
As the photoresist of dry film type, following various composition has been proposed as photoresist: for example contain urethane (methyl) acrylate compounds composition (with reference to patent documentation 1,2), contain the composition (with reference to patent documentation 3,4) of carboxyl urethane (methyl) acrylate compounds etc.But, there are the following problems: use the dry film of existing light solidifying/heat solidifying resin composition to form when being provided with the corrosion-resisting pattern of hole portion, be laminated on the printed-wiring board (PWB) and the selectivity exposure after, stripping film (carrier thin film or cover film) and when developing, the part of the residual burr shape of hole portion periphery or become the little hole portion in aperture than regulation.Like this during the vary in diameter of the part of the residual burr shape of hole portion periphery or hole portion, tack such as gold-plated reduces, and the reliability of gained printed-wiring board (PWB) has greater loss.In addition, adhering to situation according to the diameter variation situation of hole portion, gold-plated etc. becomes substandard products, therefore also has into the problem that productive rate reduces.
On the other hand, Photoepolymerizationinitiater initiater as aqueous photoresist, from curing depth, resolution, thermotolerance, the aspect that hazes, be fit to use 2-methyl isophthalic acid-[4-(methyl sulphur) phenyl]-2-morpholino propane-1,2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-alpha-aminoacetophenones such as 1-ketone are Photoepolymerizationinitiater initiater (reference example such as patent documentation 5).But, when being used for the solder resist of dry film type, above-mentioned such problem can take place.
Patent documentation 1: Japanese kokai publication sho 57-55914 communique (claims)
Patent documentation 2: Japanese kokai publication hei 7-248622 communique (claims)
Patent documentation 3: TOHKEMY 2000-131836 communique (claims)
Patent documentation 4: TOHKEMY 2002-229201 communique (claims)
Patent documentation 5: TOHKEMY 2000-214584 communique (claims)
Summary of the invention
The problem that invention will solve
The present invention finishes in view of aforementioned such prior art problems, its purpose is, a kind of dry film of light solidifying/heat solidifying resin composition is provided, it is after arriving dry film lamination printed-wiring board (PWB) and selectivity exposure, stripping film (carrier thin film or cover film), when development and formation are provided with the corrosion-resisting pattern of hole portion, the part that does not have the residual burr shape of hole portion periphery, perhaps become the little such problem of hole portion in aperture than regulation, can form the corrosion-resisting pattern as the exposing patterns of regulation, thereby the printed-wiring board (PWB) that throughput rate is good and reliability is high is provided, flexibility printed circuit board particularly.
In addition, other purpose of the present invention is to provide a kind of light solidifying/heat solidifying resin composition, even if it does not use above-mentioned dry film, also can solve the above-mentioned same problem that formation produces when the corrosion-resisting pattern of the hole portion that is provided with of film exposure.
The method that is used to deal with problems
In order to realize aforementioned purpose, according to the present invention, a kind of dry film is provided, it is characterized in that, the dry film of this light solidifying/heat solidifying resin composition uses in order to form the corrosion-resisting pattern that is provided with hole portion, wherein, the Photoepolymerizationinitiater initiater as containing photo-curable composition and Thermocurable composition simultaneously uses phosphorous Photoepolymerizationinitiater initiater.
In the scheme that is fit to, above-mentioned phosphorous Photoepolymerizationinitiater initiater is that acylphosphine oxide is a Photoepolymerizationinitiater initiater.
In addition, according to other aspects of the invention, provide a kind of printed-wiring board (PWB), it forms the solder mask that is provided with hole portion by above-mentioned dry film and forms.
In addition, the present invention is in order to realize other purpose, a kind of light solidifying/heat solidifying resin composition is provided, it is characterized in that, this light solidifying/heat solidifying resin composition is used for the formation method across the corrosion-resisting pattern that is provided with hole portion of film exposure, wherein, the Photoepolymerizationinitiater initiater as containing photo-curable composition and Thermocurable composition simultaneously uses phosphorous Photoepolymerizationinitiater initiater.According to the present invention, a kind of printed-wiring board (PWB) also is provided, it forms the solder mask that is provided with hole portion by this light solidifying/heat solidifying resin composition and forms.
The invention effect
Dry film of the present invention, use phosphorous Photoepolymerizationinitiater initiater as the Photoepolymerizationinitiater initiater that light solidifying/heat solidifying resin composition contained that is used for it, therefore, when printed-wiring board (PWB) formation is provided with the corrosion-resisting pattern of hole portion, with dry film lamination during to printed-wiring board (PWB) and selectivity exposure back, stripping film (carrier thin film or cover film), development, do not have the part of the residual burr shape of hole portion periphery or become than the regulation the little such problem of hole portion in aperture, can form as the regulation exposing patterns corrosion-resisting pattern.Its result, tack such as gold-plated also can not reduce, and the printed-wiring board (PWB) that throughput rate is good and reliability is high can be provided.
Description of drawings
Fig. 1 is the microphotograph of the hole portion that obtained in embodiment 1 by the dry film that uses phosphorous Photoepolymerizationinitiater initiater (TPO), be respectively that a-1 peels off carrier thin film after the exposure and the microphotograph of the hole portion when developing immediately, a-2 peels off carrier thin film for exposure after 5 minutes and the microphotograph of the hole portion when developing, a-3 peels off carrier thin film for exposure after 10 minutes and the microphotograph of the hole portion when developing, and a-4 peels off carrier thin film for exposure after 15 minutes and the microphotograph of the hole portion when developing.
Fig. 2 is to be the microphotograph of the hole portion that obtains in comparative example 1 of the dry film of Photoepolymerizationinitiater initiater (Irg-907) by using alpha-aminoacetophenone, is respectively that b-1 peels off carrier thin film after the exposure and microphotograph, the b-2 of the hole portion when developing peel off carrier thin film for exposure after 5 minutes and microphotograph, the b-3 of the hole portion when developing peel off carrier thin film for exposure after 10 minutes and microphotograph, the b-4 of the hole portion when developing peel off carrier thin film for exposure after 15 minutes and the microphotograph of the hole portion when developing immediately.
Fig. 3 is to be the microphotograph of the hole portion that obtains in comparative example 2 of the dry film of Photoepolymerizationinitiater initiater (Irg-369) by using alpha-aminoacetophenone, is respectively that c-1 peels off carrier thin film after the exposure and microphotograph, the c-2 of the hole portion when developing peel off carrier thin film for exposure after 5 minutes and microphotograph, the c-3 of the hole portion when developing peel off carrier thin film for exposure after 10 minutes and microphotograph, the c-4 of the hole portion when developing peel off carrier thin film for exposure after 15 minutes and the microphotograph of the hole portion when developing immediately.
Embodiment
The aforementioned phenomenon that the inventor etc. produce when using the dry film of light solidifying/heat solidifying resin composition as photo-sensitive resin is furtherd investigate.Its result thinks that such phenomenon is to produce because of following reason.Promptly, with dry film lamination when the printed-wiring board (PWB), the limit peel off carrier thin film or cover film one, after boundary layer is pressed on the printed-wiring board (PWB), carry out the selectivity exposure, stripping film (carrier thin film or cover film) after develop, thereby form the corrosion-resisting pattern of stipulating thereafter.Therefore, at stripping film (carrier thin film or cover film) before, it is the top state that is covered by film (carrier thin film or cover film) of the layer (dry film) that is formed at the light solidifying/heat solidifying resin composition on the printed-wiring board (PWB), therefore, prevented and the contacting of the oxygen of ambient atmosphere, become and do not cause that oxygen causes hindering the state of polymerization.For this reason, periphery at the hole portion pattern that is shone by photomask blocking-up active energy beam produces halation, in addition, owing to during after the exposure, before the stripping film, also carry out a lot of polyreactions, therefore, development residual fraction at hole portion periphery generation burr shape perhaps becomes the little hole portion in aperture than regulation.
The inventor etc. further study repeatedly to such phenomenon, found that, when using phosphorous Photoepolymerizationinitiater initiater as the Photoepolymerizationinitiater initiater that light solidifying/heat solidifying resin composition contained that is used for dry film, when printed-wiring board (PWB) formation is provided with the corrosion-resisting pattern of hole portion, do not have as described above in the part of the residual burr shape of hole portion periphery or become the little such problem of hole portion in aperture than regulation, can form the corrosion-resisting pattern as the exposing patterns of regulation, until finishing the present invention.This reason is felt embarrassed to mention clearly, but think that this is because even if phosphorous Photoepolymerizationinitiater initiater works as the polymerization hindrance factor and the top of layer (dry film) that be formed at light solidifying/heat solidifying resin composition on the printed-wiring board (PWB) covered to prevent the oxygen state of contact (state that does not produce oxygen and hinder) with ambient atmosphere by film (carrier thin film or cover film), do not hinder the carrying out of the polyreaction during before the stripping film after the exposure yet.
Aforementioned such effect, the phosphorous Photoepolymerizationinitiater initiater that is fit to of effect excellence are Photoepolymerizationinitiater initiater for the acylphosphine oxide with the group shown in the following general formula (I).
[Chemical formula 1]
(in the formula, R
1And R
2The straight chain shape of independent separately expression carbon number 1～10 or alkyl, alkoxy, cyclohexyl, cyclopentyl, aryl or the halogen atom of a chain, the aryl that is replaced by alkyl or alkoxy, wherein, R
1And R
2Optional R-C (=O)-(here, R represents the alkyl of carbon number 1～20 to Ji.)。)
As the acylphosphine oxide with the group shown in the above-mentioned general formula (I) is the object lesson of Photoepolymerizationinitiater initiater; can enumerate (2,6-dimethoxy benzoyl)-2,4; 4-amyl group phosphine oxide, 2; 4,6-trimethylbenzene formyl diphenyl phosphine oxide, two (2,4; 6-trimethylbenzene formyl)-phenyl phosphine oxide, two (2; 6-dimethoxy benzoyl)-2,4,4-trimethyl-amyl group phosphine oxide etc.As commercially available product, can enumerate Lucirin TPO, the LR8953X of BA SF company manufacturing, the Irgacure819 that Xiba Special Chemical Product Co.,Ltd makes etc.
In addition, aforementioned such effect, the particularly suitable phosphorous Photoepolymerizationinitiater initiater of effect excellence are Photoepolymerizationinitiater initiater for the acylphosphine oxide with the group shown in the following general formula (II).
[Chemical formula 2]
(in the formula, R
1And R
3The straight chain shape of independent separately expression carbon number 1～10 or alkyl, cyclohexyl, cyclopentyl, aryl or the halogen atom of a chain, the aryl that is replaced by alkyl or alkoxy, wherein, R
1And R
3Optional R-C (=O)-(here, R represents the alkyl of carbon number 1～20 to Ji.)。)
As the acylphosphine oxide with the group shown in the above-mentioned general formula (II) is the object lesson of Photoepolymerizationinitiater initiater, and ethyl-2,4 is arranged, 6-trimethylbenzene formylphenyl phosphinate, the Lucirin TPO-L that has BASF AG to make as commercially available product.
The use level of aforementioned phosphorous Photoepolymerizationinitiater initiater like this, contain the carboxyl photoresist or/and contain carboxy resin 100 mass parts (metering always or the independent amount when using separately with respect to described later, below same), what be fit to is 0.1～30 mass parts, be preferably 0.5～20 mass parts, the ratio of 1～15 mass parts more preferably.When the cooperation ratio of phosphorous Photoepolymerizationinitiater initiater is less than above-mentioned scope, the photo-curable variation, on the other hand, and during more than above-mentioned scope, the characteristic variation of cured coating film, in addition, so the storage stability variation is not preferred.In addition, can add known habitual Photoepolymerizationinitiater initiater, light-initiated auxiliary agent with the ratio of the amount of not damaging effect of the present invention.
Then, the light solidifying/heat solidifying resin composition that can be used for dry film formation of the present invention is described.The composition that uses among the present invention can use the light solidifying/heat solidifying resin composition of existing known various alkali developables except use phosphorous Photoepolymerizationinitiater initiater as Photoepolymerizationinitiater initiater.As the photo-curable composition in the light solidifying/heat solidifying resin composition, can use the existing known various photopolymerization monomers that contain carboxyl photonasty prepolymer, have ethylenical unsaturated double bonds alone or in combination more than 2 kinds.In addition, the carboxy resin that contains of photopolymerization monomer and alkali-soluble can be used in combination.Particularly in order to make the composition of alkali-developable, preferably contain carboxy resin, the photosensitive carboxy resin that contains that contains carboxy resin, has an ethylenical unsaturated double bonds that himself does not have ethylenical unsaturated double bonds all can use, be not limited to specific material, the compound of enumerating below can being fit to especially use (oligomer and multipolymer all can).
(1) unsaturated carboxylic acid (a) such as (methyl) acrylic acid and styrene, α-Jia Jibenyixi, low alkyl group (methyl) acrylate, isobutylene etc. have the carboxy resin that contains that compound (b) copolymerization of unsaturated double-bond obtains.
(2) part of multipolymer of unsaturated carboxylic acid (a) and compound (b) with unsaturated double-bond; with have olefinic unsaturated groups such as vinyl, allyl, (methyl) acryloyl group and epoxy radicals, the compound of acyl chlorides isoreactivity group, for example glycidyl (methyl) acrylate reactions, addition olefinic unsaturated group obtains as side chain contains the carboxyl photoresist.
(3) epoxy radicals of glycidyl (methyl) acrylate, Alpha-Methyl glycidyl (methyl) acrylate etc. with compound (c) with unsaturated double-bond, have the multipolymer of the compound (b) of unsaturated double-bond, make the reaction of itself and unsaturated carboxylic acid (a), saturated or unsaturated multi-anhydrides (d) such as the secondary hydroxyl that is generated and terephthalic anhydride, tetrahydrochysene terephthalic anhydride, six hydrogen terephthalic anhydride react and obtain contain the carboxyl photoresist.
(4) acid anhydrides (e) with unsaturated double-bond and multipolymer such as maleic anhydride, itaconic anhydride with compound (b) of unsaturated double-bond, have compound (f) reaction of 1 hydroxyl and 1 above ethylenical unsaturated double bonds with hydroxy alkyl (methyl) acrylate etc. and obtain contain the carboxyl photoresist.
(5) have in the such molecule of aftermentioned the multi-functional epoxy compound (g) of at least 2 epoxy radicals or multi-functional epoxy compound hydroxyl so that with the epoxy radicals of the polyfunctional epoxy resin of chloropropylene oxide epoxy radicalsization, with the carboxyl generation esterification of unsaturated monocarboxylic (h) such as (methyl) acrylic acid (full esterification or partial esterification, be preferably full esterification), the hydroxyl that is generated so obtain with saturated or unsaturated multi-anhydride (d) reaction contain the carboxyl photosensitive compounds.
(6) epoxy radicals of the compound (b) with unsaturated double-bond and the multipolymer of glycidyl (methyl) acrylate, with the alkyl carboxylic acid of carbon number 2～17, contain have 1 carboxyl in 1 molecules such as alkyl carboxylic acid of aromatic series base and do not have organic acid (i) reaction of ethylenic unsaturated bond, secondary hydroxyl and the saturated or unsaturated multi-anhydride (d) that is generated reacts the carboxy resin that contains that obtains.
(7) pass through aliphatic diisocyanate, the side chain aliphatic diisocyanate, the ester ring type diisocyanate, diisocyanate such as aromatic diisocyanate (j) and dihydromethyl propionic acid, dihydroxymethyl butane acid etc. contains carboxylic diol compound (k) and polycarbonate-based polyvalent alcohol, polyethers is a polyvalent alcohol, polyester is a polyvalent alcohol, the polyolefin polyvalent alcohol, acrylic acid series multiple alcohol, bisphenol-A is an alkylene oxide addition product glycol, have phenolic hydroxyl group and alcoholic extract hydroxyl group diol compounds such as compound (m) addition polymerization and obtain contain the carboxyl urethane resin.
(8) (methyl) acrylate or the anhydride modified thing of its part (n) that 2 officials such as diisocyanate (j) and bisphenol A type epoxy resin, hydrogenation bisphenol A type epoxy resin, brominated bisphenol a type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, diformazan phenol-type epoxy resin, bisphenol-type epoxy resin can epoxy resin, contain the addition polymerization of carboxylic diol compound (k) and diol compound (m) and the photosensitive carboxyl urethane resin that contains that obtains.
(9) in the resin of aforementioned (7) or (8) synthetic, what import unsaturated double-bond except hydroxy alkyl (methyl) acrylate etc. has the compound (f) of 1 hydroxyl and the ethylenical unsaturated double bonds more than 1, endways contains the carboxyl urethane resin.
(10) in the resin of aforementioned (7) or (8) synthetic, in the reaction with same mole thing equimolecular of isophorone diisocyanate and pentaerythritol triacrylate, have 1 isocyanate group and more than 1 the compound of (methyl) acryloyl group, end (methyl) acrylated contain the carboxyl urethane resin.
(11) have in the such molecule of aftermentioned primary hydroxyl in the multifunctional oxetane compound of at least 2 oxetanes rings and unsaturated monocarboxylic (h) reaction, the gained modification oxetane compound react with saturated or unsaturated multi-anhydride (d) and obtain contain the carboxyl photoresist.
(12) such 2 officials of aftermentioned can epoxy resin or the 2 officials primary hydroxyl that can oxetane resin reacts, generated with dicarboxylic acid and saturated or unsaturated multi-anhydride (d) addition and obtain contain carboxyl polyester resin.
(13) import in the reaction product of diepoxides and bisphenols unsaturated double-bond, then make itself and saturated or unsaturated multi-anhydride (d) and obtain contain the carboxyl photoresist.
(14) alkylene oxide such as phenolic varnish type phenolics and oxirane, epoxypropane, epoxy butane, oxetanes, tetrahydrofuran, oxinane and/or ethylene carbonate, propylene carbonate, carbonic acid fourth diester, 2, the reaction product of cyclic carbonates such as 3-carbonic ester propyl methyl acid esters, make the reaction of itself and unsaturated monocarboxylic (h), the gained reaction product react with saturated or unsaturated multi-anhydride (d) and obtain contain the carboxyl photoresist.
The aforesaid central preferred material of carboxy resin that contains, from aspect such as flexible, the compound with isocyanate group (yet comprising diisocyanate) that uses during the resin of preferably aforementioned (7)～(10) is synthetic does not have the situation of the diisocyanate of phenyl ring, and the multifunctional and 2 officials energy epoxy resin that uses in synthetic of the resin of aforementioned (5), (8), (12) have bisphenol-A skeleton, Bisphenol F skeleton, xenyl skeleton, xylenol skeleton linear structure compound and add the situation of hydrogen compound.In addition, from the another side, the modifier of (12) as described above of the resin of aforementioned (7)～(10) and these has urethane bond on main chain, with respect to warpage and preferred.In addition, aforementioned (1), (6), (7), (11), (12) resin in addition be owing to have photonasty base (free-radical polymerised unsaturated double-bond) in molecule, thereby preferred from the aspect of photo-curable.
In addition, in this instructions, (methyl) acrylate is meant the term of general name acrylate, methacrylate and these potpourri, and other similarly shows too.
Aforementioned such containing the carboxyl photoresist and contain carboxy resin, owing on the side chain of main chain multipolymer, have a lot of free carboxies, thereby can develop by dilute alkaline aqueous solution.The aforementioned acid number expectation that contains the carboxyl photoresist and contain carboxy resin is the scope of 40～200mgKOH/g, the scope of 45～120mgKOH/g more preferably.When containing the carboxyl photoresist and containing the acid number deficiency 40mgKOH/g of carboxy resin, alkali develops and becomes difficulty, on the other hand, when surpassing 200mgKOH/g, developing solution dissolution exposure portion, thereby become also narrow than needs of line, perhaps the indistinction ground of portion of exposure according to circumstances and unexposed portion dissolves in developer solution and peels off, be difficult to form normal corrosion-resisting pattern, so not preferred.
In addition, aforementioned to contain the carboxyl photoresist different because of resin matrix with the weight-average molecular weight that contains carboxy resin, and expectation is 2000～150000 scope, 5000～100000 scope more preferably usually.During weight-average molecular weight less than 2000, the tack-free poor performance of filming, the moisture-proof of filming after the exposure is poor, produces film during development and reduces, and resolution reduces greatly.On the other hand, weight-average molecular weight surpasses at 150000 o'clock, the remarkable variation of development, and storage stability is poor.
Like this contain the carboxyl photoresist or/and contain the use level expectation of carboxy resin for the scope of 20～70 quality % of whole compositions, be preferably the scope of 30～60 quality %.When being less than above-mentioned scope, coating strength reduces, so not preferred.On the other hand, during more than above-mentioned scope, the viscosity of composition uprises or reduction such as coating, so not preferred.
Only use aforementioned when containing carboxy resin owing to himself do not have ethylenical unsaturated double bonds, so, be necessary further to use photopolymerization monomer in order to form as light solidifying/heat solidifying resin composition.
As the aforementioned lights polymerizable monomer, for example can enumerate the esters of acrylic acid of hydroxyls such as 2-hydroxy ethyl methacrylate, 2-hydroxypropyl acrylate, pentaerythritol triacrylate, dipentaerythritol five acrylate; Water miscible esters of acrylic acid such as polyethyleneglycol diacrylate, polypropyleneglycol diacrylate; The multifunctional polyester esters of acrylic acid of polyvalent alcohols such as trimethylolpropane triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol acrylate; Polyfunctional alcohol or the ethylene oxide adduct of multi-phenols such as bisphenol-A, bis-phenol and/or the esters of acrylic acids of propylene oxide adduct such as trimethylolpropane, hydrogenation bisphenol-A; The above-mentioned isocyanate-modified thing that contains the acrylate of hydroxyl, be multifunctional or the poly-urethane acrylate of simple function; (methyl) acrylic acid addition product of bisphenol-A diglycidyl ether, hydrogenation bisphenol-A diglycidyl ether or phenolic resin varnish, be the epoxy acrylate class; The esters of acrylic acid of caprolactone modification such as the acrylate of caprolactone modification two trimethylolpropane tetra-acrylate, 6-caprolactone modification dipentaerythritol, caprolactone modification 3-hydroxypivalic acid DOPCP diacrylate and corresponding to photonasty (methyl) acrylate compounds of the methyl acrylic ester of aforesaid propylene esters of gallic acid etc., these can use more than 2 kinds alone or in combination.In the middle of these, has multifunctional (methyl) acrylate compounds of (methyl) acryloyl group more than 2 in preferred 1 molecule.The application target of these photonasty (methyl) acrylate compounds is to make composition to have photo-curable.Be aqueous photonasty (methyl) acrylate compounds under the room temperature, have the purpose of photo-curable, also play composition is adjusted to the viscosity that is suitable for various coating processes or helps deliquescent effect aqueous alkali except making composition.But, when using under the room temperature in a large number to aqueous photonasty (methyl) acrylate compounds, the dry to touch that can not get filming, and the characteristic of filming also has the tendency of deterioration, therefore, and preferred a large amount of the use.The use level of photonasty (methyl) acrylate compounds contains below preferred 100 mass parts of carboxy resin 100 mass parts with respect to aforementioned.In addition, in order to improve photoreactivity, can cooperate photonasty (methyl) acrylate compounds in the carboxyl photoresist in aforementioned containing.At this moment, the use level of photonasty (methyl) acrylate compounds contains the carboxyl photoresist or/and contain carboxy resin 100 mass parts and be preferably below 100 mass parts with respect to aforementioned.
The light solidifying/heat solidifying resin composition that uses among the present invention is in order to give thermotolerance and to contain the Thermocurable composition cured film.Preferred Thermocurable composition is the heat-curing resin that has 2 above ring-type ethers and/or cyclic thioether base (being designated hereinafter simply as ring-type (sulphur) ether) in the molecule.In the middle of these, the epoxy resin of preferred 2 functionalities removes this, also can use diisocyanate, its 2 functionality blocked isocyanate.
The Thermocurable composition that has 2 above ring-types (sulphur) ether in such molecule is the compound of group that has any or 2 kinds of the ring-type ether of 3,4 or 5 yuan of rings more than 2 or cyclic thioether base in the molecule, for example can enumerate, have in the molecule in the multifunctional oxetane compound that has the oxetanyl more than at least 2 at least among the multi-functional epoxy compound, molecule of 2 above epoxy radicals, the molecule and have sulfide resin of 2 above thioether groups etc.
Object lesson as aforementioned multi-functional epoxy compound, for example can enumerate bisphenol A type epoxy resin, the hydrogenation bisphenol A type epoxy resin, brominated bisphenol a type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenolic resin varnish type epoxy resin, phenol novolak type epoxy resin, the cresols phenolic resin varnish type epoxy resin, N-diglycidyl fundamental mode epoxy resin, the phenolic resin varnish type epoxy resin of bisphenol-A, the diformazan phenol-type epoxy resin, bisphenol-type epoxy resin, chelating type epoxy resin, glyoxal type epoxy resin, contain aminoepoxy resin, rubber modified epoxy resin, the bicyclopentadiene phenol aldehyde type epoxy resin, the diglycidyl terephthalate resin, the heterocyclic ring epoxy resins, four glycidyl group xylenols ethane resin, modifying epoxy resin by organosilicon, 6-caprolactone modified epoxy etc.In addition, in order to give anti-flammability, can use and in its structure, import the equiatomic material of phosphorus.These epoxy resin improve characteristics such as the adaptation, solder heat resistance, electroless plating patience of cured film by heat curing.In addition, when making dry film, epoxy resin preferably mixed before being applied to light solidifying/heat solidifying resin composition on the carrier thin film.By mixing before the epoxy resin coating, can avoid the tackify of light solidifying/heat solidifying resin composition.
In addition, in the light solidifying/heat solidifying resin composition that uses among the present invention, as epoxy resin, preferably use under the room temperature and consolidate shape, the preferred epoxy resin that uses or slightly solubility insoluble thinning agent (being aqueous photopolymerization monomer or organic solvent under the room temperature) for solid shape or half.By using such epoxy resin, in the light solidifying/heat solidifying resin composition before curing, Gu shape or half admittedly the epoxy resin of shape be the particulate state that is dispersed into.The preferred degree of not bringing obstacle of this particle diameter to serigraphy etc.Like this, in the light solidifying/heat solidifying resin composition before curing solid shape or half admittedly the epoxy resin of shape be dispersed into when microgranular, the working life of light solidifying/heat solidifying resin composition is elongated, so preferably.As the preferred epoxy resin of under such room temperature, consolidating shape, can enumerate bisphenol-s epoxy resin, phenol novolak type epoxy resin, diglycidyl terephthalate resin, heterocyclic ring epoxy resins, diformazan phenol-type epoxy resin, biphenyl type epoxy resin, four glycidyl group xylenols ethane resin etc. for solid shape or half.
As aforementioned multifunctional oxetane compound, can enumerate two [(3-methyl-3-oxetanes methoxyl) methyl] ethers, two [(3-ethyl-3-oxetanes methoxyl) methyl] ether, 1, two [(3-methyl-3-oxetanes methoxyl) methyl] benzene of 4-, 1, two [(3-ethyl-3-oxetanes methoxyl) methyl] benzene of 4-, (3-methyl-3-oxetanes) methacrylate, (3-ethyl-3-oxetanes) methacrylate, (3-methyl-3-oxetanes) methyl acrylate, (3-ethyl-3-oxetanes) methyl acrylate, multifunctional oxetanes classes such as these oligomer or multipolymer, and oxetanes alcohol and novolac resin, poly-(para hydroxybenzene ethene), Cardo type bisphenols, calixarene kind, cup resorcinol aromatic hydrocarbons, or believe that half siloxane etc. has the etherate etc. of the resin of hydroxyl.Remove this, also can enumerate the unsaturated monomer with oxetanes ring and the multipolymer of alkyl (methyl) acrylate etc.
Aforementioned as the compound that has 2 above cyclic thioether bases in the molecule, for example can enumerate Japan Epoxy Resins Co., the bisphenol A-type sulfide resin YL7000 that Ltd. makes etc.In addition, also can use oxygen atom to be substituted by sulfide resin of sulphur atom etc. with the epoxy radicals of phenolic resin varnish type epoxy resin.
The use level that has the Thermocurable composition of 2 above ring-types (sulphur) ether in the aforementioned molecule, with respect to aforementioned carboxyl 1 equivalent that contains the carboxyl photoresist and/or contain carboxy resin, expectation ring-type (sulphur) ether is preferably 0.6～2.5 equivalent, the scope of 0.8～2.0 equivalent more preferably.When having use level less than 0.6 equivalent of Thermocurable composition of 2 above ring-types (sulphur) ether in the molecule, the residual carboxyl of cured film, so reductions such as thermotolerance, alkali resistance, electrical insulating property are not preferred.On the other hand, when surpassing 2.5 equivalents, low-molecular-weight ring-type (sulphur) ether residues in the dry coating, thus the reductions such as intensity of filming, so not preferred.
The light solidifying/heat solidifying resin composition that uses among the present invention is owing to contain the Thermocurable composition that has 2 above ring-types (sulphur) ether in the aforementioned molecule, thereby can also have thermal curing catalyst.As such thermal curing catalyst, for example can enumerate imidazoles, glyoxal ethyline, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyano ethyl-2-phenylimidazole, 1-(2-cyano ethyl)-imdazole derivatives such as 2-ethyl-4-methylimidazole; Dicyandiamide, benzyl dimethylamine, 4-(dimethylamino)-N, N-dimethyl benzylamine, 4-methoxyl-N, N-dimethyl benzylamine, 4-methyl-N, hydrazide compounds such as amines such as N-dimethyl benzylamine, adipic dihydrazide, sebacic dihydrazide; Phosphorus compounds such as triphenylphosphine etc.In addition, as commercially available material, can enumerate four countries for example and change into U-CAT3503N, U-CAT3502T (being the trade name of the block isocyanate compound of dimethyl amine), DBU, DBN, U-CATSA102, the U-CAT5002 (being two ring type amidine compound and salt thereof) etc. that 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (being the trade name of imidazole compound), SAN-APRO Ltd. that industrial group makes make.Particularly be not limited to these, as long as for the thermal curing catalyst or the epoxy radicals that promote epoxy resin, oxetane compound and/or oxetanyl then can mix separately with the material of carboxyl reaction or use more than 2 kinds.In addition, also can use guanamines, methyl guanamines, benzoguanamine, melamine, 2,4-diamido-6-methylacryoyloxyethyl-s-triazine, 2-vinyl-4,6-diamido-s-triazine, 2-vinyl-4,6-diamido-s-triazine isocyanuric acid addition product, 2,4-diamido-6-methylacryoyloxyethyl-Striazine derivatives such as s-triazine isocyanuric acid addition product, the compound and the aforementioned hot curing catalysts that preferably these are also played the function of tackifiers are used in combination.
The use level of these thermal curing catalysts then is sufficient with the ratio of common amount, for example with respect to Thermocurable composition 100 mass parts that have 2 above ring-types (sulphur) ether in the aforementioned molecule, be preferably 0.1～20 mass parts, 0.5～15.0 mass parts more preferably.
In addition, light solidifying/heat solidifying resin composition used in the present invention in order to dissolve aforementioned lights curable composition, Thermocurable composition, and is adjusted to the viscosity that is suitable for coating process with composition, can cooperate organic solvent.
As organic solvent, for example can enumerate ketones such as MEK, cyclohexanone; Toluene, dimethylbenzene, durene etc. are aromatic hydrocarbon based; Glycol ethers such as ethylene glycol monomethyl ether, glycol monomethyl methyl ether, ethylene glycol monobutyl ether, TC, diethylene glycol monomethyl ether, diethylene glycol single-butyl ether, propylene glycol monomethyl ether, propylene glycol list ethylether, dipropylene glycol Anaesthetie Ether, triethylene glycol list ethylether; Acetates such as ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetic acid esters, TC acetic acid esters, diethylene glycol single-butyl ether acetic acid esters, propylene glycol monomethyl ether, DPGME acetic acid esters; Alcohols such as ethanol, propyl alcohol, ethylene glycol, propylene glycol; Aliphatic hydrocarbon such as octane, decane; Oil series solvents such as sherwood oil, naphtha, hydrotreated naphtha, solvent naphtha etc.These organic solvents can use separately or as the potpourri more than 2 kinds.The use level of organic solvent can be any amount according to purposes etc.
The light solidifying/heat solidifying resin composition that uses among the present invention preferably contains phenothiazine, quinhydrones, Hydroquinone monomethylether, tert-butyl catechol, 1,2, known habitual light polymerization inhibitors such as 3-benzenetriol.By containing such light polymerization inhibitor, with dry film lamination after printed-wiring board (PWB), can easier control prevent to be exposed to the carrying out of the polyreaction during the stripping film (carrier thin film or cover film) from selectivity.The use level of light polymerization inhibitor contains the carboxyl photoresist and/or contains carboxy resin 100 mass parts with respect to aforementioned, be suitably for 10 mass parts following, be preferably the following ratio of 5 mass parts.
In the light solidifying/heat solidifying resin composition that uses among the present invention, can be further as required separately or cooperate known habitual inorganic fillers such as barium sulphate more than 2 kinds, barium titanate, amorphous silica, crystallinity silicon dioxide, fused silica, spherical silicon dioxide, talcum, clay, magnesium carbonate, lime carbonate, aluminium oxide, aluminium hydroxide, mica.These are for the cure shrinkage that suppresses to film and improve characteristic such as adaptation, hardness and use.The use level of inorganic filler contains the carboxyl photoresist and/or contains carboxy resin 100 mass parts with respect to aforementioned, is suitably for the ratio that 300 mass parts are following, be preferably 30～200 mass parts.
In the light solidifying/heat solidifying resin composition that uses among the present invention, can further cooperate colorant as required.As colorant, can use phthalein cyanogen indigo plant, phthalein cyanogen is green, iodine is green, dual-azo yellow, crystal violet, titanium dioxide, carbon black, naphthalene are black etc., red, blue, green, Huang etc. is habitually practised known colorant, can be any of pigment, dyestuff, pigment.Wherein, from carrying capacity of environment being reduced and, preferably not halogen-containing to the viewpoint of the influence of human body.
In addition, in the light solidifying/heat solidifying resin composition that uses among the present invention, can and then cooperate so known habitual additive kinds such as fire retardant such as silane coupling agent, phosphorus flame retardant, Sb system fire retardant such as defoamers such as known habitual tackifier such as fine particle silica, organobentonite, smectite, silicon-type, fluorine system, macromolecular and/or levelling agent, imidazoles system, thiazole system, triazole system as required.
When dry film, light solidifying/heat solidifying resin composition of the present invention can be adjusted to suitable viscosity with aforementioned organic solvent diluting, be coated with into homogeneous thickness with comma coating machine (commacoater), oar formula coating machine, lip formula coating machine (lip coater), rod coater (rodcoater), extrusion coater, reverse coating machine (reverse coater), transfer roll coater, intaglio plate coating machine, spin coater etc. on carrier thin film (supporter), drying obtained film in 1～30 minute under 50～130 ℃ temperature usually.Coating film thickness is not particularly limited, and generally suitably selects in the scope of counting 10～150 μ m with dried thickness, be preferably 20～60 μ m.Drying can be used heated air circulation type drying oven, IR stove, hot plate, convective oven etc., and (use possesses by the device of the thermal source of the air heat mode of steam, makes the method for the hot air convection contact in the dryer; Blow to mode on the supporter by nozzle) carry out.
As carrier thin film, use plastic sheeting, preferably use plastic sheetings such as mylar, Kapton, polyamidoimide film, polypropylene film, plasticon such as polyethylene terephthalate.Thickness for carrier thin film is not particularly limited, general suitably selection in the scope of 10～150 μ m.
After film forming on the carrier thin film, and then, be desirably in film surface stacked strippable cover film (protective film) in order to prevent at film surface attachment dust etc.
As strippable cover film, for example can use, polyethylene film, polytetrafluoroethylene film, polypropylene film, surface-treated paper etc. need only the film film littler than the adhesion of film and carrier thin film with the bonding force of cover film when peeling off cover film.
Aforementioned dry film uses applyings such as hot-roll lamination machine (layer mode that contacts with base material according to aforementioned light solidifying/heat solidifying resin composition fitted) on base material.The layer of the light solidifying/heat solidifying resin composition of above-mentioned film is gone up and then when possessing the dry film of strippable cover film, after peeling off cover film (or carrier thin film), use applyings such as hot-roll lamination machine according to layer mode that contacts with base material of above-mentioned light solidifying/heat solidifying resin composition.
Thereafter, stripping film (carrier thin film or cover film) and (irradiation of active energy beam) exposes to fitting in dry film on the base material (layer of light solidifying/heat solidifying resin composition) not.Exposure can be to use contact (or noncontact mode), pass through to form the method for figuratum photomask selectivity by the active energy beam exposure; Perhaps any of the method by the direct pattern exposure of the direct exposure machine of laser.By this exposure, the exposed portion of the layer of light solidifying/heat solidifying resin composition (by the part of active energy beam irradiation) solidifies.Then, stripping film (carrier thin film or cover film) develops unexposed portion to form corrosion-resisting pattern by dilute alkaline aqueous solution (for example 0.3～3% aqueous sodium carbonate).Thereafter and then be heated to for example about 140～180 ℃ temperature so that its heat curing, or the irradiation of the back active energy beam that is heating and curing or is heating and curing after the irradiation of active energy beam makes its final curing (main curing), thereby aforementioned contain the carboxyl photoresist or/and contain the carboxyl of carboxy resin and molecule in have the Thermocurable composition reaction of 2 above ring-type ethers and/or cyclic thioether base, can form the cured film of each excellent such as adaptation, solder heat resistance, chemical proofing, anti-hydroscopicity, chemical gilding patience, electrical insulating property.
As above-mentioned base material, can use the printed-wiring board (PWB), the particularly flexibility printed circuit board that are pre-formed circuit, in addition, use the copper clad laminate, Kapton, PET film, glass substrate, ceramic substrate, wafer board etc. of all specifications (FR-4 etc.) of compound substances such as paper-phenolics, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth/nonwoven fabrics-epoxy resin, glass cloth/paper-epoxy resin, synthon-epoxy resin, fluororesin tygon PPO cyanate in addition.
As the exposure machine that is used for above-mentioned active energy beam irradiation, so long as carried high-pressure sodium lamp, ultrahigh pressure mercury lamp, metal halide lamp, mercury short-arc lamp etc. and get final product, and then also can use direct drawing apparatus (for example by from the cad data of computing machine laser direct imaging device) with the direct rendering image of laser at the device of the scope irradiation ultraviolet radiation of 350～450nm.As the LASER Light Source of directly retouching machine, be the laser of the scope of 350～410nm as long as use maximum wavelength, then can be any of gas laser, Solid State Laser.The exposure that is used to form image generally can be 20～1000mJ/cm because of differences such as thickness
2, be preferably 100～900mJ/cm
2Scope in.
As aforementioned developing method, can use infusion process, spray process, spray-on process, brush method etc., as developer solution, can use alkaline aqueous solutions such as potassium hydroxide, NaOH, sodium carbonate, sal tartari, sodium phosphate, sodium silicate, ammonia, amine.
Embodiment
Below, embodiment etc. is shown the present invention is described more specifically, but the present invention is not limited to these embodiment.In addition, below in, " part " and " % " short of special restriction then all is a quality criteria.
Synthesis example 1
In the removable flask of the 5L that possesses thermometer, stirring machine and reflux condenser, drop into 1245 parts of polycaprolactone glycols as copolymer polyols (Daicel chemical industrial company makes PLACCEL208, molecular weight 830) respectively, as 201 parts of dihydromethyl propionic acids, as 777 parts of the isophorone diisocyanate of polyisocyanate with as each 0.5 part of 119 parts of the 2-hydroxyethylmethacry,ate of (methyl) acrylate and p methoxy phenol and two-tert-butyl group-hydroxy-methylbenzene with hydroxyl with dihydroxy compounds of carboxyl.The limit is stirred and is stopped after the limit is heated to 60 ℃, adds 0.8 part of dibutyl tin dilaurate.When the temperature in reaction vessel began to reduce, heating once more continued to stir at 80 ℃, confirms the absorption spectrum (2280cm of isocyanate group in the infrared absorption spectrum
-1) disappear, reaction finishes, and obtains the thick liquid of urethane acrylate compound.Use the carbitol acetic acid esters to be adjusted to nonvolatile component 50%.Obtain the acid number 47mgKOH/g of solid constituent, the urethane with carboxyl (methyl) acrylate compounds of nonvolatile component 50%.
Synthesis example 2
In the autoclave that possesses thermometer, nitrogen gatherer and alkylene oxide gatherer and stirring apparatus, add phenolic varnish type cresol resin (trade name " ShonolCRG951 ", clear and macromolecule (strain) is made, the OH equivalent: 119.4 parts of 119.4) 119.4 parts, 1.19 ones in potassium hydroxide and toluene, nitrogen replacement, heat temperature raising will be used while stirring in the system.Then, slowly drip 63.8 parts of epoxypropane, 125～132 ℃, with 0～4.8kg/cm
2Reacted 16 hours., be cooled to room temperature thereafter, in this reaction solution, add to mix 89% phosphatase 11 .56 part with in and potassium hydroxide, obtain nonvolatile component 62.1%, hydroxyl value is the propylene oxide reaction solution of the phenolic varnish type cresol resin of 182.2g/eq..1.08 moles of the average additions of the alkylene oxide of its every phenolic hydroxyl group 1 equivalent.
0.18 part of 11.53 parts of 43.2 parts in 293.0 parts of alkylene oxide reaction solutions, acrylic acid, Loprazolams, the methylnaphthohydroquinone of gained phenolic varnish type cresol resin and toluene joined for 252.9 parts possess stirring machine, thermometer and air be blown in the reactor of pipe, speed with 10ml/ minute is blown into air, and stir on the limit, the limit makes it 110 ℃ of reactions 12 hours.The water that is generated by reaction distillates 12.6 parts water in the mode with the azeotropic mixture of toluene.Thereafter, be cooled to room temperature, the gained reaction solution is then washed with 35.35 parts of neutralizations of 15% sodium hydrate aqueous solution., in evaporator toluene with TC acetic acid esters 118.1 part replaced and heat up in a steamer, obtain phenolic varnish type acrylate resin solution thereafter.Then, 332.5 parts of gained phenolic varnish type acrylate resin solution and triphenylphosphine joined for 1.22 parts possess stirrer, thermometer and air be blown in the reactor of pipe, speed with 10ml/ minute is blown into air, stir on the limit, the limit slowly adds 60.8 parts of tetrahydrochysene terephthalic anhydride, make it 95～101 ℃ of reactions 6 hours, take out the cooling back.The nonvolatile component that contains the carboxyl photoresist that obtains of operation is 70.6% like this, the acid number of solid constituent is 87.7mgKOH/g.
Synthesis example 3
The ECON-104S of cresols phenolic resin varnish type epoxy resin (Japanese chemical drug corporate system is made, epoxide equivalent=220) 220 parts (1 equivalents) is joined in the four-hole boiling flask that has stirring machine and condenser, add 207.2 parts of propylene glycol monomethyl ether, heating for dissolving.Then, add as 0.46 part of the methylnaphthohydroquinone of polymerization inhibitor with as 1.38 parts of the triphenylphosphines of catalysts.With this mixture heated to 95～105 ℃, slowly dropwise addition of acrylic acid 50.4 parts of (0.7 equivalent), 41.5 parts of para hydroxybenzene ethyl alcohols (0.3 equivalent) make its reaction 16 hours.(hydroxyl: 1.3 equivalents) be cooled to 80～90 ℃, add 73.0 parts of terephthalic anhydride of tetrahydrochysene (0.48 equivalent), make its reaction 8 hours, take out the cooling back with this reactant.The nonvolatile component of the carboxylic photoresist that obtains of operation is 65% like this, the acid number of solid constituent is 70mgKOH/g.
Synthesis example 4
925 parts of 380 parts of bisphenol f type epoxy resins (epoxide equivalent=950,85 ℃ of softening points, average degree of polymerization n=6.2) and chloropropylene oxides are dissolved in 462.5 parts of the dimethyl sulfoxides, then, under agitation added NaOH60.9 part (1.5 moles) of 70 ℃ of purity 98.5% through 100 minutes.After adding and then 70 ℃ of reactions 3 hours.Reaction adds entry and washes for 250 parts after finishing.After the oil and water separation, decompression is reclaimed a greater part of dimethyl sulfoxide and superfluous unreacted chloropropylene oxide from the oil reservoir distillation down, to comprise the salt of residual pair generation and the reaction product of dimethyl sulfoxide and be dissolved in 750 parts of methyl isobutyl ketones, and then add 10 parts of 30%NaOH aqueous solution, make it 70 ℃ of reactions 1 hour.After reaction finishes, 200 parts of washings of water 2 times.After the oil and water separation, reclaim methyl isobutyl ketone, obtain the polyfunctional epoxy resin of 69 ℃ of epoxide equivalent=310, softening point from oil reservoir distillation.When the gained polyfunctional epoxy resin is calculated by epoxide equivalent.In the middle of 6.2 of the alcoholic extract hydroxyl groups in the aforementioned parent material bisphenol f type epoxy resin about 5 by epoxy radicalsization.310 parts of this polyfunctional epoxy resins and propylene glycol monomethyl ether are joined in the four-hole boiling flask that has stirring machine and reflux condenser for 282 parts, in 90 ℃ of heated and stirred, dissolving.In a single day gained solution be cooled to 60 ℃, adds 72 parts in acrylic acid, 0.5 part of methylnaphthohydroquinone, 2 parts of triphenylphosphines, is heated to 100 ℃, and it was reacted about 60 hours, obtains the reactant that acid number is 0.2mgKOH/g.To wherein adding 140 parts of tetrahydrochysene terephthalic anhydride, be heated to 90 ℃ and react that to divide acid number until solid shape be 100mgKOH/g, obtain containing solid shape and divide 65% solution.
Synthesis example 5
Cresols phenolic resin varnish type epoxy resin (EPICLON N-695, big Japanese ink chemical industrial company make, epoxide equivalent 220) joined for 330 parts possess gas introduction tube, in the flask of stirring apparatus, cooling tube and thermometer, add 340 parts of carbitol acetic acid esters, heating for dissolving adds 1.38 parts of 0.46 part of quinhydrones and triphenylphosphines.With this mixture heated to 95～105 ℃, slowly dropwise addition of acrylic acid is 108 parts, makes its reaction 16 hours.This reaction product is cooled to 80～90 ℃, adds 68 parts of tetrahydrochysene terephthalic anhydride, make its reaction 8 hours, its cooling.Obtain solid constituent acid number 50mgKOH/g, nonvolatile component 60% contain the carboxyl photoresist.
The modulation of light solidifying/heat solidifying resin composition
(1) discussion of Photoepolymerizationinitiater initiater
With the gradation composition shown in the table 1 of the varnish that obtains in aforementioned synthesis example 1 of the mixing use of 3 roller roller mills and the synthesis example 2, obtain the host of light solidifying/heat solidifying resin composition.In addition, after each components matching stirring shown in the table 2, with 3 roller dispersion millings, modulation hardening agent.
Table 1
Table 2
(2) contain the discussion of carboxyl photoresist
With the gradation composition shown in the table 3 of each varnish that obtains in the aforementioned synthesis example 1～5 of the mixing use of 3 roller roller mills, obtain the host of light solidifying/heat solidifying resin composition.In addition, hardening agent uses each components matching shown in the aforementioned table 2 is stirred the back, obtains hardening agent with 3 roller dispersion millings.
Table 3
(3) discussion of phosphorous Photoepolymerizationinitiater initiater
With the gradation composition shown in the table 4 of each varnish that obtains in aforementioned synthesis example 1 of the mixing use of 3 roller roller mills and the synthesis example 2, obtain the host of light solidifying/heat solidifying resin composition.In addition, hardening agent uses the hardening agent that each components matching shown in the aforementioned table 2 is stirred the back, obtains with 3 roller dispersion millings.
Table 4
The making of dry film
With each host of embodiment 1～9 shown in aforementioned table 1, table 3 and the table 4 and comparative example 1～7 and the hardening agent shown in the table 2 respectively with carboxyl: epoxy radicals is that 1: 1.5 ratio is mixed, the modulation light solidifying/heat solidifying resin composition.Using applicator is that the mode of 30 μ m is applied on the PET film (Mitsubishi Polyester company makes R310:16 μ m) with each light solidifying/heat solidifying resin composition of gained according to dry back coating film thickness respectively, makes it obtain dry film 40～100 ℃ of dryings.
Estimate the making of substrate
After the FR-4 substrate polishing grinding that is formed with circuit, use each dry film (name mechanism is done company of institute and made MVLP-500) that vacuum laminator makes said method heated lamination under 0.8MPa, 80 ℃, 1 minute, the condition of 133.3Pa, make and respectively estimate substrate.
(1) evaluation result of Photoepolymerizationinitiater initiater
Stage metraster by Kodak No.2 is respectively estimated base plate exposure to what the hardening agent of the host of using aforementioned table 1 and table 2 obtained, after peeling off carrier thin film, the suitableeest exposure of conduct when the pattern of residual stage metraster is 3 sections in the time of will carrying out developing for 60 seconds under spray pressure 0.2MPa by 30 ℃ 1 quality % aqueous sodium carbonate.
Then, respectively estimate the negative mask that substrate sticks the circular shading light part that is formed with diameter 80 μ m to aforementioned, after with the exposure of the suitableeest exposure immediately, after 5 minutes, after 10 minutes, peel off carrier thin film after 15 minutes, press in spray by 30 ℃ 1 quality % aqueous sodium carbonates and carry out under the 0.2MPa developing for 60 seconds.Visual and the shape of gained corrosion-resisting pattern is estimated with the following commentary valency of microphotograph benchmark.It the results are shown in table 5 and Fig. 1～3.
Zero: do not have the contraction in the opening footpath of hole portion, the generation of burr etc.
△: the opening footpath shrink slightly of hole portion.
*: hole portion produces burr.
Table 5
(2) contain the evaluation result of carboxyl photoresist
Stage metraster by Kodak No.2 is respectively estimated base plate exposure to what the hardening agent of the host of using aforementioned table 3 and table 2 obtained, after peeling off carrier thin film, the suitableeest exposure of conduct when the pattern of residual stage metraster is 3 sections in the time of will carrying out developing for 60 seconds under spray pressure 0.2MPa by 30 ℃ 1 quality % aqueous sodium carbonate.
Then, respectively estimate the negative mask that substrate sticks the circular shading light part that is formed with diameter 80 μ m to aforementioned, after with the exposure of the suitableeest exposure immediately, after 10 minutes, peel off carrier thin film after 30 minutes, press in spray by 30 ℃ 1 quality % aqueous sodium carbonates and carry out under the 0.2MPa developing for 60 seconds.Visual and the shape of gained corrosion-resisting pattern is estimated with the following commentary valency of microphotograph benchmark.It the results are shown in table 6.
Zero: do not have the contraction in the opening footpath of hole portion, the generation of burr etc.
△: the opening footpath shrink slightly of hole portion.
*: hole portion produces burr.
Table 6
(3) evaluation result of phosphorous Photoepolymerizationinitiater initiater
Stage metraster by Kodak No.2 is respectively estimated base plate exposure to what the hardening agent of the host of using aforementioned table 4 and table 2 obtained, after peeling off carrier thin film, the suitableeest exposure of conduct when the pattern of residual stage metraster is 3 sections in the time of will carrying out developing for 60 seconds under spray pressure 0.2MPa by 30 ℃ 1 quality % aqueous sodium carbonate.
Then, respectively estimate the negative mask that substrate sticks the circular shading light part that is formed with diameter 80 μ m to aforementioned, after with the exposure of the suitableeest exposure immediately, after 10 minutes, peel off carrier thin film after 30 minutes, press in spray by 30 ℃ 1 quality % aqueous sodium carbonates and carry out under the 0.2MPa developing for 60 seconds.Visual and the shape of gained corrosion-resisting pattern is estimated with the following commentary valency of microphotograph benchmark.It the results are shown in table 7.
Zero: do not have the contraction in the opening footpath of hole portion, the generation of burr etc.
△: the opening footpath shrink slightly of hole portion.
*: hole portion produces burr.
Table 7
As table 5 and Fig. 1～Fig. 3 as can be known, in the embodiment 1 that uses phosphorous Photoepolymerizationinitiater initiater, immediately and carrier thin film is peeled off after placing in exposure back and when developing, the shape of hole portion almost as the contraction directly of opening that can't see hole portion the design and the generation of burr etc. after exposure.On the other hand, used that normally used alpha-aminoacetophenone is the comparative example 1 and the comparative example 2 of Photoepolymerizationinitiater initiater in the aqueous photoresist, seen the contraction of hole portion and the generation of burr.
In addition, as known from Table 6, contain the carboxyl photoresist even if change, the example that uses phosphorous Photoepolymerizationinitiater initiater dry film (embodiment 2～6) is the dimensionally stable of hole portion of the dry film (comparative example 3～7) of Photoepolymerizationinitiater initiater than using normally used alpha-aminoacetophenone also.
In addition, as table 7 as can be known, even if change the kind of phosphorous Photoepolymerizationinitiater initiater, the shape of hole portion also almost like that as design, the contraction directly of opening that can't see hole portion and the generation of burr etc. also be can't see over time.
In addition, among the embodiment 1, use except replacing phenothiazine the Hydroquinone monomethylether as the light polymerization inhibitor, be grouped into light modulated curable hot curing resin composition and estimate with same one-tenth, the result obtains result similarly to Example 1.
Claims (8)
1. dry film, it is characterized in that it is in order to form the dry film of the light solidifying/heat solidifying resin composition that the corrosion-resisting pattern that is provided with hole portion uses, wherein, Photoepolymerizationinitiater initiater as containing photo-curable composition and Thermocurable composition simultaneously uses phosphorous Photoepolymerizationinitiater initiater.
2. dry film according to claim 1 is characterized in that, aforementioned phosphorous Photoepolymerizationinitiater initiater is that acylphosphine oxide is a Photoepolymerizationinitiater initiater.
3. dry film according to claim 1 is characterized in that it comprises the light polymerization inhibitor.
4. printed-wiring board (PWB), it forms the solder mask that is provided with hole portion by each described dry film of claim 1～3 and forms.
5. light solidifying/heat solidifying resin composition, it is characterized in that, this light solidifying/heat solidifying resin composition is used for the formation method across the corrosion-resisting pattern that is provided with hole portion of film exposure, wherein, Photoepolymerizationinitiater initiater as containing photo-curable composition and Thermocurable composition simultaneously uses phosphorous Photoepolymerizationinitiater initiater.
6. light solidifying/heat solidifying resin composition according to claim 5 is characterized in that, aforementioned phosphorous Photoepolymerizationinitiater initiater is that acylphosphine oxide is a Photoepolymerizationinitiater initiater.
7. light solidifying/heat solidifying resin composition according to claim 5 is characterized in that, comprises the light polymerization inhibitor.
8. printed-wiring board (PWB), it forms the solder mask that is provided with hole portion by each described light solidifying/heat solidifying resin composition of claim 5～7 and forms.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007330338 | 2007-12-21 | ||
| JP2007330338 | 2007-12-21 |
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| Publication Number | Publication Date |
|---|---|
| CN101464632A true CN101464632A (en) | 2009-06-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008101864585A Pending CN101464632A (en) | 2007-12-21 | 2008-12-19 | Light solidifying/heat solidifying resin composition and dry film and printed circuit board using the same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2009169416A (en) |
| KR (1) | KR20090068158A (en) |
| CN (1) | CN101464632A (en) |
| TW (1) | TWI395059B (en) |
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- 2008-12-19 CN CNA2008101864585A patent/CN101464632A/en active Pending
- 2008-12-19 TW TW097149578A patent/TWI395059B/en active
- 2008-12-19 KR KR1020080130148A patent/KR20090068158A/en not_active Application Discontinuation
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Also Published As
| Publication number | Publication date |
|---|---|
| TWI395059B (en) | 2013-05-01 |
| TW200935172A (en) | 2009-08-16 |
| KR20090068158A (en) | 2009-06-25 |
| JP2009169416A (en) | 2009-07-30 |
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