JP4191956B2 - Photosensitive resin composition - Google Patents
Photosensitive resin composition Download PDFInfo
- Publication number
- JP4191956B2 JP4191956B2 JP2002151632A JP2002151632A JP4191956B2 JP 4191956 B2 JP4191956 B2 JP 4191956B2 JP 2002151632 A JP2002151632 A JP 2002151632A JP 2002151632 A JP2002151632 A JP 2002151632A JP 4191956 B2 JP4191956 B2 JP 4191956B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- group
- base
- photosensitive resin
- resin composition
- 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.)
- Expired - Fee Related
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- 239000011342 resin composition Substances 0.000 title claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 61
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 125000003277 amino group Chemical group 0.000 claims description 18
- 230000002062 proliferating effect Effects 0.000 claims description 15
- 125000001424 substituent group Chemical group 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000004132 cross linking Methods 0.000 claims description 8
- 125000003700 epoxy group Chemical group 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 4
- WYBZFSGKJOYRQH-UHFFFAOYSA-N [nitro(phenyl)methyl] carbamate Chemical group NC(=O)OC([N+]([O-])=O)C1=CC=CC=C1 WYBZFSGKJOYRQH-UHFFFAOYSA-N 0.000 claims description 4
- 125000006307 alkoxy benzyl group Chemical group 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 2
- 230000035755 proliferation Effects 0.000 claims 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 150000003462 sulfoxides Chemical class 0.000 claims 1
- 239000002585 base Substances 0.000 description 21
- -1 carboxyl compound Chemical class 0.000 description 21
- 238000000034 method Methods 0.000 description 18
- 125000004432 carbon atom Chemical group C* 0.000 description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000003822 epoxy resin Substances 0.000 description 12
- 229920000647 polyepoxide Polymers 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 10
- 238000001723 curing Methods 0.000 description 10
- 238000007772 electroless plating Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 230000018109 developmental process Effects 0.000 description 8
- 229910000679 solder Inorganic materials 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 230000002194 synthesizing effect Effects 0.000 description 8
- 230000035939 shock Effects 0.000 description 7
- 150000005846 sugar alcohols Polymers 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 5
- 230000007774 longterm Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000012965 benzophenone Substances 0.000 description 4
- 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 4
- 230000000052 comparative effect Effects 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
- 239000011229 interlayer Substances 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 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
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 150000002923 oximes Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- 229920003319 Araldite® Polymers 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 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
- 239000003085 diluting agent Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- IRXSLJNXXZKURP-UHFFFAOYSA-N fluorenylmethyloxycarbonyl chloride Chemical compound C1=CC=C2C(COC(=O)Cl)C3=CC=CC=C3C2=C1 IRXSLJNXXZKURP-UHFFFAOYSA-N 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- XHXSXTIIDBZEKB-UHFFFAOYSA-N 1,2,3,4,5,6,7,8-octamethylanthracene-9,10-dione Chemical compound CC1=C(C)C(C)=C2C(=O)C3=C(C)C(C)=C(C)C(C)=C3C(=O)C2=C1C XHXSXTIIDBZEKB-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
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-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
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- JTINZFQXZLCHNS-UHFFFAOYSA-N 2,2-bis(oxiran-2-ylmethoxymethyl)butan-1-ol Chemical compound C1OC1COCC(CO)(CC)COCC1CO1 JTINZFQXZLCHNS-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-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
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- LZWVPGJPVCYAOC-UHFFFAOYSA-N 2,3-diphenylanthracene-9,10-dione Chemical compound C=1C=CC=CC=1C=1C=C2C(=O)C3=CC=CC=C3C(=O)C2=CC=1C1=CC=CC=C1 LZWVPGJPVCYAOC-UHFFFAOYSA-N 0.000 description 1
- UXCIJKOCUAQMKD-UHFFFAOYSA-N 2,4-dichlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC(Cl)=C3SC2=C1 UXCIJKOCUAQMKD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- LZHUBCULTHIFNO-UHFFFAOYSA-N 2,4-dihydroxy-1,5-bis[4-(2-hydroxyethoxy)phenyl]-2,4-dimethylpentan-3-one Chemical compound C=1C=C(OCCO)C=CC=1CC(C)(O)C(=O)C(O)(C)CC1=CC=C(OCCO)C=C1 LZHUBCULTHIFNO-UHFFFAOYSA-N 0.000 description 1
- CZZZABOKJQXEBO-UHFFFAOYSA-N 2,4-dimethylaniline Chemical group CC1=CC=C(N)C(C)=C1 CZZZABOKJQXEBO-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
- UMLWXYJZDNNBTD-UHFFFAOYSA-N 2-(dimethylamino)-1-phenylethanone Chemical compound CN(C)CC(=O)C1=CC=CC=C1 UMLWXYJZDNNBTD-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- FGTYTUFKXYPTML-UHFFFAOYSA-N 2-benzoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 FGTYTUFKXYPTML-UHFFFAOYSA-N 0.000 description 1
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-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
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-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
- QPXVRLXJHPTCPW-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-(4-propan-2-ylphenyl)propan-1-one Chemical compound CC(C)C1=CC=C(C(=O)C(C)(C)O)C=C1 QPXVRLXJHPTCPW-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- MYISVPVWAQRUTL-UHFFFAOYSA-N 2-methylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3SC2=C1 MYISVPVWAQRUTL-UHFFFAOYSA-N 0.000 description 1
- YTPSFXZMJKMUJE-UHFFFAOYSA-N 2-tert-butylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(C(C)(C)C)=CC=C3C(=O)C2=C1 YTPSFXZMJKMUJE-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Materials For Photolithography (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は、光または光と熱で硬化する感光性樹脂組成物に関し、更に詳しくは光硬化性塗料、光硬化性インク、絶縁材料、接着剤等に広く用いられるものである。特にプリント配線板に使用される、ソルダーレジストや層間絶縁材料、めっきレジスト、エッチングレジストとして解像度、耐熱性、絶縁性、耐熱衝撃性、耐ＰＣＴ特性、耐無電解めっき性に優れる感光性樹脂組成物に関するものである。
【０００２】
【従来の技術】
電子機器の小型化、高密度化、高性能化によって、それに使用されるプリント配線板も高密度化、高信頼性化が進み、いわゆるビルドアップ配線板が広く使用されるようになってきている。またビルドアップ基板は半導体を搭載するパッケージ基板として使用されるようになってきた。よって使用される材料も高密度化、高信頼性に対応できるように、高解像度化や厳しい耐熱性、密着性、電気特性、耐無電解めっき性、耐熱衝撃性、耐ＰＣＴ（プレッシャクッカーテスト）性が要求されている。ソルダーレジストや層間絶縁材料、永久無電解めっきレジストは、高精度、高密度のパターン形成を行う必要があるため、紫外露光後、現像することによりパターン形成し、光および熱硬化で完全硬化する写真現像型レジストが使用されている。一般的には現像液としてアルカリ水溶液を用いるアルカリ現像タイプのレジストが主流となっている。このようなアルカリ現像型レジストとしては、特開平６−３２４４９０のような不飽和基含有ポリカルボン酸と光重合開始剤、希釈剤、および硬化剤からなるレジストインキや特開平６−３３２１７１のようなエチレン性不飽和基含有重合性化合物、カルボキシル基を有する熱可塑性重合体および光重合開始剤を含む感光性樹脂組成物が示されている。
【０００３】
【発明が解決しようとする課題】
これらのレジスト組成物は解像度や耐熱性には優れているが、アルカリ水溶液で現像するために組成中にカルボキシル基を含み硬化後に未反応のカルボキシル基が多く残るため、絶縁特性や耐ＰＣＴ性などの長期信頼性が十分でない。またこれらのレジスト組成物はエポキシ樹脂とカルボキシル基、更にアミン類、イミダゾール類、酸無水物類など硬化剤、硬化促進剤を含むため、混合後に反応が進行し可使時間の制御ができず、粘度安定性も悪く、長期保存性に欠ける。これを防ぐために、エポキシ樹脂とカルボキシル化合物、硬化剤、触媒及び促進剤成分を分け、２液にして保存する必要があった。よって使用前に混合する必要があり作業性が問題となっている。よって本発明の目的はプリント配線板のソルダーレジストや層間絶縁材料、無電解めっきレジストとして要求される高解像度、耐熱性、絶縁性、耐熱衝撃性、耐ＰＣＴ特性、耐無電解めっき性に優れ、かつ長期保存安定性に優れた感光性樹脂組成物を提供することにある。
【０００４】
【課題を解決するための手段】
本発明者等は、上記問題を解決すべく鋭意検討した結果、一分子中に少なくとも２個のエポキシ基を有する化合物（Ａ）と一分子中に少なくとも２個のフェノール性水酸基を有する化合物（Ｂ）と光塩基発生剤（Ｃ）と塩基の作用により分解してウレタン結合由来の塩基を発生する塩基増殖剤（Ｄ）とからなり、
化合物（Ａ）及び化合物（Ｂ）以外の架橋成分を含まず、
塩基発生剤（Ｃ）及び塩基増殖剤（Ｄ）が化合物（Ａ）及び化合物（Ｂ）の総重量に対してそれぞれ０．０１〜１０質量％である感光性樹脂組成物を用いることにより達成されることを見いだし本発明に到達した。
また、一分子中に少なくとも２個のエポキシ基を有する化合物（Ａ）と一分子中に少なくとも２個のフェノール性水酸基を有する化合物（Ｂ）と光塩基発生剤（Ｃ）と塩基の作用により分解してウレタン結合由来の塩基を発生する塩基増殖剤（Ｄ）とエチレン性不飽和化合物（Ｅ）と光照射によりラジカルを発生する光重合開始剤（Ｆ）とからなり、
化合物（Ａ）、化合物（Ｂ）及びエチレン性不飽和化合物（Ｅ）以外の架橋成分を含まず、
塩基発生剤（Ｃ）及び塩基増殖剤（Ｄ）が化合物（Ａ）及び化合物（Ｂ）の総重量に対してそれぞれ０．０１〜１０質量％である感光性樹脂組成物を用いることにより達成されることを見いだし本発明に到達した。
【０００５】
従来の組成物において、絶縁特性や耐ＰＣＴ性などの長期信頼性が十分でない主要因は硬化物中に未反応のカルボキシル基やアミノ基が残るためである。本発明の感光性樹脂組成物は、架橋成分としてカルボキシル基やアミノ基を含まないことから絶縁特性や耐ＰＣＴ性などの長期信頼性に優れた硬化物が得られる。
【００６】
また従来の組成物において、粘度安定性を悪くする主因は、保存中にカルボキシル基、アミン類、イミダゾール類、酸無水物類など硬化剤、硬化促進剤がエポキシ樹脂と架橋反応が進行するためである。本発明の感光性樹脂組成物は、 化合物（Ｃ）に光照射するとアミン類を生成し、このアミン類の作用によって化合物（Ｄ）からもアミン類が新たに生成する。生成したアミン類は少量で化合物（Ａ）と（Ｂ）の架橋反応の硬化促進剤として働く。よって光を照射しない限りアミン類は発生せず化合物（Ａ）と（Ｂ）は架橋しないので粘度安定性の良い感光性樹脂組成物となる。また化合物（Ｃ）と（Ｄ）から生成させるアミン類の量も少量でよいので絶縁性や耐ＰＣＴ性にも悪影響は与えない。
【０００７】
一分子中に少なくとも２個のエポキシ基を有する化合物（Ａ）の具体例としては、例えば ＤＥＲ３３１Ｊ、ＤＥＲ６６１Ｊ、（以上、ダウケミカル製）、エピクロン８００（以上、大日本インキ化学工業製）、エピコート１００１、エピコート８２８（以上、ジャパンエポキシレジン製）などのビスフェノールＡ型エポキシ樹脂；ＤＥＲ４３１（以上、ダウケミカル製）、アラルダイトＥＰＮ１１３８（チバガイギー社製）、エピコート１５４、エピコート１８０Ｓ６５（以上、ジャパンエポキシレジン製）などのノボラック型エポキシ樹脂；シラキュアー６１００、ＥＲＬ２２５６（以上、ユニオンカーバイド製）、アラルダイトＣＹ−１７５（以上、チバガイギー製）、チッソノックス０９０、チッソノックス３０１（以上、チッソ製）などの脂環式エポキシ樹脂；１，６−ヘキサンジオールジグリシジルエーテル、２，２−ジブロモネオペンチルグリコールジグリシジルエーテル、エチレングリコールジグリシジルエーテル、グリセリンジグリシジルエーテル、トリメチロールプロパンジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルーエテル、水素添加ビスフェノールＡのジグリシジルエーテルなどの脂肪族多価アルコールの多価グリシジルエーテル；ビスフェノールＡアルキレンオキシド付加体ジグリシジルエーテル、ビスフェノールＦアルキレンオキシド付加体ジグリシジルエーテル、ビスフェノールＳアルキレンオキシド付加体ジグリシジルエーテルなどの芳香族多価アルコール誘導体多価グリシジルエーテル；ジグリシジルｐ−オキシ安息香酸、ダイマー酸グリシジルエステル、テトラヒドロフタル酸ジグリシジルエステル、フタル酸ジグリシジルエステル、ヘキサヒドロフタル酸ジグリシジルエステルなどのグリシジルエステル；Ｎ，Ｎ−ジグリシジルアニリン、テトラグリシジルジアミノジフェニルメタン、トリグリシジルｐ−アミノフェノールなどのグリシジルアミン；トリグリシジルイソシアヌレート、ヒダントイン型エポキシ樹脂などの複素環式エポキシ樹脂などが挙げられる。更にノボラック型多官能エポキシ樹脂のエポキシ基の部分（メタ）アクリレートもふくまれる。
【０００８】
少なくとも２個のフェノール性水酸基を有する化合物（Ｂ）の具体例としては、例えばフェノライトＴＤ−２１３１、フェノライトＴＤ−２０９０（大日本インキ化学工業製）などのノボラック型フェノール樹脂。フェノライトＶＨ−４１５０、フェライトＶＨ−４２９０（大日本インキ化学工業製）のノボラック型アルキルフェノール樹脂。フェノライトＬＡ−７０５１、フェノライトＬＡ−７０５４（大日本インキ化学工業製）などのトリアジン変性フェノールノボラック樹脂。ＤＰＰ−Ｍ、ＤＰＡ−１４５−Ｌ（日本石油化学製）のジシクロペンタジエンクレゾール樹脂などがあげられる。
【０００９】
塩基発生剤（Ｃ）としてはアシルオキシイミノ基，Ｎ−ホルミル化芳香族アミノ基，Ｎ−アシル化芳香族アミノ基、ニトロベンジルカーバメイト基、アルコオキシベンジルカーバメート基 から選ばれる少なくとも一個の置換基を含む化合物などが用いられる。
【００１０】
アシルオキシイミノ基を少なくとも１個含む化合物の具体例としては，ＯＯ’−コハク酸ジアセトフェノンオキシム，Ｏ，Ｏ’−コハク酸ジナフトフェノンオキシム、ベンゾフェノンオキシムアクリレートースチレン共重合体などがあげられる。
【００１１】
このような、アシルオキシイミノ基を少なくとも１個含む化合物物を合成する方法としては例えばカルボン酸ハライドとオキシムから合成する方法、ジシクロヘキシルカルボンイミドの存在下、カルボン酸とオキシムとから直接合成する方法などがある。またアシルオキシイミノ基を有する重合体をえるには上記の方法を用いてオキシムアクリレートを合成し、単独重合または他のモノマーと共重合する事により得られる。またカルボキシル基を含む重合体を合成し、その後上記の方法にて目的物を合成しても良い。
【００１２】
Ｎ−ホルミル化芳香族アミノ基，Ｎ−アシル化芳香族アミノ基を含む化合物の具体例としては、例えば、ジ−Ｎ−（ｐ−ホルミルアミノ）ジフェニルメタン、ジ−Ｎ（ｐ−アセエチルアミノ）ジフェニルメラン、ジ−Ｎ−（ｐ−ベンゾアミド）ジフェニルメタン、４−ホルミルアミノトルイレン、４−アセチルアミノトルイレン、２，４−ジホルミルアミノトルイレン、１−ホルミルアミノナフタレン、１−アセチルアミノナフタレン、１，５−ジホルミルアミノナフタレン、１−ホルミルアミノアントラセン、１，４−ジホルミルアミノアントラセン、１−アセ チルアミノアントラセン、１，４−ジホルミルアミノアントラキノン、１，５−ジホルミルアミノアントラキノン、３，３’−ジメチル−４，４’−ジホルミルアミノビフェニル、４，４’−ジホルミルアミノベンゾフェノンなどがあげられる。
【００１３】
このようなＮ−ホルミル化芳香族アミノ基，Ｎ−アシル化芳香族アミノ基を少なくとも１個含む化合物の合成方法としては、例えば、芳香族ジイソシアネートとギ酸、酢酸、プロピオン酸、安息香酸などとの反応、芳香族アミンと上記カルボン酸とをジシクロヘキシルカルボジイミドを縮合剤として用いて合成する方法、芳香族アミンと上記のカルボン酸のカルボン酸ハライドとから合成す方法などがあげられる。
【００１４】
ニトロベンジルカーバメイト基、アルコオキシベンジルカーバメート基を少なくとも１個含む化合物の具体例としては、例えば、ビス｛｛（２−ニトロベンジル）オキシ｝カルボニル｝ジアミノジフェニルメタン、２，４−ジ｛｛（２−ニトロベンジル）オキシ｝トルイレン、ビス｛｛（２−ニトロベンジルオキシ）カルボニル｝ヘキサン−１，６−ジアミン、ｍ−キシリジン｛｛（２−ニトロ−４−クロロベンジル）オキシ｝アミド｝などがあげられる。
【００１５】
このようなニトロベンジルカーバメイト基、アルコオキシベンジルカーバメート基 を含む化合物の合成方法として例えば、芳香族、脂環族または脂肪族の 多官能性イソシアネートとニトロ基またはメトキシ基を含むベンジルアルコールとの反応によって合成される。このとき触媒としてトリエチルアミン、ジブチル錫ジラウレートなどの触媒を用いることが出来る。
【００１６】
塩基の作用により分解してウレタン結合由来の塩基を発生する塩基増殖剤（Ｄ）は下記一般式（１）で表されるウレタン化合物からなる。
【化４】
【００１７】
前記アミノ基は下記一般式（４）で表すことができる。
【化５】
前記式中Ｒ５およびＲ６は水素または置換基を示す。この置換基には炭素数１から１２、好ましくは１から６のアルキル基、炭素数４から１０、好ましくは５から８のシクロアルキル基、炭素数６から１４、好ましくは６から１０のアリール基、炭素数７から１５、好ましくは７から１１のアリールアルキル基がなどが用いられる。具体例としてはメチル基、エチル基、プロピル基、ブチル基、シクロヘキシル基、フェニル基、トリル基、ナフチル基、ベンジル基、フェネチル基、ナフチルメチル基などが挙げられる。
【００１９】
前記一般式（４）のアミノ基においてＲ５およびＲ６は連結して含窒素環を形成することができる。この場合の含窒素環の環構成原子数は３から１２、好ましくは５から８である。前記含窒素環はその環構成原子に複数のヘテロ原子（Ｎ、Ｓ、Ｏ等）を含有することができる。
【００２０】
また、前記アミノ基は置換基を介して２つの塩基増殖機能を有するウレタン化合物の残基であってもよい。
【００２１】
本発明の塩基増殖剤（Ｄ）はアルコールにクロロ蟻酸エステルを反応させて非対称な炭酸エステルを生成し、次いでこの炭酸エステルに塩基を反させるか、あるいはアルコールにイソシアネート化合物を反応させることにより得られる。
【００２２】
本発明の塩基増殖剤（Ｄ）の具体例を以下に示す。
【化６】
エチレン性不飽和化合物（Ｅ）は反応性希釈剤としてや架橋密度を調整するために使用することができる。エチレン性不飽和化合物（Ｅ）の具体例としてはメチル（メタ）アクリレート［以下、（メタ）アクリレートとはアクリレートとメタクリレートのいずれでも使用可能なことを意味する。］、ブチル（メタ）アクリレートなどのアルキル（メタ）アクリレート類；ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレートなどのヒドロキシ基含有（メタ）アクリレート類；１，６−ヘキサンジオールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレートなどの多価アルコールまたは多価アルコールのアルキレンオキサイド付加物の（メタ）アクリレート類；フタル酸と１，６−ヘキサンジオールからなるポリエステルジオールのジ（メタ）アクリレート、アジピン酸とエチレングリコ−ルからなるポリエステルジオ−ルのジ（メタ）アクリレ−トなどの多塩基酸と多価アルコールからのポリエステル樹脂の末端に（メタ）アクリレート基を有するポリエステル（メタ）アクリレート類；ポリエステルジオール・ＴＤＩ付加物ジ（メタ）アクリレート、ポリエーテルトリオール・ＭＤＩ付加物トリ（メタ）アクリレートなどの多価イソシアネートとヒドロキシ基、カルボキシル基、アミノ基等の活性水素基を有する（メタ）アクリレートとの反応物であるウレタン（メタ）アクリレート類；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、フェノールノボラック（メタ）アクリレートなどの多官能エポキシ樹脂と（メタ）アクリ酸との反応物であるエポキシ（メタ）アクリレート類；グリシジル（メタ）アクリレート；（メタ）アクリル酸；（メタ）アクリルアミド；スチレン類；不飽和ポリエステル樹脂など、およびこれらの混合物を挙げることが出来る。これらのうち多価アルコールまたは多価アルコールのアルキレンオキサイド付加物の（メタ）アクリレート類が好ましい。
【００２４】
光ラジカル発生剤（Ｆ）は光照射によりラジカルを発生させエチレン性不飽和化合物（Ｅ）を架橋させるものであり、具体例としては、例えば１−（４−イソプロピルフェニル）−２−ヒドロキシ−２−メチルプロパン−１−オン、１−ヒドロキシシクロヘキシルフェニルケトン、２，２−ジエトキシアセトフェノン、２，２−ジメトキシ−２−フェニルアセトフェノン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、２−メチル−１−（４−（メチルチオ）フェニル）−２−モルホリノプロパン−１、４−フェノキシジクロロアセトフェノン、４−（２−ヒドロキシエトキシ）−フェニル（２−ヒドロキシ−２−プロピル）ケトン、ｐ−ｔ−ブチルジクロロアセトフェノン、ｐ−ｔ−ブチルトリクロロアセトフェノン、ｐ−ジメチルアミノアセトフェノンなどのアセトフェノン類；ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾイン−ｎ−ブチルエーテル、ベンゾインイソブチルエーテル、ベンジルジメチルケタールなどのベンゾイン類；ベンゾフェノン、ベンゾフェノンメチルエーテル、ベンゾイル安息香酸、ベンゾイル安息香酸メチル、ヒドロキシベンゾフェノン、４−フェニルベンゾフェノン、３，３’−ジメチル−４−メトキシベンゾフェノン、３，３’−ビス（Ｎ，Ｎ−ジエチルアミノ）ベンゾフェノン、４，４’−ビス（Ｎ，Ｎ−ジエチルアミノ）ベンゾフェノン、４’，４”−ジエチルイソフタロフェノン、３，３’，４，４’−テトラ（ｔ−ブチルパーオキシカルボニル）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、アクリル化ベンゾフェノンなどのベンゾフェノン類；チオキサントン、２−メチルチオキサントン、イソプロピルチオキサントン、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、２，４−ジイソプロピルチオキサントン、２−クロロチオキサントン、２，４−ジクロロチオキサントンなどのキサントン類；ジアセチル、ベンジルなどのジケトン類；２−エチルアントラキノン、２−ｔ−ブチルアントラキノン、２，３−ジフェニルアントラキノン、１，２−ベンズアントラキノン、オクタメチルアントラキノン、カンファーキノン、ジベンゾスベロン、９，１０−フェナンスレンキノンなどのキノン類などが挙げられる。
【００２５】
次に組成比について説明する。化合物（Ａ）と化合物（Ｂ）の配合比は化合物（Ａ）のエポキシ基のモル数をＭ、化合物（Ｂ）のフェノール性水酸基のモル数をＸとするとＭ：Ｘ＝１．０：０．５から１．５、好ましくは０．８から１．２である。Ｘが０．５未満の場合、未反応のエポキシ基が多く残りはんだ耐熱性や耐熱衝撃性が低下する。Ｘが１．５を超えると未反応のフェノール性水酸基が残り耐ＰＣＴ性、無電解めっき性が低下する。化合物（Ｃ）及び（Ｄ）の比率は化合物（Ａ）と化合物（Ｂ）の総質量に対してそれぞれ０．０１〜２０質量％、好ましくは０．１から１０質量％である。０．０１質量％未満の場合は塩基が十分に発生せずに硬化反応が起こらない。２０質量％を超えると、発生するアミン類が過剰となり絶縁性、耐ＰＣＴ性、耐無電解めっき性が低下する。化合物（Ｅ）の比率は化合物（Ａ）と化合物（Ｂ）の総重量に対して５００質量％以下、好ましくは１から１００質量％である。５００質量％を超えると、エチレン性不飽和結合の重合に伴う架橋が多くなり耐熱衝撃性が低下する。化合物（Ｆ）の比率は化合物（Ｅ）の質量に対して０．１から５０質量％以下、好ましくは１から２０質量％である。０．１質量％以下の場合は化合物（Ｅ）の反応が十分に起こららず、５０質量％を超えると解像度、はんだ耐熱性が低下する。
【００２６】
さらに、本発明の硬化性樹脂組成物には、必要に応じて、オリゴマー、ポリマー、充填剤、染料や顔料などの着色剤、熱安定剤、密着促進剤、可塑剤、シリカやタルクなどの顔料、塗工適性を与えるレベリング剤などを添加してもよい。
【００２７】
本発明の硬化物は、デイップ法、スプレー法、ロールコート法、フローコート法、スピンコート法、アプリケータ法、バーコート法、スクリーン印刷法などの方法により任意の厚さに塗布することが出来る。このとき必要により、硬化性組成物を溶解する溶剤をしようする事が出来る。例えば、トルエン、アセトン、メチルエチルケトン、ジエチレングリコールジメチルエーテル、ジメチルホルムアミドなどがある。これらの溶剤は単独または混合して用いられる。
更に硬化性組成物をポリエステルフイルに塗布、乾燥後ポリエチレンフイルム等のフイルでラミネートしドライフイルムを形成後、基材にラミネートし転写する方法も有効である。
【００２８】
光照射を行う場合の光源としては、高圧水銀灯、低圧水銀灯、メタルハライドランプ、キセノンランプ、蛍光灯、タングステンランプ、アルゴンレーザー、ヘリウメカドミウムレーザーなどがあげられる。
【００２９】
光照射後、必要により加熱を行い反応を促進する事が出来る。温度は、通常５〜２５０℃、好ましくは６０〜１８０℃である。
【００３０】
次に、本発明の硬化性樹脂組成物の使用方法について説明する。まず、硬化性樹脂組成物を基材上に前記方法で塗布し、必要に応じて加熱乾燥または熱風乾燥により溶剤を除去し塗膜を基材上に形成する。その後光照射を行い、必要により後加熱を行なう。
【００３１】
パターンを形成する場合は、ネガマスクまたはポジマスクを通して、乾燥途膜に光照射を行う。次いで、現像液を用いて未露光部分を現像する。現像液としは水酸化ナトリウム水溶液、炭酸ナトリウム水溶液、アンモニウムハイドロキサイド水溶液などのアルカリ水溶液が用いられる。現像後、必要により後露光、後加熱をしても良い。
【００３２】
【実施例】
次に、実施例により本発明を繊細に説明するが、本発明は以下の実施例により限定されるものではない。
【００３３】
合成例−１
９−フルオレニルメチルクロロホーメートのジクロロメタン溶液（１０ｇ／３２０ｍＬ）に、１，３−ビス（４−ピペリジル）プロパンのジクロロメタン溶液（１２ｇ／８０ｍＬ）を氷浴中でゆっくりと滴下した。滴下後、氷浴中で２０分間攪拌し、さらに室温で１．５時間攪拌した。反応終了後、反応溶液を水、５％塩酸、飽和食塩水の順で洗浄し、無水硫酸マグネシウムで乾燥させた後、溶媒を減圧留去した。得られた固体をシリカゲルカラムクロマトグラフィー（展開溶媒；ヘキサン：酢酸エチル＝２：１）により精製して９ｇの白色結晶を得た。これを塩基増殖剤Ｄ1とする。
【００３４】
合成例−２
合成例−１と同様の方法で９−フルオレニルメチルクロロホーメートとジシクロヘキシルアミンと反応させ、生成物をシリカゲルカラムクロマトグラフィー（展開溶媒；ヘキサン：酢酸エチル＝２：１）により精製して８ｇの白色結晶を得た。これを塩基増殖剤Ｄ２とする。
【００３５】
合成例−３
９−フルオレニルメチルアルコールのジクロロメタン溶液（１０．０ｇ／３２０ｍＬ）に、イソホロンジイソシアネートのジクロロメタン溶液（１２．２ｇ／８０ｍＬ）を氷浴中でゆっくりと滴下した。滴下後、氷浴中で２０分間攪拌し、さらに室温で１．５時間攪拌した。反応終了後、反応溶液を水、５％塩酸、飽和食塩水の順で洗浄し、無水硫酸マグネシウムで乾燥させた後、溶媒を減圧留去した。得られた固体をシリカゲルカラムクロマトグラフィー（展開溶媒；ヘキサン：酢酸エチル＝２：１）により精製して８ｇの白色結晶を得た。これを塩基増殖剤Ｄ３とする。
【００３６】
合成例１から３で調整した化合物を用い、表１に示す配合比率で混合した後、３本ロールで混練して実施例１から６、比較例１から５の感光性樹脂組成物を作成した。
【００３７】
【表１】
表１に示す実施例１から６、比較例１から５で調製した感光性樹脂組成物を、エッチングにより配線パターンを形成したガラスエポキシ樹脂基板上にスクリーン印刷により塗布し、８０℃の順風乾燥器で３０分間加熱乾燥して厚さ２０μｍの感光性樹脂層を得た。次にフォトマスクを通して、高圧水銀灯を用い５００ｍＪ／ｃｍ2の露光を行なった。露光後、８０℃で３０分加熱処理した後、５％水酸化ナトリウム水溶液からなる現像液で現像温度３０℃、スプレー圧２Kgf/cm2で６０秒間スプレー現像した。現現像後、水洗によりプリント基板上に残った現像液を除去し、乾燥後、次いで、１８０℃で６０分間加熱処理し熱硬化を行なった。
【００３９】
このようにして得たプリント基板上の感光性樹脂組成物の硬化物の性能を以下の方法により評価した。結果を表２に示す。
（１）解像度
現像後に形成されたライン／スペース（＝１／１）の最小幅（μｍ）を解像度とした。パターン形成できない場合は×とした。
（２）はんだ耐熱性
２６０℃のはんだ浴に３０秒浸漬した後の外観を目視により観察した。
○：変化なし、×：われ、膨れあり
（３）絶縁性
８５℃、湿度８５％で２４時間処理した後に、表面抵抗値を測定した。
○：１×１０10Ω以上
×：１×１０10Ω未満
（４）耐熱衝撃性
−５５℃から１２５℃で５００サイクルのヒートサイクル処理を実施した後、クラック発生の有無を確認した。
○：クラックなし、×：クラック発生
（５）耐ＰＣＴ性
１２１℃、２気圧で１６８時間の処理を実施した後、硬化被膜外観の状態を評価した。
○：はがれ、変色なし、×：はがれまたは変色発生
（６）耐無電解めっき性
硬化後のレジストを硫酸銅、エチレンジアミン四酢酸ナトリウム、ポリエチレングリコール、ジピリジル、ホルマリン、水酸化ナトリウム、水を含む無電解銅めっき液にｐＨ１２、浴温度７０℃の条件で１５時間浸漬した後のレジスト外観、銅への密着性を観察し、次の基準で評価した。
外観○：変化なし
×：変色、しみ、はがれ、ふくれ、異常析出あり
（７）溶出率
アセトン中に３０分間浸漬した。浸漬前の重量をＷ１として、浸漬後の重量をＷ２、塗布前のガラス板の重量をＷ３として（Ｗ１−Ｗ３）−（Ｗ２−Ｗ３）×１００／（Ｗ１−Ｗ３）より溶出率を算出した。
【００４０】
表１に示す実施例１から６、比較例１から５で調製した感光性樹脂組成物を４０℃の恒温槽に５日間入れ、５日後の粘度を測定した。配合時の粘度をＶ１として、４０℃、５日後の粘度をＶ２とし、（Ｖ２−Ｖ１）×１００／Ｖ１粘度上昇率とした。結果を表２に示す。
【００４１】
表１に示す実施例１から６、比較例１から５で調製した感光性樹脂組成物をガラス板、鋼板、アルミ板に塗布して、８０℃の順風乾燥器で３０分間加熱乾燥して厚さ１０μｍの感光性樹脂層を得た。次に高圧水銀灯を用い５００ｍＪ／ｃｍ2の露光を行なった後、１００℃で２０分加熱処理した後、次いで１５０℃で６０分間加熱処理し熱硬化を行なった。このようにして得られた硬化物をセロハン粘着テープ剥離によるゴバン目接着性試験を行った。結果を表２に示す。
○：１００／１００、×：１００／１００未満
【００４２】
【表２】
【発明の効果】
本発明の感光性樹脂組成物は耐熱性、絶縁性、密着性、耐熱衝撃性、耐熱湿性、耐ＰＣＴ性、耐無電解めっき性に優れ、使用する現像液もリサイクル可能で廃液が発生しないことからプリント配線板の製造時に用いられるソルダーレジスト、層間絶縁材料、無電解めっきレジストとして好適である。[0001]
[Industrial application fields]
The present invention relates to a photosensitive resin composition that is cured by light or light and heat, and more specifically, is widely used for a photocurable paint, a photocurable ink, an insulating material, an adhesive, and the like. A photosensitive resin composition excellent in resolution, heat resistance, insulation, thermal shock resistance, PCT characteristics, and electroless plating resistance as a solder resist, interlayer insulating material, plating resist, etching resist, especially used for printed wiring boards It is about.
[0002]
[Prior art]
With the downsizing, higher density, and higher performance of electronic devices, the printed wiring boards used for them are also becoming more dense and more reliable, and so-called build-up wiring boards are becoming widely used. . The build-up substrate has been used as a package substrate on which a semiconductor is mounted. Therefore, high resolution and strict heat resistance, adhesion, electrical characteristics, electroless plating resistance, thermal shock resistance, and PCT (pressure cooker test) are required so that the materials used can be made denser and more reliable. Sex is required. Solder resists, interlayer insulation materials, and permanent electroless plating resists require high-precision and high-density pattern formation. Therefore, after UV exposure, the pattern is formed by development, and is completely cured by light and heat curing. A development type resist is used. In general, an alkali development type resist using an aqueous alkali solution as a developing solution is mainly used. Examples of such an alkali development type resist include a resist ink comprising an unsaturated group-containing polycarboxylic acid such as JP-A-6-324490, a photopolymerization initiator, a diluent, and a curing agent, and JP-A-6-332171. A photosensitive resin composition containing an ethylenically unsaturated group-containing polymerizable compound, a thermoplastic polymer having a carboxyl group, and a photopolymerization initiator is shown.
[0003]
[Problems to be solved by the invention]
These resist compositions are excellent in resolution and heat resistance, but since they are developed with an alkaline aqueous solution, they contain carboxyl groups in the composition and many unreacted carboxyl groups remain after curing, so that insulating properties, PCT resistance, etc. The long-term reliability is not enough. In addition, these resist compositions contain an epoxy resin and a carboxyl group, and further a curing agent such as amines, imidazoles, and acid anhydrides, and a curing accelerator, so that the reaction proceeds after mixing and the pot life cannot be controlled. Viscosity stability is also poor and long-term storage is lacking. In order to prevent this, it was necessary to separate the epoxy resin and the carboxyl compound, the curing agent, the catalyst and the accelerator component into two liquids and store them. Therefore, it is necessary to mix before use, and workability is a problem. Therefore, the object of the present invention is excellent in the high resolution, heat resistance, insulation, thermal shock resistance, PCT characteristics, and electroless plating resistance required as a solder resist and interlayer insulation material for printed wiring boards and electroless plating resists. And it is providing the photosensitive resin composition excellent in long-term storage stability.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have found that a compound (A) having at least two epoxy groups in one molecule and a compound having at least two phenolic hydroxyl groups in one molecule (B ), A photobase generator (C), and a base proliferating agent (D) that decomposes by the action of a base to generate a base derived from a urethane bond,
Does not contain crosslinking components other than compound (A) and compound (B),
It is achieved by using a photosensitive resin composition in which the base generator (C) and the base proliferating agent (D) are each 0.01 to 10% by mass based on the total weight of the compound (A) and the compound (B). As a result, the present invention has been achieved.
In addition, the compound (A) having at least two epoxy groups in one molecule, the compound (B) having at least two phenolic hydroxyl groups in one molecule, a photobase generator (C), and a base are decomposed. And a base proliferating agent (D) that generates a base derived from a urethane bond, an ethylenically unsaturated compound (E), and a photopolymerization initiator (F) that generates radicals by light irradiation,
It contains no crosslinking component other than compound (A), compound (B) and ethylenically unsaturated compound (E),
It is achieved by using a photosensitive resin composition in which the base generator (C) and the base proliferating agent (D) are each 0.01 to 10% by mass based on the total weight of the compound (A) and the compound (B). As a result, the present invention has been achieved.
[0005]
In the conventional composition, the main factor that the long-term reliability such as insulation properties and PCT resistance is not sufficient is that unreacted carboxyl groups and amino groups remain in the cured product. Since the photosensitive resin composition of the present invention does not contain a carboxyl group or an amino group as a crosslinking component, a cured product having excellent long-term reliability such as insulation properties and PCT resistance can be obtained.
[006]
In addition, in the conventional composition, the main cause of poor viscosity stability is that a curing reaction such as a carboxyl group, amines, imidazoles, and acid anhydrides and a curing accelerator proceed with the epoxy resin during storage. is there. The photosensitive resin composition of the present invention generates amines when the compound (C) is irradiated with light, and amines are newly generated from the compound (D) by the action of the amines. The produced amines act as a curing accelerator for the crosslinking reaction between the compounds (A) and (B) in a small amount. Therefore, amines are not generated unless light is irradiated, and the compounds (A) and (B) are not crosslinked, so that a photosensitive resin composition having good viscosity stability is obtained. In addition, since the amount of amines generated from the compounds (C) and (D) may be small, the insulating property and PCT resistance are not adversely affected.
[0007]
Specific examples of the compound (A) having at least two epoxy groups in one molecule include, for example, DER331J, DER661J (above, manufactured by Dow Chemical), Epicron 800 (above, manufactured by Dainippon Ink and Chemicals), Epicoat 1001 Bisphenol A type epoxy resins such as Epicoat 828 (above, Japan Epoxy Resin); DER431 (above, Dow Chemical), Araldite EPN1138 (Ciba Geigy), Epicoat 154, Epicoat 180S65 (above, Japan Epoxy Resin), etc. Novolak-type epoxy resin: Syracure 6100, ERL2256 (above, manufactured by Union Carbide), Araldite CY-175 (above, made by Ciba Geigy), Chisso Nox 090, Chisso Nox 301 (above, made by Chisso) 1,6-hexanediol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane diglycidyl ether, neopentyl Polyhydric glycidyl ether of aliphatic polyhydric alcohols such as glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, diglycidyl ether of hydrogenated bisphenol A; bisphenol A alkylene oxide addition Diglycidyl ether, bisphenol F alkylene oxide adduct diglycidyl ether, bisphenol S al Aromatic polyhydric alcohol derivative polyglycidyl ether such as dioxide adduct diglycidyl ether; diglycidyl p-oxybenzoic acid, dimer acid glycidyl ester, tetrahydrophthalic acid diglycidyl ester, phthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl Glycidyl esters such as esters; glycidyl amines such as N, N-diglycidyl aniline, tetraglycidyl diaminodiphenylmethane, and triglycidyl p-aminophenol; heterocyclic epoxy resins such as triglycidyl isocyanurate and hydantoin type epoxy resins . Furthermore, the partial (meth) acrylate of the epoxy group of the novolac type polyfunctional epoxy resin is also included.
[0008]
Specific examples of the compound (B) having at least two phenolic hydroxyl groups include novolak type phenol resins such as Phenolite TD-2131 and Phenolite TD-2090 (manufactured by Dainippon Ink & Chemicals, Inc.). A novolac-type alkylphenol resin of phenolite VH-4150 and ferrite VH-4290 (manufactured by Dainippon Ink & Chemicals, Inc.). Triazine-modified phenol novolac resins such as Phenolite LA-7051 and Phenolite LA-7054 (Dainippon Ink Chemical Co., Ltd.). Examples thereof include dicyclopentadiene cresol resins such as DPP-M and DPA-145-L (manufactured by Nippon Petrochemical).
[0009]
The base generator (C) contains at least one substituent selected from an acyloxyimino group, an N-formylated aromatic amino group, an N-acylated aromatic amino group, a nitrobenzyl carbamate group, and an alkoxybenzyl carbamate group. A compound or the like is used.
[0010]
Specific examples of the compound containing at least one acyloxyimino group include OO′-diacetphenone oxime succinate, dinaphthophenone oxime O, O′-succinate, and benzophenone oxime acrylate-styrene copolymer.
[0011]
Examples of a method for synthesizing a compound containing at least one acyloxyimino group include a method of synthesizing from a carboxylic acid halide and an oxime, and a method of synthesizing directly from a carboxylic acid and an oxime in the presence of dicyclohexylcarbonimide. is there. Further, in order to obtain a polymer having an acyloxyimino group, it can be obtained by synthesizing oxime acrylate using the above method and homopolymerizing or copolymerizing with other monomers. Alternatively, a polymer containing a carboxyl group may be synthesized, and then the target product may be synthesized by the above method.
[0012]
Specific examples of the compound containing an N-formylated aromatic amino group and an N-acylated aromatic amino group include, for example, di-N- (p-formylamino) diphenylmethane, di-N (p-aceethylamino). Diphenylmelane, di-N- (p-benzamido) diphenylmethane, 4-formylaminotoluylene, 4-acetylaminotoluylene, 2,4-diformylaminotoluylene, 1-formylaminonaphthalene, 1-acetylaminonaphthalene, 1,5-diformylaminonaphthalene, 1-formylaminoanthracene, 1,4-diformylaminoanthracene, 1-acetylaminoanthracene, 1,4-diformylaminoanthraquinone, 1,5-diformylaminoanthraquinone, 3 , 3′-dimethyl-4,4′-diformylaminobiphenyl, And 4'-formyl-amino benzophenone and the like.
[0013]
As a method for synthesizing such a compound containing at least one N-formylated aromatic amino group or N-acylated aromatic amino group, for example, an aromatic diisocyanate and formic acid, acetic acid, propionic acid, benzoic acid, etc. Examples thereof include a reaction, a method of synthesizing an aromatic amine and the above carboxylic acid using dicyclohexylcarbodiimide as a condensing agent, a method of synthesizing from an aromatic amine and a carboxylic acid halide of the above carboxylic acid, and the like.
[0014]
Specific examples of the compound containing at least one nitrobenzyl carbamate group and alkoxybenzyl carbamate group include, for example, bis {{(2-nitrobenzyl) oxy} carbonyl} diaminodiphenylmethane, 2,4-di {{(2- Nitrobenzyl) oxy} toluylene, bis {{(2-nitrobenzyloxy) carbonyl} hexane-1,6-diamine, m-xylidine {{(2-nitro-4-chlorobenzyl) oxy} amide} and the like. .
[0015]
As a method for synthesizing such a compound containing a nitrobenzyl carbamate group or an alkoxybenzyl carbamate group, for example, by reacting an aromatic, alicyclic or aliphatic polyfunctional isocyanate with benzyl alcohol containing a nitro group or a methoxy group. Synthesized. At this time, a catalyst such as triethylamine or dibutyltin dilaurate can be used as the catalyst.
[0016]
The base proliferating agent (D) that decomposes by the action of a base to generate a base derived from a urethane bond is composed of a urethane compound represented by the following general formula (1).
[Formula 4]
[0017]
The amino group can be represented by the following general formula (4).
[Chemical formula 5]
In the above formula, R 5 and R 6 represent hydrogen or a substituent. This substituent includes an alkyl group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, preferably 5 to 8 carbon atoms, and an aryl group having 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms. An arylalkyl group having 7 to 15 carbon atoms, preferably 7 to 11 carbon atoms, and the like are used. Specific examples include methyl group, ethyl group, propyl group, butyl group, cyclohexyl group, phenyl group, tolyl group, naphthyl group, benzyl group, phenethyl group, and naphthylmethyl group.
[0019]
In the amino group of the general formula (4), R 5 and R 6 can be linked to form a nitrogen-containing ring. In this case, the number of atoms constituting the nitrogen-containing ring is 3 to 12, preferably 5 to 8. The nitrogen-containing ring can contain a plurality of heteroatoms (N, S, O, etc.) in its ring constituent atoms.
[0020]
The amino group may be a residue of a urethane compound having two base-proliferating functions via a substituent.
[0021]
The base proliferating agent (D) of the present invention is obtained by reacting a chloroformate with alcohol to form an asymmetric carbonate, and then reacting the carbonate with a base or reacting an alcohol with an isocyanate compound. .
[0022]
Specific examples of the base proliferating agent (D) of the present invention are shown below.
[Chemical 6]
The ethylenically unsaturated compound (E) can be used as a reactive diluent or for adjusting the crosslinking density. Specific examples of the ethylenically unsaturated compound (E) include methyl (meth) acrylate [hereinafter, (meth) acrylate means that either acrylate or methacrylate can be used. ], Alkyl (meth) acrylates such as butyl (meth) acrylate; hydroxy group-containing (meth) acrylates such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; 1,6-hexanediol di (meth) (Meth) acrylates of polyhydric alcohols such as acrylates and polyethylene glycol di (meth) acrylates or alkylene oxide adducts of polyhydric alcohols; di (meth) acrylates of polyester diols comprising phthalic acid and 1,6-hexanediol, Polyester (meth) acrylate having a (meth) acrylate group at the end of a polyester resin from a polybasic acid and a polyhydric alcohol such as di (meth) acrylate of a polyester diol composed of adipic acid and ethylene glycol Polyhydric isocyanate such as polyester diol / TDI adduct di (meth) acrylate, polyether triol / MDI adduct tri (meth) acrylate, and active hydrogen groups such as hydroxy group, carboxyl group, amino group (meth) Urethane (meth) acrylates that are reactants with acrylates; Epoxy that is a reactant between polyfunctional epoxy resins such as bisphenol A diglycidyl ether di (meth) acrylate and phenol novolac (meth) acrylate and (meth) acrylic acid Mention may be made of (meth) acrylates; glycidyl (meth) acrylate; (meth) acrylic acid; (meth) acrylamide; styrenes; unsaturated polyester resins and the like, and mixtures thereof. Of these, polyhydric alcohols or (meth) acrylates of polyhydric alcohol alkylene oxide adducts are preferred.
[0024]
The photoradical generator (F) generates radicals by light irradiation to crosslink the ethylenically unsaturated compound (E). As a specific example, for example, 1- (4-isopropylphenyl) -2-hydroxy-2 -Methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1, 4-phenoxydichloroacetophenone, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, pt-butyldichloroacetophenone, pt-butyltrichloroacetophenone, -Acetophenones such as dimethylaminoacetophenone; benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzyldimethyl ketal; benzophenone, benzophenone methyl ether, benzoylbenzoic acid , Methyl benzoylbenzoate, hydroxybenzophenone, 4-phenylbenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 3,3′-bis (N, N-diethylamino) benzophenone, 4,4′-bis (N, N-diethylamino) benzophenone, 4 ′, 4 ″ -diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophen Benzophenones such as 4-benzoyl-4′-methyldiphenyl sulfide and acrylated benzophenone; thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropyl Xanthones such as thioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone; diketones such as diacetyl and benzyl; 2-ethylanthraquinone, 2-t-butylanthraquinone, 2,3-diphenylanthraquinone, 1,2-benz And quinones such as anthraquinone, octamethylanthraquinone, camphorquinone, dibenzosuberone, and 9,10-phenanthrenequinone.
[0025]
Next, the composition ratio will be described. The compounding ratio of the compound (A) and the compound (B) is M: X = 1.0: 0, where M is the number of moles of the epoxy group of the compound (A) and X is the number of moles of the phenolic hydroxyl group of the compound (B). .5 to 1.5, preferably 0.8 to 1.2. When X is less than 0.5, many unreacted epoxy groups remain and solder heat resistance and thermal shock resistance deteriorate. When X exceeds 1.5, an unreacted phenolic hydroxyl group remains and PCT resistance and electroless plating properties are deteriorated. The ratio of compound (C) and (D) is 0.01-20 mass% with respect to the total mass of a compound (A) and a compound (B), respectively, Preferably it is 0.1-10 mass%. When the amount is less than 0.01% by mass, the base is not sufficiently generated and the curing reaction does not occur. If it exceeds 20% by mass, the generated amines become excessive, and the insulation, PCT resistance, and electroless plating resistance deteriorate. The ratio of the compound (E) is 500% by mass or less, preferably 1 to 100% by mass with respect to the total weight of the compound (A) and the compound (B). When it exceeds 500 mass%, the crosslinking accompanying the polymerization of the ethylenically unsaturated bond increases and the thermal shock resistance decreases. The ratio of the compound (F) is 0.1 to 50% by mass or less, preferably 1 to 20% by mass with respect to the mass of the compound (E). When the amount is 0.1% by mass or less, the reaction of the compound (E) does not occur sufficiently, and when it exceeds 50% by mass, the resolution and solder heat resistance are lowered.
[0026]
Furthermore, in the curable resin composition of the present invention, oligomers, polymers, fillers, colorants such as dyes and pigments, heat stabilizers, adhesion promoters, plasticizers, and pigments such as silica and talc are included as necessary. Further, a leveling agent or the like that imparts coating suitability may be added.
[0027]
The cured product of the present invention can be applied to any thickness by a method such as a dip method, a spray method, a roll coating method, a flow coating method, a spin coating method, an applicator method, a bar coating method, or a screen printing method. . At this time, if necessary, a solvent for dissolving the curable composition can be used. For example, there are toluene, acetone, methyl ethyl ketone, diethylene glycol dimethyl ether, dimethylformamide and the like. These solvents are used alone or in combination.
It is also effective to apply a curable composition to a polyester film, dry it and laminate it with a film such as polyethylene film to form a dry film, and then laminate and transfer it to a substrate.
[0028]
Examples of the light source for light irradiation include a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a xenon lamp, a fluorescent lamp, a tungsten lamp, an argon laser, and a helium mecadmium laser.
[0029]
After light irradiation, the reaction can be promoted by heating if necessary. The temperature is usually 5 to 250 ° C, preferably 60 to 180 ° C.
[0030]
Next, the usage method of the curable resin composition of this invention is demonstrated. First, a curable resin composition is applied onto a substrate by the above method, and the solvent is removed by heat drying or hot air drying as necessary to form a coating film on the substrate. Thereafter, light irradiation is performed, and post-heating is performed if necessary.
[0031]
In the case of forming a pattern, the dried film is irradiated with light through a negative mask or a positive mask. Subsequently, an unexposed part is developed using a developing solution. As the developer, an alkaline aqueous solution such as a sodium hydroxide aqueous solution, a sodium carbonate aqueous solution, or an ammonium hydroxide aqueous solution is used. After development, if necessary, post-exposure and post-heating may be performed.
[0032]
【Example】
Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples.
[0033]
Synthesis Example-1
To a dichloromethane solution (10 g / 320 mL) of 9-fluorenylmethyl chloroformate, a dichloromethane solution (12 g / 80 mL) of 1,3-bis (4-piperidyl) propane was slowly added dropwise in an ice bath. After dropping, the mixture was stirred for 20 minutes in an ice bath and further stirred at room temperature for 1.5 hours. After completion of the reaction, the reaction solution was washed with water, 5% hydrochloric acid and saturated brine in that order and dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The obtained solid was purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 2: 1) to obtain 9 g of white crystals. This is designated as base proliferating agent D1.
[0034]
Synthesis Example-2
In the same manner as in Synthesis Example-1, 9-fluorenylmethyl chloroformate and dicyclohexylamine were reacted, and the product was purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 2: 1) to obtain 8 g Of white crystals were obtained. This is designated as base proliferating agent D2.
[0035]
Synthesis example-3
To a dichloromethane solution of 9-fluorenylmethyl alcohol (10.0 g / 320 mL), a dichloromethane solution of isophorone diisocyanate (12.2 g / 80 mL) was slowly added dropwise in an ice bath. After dropping, the mixture was stirred for 20 minutes in an ice bath and further stirred at room temperature for 1.5 hours. After completion of the reaction, the reaction solution was washed with water, 5% hydrochloric acid and saturated brine in that order and dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The obtained solid was purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 2: 1) to obtain 8 g of white crystals. This is designated as base proliferating agent D3.
[0036]
The compounds prepared in Synthesis Examples 1 to 3 were mixed at the blending ratio shown in Table 1, and then kneaded with three rolls to prepare photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 5. .
[0037]
[Table 1]
The photosensitive resin compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 5 shown in Table 1 were applied by screen printing onto a glass epoxy resin substrate on which a wiring pattern had been formed by etching, and a 80 ° C forward air dryer. And dried for 30 minutes to obtain a photosensitive resin layer having a thickness of 20 μm. Next, exposure was performed at 500 mJ / cm 2 using a high-pressure mercury lamp through a photomask. After the exposure, the film was heat treated at 80 ° C. for 30 minutes, and then developed with a developer composed of a 5% aqueous sodium hydroxide solution at a development temperature of 30 ° C. and a spray pressure of 2 kgf / cm 2 for 60 seconds. After the current development, the developer remaining on the printed board was removed by washing with water, dried, and then heat-treated at 180 ° C. for 60 minutes for thermal curing.
[0039]
The performance of the cured product of the photosensitive resin composition on the printed board thus obtained was evaluated by the following method. The results are shown in Table 2.
(1) The minimum width (μm) of the line / space (= 1/1) formed after resolution development was defined as the resolution. When a pattern could not be formed, it was set as x.
(2) Solder heat resistance The appearance after being immersed in a solder bath at 260 ° C. for 30 seconds was visually observed.
○: No change, ×: Cracked and swollen (3) After treatment for 24 hours at 85 ° C. and 85% humidity, the surface resistance value was measured.
○: 1 × 10 10 Ω or more × 1: less than 10 × 10 10 Ω (4) Thermal shock resistance −After performing 500 cycles of heat cycle treatment from 55 ° C. to 125 ° C., the presence or absence of cracks was confirmed.
(Circle): No crack, x: Crack generation (5) PCT resistance 121 degreeC, and 2 atmospheres were processed for 168 hours, Then, the state of the cured film external appearance was evaluated.
○: No peeling, no discoloration, x: No peeling or discoloration (6) Electroless plating resistance The resist after curing is electroless including copper sulfate, ethylenediaminetetraacetate, polyethylene glycol, dipyridyl, formalin, sodium hydroxide, water The resist appearance and the adhesion to copper after immersing in a copper plating solution for 15 hours under conditions of pH 12 and bath temperature 70 ° C. were observed and evaluated according to the following criteria.
Appearance ○: No change ×: Discoloration, blotting, peeling, blistering, abnormal precipitation (7) Elution rate The sample was immersed in acetone for 30 minutes. The weight before immersion as W 1, the weight after immersion W 2, the weight of the glass plate before coating as W 3 (W 1 -W 3) - (W 2 -W 3) × 100 / (W 1 - The elution rate was calculated from W 3 ).
[0040]
The photosensitive resin compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 5 shown in Table 1 were placed in a constant temperature bath at 40 ° C. for 5 days, and the viscosity after 5 days was measured. The viscosity during compounding as V 1, 40 ℃, the viscosity after 5 days and V 2, and the (V 2 -V 1) × 100 / V 1 viscosity increase. The results are shown in Table 2.
[0041]
The photosensitive resin compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 5 shown in Table 1 were applied to a glass plate, a steel plate, and an aluminum plate, and then heated and dried for 30 minutes in a 80 ° C forward air dryer. A photosensitive resin layer having a thickness of 10 μm was obtained. Next, after exposure at 500 mJ / cm 2 using a high-pressure mercury lamp, heat treatment was performed at 100 ° C. for 20 minutes, and then heat treatment was performed by heat treatment at 150 ° C. for 60 minutes. The cured product thus obtained was subjected to a gobang eye adhesion test by peeling the cellophane adhesive tape. The results are shown in Table 2.
○: 100/100, ×: less than 100/100
[Table 2]
【The invention's effect】
The photosensitive resin composition of the present invention has excellent heat resistance, insulation, adhesion, thermal shock resistance, thermal moisture resistance, PCT resistance, and electroless plating resistance, and the developer used can be recycled and no waste liquid is generated. From the above, it is suitable as a solder resist, an interlayer insulating material, and an electroless plating resist used in the production of printed wiring boards.
Claims (6)
化合物（Ａ）及び化合物（Ｂ）以外の架橋成分を含まず、
塩基発生剤（Ｃ）及び塩基増殖剤（Ｄ）が化合物（Ａ）及び化合物（Ｂ）の総重量に対してそれぞれ０．０１〜１０質量％である感光性樹脂組成物。Decomposed by the action of a compound (A) having at least two epoxy groups in one molecule, a compound (B) having at least two phenolic hydroxyl groups in one molecule, a photobase generator (C) and a base. A base proliferating agent (D) that generates a base derived from a urethane bond,
Does not contain crosslinking components other than compound (A) and compound (B),
The photosensitive resin composition whose base generator (C) and base proliferation agent (D) are 0.01-10 mass% with respect to the total weight of a compound (A) and a compound (B), respectively.
化合物（Ａ）、化合物（Ｂ）及びエチレン性不飽和化合物（Ｅ）以外の架橋成分を含まず、It contains no crosslinking component other than compound (A), compound (B) and ethylenically unsaturated compound (E),
塩基発生剤（Ｃ）及び塩基増殖剤（Ｄ）が化合物（Ａ）及び化合物（Ｂ）の総重量に対してそれぞれ０．０１〜１０質量％である感光性樹脂組成物。The photosensitive resin composition whose base generator (C) and base proliferation agent (D) are 0.01-10 mass% with respect to the total weight of a compound (A) and a compound (B), respectively.
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| JP2002151632A JP4191956B2 (en) | 2002-05-24 | 2002-05-24 | Photosensitive resin composition |
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| JP2002151632A JP4191956B2 (en) | 2002-05-24 | 2002-05-24 | Photosensitive resin composition |
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| JP3884758B2 (en) | 2005-03-11 | 2007-02-21 | 積水化学工業株式会社 | Base proliferating agent and base-reactive curable composition |
| JP5224016B2 (en) * | 2006-03-10 | 2013-07-03 | 晃二 有光 | Active energy ray base generator, active energy ray base generator composition, base-reactive composition, and pattern forming method |
| JP4790460B2 (en) * | 2006-03-24 | 2011-10-12 | 富士フイルム株式会社 | Photosensitive composition, photosensitive film, photosensitive laminate, permanent pattern forming method, and printed circuit board |
| JP4930883B2 (en) * | 2006-05-22 | 2012-05-16 | 公立大学法人大阪府立大学 | Photosensitive resin composition and circuit board using the same |
| JP5612373B2 (en) * | 2010-06-16 | 2014-10-22 | 旭化成イーマテリアルズ株式会社 | Photocurable resin composition, method for producing patterned substrate, and electronic component |
| WO2013171888A1 (en) * | 2012-05-17 | 2013-11-21 | 太陽インキ製造株式会社 | Alkali-development-type thermoset resin composition and printed circuit board |
| KR102073440B1 (en) * | 2012-05-17 | 2020-02-04 | 다이요 잉키 세이조 가부시키가이샤 | Alkaline-developable thermosetting resin composition and printed circuit board |
| CN104334604A (en) * | 2012-05-17 | 2015-02-04 | 太阳油墨制造株式会社 | Alkali-developable thermosetting resin composition, and printed wiring board |
| JP6105858B2 (en) * | 2012-05-17 | 2017-03-29 | 太陽インキ製造株式会社 | Pattern forming method, alkali-developable thermosetting resin composition, and printed wiring board |
| JP5920232B2 (en) * | 2013-02-01 | 2016-05-18 | 信越化学工業株式会社 | Photocurable resin composition, photocurable dry film, pattern forming method, and method for producing electrical / electronic component protecting film |
| JP6306296B2 (en) * | 2013-07-09 | 2018-04-04 | 太陽インキ製造株式会社 | Photosensitive thermosetting resin composition and flexible printed wiring board |
| JP7015220B2 (en) * | 2018-07-02 | 2022-02-15 | 日本化薬株式会社 | Adhesive for electronic components |
| KR102836294B1 (en) * | 2020-09-16 | 2025-07-21 | 후지필름 가부시키가이샤 | Resin composition, cured product, laminate, method for producing cured product, and semiconductor device |
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