JP2005195943A - Alkali developable photosensitive resin composition and printed wiring board using the same - Google Patents
Alkali developable photosensitive resin composition and printed wiring board using the same Download PDFInfo
- Publication number
- JP2005195943A JP2005195943A JP2004002962A JP2004002962A JP2005195943A JP 2005195943 A JP2005195943 A JP 2005195943A JP 2004002962 A JP2004002962 A JP 2004002962A JP 2004002962 A JP2004002962 A JP 2004002962A JP 2005195943 A JP2005195943 A JP 2005195943A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- photosensitive resin
- wiring board
- meth
- printed wiring
- 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.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 26
- 239000003513 alkali Substances 0.000 title claims description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 38
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 239000011347 resin Substances 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 239000004593 Epoxy Substances 0.000 claims abstract description 19
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 14
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 12
- 238000005476 soldering Methods 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 239000003085 diluting agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims description 31
- 239000011248 coating agent Substances 0.000 claims description 28
- 238000011161 development Methods 0.000 claims description 17
- 238000009736 wetting Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- 229910000679 solder Inorganic materials 0.000 abstract description 53
- 239000000203 mixture Substances 0.000 abstract description 17
- 230000004907 flux Effects 0.000 description 32
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 28
- 229920000647 polyepoxide Polymers 0.000 description 23
- -1 polydimethylsiloxane Polymers 0.000 description 20
- 239000000758 substrate Substances 0.000 description 19
- 239000003822 epoxy resin Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 239000000126 substance Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 239000004020 conductor Substances 0.000 description 8
- 125000002887 hydroxy group Polymers [H]O* 0.000 description 8
- 150000008065 acid anhydrides Chemical class 0.000 description 7
- 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 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000002845 discoloration Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 5
- 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 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 150000007519 polyprotic acids Polymers 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 238000007650 screen-printing Methods 0.000 description 5
- 229920000298 Cellophane Polymers 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002390 adhesive tape Substances 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000001846 repelling effect Effects 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 244000028419 Styrax benzoin Species 0.000 description 3
- 235000000126 Styrax benzoin Nutrition 0.000 description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229960002130 benzoin Drugs 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 235000019382 gum benzoic Nutrition 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 239000003504 photosensitizing agent Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 2
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-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
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- UMLWXYJZDNNBTD-UHFFFAOYSA-N alpha-dimethylaminoacetophenone Natural products CN(C)CC(=O)C1=CC=CC=C1 UMLWXYJZDNNBTD-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 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 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- CKGKXGQVRVAKEA-UHFFFAOYSA-N (2-methylphenyl)-phenylmethanone Chemical compound CC1=CC=CC=C1C(=O)C1=CC=CC=C1 CKGKXGQVRVAKEA-UHFFFAOYSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- XKSUVRWJZCEYQQ-UHFFFAOYSA-N 1,1-dimethoxyethylbenzene Chemical compound COC(C)(OC)C1=CC=CC=C1 XKSUVRWJZCEYQQ-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical class C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical class NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 1
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical group C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- CERJZAHSUZVMCH-UHFFFAOYSA-N 2,2-dichloro-1-phenylethanone Chemical compound ClC(Cl)C(=O)C1=CC=CC=C1 CERJZAHSUZVMCH-UHFFFAOYSA-N 0.000 description 1
- GIMQKKFOOYOQGB-UHFFFAOYSA-N 2,2-diethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)(OCC)C(=O)C1=CC=CC=C1 GIMQKKFOOYOQGB-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- BRKORVYTKKLNKX-UHFFFAOYSA-N 2,4-di(propan-2-yl)thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC(C(C)C)=C3SC2=C1 BRKORVYTKKLNKX-UHFFFAOYSA-N 0.000 description 1
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- DRLRGHZJOQGQEC-UHFFFAOYSA-N 2-(2-methoxypropoxy)propyl acetate Chemical compound COC(C)COC(C)COC(C)=O DRLRGHZJOQGQEC-UHFFFAOYSA-N 0.000 description 1
- XOGPDSATLSAZEK-UHFFFAOYSA-N 2-Aminoanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(N)=CC=C3C(=O)C2=C1 XOGPDSATLSAZEK-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 1
- SEFYJVFBMNOLBK-UHFFFAOYSA-N 2-[2-[2-(oxiran-2-ylmethoxy)ethoxy]ethoxymethyl]oxirane Chemical compound C1OC1COCCOCCOCC1CO1 SEFYJVFBMNOLBK-UHFFFAOYSA-N 0.000 description 1
- HEQOJEGTZCTHCF-UHFFFAOYSA-N 2-amino-1-phenylethanone Chemical class NCC(=O)C1=CC=CC=C1 HEQOJEGTZCTHCF-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
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- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 1
- 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 1
- UMWZLYTVXQBTTE-UHFFFAOYSA-N 2-pentylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(CCCCC)=CC=C3C(=O)C2=C1 UMWZLYTVXQBTTE-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Materials For Photolithography (AREA)
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Abstract
Description
本発明は、アルカリ現像型感光性樹脂組成物、及び該組成物の硬化塗膜であるソルダーレジストを有するプリント配線板に関するものである。 The present invention relates to an alkali development type photosensitive resin composition and a printed wiring board having a solder resist which is a cured coating film of the composition.
プリント配線板に電子部品を搭載する方法として、導体パッド部分に該電子部品をはんだ付けして接続、固着する方法がある。この際、導体パッド部分を除いた他の回路配線部分を含む基板の表面全体にソルダーレジストを形成してから、はんだ付け処理が行われている。また、プリント配線板に電子部品をはんだ付けする際には、予め基板表面にフラックスが塗布される。このようにはんだ付け時にフラックスが塗布されると、その膜が酸素を遮断して導体の酸化を防止するとともに、既に生じている酸化物を還元し、はんだをよく濡らすようになる。 As a method of mounting an electronic component on a printed wiring board, there is a method of soldering and connecting and fixing the electronic component to a conductor pad portion. At this time, a soldering process is performed after a solder resist is formed on the entire surface of the substrate including other circuit wiring portions excluding the conductor pad portions. Further, when soldering an electronic component to the printed wiring board, a flux is applied to the substrate surface in advance. Thus, when flux is applied during soldering, the film blocks oxygen and prevents oxidation of the conductor, while reducing the already generated oxide and wets the solder well.
しかし、従来より用いられていたフラックスはハロゲンを含有するものであり、ソルダーレジスト上にフラックスがはじきれずに少量でも残ると、ハロゲンイオン残渣のためにマイグレーション特性が悪化するという問題点を有していた。 However, the flux conventionally used contains halogen, and if the flux remains on the solder resist without being repelled, it has a problem that the migration characteristics deteriorate due to the halogen ion residue. It was.
そのため、フラックスの塗布に際しては、導体パッド上のみにフラックスを付着させるべく、ソルダーレジスト上のフラックスをはじかせるために、ソルダーレジスト組成物として非水溶性シリコーンを含有させた組成物が提案され用いられている（例えば、特許文献１参照。）。 Therefore, a composition containing a water-insoluble silicone is proposed and used as a solder resist composition in order to repel the flux on the solder resist so that the flux is applied only on the conductor pad when applying the flux. (For example, refer to Patent Document 1).
また一方で、フラックスのハロゲンフリー化が進められ、低イオン性のフラックスが開発されている（例えば、特許文献２参照。）。このフラックスによれば、確かにソルダーレジスト上にフラックスが残存しても、低イオン性のためマイグレーション特性に悪影響を及ぼすことは殆どない。 On the other hand, the flux has been made halogen-free, and a low-ionic flux has been developed (see, for example, Patent Document 2). According to this flux, even if the flux remains on the solder resist, the migration characteristics are hardly adversely affected due to low ionicity.
しかし、上記いずれのフラックスを用いた場合であっても、はんだ付け時に球状のはんだ（いわゆるはんだボール）がソルダーレジスト上に残ることがある。
このように、ソルダーレジスト上にはんだボールが残留すると、特に微細な回路間のソルダーレジスト上に付着した場合に、そのはんだボールによって回路間に電気的障害を引き起こしやすいという問題点がある。 As described above, when the solder balls remain on the solder resist, there is a problem that an electrical failure is easily caused between the circuits due to the solder balls, particularly when the solder balls adhere to the solder resist between the fine circuits.
本発明は係る問題点に鑑みなされたものであり、プリント配線板のはんだ付け時におけるソルダーレジスト上のはんだボールの残留がなく、導体パッドのみへのはんだの供給を可能とするソルダーレジスト組成物を提供することを目的とする。 The present invention has been made in view of such problems, and there is no solder ball residue on the solder resist at the time of soldering a printed wiring board, and a solder resist composition capable of supplying solder only to the conductor pads is provided. The purpose is to provide.
本発明者は、導体パッドだけでなくソルダーレジストを含む基板全面にフラックス膜を形成することにより、ソルダーレジスト上におけるはんだボールの残留を防止することが可能となる点、またハロゲンフリーの低イオン性のフラックスは残存してもマイグレーション特性を悪化させないことからフラックス膜を残したまま製品とすることができる点に着目し、鋭意研究を行った結果、フラックスとの濡れ性を向上させるソルダーレジスト組成物を開発することにより前記課題が解決されることを見出し、本発明を完成するに至った。 The present inventor can prevent the solder balls from remaining on the solder resist by forming a flux film on the entire surface of the substrate including not only the conductor pad but also the solder resist, and also has a halogen-free low ionicity. As a result of earnest research, the solder resist composition improves the wettability with the flux. The inventors have found that the above problems can be solved by developing the present invention, and have completed the present invention.
すなわち、本発明によれば、（Ａ）１分子中に１個以上のカルボキシル基を有するカルボキシル基含有樹脂、（Ｂ）光重合開始剤、（Ｃ）反応性希釈剤、（Ｄ）水溶性シリコーン、及び（Ｅ）１分子中に２個以上のエポキシ基を有する多官能エポキシ化合物を含有することを特徴とするアルカリ現像型感光性樹脂組成物が提供される。 That is, according to the present invention, (A) a carboxyl group-containing resin having one or more carboxyl groups in one molecule, (B) a photopolymerization initiator, (C) a reactive diluent, (D) a water-soluble silicone And (E) an alkali-developable photosensitive resin composition comprising a polyfunctional epoxy compound having two or more epoxy groups in one molecule.
かかるアルカリ現像型感光性樹脂組成物は、その硬化塗膜の濡れ指数が３８ｍＮ／ｍ以上であることが好ましく、また水溶性シリコーン（Ｄ）の配合量は、カルボキシル基含有樹脂（Ａ）の固形分１００質量部に対して０．５〜１０質量部であることが好ましい。 Such an alkali-developable photosensitive resin composition preferably has a cured coating film having a wetting index of 38 mN / m or more, and the amount of the water-soluble silicone (D) is the solid content of the carboxyl group-containing resin (A). It is preferable that it is 0.5-10 mass parts with respect to 100 mass parts per minute.
また、本発明により、前記アルカリ現像型感光性樹脂組成物を用いて形成されたソルダーレジストを有するプリント配線板が提供される。 Moreover, the printed wiring board which has a soldering resist formed using the said alkali development type photosensitive resin composition by this invention is provided.
本発明によれば、はんだ付け時にはんだボールの残留のないプリント配線板の提供が可能となった。しかも、フラックスとして低イオン性のフラックスを使用した場合にははんだ付け時にはんだボールの残留がなく、且つイオン残渣によるマイグレーション特性の悪化の問題も生じないプリント配線板を提供することができる。 According to the present invention, it is possible to provide a printed wiring board having no solder balls remaining during soldering. In addition, when a low ionic flux is used as the flux, it is possible to provide a printed wiring board in which no solder balls remain at the time of soldering and the problem of deterioration in migration characteristics due to ion residues does not occur.
本発明のアルカリ現像型感光性樹脂組成物は、該アルカリ現像型感光性樹脂組成物の塗布膜であって、光硬化および熱硬化させて形成されるソルダーレジスト（以下、「本発明のソルダーレジスト」とも言う。）と該ソルダーレジスト上に形成されるフラックス膜との濡れ性を向上させるために、水溶性シリコーンを含有させたことを特徴とするものである。プリント配線板のはんだ付け時において、導体パッド及びフラックスとの濡れ性が向上した本発明のソルダーレジストを含めた基板上にフラックス膜が形成され、はんだは導体パッド上のフラックス膜上に供給される。このようにソルダーレジスト上にフラックス膜を形成することにより、従来においてフラックス膜が形成されていないソルダーレジスト上で起こりやすかったはんだボールの残留を防止することができる。 The alkali-developable photosensitive resin composition of the present invention is a coating film of the alkali-developable photosensitive resin composition, and is formed by photo-curing and heat-curing a solder resist (hereinafter referred to as “the solder resist of the present invention”). In order to improve wettability between the flux resist formed on the solder resist and water-soluble silicone, the water-soluble silicone is contained. When soldering the printed wiring board, a flux film is formed on the substrate including the solder resist of the present invention with improved wettability with the conductor pad and flux, and the solder is supplied onto the flux film on the conductor pad. . By forming the flux film on the solder resist in this manner, it is possible to prevent the solder balls from remaining on the solder resist that has not been formed with the flux film in the past.
本発明のアルカリ現像型感光性樹脂組成物を用いたプリント配線板の製造において用い得るフラックスとしては、フラックス膜を残したまま製品化する観点からは、ハロゲンフリーの低イオン性フラックスを好適に用いることができる。該フラックスを用いることによりハロゲンイオン残渣によるマイグレーション特性の悪化という問題も生じない。 As a flux that can be used in the production of a printed wiring board using the alkali development type photosensitive resin composition of the present invention, a halogen-free low ionic flux is preferably used from the viewpoint of commercialization while leaving the flux film. be able to. By using the flux, there is no problem of deterioration of migration characteristics due to halogen ion residues.
以下、本発明のアルカリ現像型感光性樹脂組成物について更に詳細に説明する。
上述の通り、本発明のアルカリ現像型感光性樹脂組成物はフラックスとの濡れ性を向上させるために水溶性シリコーン（Ｄ）を含有することを特徴とし、該水溶性シリコーンは特に限定されるものではなく公知のものを用いることができる。具体例としてはポリエーテル変性ポリジメチルシロキサン、ポリエーテル変性ポリメチルアルキルシロキサン、ポリエーテルエステル変性水酸基含有ポリジメチルシロキサン、ポリオキシエチレン変性ポリフェニルシロキサン、ポリオキシプロピレン変性ポリフェニルシロキサン等が挙げられ、１種を単独で又は２種以上を混合して用いることができる。
Hereinafter, the alkali development type photosensitive resin composition of the present invention will be described in more detail.
As described above, the alkali-developable photosensitive resin composition of the present invention contains a water-soluble silicone (D) in order to improve wettability with a flux, and the water-soluble silicone is particularly limited. Instead, known ones can be used. Specific examples include polyether-modified polydimethylsiloxane, polyether-modified polymethylalkylsiloxane, polyetherester-modified hydroxyl group-containing polydimethylsiloxane, polyoxyethylene-modified polyphenylsiloxane, and polyoxypropylene-modified polyphenylsiloxane. A seed can be used individually or in mixture of 2 or more types.
本発明の一態様において、水溶性シリコーン種の選択、配合量等は、ＪＩＳ Ｋ ６７６８（１９９９年）に準拠した濡れ指数が３８ｍＮ／ｍ以上となるように決定することができる。水溶性シリコーン（Ｄ）の配合量の目安としては、前記カルボキシル基含有樹脂（Ａ）の固形分１００質量部に対して０．５〜１０質量部とすることが好ましく、１〜５質量部とすることがより好ましい。 In one embodiment of the present invention, the selection and blending amount of the water-soluble silicone species can be determined so that the wetting index based on JIS K 6768 (1999) is 38 mN / m or more. As a standard of the compounding amount of the water-soluble silicone (D), it is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the solid content of the carboxyl group-containing resin (A). More preferably.
以下、本発明のアルカリ現像型感光性樹脂組成物の水溶性シリコーン（Ｄ）以外の各構成成分について詳細に説明する。
まず、前記１分子中に１個以上のカルボキシル基を有するカルボキシル基含有樹脂（Ａ）としては、カルボキシル基を有する樹脂、具体的にはそれ自体に感光性の不飽和二重結合を２個以上有するカルボキシル基含有樹脂及び感光性の不飽和二重結合を持たないカルボキシル基含有樹脂のいずれも使用可能であり、特定のものに限定されるものではないが、特に以下に列挙するような樹脂（オリゴマー及びポリマーのいずれでもよい）を好適に使用できる。
Hereinafter, each component other than the water-soluble silicone (D) of the alkali development type photosensitive resin composition of the present invention will be described in detail.
First, the carboxyl group-containing resin (A) having one or more carboxyl groups in one molecule is a resin having a carboxyl group, specifically, two or more photosensitive unsaturated double bonds in itself. Any of the carboxyl group-containing resins having a photosensitive group and a carboxyl group-containing resin having no photosensitive unsaturated double bond can be used, and are not limited to specific ones. Any of an oligomer and a polymer) can be preferably used.
（１）不飽和カルボン酸と不飽和二重結合を有する化合物の共重合によって得られるカルボキシル基含有樹脂、
（２）不飽和カルボン酸と不飽和二重結合を有する化合物の共重合体に、エチレン性不飽和基をペンダントとして付加させることによって得られる感光性のカルボキシル基含有樹脂、
（３）１分子中にそれぞれ１個のエポキシ基と不飽和二重結合を有する化合物と不飽和二重結合を有する化合物の共重合体に、不飽和モノカルボン酸を反応させ、生成した第２級の水酸基に飽和又は不飽和多塩基酸無水物を反応させて得られる感光性のカルボキシル基含有樹脂、
（４）不飽和二重結合を有する酸無水物と不飽和二重結合を有する化合物の共重合体に、水酸基と不飽和二重結合を有する化合物を反応させて得られる感光性のカルボキシル基含有樹脂、
（５）１分子中に２個以上のエポキシ基を有する多官能エポキシ化合物と不飽和モノカルボン酸を反応させ、生成した水酸基に飽和又は不飽和多塩基酸無水物を反応させて得られる感光性のカルボキシル基含有樹脂、
（６）１分子中に２個以上のエポキシ基を有する多官能エポキシ化合物と、不飽和モノカルボン酸と、１分子中に少なくとも１個のアルコール性水酸基と、エポキシ基と反応するアルコール性水酸基以外の１個の反応性基を有する化合物との反応生成物に、飽和又は不飽和多塩基酸無水物を反応させて得られる感光性のカルボキシル基含有樹脂
（７）水酸基含有ポリマーに飽和又は不飽和多塩基酸無水物を反応させた後、生成したカルボン酸に１分子中にそれぞれ１個のエポキシ基と不飽和二重結合を有する化合物を反応させて得られる感光性の水酸基、カルボキシル基含有樹脂、及び
（８）１分子中に２個以上のオキセタン環を有する多官能オキセタン化合物に不飽和モノカルボン酸を反応させ、得られた変性オキセタン樹脂中の第１級水酸基に対して飽和又は不飽和多塩基酸無水物を反応させて得られる感光性のカルボキシル基含有樹脂。
(1) a carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid and a compound having an unsaturated double bond,
(2) a photosensitive carboxyl group-containing resin obtained by adding an ethylenically unsaturated group as a pendant to a copolymer of an unsaturated carboxylic acid and a compound having an unsaturated double bond,
(3) A second product produced by reacting an unsaturated monocarboxylic acid with a copolymer of a compound having one epoxy group and an unsaturated double bond and a compound having an unsaturated double bond in each molecule. A photosensitive carboxyl group-containing resin obtained by reacting a saturated or unsaturated polybasic acid anhydride with a primary hydroxyl group,
(4) Contains a photosensitive carboxyl group obtained by reacting a compound having a hydroxyl group and an unsaturated double bond with a copolymer of an acid anhydride having an unsaturated double bond and a compound having an unsaturated double bond resin,
(5) Photosensitivity obtained by reacting a polyfunctional epoxy compound having two or more epoxy groups in one molecule with an unsaturated monocarboxylic acid, and reacting the resulting hydroxyl group with a saturated or unsaturated polybasic acid anhydride. A carboxyl group-containing resin,
(6) Other than a polyfunctional epoxy compound having two or more epoxy groups in one molecule, an unsaturated monocarboxylic acid, at least one alcoholic hydroxyl group in one molecule, and an alcoholic hydroxyl group that reacts with an epoxy group A photosensitive carboxyl group-containing resin obtained by reacting a reaction product with a compound having one reactive group with a saturated or unsaturated polybasic acid anhydride (7) Saturated or unsaturated with a hydroxyl group-containing polymer Photosensitive hydroxyl group- and carboxyl group-containing resin obtained by reacting a polybasic acid anhydride and then reacting the resulting carboxylic acid with a compound having one epoxy group and an unsaturated double bond in each molecule. And (8) a primary compound in the modified oxetane resin obtained by reacting an unsaturated monocarboxylic acid with a polyfunctional oxetane compound having two or more oxetane rings in one molecule. Saturated or unsaturated polybasic acid anhydride is reacted obtained photosensitive carboxyl resin toward acid groups.
これらの中でも、１分子中に感光性の不飽和二重結合を２個以上有するカルボキシル基含有樹脂、特に前記（５）の感光性のカルボキシル基含有樹脂が、耐熱性、金めっき耐性等の特性面から好ましい。 Among these, the carboxyl group-containing resin having two or more photosensitive unsaturated double bonds in one molecule, in particular, the photosensitive carboxyl group-containing resin of the above (5) has characteristics such as heat resistance and gold plating resistance. From the aspect, it is preferable.
上記のようなカルボキシル基含有樹脂（Ａ）は、バックボーン・ポリマーの側鎖に多数の遊離のカルボキシル基を有するため、希アルカリ水溶液による現像が可能になる。 Since the carboxyl group-containing resin (A) as described above has a large number of free carboxyl groups in the side chain of the backbone polymer, development with a dilute aqueous alkali solution is possible.
また、上記カルボキシル基含有樹脂（Ａ）の酸価は、４５〜２００ｍｇＫＯＨ／ｇの範囲にあることが好ましい。カルボキシル基含有樹脂の酸価が４５ｍｇＫＯＨ／ｇ未満であるとアルカリ現像が困難となり、一方、２００ｍｇＫＯＨ／ｇを超えると現像液による露光部の溶解が進むために、必要以上にラインが痩せたり、場合によっては、露光部と未露光部の区別なく現像液で溶解剥離してしまい、正常なレジストパターンの描画が困難となるので好ましくない。 Moreover, it is preferable that the acid value of the said carboxyl group-containing resin (A) exists in the range of 45-200 mgKOH / g. When the acid value of the carboxyl group-containing resin is less than 45 mgKOH / g, alkali development becomes difficult. On the other hand, when it exceeds 200 mgKOH / g, dissolution of the exposed portion by the developer proceeds, and the line becomes thinner than necessary. Depending on the case, the exposed portion and the unexposed portion are not distinguished from each other by dissolution and peeling with a developer, which makes it difficult to draw a normal resist pattern.
次に、本発明のアルカリ現像型感光性樹脂組成物を構成する光重合開始剤（Ｂ）としては、例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインイソプロピルエーテル等のベンゾインとベンゾインアルキルエーテル類；アセトフェノン、２，２−ジメトキシ−２−フェニルアセトフェノン、２，２−ジエトキシ−２−フェニルアセトフェノン、１，１−ジクロロアセトフェノン、１−ヒドロキシシクロヘキシルフェニケトン等のアセトフェノン類；２−メチル−１−［４−（メチルチオ）フェニル］−２−モルホリノアミノプロパノン−１、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）−ブタン−１−オン、Ｎ，Ｎ−ジメチルアミノアセトフェノン等のアミノアセトフェノン類；２−メチルアントラキノン、２−エチルアントラキノン、２−ｔｅｒｔ−ブチルアントラキノン、１−クロロアントラキノン、２−アミルアントラキノン、２−アミノアントラキノン等のアントラキノン類；２，４−ジメチルチオキサントン、２，４−ジエチルチオキサントン、２−クロロチオキサントン、２，４−ジイソプロピルチオキサントン等のチオキサントン類；アセトフェノンジメチルケタール、ベンジルジメチルケタール等のケタール類；ベンゾフェノン、メチルベンゾフェノン、４，４´−ジクロロベンゾフェノン、４，４´−ビスジエチルアミノベンゾフェノン、４−ベンゾイル−４´−メチルジフェニルサルファイド等のベンゾフェノン類；２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキサイド等が挙げられる。これらの光重合開始剤は、単独であるいは２種以上を組合せて用いることができる。さらに、かかる光重合開始剤（Ｂ）は、Ｎ，Ｎ−ジメチルアミノ安息香酸エチルエステル、Ｎ，Ｎ−ジメチルアミノ安息香酸イソアミルエステル、ペンチル−４−ジメチルアミノベンゾエート、トリエチルアミン、トリエタノールアミン等の三級アミン類のような光増感剤もしくは光開始助剤の１種あるいは２種以上と組合せて用いることができる。また、可視光領域に吸収のあるＣＧＩ−７８４等（チバ・スペシャルティ・ケミカルズ社製）のチタノセン化合物等も、光反応を促進するために添加することもできる。特にこれらに限られるものではなく、紫外光もしくは可視光領域で光を吸収し、（メタ）アクリロイル基等の不飽和基をラジカル重合させるものであれば、光重合開始剤、光増感剤（光開始助剤）に限らず、単独であるいは複数併用して使用できる。 Next, examples of the photopolymerization initiator (B) constituting the alkali development type photosensitive resin composition of the present invention include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; acetophenone, 2 , 2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylpheniketone and other acetophenones; 2-methyl-1- [4- (methylthio ) Phenyl] -2-morpholinoaminopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, aminoacetophenones such as N, N-dimethylaminoacetophenone; 2-Methylanthraquinone Anthraquinones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, Thioxanthones such as 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, methylbenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bisdiethylaminobenzophenone, 4-benzoyl-4 Benzophenones such as' -methyldiphenyl sulfide; 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like. These photopolymerization initiators can be used alone or in combination of two or more. Further, the photopolymerization initiator (B) includes three compounds such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, and triethanolamine. It can be used in combination with one kind or two or more kinds of photosensitizers or photoinitiating assistants such as a class of amines. In addition, a titanocene compound such as CGI-784 (manufactured by Ciba Specialty Chemicals Co., Ltd.) having absorption in the visible light region can also be added to promote the photoreaction. The photopolymerization initiator and the photosensitizer (in particular, are not limited to these, as long as they absorb light in the ultraviolet or visible light region and radically polymerize an unsaturated group such as a (meth) acryloyl group. It is not limited to photoinitiator aids, and can be used alone or in combination.
好ましい組合せは、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルホリノ−アミノプロパノン−１と２，４−ジエチルチオキサントンや２−イソプロピルチオキサントン、４−ベンゾイル−４´−メチルジフェニルサルファイドとの組合せ等である。 A preferred combination is 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-aminopropanone-1, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 4-benzoyl-4'-methyldiphenyl For example, a combination with sulfide.
前記光重合開始剤（Ｂ）の配合量（光増感剤もしくは光開始助剤を用いる場合にはそれらの合計量）は、カルボキシル基含有樹脂（Ａ）１００質量部（固形分として、以下同様）に対して０．１〜３０質量部の割合が好ましく、０．５〜２０質量部の割合がより好ましい。光重合開始剤（Ｂ）の配合量が上記範囲よりも少ない場合、活性エネルギー線の照射を行なっても硬化しないか、もしくは照射時間を増やす必要があり、適切な皮膜特性が得られ難くなる。一方、上記範囲よりも多量に光重合開始剤を添加しても、光硬化性に変化は無く、経済的に好ましくない。 The blending amount of the photopolymerization initiator (B) (when using a photosensitizer or photoinitiator auxiliary, the total amount thereof) is 100 parts by weight of the carboxyl group-containing resin (A) (as solid content, the same applies hereinafter). ) To 0.1 to 30 parts by mass, and more preferably 0.5 to 20 parts by mass. When the blending amount of the photopolymerization initiator (B) is less than the above range, it is not cured even when active energy rays are irradiated, or it is necessary to increase the irradiation time, and it becomes difficult to obtain appropriate film properties. On the other hand, even if a photopolymerization initiator is added in a larger amount than the above range, there is no change in photocurability, which is economically undesirable.
本発明のアルカリ現像型感光性樹脂組成物に用いられる反応性希釈剤（Ｃ）は、該組成物の粘度を調整して作業性を向上させるとともに、架橋密度を上げ、密着性などを有する塗膜を得るために使用する液状感光性化合物である。このような反応性希釈剤（Ｃ）としては、多価アルコールにα，β−不飽和カルボン酸を付加して得られる化合物、例えばエチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ブチレングリコールジ（メタ）アクリレート、ペンチルグリコールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等；グリシジル基含有化合物にα，β−不飽和カルボン酸を付加して得られる化合物、例えばエチレングリコールジグリシジルエーテルジ（メタ）アクリレート、ジエチレングリコールジグリシジルエーテルジ（メタ）アクリレート、トリメチロールプロパントリグリシジルエーテルトリアクリレート、ビスフェノールＡジグリシジルエーテルジ（メタ）アクリレート、フタル酸ジグリシジルエステルジ（メタ）アクリレート、グリセリンポリグリシジルエーテルポリ（メタ）アクリレート等；その他、２，２−ビス（４−（メタ）アクリロイルオキシジエトキシフェニル）プロパン、２，２−ビス−（４−（メタ）アクリロイルオキシポリエトキシフェニル）プロパン、２−ヒドロキシ−３−（メタ）アクリロイルオキシプロピル（メタ）アクリレート、等の多官能モノマーが挙げられ、１種又は２種以上が用いられる。これらの多官能モノマーと共に、単官能モノマーを適当量併用することもできる。 The reactive diluent (C) used in the alkali-developable photosensitive resin composition of the present invention improves the workability by adjusting the viscosity of the composition, increases the crosslink density, and has adhesion and the like. It is a liquid photosensitive compound used for obtaining a film. Examples of such a reactive diluent (C) include compounds obtained by adding an α, β-unsaturated carboxylic acid to a polyhydric alcohol, such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetra Ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, pentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) ) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc .; α, β-unsaturated glycidyl group-containing compounds Compounds obtained by adding carboxylic acid, such as ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, trimethylolpropane triglycidyl ether triacrylate, bisphenol A diglycidyl ether di (meth) Acrylate, diglycidyl phthalate di (meth) acrylate, glycerin polyglycidyl ether poly (meth) acrylate, etc .; -Bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2,2-bis- (4- (meth) acryloyloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meta And polyfunctional monomers such as acrylates are used, and one or more are used. An appropriate amount of a monofunctional monomer can be used in combination with these polyfunctional monomers.
単官能モノマーの例としては、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、２−フェノキシエチル（メタ）アクリレート、２−（メタ）アクリロイルオキシエチル−２−ヒドロキシプロピルフタレート、３−クロロ−２−ヒドロキシプロピル（メタ）アクリレート、グリセリンモノ（メタ）アクリレート、２−（メタ）アクリロイルオキシエチルアシッドホスフェート、フタル酸誘導体のハーフ（メタ）アクリレート、Ｎ−メチロール（メタ）アクリルアミド等が挙げられる。 Examples of monofunctional monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 2- (meth) acryloyl Oxyethyl-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, phthalic acid derivative half (meth) acrylate, N-methylol (meth) acrylamide etc. are mentioned.
これらの反応性希釈剤（Ｃ）の配合量は、前記カルボキシル基含有樹脂（Ａ）１００質量部に対し、好ましくは６０質量部以下、より好ましくは２〜５０質量部の割合で用いる。反応性希釈剤（Ｃ）の配合量が上記範囲よりも多い場合には、指触乾燥性が悪くなるので好ましくない。 The compounding amount of these reactive diluents (C) is preferably 60 parts by mass or less, more preferably 2 to 50 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A). When the amount of the reactive diluent (C) is more than the above range, it is not preferable because the dryness to touch becomes worse.
本発明のアルカリ現像型感光性樹脂組成物は、基本的には前記した反応性希釈剤（Ｃ）を用いているので有機溶剤を用いる必要はないが、前記目的の一つである指触乾燥性が必要な場合（接触露光の場合）、有機溶剤を添加することもできる。有機溶剤としては、乾燥が容易で毒性の少ない有機溶剤が選ばれる。例えば、メタノール、エタノール、プロピルアルコール、イソプロピルアルコール、ブタノール、イソブタノール、α−テルピオネール等のアルコール類；シクロヘキサノン、メチルシクロヘキサノン、２−ブタノン、メチルイソブチルケトン、アセトン等のケトン類；セロソルブ、メチルセロソルブ、ブチルセロソルブ、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、エチレングリコールジブチルエーテル、カルビトール、メチルカルビトール、ブチルカルビトール、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールジエチルエーテル、トリプロピレングリコールモノメチルエーテル等のグリコールエーテル類；酢酸エチル、酢酸ブチル、酢酸アミル、酢酸シクロヘキシル、乳酸ブチル、セロソルブアセテート、ブチルセロソルブアセテート、カルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート、炭酸プロピレン等のエステル類；及びトルエン、ミネラルスピリットなどを好適に用いることができる。これらの有機溶剤は、単独で又は２種以上を混合して前記アルカリ水溶液に可溶なカルボキシル基含有樹脂と光重合性不飽和化合物（反応性希釈剤）を溶解し、他の成分と添加混合されて、アルカリ現像型感光性樹脂組成物となる。 The alkali-developable photosensitive resin composition of the present invention basically uses the above-described reactive diluent (C), so it is not necessary to use an organic solvent. When the property is required (in the case of contact exposure), an organic solvent can be added. As the organic solvent, an organic solvent that is easy to dry and less toxic is selected. For example, alcohols such as methanol, ethanol, propyl alcohol, isopropyl alcohol, butanol, isobutanol, and α-terpione; ketones such as cyclohexanone, methylcyclohexanone, 2-butanone, methyl isobutyl ketone, and acetone; cellosolve, methyl cellosolve, Butyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, carbitol, methyl carbitol, butyl carbitol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene Propylene glycol Glycol ethers such as rudiethyl ether and tripropylene glycol monomethyl ether; ethyl acetate, butyl acetate, amyl acetate, cyclohexyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate , Esters such as dipropylene glycol monomethyl ether acetate and propylene carbonate; and toluene and mineral spirits can be suitably used. These organic solvents are used alone or in combination of two or more to dissolve the carboxyl group-containing resin and photopolymerizable unsaturated compound (reactive diluent) that are soluble in the alkaline aqueous solution, and are added and mixed with other components. Thus, an alkali development type photosensitive resin composition is obtained.
前記１分子中に２個以上のエポキシ基を有する多官能エポキシ化合物（Ｅ）としては、従来公知の全ての多官能エポキシ化合物を用いることができ、例えば、ジャパンエポキシレジン（株）製のエピコート８２８、エピコート８３４、エピコート１００１、エピコート１００４、大日本インキ化学工業（株）製のエピクロン８４０、エピクロン８５０、エピクロン１０５０、エピクロン２０５５、東都化成（株）製のエポトートＹＤ−０１１、ＹＤ−０１３、ＹＤ−１２７、ＹＤ−１２８、住友化学工業（株）製のスミ−エポキシＥＳＡ−０１１、ＥＳＡ−０１４、ＥＬＡ−１１５、ＥＬＡ−１２８（何れも商品名）等のビスフェノールＡ型エポキシ樹脂；ジャパンエポキシレジン（株）製のエピコートＹＬ９０３、大日本インキ化学工業（株）製のエピクロン１５２、エピクロン１６５、東都化成（株）製のエポトートＹＤＢ−４００、ＹＤＢ−５００、住友化学工業（株）製のスミ−エポキシＥＳＢ−４００、ＥＳＢ−７００（何れも商品名）等のブロム化エポキシ樹脂；ジャパンエポキシレジン（株）製のエピコート１５２、エピコート１５４、大日本インキ化学工業（株）製のエピクロンＮ−７３０、エピクロンＮ−７７０、エピクロンＮ−６８０、エピクロンＮ−６９５、エピクロンＮ−８６５、東都化成（株）製のエポトートＹＤＣＮ−７０１、ＹＤＣＮ−７０４、日本化薬（株）製のＥＰＰＮ−２０１、ＥＯＣＮ−１０２５、ＥＯＣＮ―１０２０，ＥＯＣＮ−１０４Ｓ、ＲＥ−３０６、住友化学工業（株）製のスミ−エポキシＥＳＣＮ−１９５Ｘ、ＥＳＣＮ−２２０（何れも商品名）等のノボラック型エポキシ樹脂；大日本インキ化学工業（株）製のエピクロン８３０、ジャパンエポキシレジン社製のエピコート８０７、東都化成（株）製のエポトートＹＤＦ−１７０、ＹＤＦ−１７５、ＹＤＦ−２００４（何れも商品名）等のビスフェノールＦ型エポキシ樹脂；東都化成（株）製のエポトートＳＴ−２００４、ＳＴ−２００７、ＳＴ−３０００（何れも商品名）等の水添ビスフェノールＡ型エポキシ樹脂；ジャパンエポキシレジン（株）製のエピコート６０４、東都化成（株）製のエポトートＹＨ−４３４、住友化学工業（株）製のスミ−エポキシＥＬＭ−１２０（何れも商品名）等のグリシジルアミン型エポキシ樹脂；ダイセル化学工業（株）製のセロキサイド２０２１（商品名）等の脂環式エポキシ樹脂；ジャパンエポキシレジン（株）製のＹＬ−９３３、日本化薬（株）製のＥＰＰＮ−５０１、ＥＰＰＮ−５０２（何れも商品名）等のトリヒドロキシフェニルメタン型エポキシ樹脂；ジャパンエポキシレジン（株）製のＹＬ−６０５６、ＹＸ−４０００、ＹＬ−６１２１（何れも商品名）等のビキシレノール型もしくはビフェノール型エポキシ樹脂又はそれらの混合物；日本化薬（株）製のＥＢＰＳ−２００、旭電化工業（株）製のＥＰＸ−３０、大日本インキ化学工業（株）製のＥＸＡ−１５１４（何れも商品名）等のビスフェノールＳ型エポキシ樹脂；ジャパンエポキシレジン（株）製のエピコート１５７Ｓ（商品名）等のビスフェノールＡノボラック型エポキシ樹脂；ジャパンエポキシレジン（株）製のエピコートＹＬ−９３１（商品名）等のテトラフェニロールエタン型エポキシ樹脂；日産化学（株）製のＴＥＰＩＣ、高融点タイプのＴＥＰＩＣ−Ｈ（何れも商品名）等の複素環式エポキシ樹脂；日本油脂（株）製のブレンマーＤＧＴ（商品名）等のジグリシジルフタレート樹脂；東都化成（株）製のＺＸ−１０６３（商品名）等のテトラグリシジルキシレノイルエタン樹脂；新日鉄化学（株）製のＥＳＮ−１９０、ＥＳＮ−３６０、大日本インキ化学工業（株）製のＨＰ−４０３２、ＥＸＡ−４７５０、ＥＸＡ−４７００（何れも商品名）等のナフタレン基含有エポキシ樹脂；大日本インキ化学工業（株）製のＨＰ−７２００、ＨＰ−７２００Ｈ（何れも商品名）等のジシクロペンタジエン骨格を有するエポキシ樹脂；日本油脂（株）製のＣＰ−５０Ｓ、ＣＰ−５０Ｍ（何れも商品名）等のグリシジルメタアクリレート共重合系エポキシ樹脂；さらにシクロヘキシルマレイミドとグリシジルメタアクリレートの共重合エポキシ樹脂などの１分子中に２個以上のエポキシ基を有する化合物などが挙げられる。これらは、それぞれ単独で用いてもよいし、２種以上を組み合わせて用いてよい。 As the polyfunctional epoxy compound (E) having two or more epoxy groups in one molecule, all conventionally known polyfunctional epoxy compounds can be used. For example, Epicoat 828 manufactured by Japan Epoxy Resins Co., Ltd. Epicoat 834, Epicoat 1001, Epicoat 1004, Epicron 840, Epicron 850, Epicron 1050, Epicron 2055, Daito Ink Chemical Co., Ltd., Epototo YD-011, YD-013, YD- 127, YD-128, Sumitomo Chemical Industries Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128 (all trade names) and other bisphenol A type epoxy resins; Japan Epoxy Resin ( Epicoat YL903 manufactured by Dainippon Ink and Chemicals ( ) Epicron 152, Epicron 165, Etototo YDB-400, YDB-500 manufactured by Toto Kasei Co., Ltd., Sumi-Epoxy ESB-400, ESB-700 (all trade names) manufactured by Sumitomo Chemical Co., Ltd., etc. Brominated epoxy resin: Epicoat 152, Epicoat 154 manufactured by Japan Epoxy Resin Co., Ltd., Epicron N-730, Epicron N-770, Epicron N-680, Epicron N-695, manufactured by Dainippon Ink & Chemicals, Inc. Epicron N-865, Etototo YDCN-701, YDCN-704, manufactured by Tohto Kasei Co., Ltd., EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, manufactured by Nippon Kayaku Co., Ltd. SUMI-EPOXY ESCN-195X, ESCN-220 manufactured by Chemical Industry Co., Ltd. Novolak type epoxy resins such as trade names); Epicron 830 manufactured by Dainippon Ink & Chemicals, Epicoat 807 manufactured by Japan Epoxy Resin Co., Ltd. Epototo YDF-170, YDF-175 manufactured by Toto Kasei Co., Ltd. Bisphenol F type epoxy resin such as YDF-2004 (all trade names); Hydrogenated bisphenol A type epoxy such as Epototo ST-2004, ST-2007, ST-3000 (all trade names) manufactured by Tohto Kasei Co., Ltd. Resin; Glycidylamine type such as Epicoat 604 manufactured by Japan Epoxy Resin Co., Ltd., Epototo YH-434 manufactured by Toto Kasei Co., Ltd., Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. (all trade names) Epoxy resin; alicyclic epoxy tree such as Celoxide 2021 (trade name) manufactured by Daicel Chemical Industries, Ltd. Fats; trihydroxyphenylmethane type epoxy resins such as YL-933 manufactured by Japan Epoxy Resin Co., Ltd., EPPN-501 manufactured by Nippon Kayaku Co., Ltd., and EPPN-502 (both are trade names); Japan Epoxy Resin Co., Ltd. ) YL-6056, YX-4000, YL-6121 (all are trade names) manufactured by Nippon Kayaku Co., Ltd. EBPS-200, Asahi Denka Kogyo Co., Ltd. Bisphenol S type epoxy resins such as EPX-30 manufactured by Dainippon Ink and Chemicals, Inc. EXA-1514 manufactured by Dainippon Ink and Chemicals, Inc. 157S manufactured by Japan Epoxy Resin Co., Ltd. Bisphenol A novolac type epoxy resin, etc .; Epicoat YL-931 (trade) manufactured by Japan Epoxy Resin Co., Ltd. Name) Tetraphenylol ethane type epoxy resin; Nissan Chemical Co., Ltd. TEPIC, high melting point type TEPIC-H (both trade names), etc .; Nippon Oil & Fats Co., Ltd. Diglycidyl phthalate resin such as DGT (trade name); Tetraglycidyl xylenoylethane resin such as ZX-1063 (trade name) manufactured by Tohto Kasei Co., Ltd .; ESN-190 and ESN-360 manufactured by Nippon Steel Chemical Co., Ltd. Naphthalene group-containing epoxy resins such as HP-4032, EXA-4750, EXA-4700 (all trade names) manufactured by Dainippon Ink & Chemicals, Inc .; HP-7200 manufactured by Dainippon Ink & Chemicals, Inc. Epoxy resins having a dicyclopentadiene skeleton such as HP-7200H (both trade names); CP-50S and CP-50M manufactured by NOF Corporation Both glycidyl methacrylate copolymerization system epoxy resin trade name) and the like; and the like compounds having a further two or more epoxy groups in one molecule, such as a copolymer epoxy resins of cyclohexylmaleimide and glycidyl methacrylate. These may be used alone or in combination of two or more.
これらの多官能エポキシ化合物（Ｅ）の配合量は、前記カルボキシル基含有樹脂（Ａ）のカルボキシル基１当量当たり、好ましくはエポキシ基が０．６〜２．０当量、より好ましくは、１．０〜１．８当量である。これらの多官能エポキシ化合物（Ｅ）は、パターン形成された塗膜を熱硬化させることにより、硬化塗膜の耐熱性、耐薬品性、密着性、鉛筆硬度などの諸特性を向上させることができる。多官能エポキシ化合物の添加量が、０．６当量未満の場合、カルボキシル基が残り、電気絶縁性、耐熱性が得られ難くなるので好ましくなく、一方、２．０当量を超えた場合、現像性の低下、現像ライフの低下が起こり好ましくない。 The compounding amount of these polyfunctional epoxy compounds (E) is preferably 0.6 to 2.0 equivalents of epoxy groups, more preferably 1.0 equivalents per equivalent of carboxyl groups of the carboxyl group-containing resin (A). -1.8 equivalents. These polyfunctional epoxy compounds (E) can improve various properties such as heat resistance, chemical resistance, adhesion, and pencil hardness of the cured coating film by thermosetting the patterned coating film. . When the addition amount of the polyfunctional epoxy compound is less than 0.6 equivalent, the carboxyl group remains, which is not preferable because it is difficult to obtain electrical insulation and heat resistance. Decrease in development life and development life are undesirable.
また、上記カルボキシル基とエポキシ基の反応促進剤として、アミン類、ジシアンジアミド、尿素誘導体、メラミン、Ｓ−トリアジン化合物、グアナミン化合物、２−エチル−４−メチルイミダゾール等のイミダゾール化合物及びその誘導体、フェノール化合物等の公知のエポキシ硬化促進剤を併用することもできる。 Further, as a reaction accelerator for the carboxyl group and epoxy group, amines, dicyandiamide, urea derivatives, melamine, S-triazine compounds, guanamine compounds, imidazole compounds such as 2-ethyl-4-methylimidazole and derivatives thereof, phenol compounds It is also possible to use a known epoxy curing accelerator such as
さらに本発明の感光性樹脂組成物には、特性を向上させるために無機及び／又は有機フィラーを添加することもでき、その配合量は、カルボキシル基含有樹脂（Ａ）１００質量部に対し好ましくは３００質量部以下、より好ましくは５〜２００質量の割合とする。 Furthermore, in order to improve the characteristics, the photosensitive resin composition of the present invention may contain an inorganic and / or organic filler, and the blending amount thereof is preferably 100 parts by weight of the carboxyl group-containing resin (A). 300 parts by mass or less, more preferably 5 to 200 parts by mass.
無機フィラーとしては硫酸バリウム、チタン酸バリウム、微粉状酸化ケイ素、無定形シリカ、結晶性シリカ、溶融シリカ、タルク、クレー、炭酸マグネシウム、炭酸カルシウム、酸化アルミニウム、水酸化アルミニウム、雲母粉等の公知慣用の無機充填剤が使用できる。有機フィラーとしては、エポキシ系、ゴム系、アクリル系、ウレタン系、ポリイミド系、ポリアミド系の物が使用でき、１０μｍ以下の粒径のものが好ましい。 Known inorganic fillers such as barium sulfate, barium titanate, finely divided silicon oxide, amorphous silica, crystalline silica, fused silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica powder, etc. Inorganic fillers can be used. As the organic filler, epoxy-based, rubber-based, acrylic-based, urethane-based, polyimide-based, and polyamide-based materials can be used, and those having a particle size of 10 μm or less are preferable.
本発明の感光性樹脂組成物は、さらに必要に応じて、フタロシアニン・ブルー、フタロシアニン・グリーン、アイオジン・グリーン、ジスアゾイエロー、クリスタルバイオレット、酸化チタン、カーボンブラック、ナフタレンブラックなどの公知慣用の着色剤、ハイドロキノン、ハイドロキノンモノメチルエーテル、ｔｅｒｔ−ブチルカテコール、ピロガロール、フェノチアジン等の公知慣用の重合禁止剤、アスベスト、オルベン、ベントン、モンモリロナイト等の公知慣用の増粘剤、フッ素系、高分子系等の消泡剤及び／又はレベリング剤、イミダゾール系、チアゾール系、トリアゾール系、シランカップリング剤等の密着性付与剤のような公知慣用の添加剤類を配合することができる。 The photosensitive resin composition of the present invention may further include, as necessary, known and commonly used colorants such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, Known and conventional polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, pyrogallol and phenothiazine, known and conventional thickeners such as asbestos, olben, benton and montmorillonite, defoamers such as fluorine and polymers In addition, known additives such as leveling agents, imidazole-based, thiazole-based, triazole-based, and adhesion-imparting agents such as silane coupling agents can be blended.
以上のような成分組成を有するアルカリ現像型感光性樹脂組成物からなるレジスト材料は、従来知られている方法と同様の方法にて容易に硬化塗膜を得ることができる。 A resist material composed of the alkali development type photosensitive resin composition having the above component composition can easily obtain a cured coating film by a method similar to a conventionally known method.
例えば、本発明のアルカリ現像型感光性樹脂組成物を、必要に応じて塗布方法に適した粘度に調整し、基材上に、ディップコート法、フローコート法、ロールコート法、バーコーター法、スクリーン印刷法、カーテンコート法等の方法により塗布し、例えば約６０〜１００℃の温度で感光性樹脂組成物中に含まれる有機溶剤を揮発乾燥（仮乾燥）させることにより、タックフリーの塗膜を形成する。この工程では、上記感光性樹脂組成物をプラスチックフィルム上に塗布し、乾燥させてフィルムとして巻き取ったものを基材上に張り合わせることにより、塗膜を形成することもできる。その後、接触方式（又は非接触方式）により、パターンを形成したフォトマスクを通して選択的に活性光線により露光して硬化させ、未露光部をアルカリ水溶液（例えば０．３〜３％炭酸ソーダ水溶液）により現像してレジストパターン（または絶縁層パターン）が形成される。その後、さらに諸特性の向上のために、紫外線の照射及び／又は加熱（例えば、約１２０〜１８０℃で０．５〜１時間程度）によって充分な仕上げ硬化を行ない、硬化塗膜を得る。 For example, the alkali-developable photosensitive resin composition of the present invention is adjusted to a viscosity suitable for the coating method as necessary, and on the substrate, a dip coating method, a flow coating method, a roll coating method, a bar coater method, A tack-free coating film is applied by a method such as a screen printing method or a curtain coating method, and by evaporating and drying (preliminarily drying) an organic solvent contained in the photosensitive resin composition at a temperature of about 60 to 100 ° C., for example. Form. In this step, a coating film can also be formed by applying the photosensitive resin composition on a plastic film, drying it and winding it as a film on a substrate. Thereafter, the contact method (or non-contact method) is selectively exposed to actinic light through a photomask having a pattern formed thereon and cured, and the unexposed portion is subjected to an alkaline aqueous solution (for example, 0.3 to 3% sodium carbonate aqueous solution). Development is performed to form a resist pattern (or an insulating layer pattern). Thereafter, in order to further improve various properties, sufficient finish curing is performed by irradiation with ultraviolet rays and / or heating (for example, at about 120 to 180 ° C. for about 0.5 to 1 hour) to obtain a cured coating film.
ここで、塗膜を光硬化させるための照射光源としては、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、キセノンランプ又はメタルハライドランプが適当である。その他、レーザー光線なども露光用活性光源として利用し、直接描画することができる。 Here, as an irradiation light source for photocuring the coating film, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp or a metal halide lamp is suitable. In addition, a laser beam or the like can also be used as an exposure active light source for direct drawing.
また、上記現像に用いられる希アルカリ水溶液としては、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、ケイ酸ナトリウム、アンモニア、アミン類などのアルカリ水溶液が使用でき、特に、炭酸ナトリウムが好ましい。 As the dilute alkaline aqueous solution used for the development, alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, ammonia and amines can be used, and sodium carbonate is particularly preferable.
このようにして塗膜形成されたプリント配線板においては、その最終製品に製品のロット番号、型式等のマーキングが付与され、該マーキングは一般にインクジェット法またはスクリーン印刷法等によりソルダーレジストの表面に印字される。この点、本発明の組成物を用いたソルダーレジストは、後掲の実施例において明らかであるように、従来の非水溶性シリコーン含有組成物を用いたソルダーレジストに比べマーキング密着性においても優れたものである。 In the printed wiring board thus formed, the final product is marked with a product lot number, model, etc., and the marking is generally printed on the surface of the solder resist by an ink jet method or a screen printing method. Is done. In this regard, the solder resist using the composition of the present invention is superior in marking adhesion as compared with the solder resist using the conventional water-insoluble silicone-containing composition, as will be apparent from the examples described later. Is.
（実施例）
以下、本発明を実施例に基づいて具体的に説明するが、本発明は以下の実施例に限定されるものではなく、本発明の範囲内で適宜変更して実施することが可能である。なお、以下において数値の単位は、特に断りのない限りすべて質量部であるものとする。
(Example)
EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to a following example, It is possible to implement suitably changing within the scope of the present invention. In the following, all numerical units are parts by mass unless otherwise specified.
表１に示す各成分を所定の組成比にて配合し、攪拌機により攪拌後、３本ロールミルにより練肉してソルダーレジスト組成物（実施例１〜３、比較例１〜６）を作製した。
カルボキシル基含有樹脂（Ａワニス）の合成例
クレゾールノボラック型エポキシ樹脂のエピクロンＮ−６９５（大日本インキ化学工業（株）製、エポキシ当量＝２２０）２２０部を攪拌機及び還流冷却器を備えた四つ口フラスコに入れ、ジエチレングリコールモノエチルエーテルアセテート２１４部を加え、加熱溶解した。次に、重合禁止剤としてハイドロキノン０．１部と、反応触媒としてトリフェニルホスフィン２．０部を加えた。この混合溶液を９５〜１０５℃に加熱し、アクリル酸７２部を徐々に滴下し、反応液の酸価が２ｍｇＫＯＨ／ｇ以下になるまで、約１８時間反応させた。この反応液に、テトラヒドロ無水フタル酸１０６部を加え、さらに８時間反応させ、冷却後、取り出し感光性のカルボキシル基含有樹脂Ａを得た。このようにして得られた感光性のカルボキシル基含有樹脂Ａは、不揮発分６５％、固形分の酸価１００ｍｇＫＯＨ／ｇ、重量平均分子量（Ｍｗ）３，５００であった。
Example of Synthesis of Carboxyl Group-Containing Resin (A Varnish) 220 parts of cresol novolac type epoxy resin Epicron N-695 (Dainippon Ink Chemical Co., Ltd., epoxy equivalent = 220) equipped with stirrer and reflux condenser Into the neck flask, 214 parts of diethylene glycol monoethyl ether acetate was added and dissolved by heating. Next, 0.1 part of hydroquinone as a polymerization inhibitor and 2.0 parts of triphenylphosphine as a reaction catalyst were added. This mixed solution was heated to 95 to 105 ° C., 72 parts of acrylic acid was gradually added dropwise, and allowed to react for about 18 hours until the acid value of the reaction solution became 2 mgKOH / g or less. To this reaction solution, 106 parts of tetrahydrophthalic anhydride was added and reacted for another 8 hours. After cooling, the photosensitive carboxyl group-containing resin A was obtained after cooling. The thus obtained photosensitive carboxyl group-containing resin A had a non-volatile content of 65%, a solid acid value of 100 mgKOH / g, and a weight average molecular weight (Mw) of 3,500.
試験片作製：
予め面処理済みの基板（銅張り積層板）に、スクリーン印刷法により、上記実施例１〜３、比較例１〜６各々のソルダーレジスト組成物を３５μｍの厚さ（乾燥前）に塗工してそれぞれの塗工基板を作製し、それぞれの塗工基板を８０℃、２０分間予備乾燥した。この基板にネガフィルムを密着させて、５００ｍＪ／ｃｍ２の露光量で紫外線を照射させて露光を行い、次いで１％炭酸ナトリウム水溶液で６０秒間現像してパターン形成した。次にこの基板を１５０℃、６０分間熱硬化を行い、硬化塗膜を有する試験片を作製し、以下に示す塗膜性能の評価を行った。
Test piece preparation:
The surface-treated substrate (copper-clad laminate) was coated with the solder resist compositions of Examples 1 to 3 and Comparative Examples 1 to 6 to a thickness of 35 μm (before drying) by screen printing. Each coated substrate was prepared, and each coated substrate was pre-dried at 80 ° C. for 20 minutes. A negative film was brought into close contact with the substrate and exposed by irradiating with ultraviolet rays at an exposure amount of 500 mJ / cm 2 , and then developed with a 1% aqueous sodium carbonate solution for 60 seconds to form a pattern. Next, the substrate was thermally cured at 150 ° C. for 60 minutes to prepare a test piece having a cured coating film, and the coating film performance shown below was evaluated.
（ＵＶマーキング密着性）：硬化塗膜を有する塗工基板に、ＵＶマーキングインキ（ＵＶＲ−１５０ Ｎ１８４：太陽インキ社製）を塗布し、高圧水銀灯で１５００ｍＪ／ｃｍ２硬化した。セロハン粘着テープによるピーリング試験を行い、マーキングの剥がれを評価した。 (UV marking adhesion): A UV marking ink (UVR-150 N184: manufactured by Taiyo Ink Co., Ltd.) was applied to a coated substrate having a cured coating film, and cured at 1500 mJ / cm 2 with a high-pressure mercury lamp. A peeling test using a cellophane adhesive tape was conducted to evaluate the peeling of the marking.
○・・・まったく剥がれが認められなかったもの
△・・・一部剥がれが認められたもの
×・・・全体的に剥がれが認められたもの。
○: No peeling was observed Δ: Partial peeling was observed ×: Overall peeling was observed
（硬化塗膜濡れ指数）：ＪＩＳ Ｋ ６７６８（１９９９）に準拠して濡れ性試験を行った。硬化塗膜を有する塗工基板に、硬化塗膜上に濡れ指数標準液（和光純薬工業社製）を塗りはじく前の指数を濡れ指数とした。 (Hardened coating film wetting index): A wettability test was performed in accordance with JIS K 6768 (1999). The index before applying a wetting index standard solution (manufactured by Wako Pure Chemical Industries, Ltd.) onto the coated film having a cured coating film was defined as the wetting index.
（ポストフラックス濡れ性）：硬化塗膜を有する塗工基板に、無洗浄型フラックス（商品名：ソルボンドＳＭ４５９２；日本アルファメタルズ社製）を塗布し、２６０℃のはんだ槽に１０秒浸漬後、塗膜表面のフラックスのはじきを確認した。 (Post-flux wettability): A non-cleaning type flux (trade name: Solbond SM4592; manufactured by Nippon Alpha Metals Co., Ltd.) is applied to a coated substrate having a cured coating film, and immersed in a solder bath at 260 ° C. for 10 seconds, and then applied. The repelling of the flux on the film surface was confirmed.
○・・・フラックスのはじきがまったく認められなかったもの
△・・・一部はじきが認められたもの
×・・・全体的にはじきが認められたもの。
○: Flux repelling was not observed at all Δ: Partial repelling was observed ×: Repelling was observed as a whole.
（はんだボール試験）
硬化塗膜を有する塗工基板に、無機洗浄型フラックス（商品名：ソルボンドＳＭ４５９２；日本アルファメタルズ社製）を塗布し、２６０℃のはんだ槽に１０秒浸漬後、塗膜上のはんだボールの付着について確認した。
(Solder ball test)
An inorganic cleaning flux (trade name: Solbond SM4592; manufactured by Nippon Alpha Metals Co., Ltd.) is applied to a coated substrate having a cured coating film, immersed in a solder bath at 260 ° C. for 10 seconds, and then solder balls on the coating film are adhered. Confirmed.
○・・・はんだボールがまったく認められなかったもの
△・・・一部塗膜上にはんだボールが認められたもの
×・・・全体的に塗膜上にはんだボールが認められるもの。
○: Solder balls were not recognized at all Δ: Solder balls were partially recognized on the coating film ×: Solder balls were generally recognized on the coating film
（密着性）：ＪＩＳ Ｄ ５６００−５−６（１９９９）に準拠して、碁盤目試験により評価した。 (Adhesiveness): Based on JIS D 5600-5-6 (1999), it was evaluated by a cross cut test.
○・・・まったく剥がれが認められなかったもの
△・・・一部剥がれが認められたもの
×・・・全体的に剥がれが認められたもの。
○: No peeling was observed Δ: Partial peeling was observed ×: Overall peeling was observed
（鉛筆硬度）：ＪＩＳ Ｋ ５６００−５−６（１９９９）に準拠して評価した。 (Pencil hardness): It evaluated based on JISK5600-5-6 (1999).
（耐アルカリ性）：硬化塗膜を有する塗工基板を常温の１０質量％ＮａＯＨ水溶液に３０分浸漬した後、水洗・乾燥後、セロハン粘着テープによるピーリング試験を行い、塗膜の剥がれ・変色について観察し評価した。 (Alkali resistance): A coated substrate having a cured coating film is immersed in a 10% by weight NaOH aqueous solution at room temperature for 30 minutes, washed with water, dried, and then subjected to a peeling test with a cellophane adhesive tape to observe peeling and discoloration of the coating film. And evaluated.
○・・・まったく変化が認められなかったもの
△・・・一部変化が認められたもの
×・・・塗膜が膨潤して剥がれが認められたもの。
○: No change was observed at all Δ: Partial change was observed ×: The film was swollen and peeled off.
（耐熱性）：硬化塗膜を有する塗工基板を、ＪＩＳ Ｃ ６４８１（１９９６）の試験方法に従って、２６０℃のはんだ槽に３０秒浸漬後、セロハン粘着テープによるピーリング試験を１サイクルとした計１〜３サイクルを行った後の塗膜状態を目視により評価した。 (Heat resistance): A coated substrate having a cured coating film was immersed in a solder bath at 260 ° C. for 30 seconds in accordance with a test method of JIS C 6481 (1996), and then a peeling test with a cellophane adhesive tape was taken as one cycle. The coating film state after performing 3 cycles was visually evaluated.
○・・・３サイクル後まったく変化が認められなかったもの。 ○: No change was observed after 3 cycles.
△・・・３サイクル後に一部変化が認められたもの
×・・・２サイクル以内に変化が認められたもの。
Δ: Some change was observed after 3 cycles ×: Change was observed within 2 cycles.
（消泡性）：予め面処理済みの基板（銅張り積層板）に、スクリーン印刷法により、各々のソルダーレジスト組成物を３５μｍの厚さ（乾燥前）に塗工して、表面状態の泡の観察、及び乾燥（８０℃、２０分）後の塗膜表面の観察を行った。 (Defoaming property): A surface-treated foam is applied to a surface-treated substrate (copper-clad laminate) by a screen printing method to each solder resist composition to a thickness of 35 μm (before drying). And the surface of the coating film after drying (80 ° C., 20 minutes) were observed.
○・・・印刷・乾燥後いずれにおいても消泡性が著しく良好なもの。 ○: Defoaming property is remarkably good both after printing and drying.
△・・・印刷後はやや泡が認められるが、乾燥後には良好なもの。 Δ: Bubbles are slightly observed after printing, but good after drying.
×・・・印刷・乾燥後いずれにおいても消泡性が悪いもの。 X: Defoaming property is poor both after printing and drying.
（耐金めっき性）：硬化塗膜を有する評価基板に金めっき加工後、セロハン粘着テープによるピーリング試験を行い、レジスト層の剥がれ、変色について観察して評価した。 (Gold-proofing property): The evaluation board | substrate which has a cured coating film was gold-plated, and the peeling test by a cellophane adhesive tape was done, and the peeling of the resist layer and discoloration were observed and evaluated.
○・・・まったく変化が認められなかったもの
△・・・顕著に変化が認められたもの
×・・・塗膜が膨潤して剥がれが認められたもの。
○: No change was observed at all Δ: Significant change was observed ×: Coating was swollen and peeled off.
（絶縁抵抗と変色）：ＩＰＣ−ＳＭ−８４０Ｂ Ｂ−２５のくし型電極Ｂクーポン基板を、予め面処理した後、スクリーン印刷法により、各々のソルダーレジスト組成物を３５μｍの厚さ（乾燥前）になるように塗工して、８５℃、８５％ＲＨ（相対湿度）の恒温恒湿槽中で１００Ｖの直流電圧を印加し、５００時間後の絶縁抵抗及び変色を目視により評価した。 (Insulation resistance and discoloration): IPC-SM-840B B-25 comb-shaped electrode B Coupon substrate was surface-treated in advance, and each solder resist composition was 35 μm thick (before drying) by screen printing. Then, a DC voltage of 100 V was applied in a constant temperature and humidity chamber at 85 ° C. and 85% RH (relative humidity), and the insulation resistance and discoloration after 500 hours were visually evaluated.
○・・・まったく変色していないもの
△・・・顕著に変色しているもの
×・・・黒く焦げ付いているもの。
○: No discoloration at all Δ: Significant discoloration ×: Black scorch
評価結果を表２に示す。
表２より、実施例１〜３は、比較例１〜６のものに比べ、ＵＶマーキング密着性及びポストフラックス濡れ性がはるかに優れていることがわかった。 From Table 2, it was found that Examples 1 to 3 were much more excellent in UV marking adhesion and post flux wettability than those in Comparative Examples 1 to 6.
Claims (4)
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| JP2011060892A (en) * | 2009-09-08 | 2011-03-24 | Renesas Electronics Corp | Electronic device and method for manufacturing the same |
| WO2013012035A1 (en) * | 2011-07-20 | 2013-01-24 | 日本ゼオン株式会社 | Negative-type photosensitive resin composition, resin film, and electronic component |
| WO2020194885A1 (en) * | 2019-03-27 | 2020-10-01 | 太陽インキ製造株式会社 | Curable composition, dry film, cured product, and electronic component |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2011060892A (en) * | 2009-09-08 | 2011-03-24 | Renesas Electronics Corp | Electronic device and method for manufacturing the same |
| WO2013012035A1 (en) * | 2011-07-20 | 2013-01-24 | 日本ゼオン株式会社 | Negative-type photosensitive resin composition, resin film, and electronic component |
| CN103718107A (en) * | 2011-07-20 | 2014-04-09 | 日本瑞翁株式会社 | Negative-type photosensitive resin composition, resin film, and electronic component |
| TWI475322B (en) * | 2011-07-20 | 2015-03-01 | Zeon Corp | A negative-type photosensitive resin composition, a resin film, and an electronic component |
| WO2020194885A1 (en) * | 2019-03-27 | 2020-10-01 | 太陽インキ製造株式会社 | Curable composition, dry film, cured product, and electronic component |
| JP2020161673A (en) * | 2019-03-27 | 2020-10-01 | 太陽インキ製造株式会社 | Curable composition, dry film, cured product and electronic component |
| JP7383388B2 (en) | 2019-03-27 | 2023-11-20 | 太陽ホールディングス株式会社 | Curable compositions, dry films, cured products, and electronic components |
| TWI825246B (en) * | 2019-03-27 | 2023-12-11 | 日商太陽控股股份有限公司 | Hardening compositions, dry films, hardened materials and electronic parts |
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