JPS63124046A - Photosensitive resin composition - Google Patents
Photosensitive resin compositionInfo
- Publication number
- JPS63124046A JPS63124046A JP27127886A JP27127886A JPS63124046A JP S63124046 A JPS63124046 A JP S63124046A JP 27127886 A JP27127886 A JP 27127886A JP 27127886 A JP27127886 A JP 27127886A JP S63124046 A JPS63124046 A JP S63124046A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- photosensitive resin
- photosensitive
- pattern
- binder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims description 25
- 239000011230 binding agent Substances 0.000 claims abstract description 13
- 150000003335 secondary amines Chemical class 0.000 claims abstract description 13
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims abstract description 5
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 5
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims abstract description 4
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims abstract description 4
- -1 glycidylhydantoin acrylate Chemical compound 0.000 claims description 13
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical group C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- DFENKTCEEGOWLB-UHFFFAOYSA-N n,n-bis(methylamino)-2-methylidenepentanamide Chemical compound CCCC(=C)C(=O)N(NC)NC DFENKTCEEGOWLB-UHFFFAOYSA-N 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052802 copper Inorganic materials 0.000 abstract description 13
- 239000010949 copper Substances 0.000 abstract description 13
- 238000007747 plating Methods 0.000 abstract description 11
- 239000003929 acidic solution Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000011347 resin Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 238000007598 dipping method Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 229920002554 vinyl polymer Polymers 0.000 abstract 2
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 125000005641 methacryl group Chemical group 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 8
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 8
- 239000012965 benzophenone Substances 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000007772 electroless plating Methods 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 5
- 238000000059 patterning Methods 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 125000004386 diacrylate group Chemical group 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- MHQZDNQHLGFBRN-UHFFFAOYSA-N 5-ethenyl-1h-imidazole Chemical compound C=CC1=CNC=N1 MHQZDNQHLGFBRN-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-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
- 239000004677 Nylon Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000002585 base Substances 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
- 229960002130 benzoin Drugs 0.000 description 2
- 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 2
- 239000002775 capsule Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 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
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- IMDHDEPPVWETOI-UHFFFAOYSA-N 1-(4-tert-butylphenyl)-2,2,2-trichloroethanone Chemical compound CC(C)(C)C1=CC=C(C(=O)C(Cl)(Cl)Cl)C=C1 IMDHDEPPVWETOI-UHFFFAOYSA-N 0.000 description 1
- VMCRQYHCDSXNLW-UHFFFAOYSA-N 1-(4-tert-butylphenyl)-2,2-dichloroethanone Chemical compound CC(C)(C)C1=CC=C(C(=O)C(Cl)Cl)C=C1 VMCRQYHCDSXNLW-UHFFFAOYSA-N 0.000 description 1
- HUDYANRNMZDQGA-UHFFFAOYSA-N 1-[4-(dimethylamino)phenyl]ethanone Chemical compound CN(C)C1=CC=C(C(C)=O)C=C1 HUDYANRNMZDQGA-UHFFFAOYSA-N 0.000 description 1
- YNSNJGRCQCDRDM-UHFFFAOYSA-N 1-chlorothioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl YNSNJGRCQCDRDM-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- HJKLEAOXCZIMPI-UHFFFAOYSA-N 2,2-diethoxyethanamine Chemical compound CCOC(CN)OCC HJKLEAOXCZIMPI-UHFFFAOYSA-N 0.000 description 1
- KKLBPVXKMBLCQX-UHFFFAOYSA-N 2,5-bis[[4-(diethylamino)phenyl]methylidene]cyclopentan-1-one Chemical compound C1=CC(N(CC)CC)=CC=C1C=C(CC1)C(=O)C1=CC1=CC=C(N(CC)CC)C=C1 KKLBPVXKMBLCQX-UHFFFAOYSA-N 0.000 description 1
- DGPBVJWCIDNDPN-UHFFFAOYSA-N 2-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=CC=C1C=O DGPBVJWCIDNDPN-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
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical compound O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-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
- 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
- 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
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-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
- GSYAJEMURUKZNI-UHFFFAOYSA-N 3-methylbutyl 1,4-dimethylcyclohexa-2,4-diene-1-carboxylate Chemical compound CC1(C(=O)OCCC(C)C)CC=C(C=C1)C GSYAJEMURUKZNI-UHFFFAOYSA-N 0.000 description 1
- OKISUZLXOYGIFP-UHFFFAOYSA-N 4,4'-dichlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=C(Cl)C=C1 OKISUZLXOYGIFP-UHFFFAOYSA-N 0.000 description 1
- YDIYEOMDOWUDTJ-UHFFFAOYSA-N 4-(dimethylamino)benzoic acid Chemical compound CN(C)C1=CC=C(C(O)=O)C=C1 YDIYEOMDOWUDTJ-UHFFFAOYSA-N 0.000 description 1
- BMVWCPGVLSILMU-UHFFFAOYSA-N 5,6-dihydrodibenzo[2,1-b:2',1'-f][7]annulen-11-one Chemical compound C1CC2=CC=CC=C2C(=O)C2=CC=CC=C21 BMVWCPGVLSILMU-UHFFFAOYSA-N 0.000 description 1
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 description 1
- CUARLQDWYSRQDF-UHFFFAOYSA-N 5-Nitroacenaphthene Chemical compound C1CC2=CC=CC3=C2C1=CC=C3[N+](=O)[O-] CUARLQDWYSRQDF-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- WYWZRNAHINYAEF-UHFFFAOYSA-N Padimate O Chemical compound CCCCC(CC)COC(=O)C1=CC=C(N(C)C)C=C1 WYWZRNAHINYAEF-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- SKACCCDFHQZGIA-UHFFFAOYSA-N n-(4-nitronaphthalen-1-yl)acetamide Chemical compound C1=CC=C2C(NC(=O)C)=CC=C([N+]([O-])=O)C2=C1 SKACCCDFHQZGIA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
- BNMMXDHVMLZQGP-UHFFFAOYSA-N phosphono prop-2-eneperoxoate Chemical compound OP(O)(=O)OOC(=O)C=C BNMMXDHVMLZQGP-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- BGUWFUQJCDRPTL-UHFFFAOYSA-N pyridine-4-carbaldehyde Chemical compound O=CC1=CC=NC=C1 BGUWFUQJCDRPTL-UHFFFAOYSA-N 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0073—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces
- H05K3/0076—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces characterised by the composition of the mask
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
- H05K3/182—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method
- H05K3/184—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method using masks
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Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は基板に塗布後ネガマスクを通して光を照射し
、有機溶剤、酸性水溶液または水で現像してパターンを
形成し、必要に応じてこのパターンを有機溶剤または酸
性水溶液で剥離し得る耐アルカリ水溶液性に優れた感光
性樹脂組成物に関するものである。[Detailed Description of the Invention] [Industrial Application Field] This invention involves coating a substrate, irradiating it with light through a negative mask, and developing it with an organic solvent, acidic aqueous solution, or water to form a pattern. The present invention relates to a photosensitive resin composition that has excellent resistance to alkali aqueous solutions and can be peeled off with organic solvents or acidic aqueous solutions.
従来のプリント配線板の製造方法としては１例えば「電
子技術Ｊ１９８２年刊行、第２３巻１４号、１０８〜ｌ
１１頁に記載されているように、銅張り積層板の不要銅
箔部分をエツチングすることにより除去するサブストラ
クティブ法が主体であったが、銅箔のエツチングによる
無駄をなくし、低コストで。Conventional printed wiring board manufacturing methods include 1, for example, ``Electronic Technology J, published in 1982, Vol. 23, No. 14, 108-l.
As described on page 11, the substructive method has mainly been used to remove unnecessary copper foil portions of copper-clad laminates by etching, but this method eliminates the waste caused by etching the copper foil and can be done at a low cost.
高密度のパターニングが可能なアデティブ法が開発され
て来た。Additive methods have been developed that allow high-density patterning.
このアデティブ法には、基板を穴あけした後全面活性化
処理した基板、または触媒入り基板にレジストを印刷ま
たは写真製版し、必要な導体パターンを無電解メッキの
みにより付加するツルアブチイブ法、全面に無電解メッ
キをし、レジストを印刷または写真製版し、電解メッキ
法により必要な導体パターンを形成した後、メツキレシ
ストと導体パターン部分以外の無電解鋼メッキを除去す
るセミアデティブ法、配線パターンを従来のサブストラ
クティブ法で形成した後、スルーホールのみを無電解メ
ッキを用いて形成するパートリーアデティブ法がある。This additive method involves printing or photoengraving a resist on a board that has been fully activated after drilling a hole, or a catalyst-containing board, and then adding the necessary conductor pattern only by electroless plating. After plating, printing a resist or photolithography, and forming the necessary conductor pattern by electrolytic plating, the wiring pattern can be formed using the semi-additive method, which removes the metal resist and the electroless steel plating other than the conductor pattern, and the conventional substructive method. There is a part-additive method in which only the through holes are formed using electroless plating.
これらのアデティブ法に用いるレジストは、厚付無電解
メッキ浴が１２以上のｐＨを持ちしかも８０℃前後の温
度に保たれているので、通常のエツチングレジストでは
加水分解を起こし、無電解メッキ浴に耐えられないため
、耐アルカリ性の優れたレジストが必要となる。The resists used in these additive methods have a thick electroless plating bath that has a pH of 12 or higher and is maintained at a temperature of around 80°C. Therefore, a resist with excellent alkali resistance is required.
またパターニング法としてはスクリーン印刷法と写真製
版法とがあるが、スクリーン印刷法は手軽な反面、最少
パターン幅２００μｍ程度で、また位置ずれも起きやす
い、一方写真製版法は前者に比較し１００μ■以下のパ
ターニングも可能で、パターンの位置精度が非常に良い
が、レジスト自身に感光性を持たせなければならないた
め、材料開発が難しく、耐熱性や密着性の点で前者に劣
る。In addition, there are two patterning methods: screen printing and photoengraving, but while screen printing is easy, the minimum pattern width is about 200 μm, and misalignment is more likely to occur. The following patterning is also possible, and the positional accuracy of the pattern is very good, but since the resist itself must have photosensitivity, material development is difficult, and it is inferior to the former in terms of heat resistance and adhesion.
上記アデティブ用レジストは、従来−度硬化させると簡
単には基板から除去することができないので、永久レジ
ストとして用いられてきた。しかし写真製版用レジスト
は密着性や耐熱性の面で永久レジストとして十分なもの
はなく、特に多層基板の内層に用いることができるもの
はまだ開発されていない。The above-mentioned additive resists have conventionally been used as permanent resists because they cannot be easily removed from the substrate once they have been cured. However, there are no photolithographic resists that are sufficient as permanent resists in terms of adhesion and heat resistance, and in particular, one that can be used as an inner layer of a multilayer substrate has not yet been developed.
一方、もし無電解鋼パターンを形成後にレジストが簡単
に除去できれば、従来のソルダーレジストやプリプレグ
を用いることによりレジストそのものの密着性や耐熱性
は無視できる。しかし無電解鋼パターン形成後、簡単に
除去できるレジストはまだ開発されていない。On the other hand, if the resist can be easily removed after forming the electroless steel pattern, the adhesion and heat resistance of the resist itself can be ignored by using a conventional solder resist or prepreg. However, a resist that can be easily removed after forming an electroless steel pattern has not yet been developed.
この発明は上記のような問題点を解決するためになされ
たもので、パターニングにより無電解鋼メッキパターン
を形成した後でも簡単に除去可能な感光性樹脂組成物を
提供することを目的とする。This invention was made to solve the above-mentioned problems, and an object thereof is to provide a photosensitive resin composition that can be easily removed even after forming an electroless steel plating pattern by patterning.
この発明の感光性樹脂組成物はバインダー成分に三級ア
ミンまたは二級アミンを有するポリマーを用いたもので
ある。The photosensitive resin composition of the present invention uses a polymer having a tertiary amine or a secondary amine as a binder component.
この発明におけるバインダー成分は分子内に三級アミン
または二級アミンを有するポリマーであり、その分子量
はｚ、ｏｏｏ〜ｓｏｏ、ｏｏｏが好ましく、具体的には
ビニルイミダゾール、ビニルピリジン、ビニルピロリド
ン、Ｎ、Ｎ−ジメチルアクリルアミド。The binder component in this invention is a polymer having a tertiary amine or a secondary amine in the molecule, and its molecular weight is preferably z, ooo to soo, ooo, and specifically vinylimidazole, vinylpyridine, vinylpyrrolidone, N, N-dimethylacrylamide.
Ｎ、Ｎ−ジメチルアミノエチルアクリレート、 Ｎ、Ｎ
−ジメチルアミノプロピルアクリルアミドなどのホモポ
リマー、これらの少なくとも二種の共重合体、上記七ツ
マー単位を少なくとも１０％以上含む共重合体、あるい
はアミノアセタール、ピリジンアルデヒド、ジメチルア
ミノベンズアルデヒドのうち少なくとも一種を用いてア
セタール化された重合度５００〜４０００のポリビニル
アルコールまたはポリエチレンイミンなどが好ましい。N,N-dimethylaminoethyl acrylate, N,N
- Using a homopolymer such as dimethylaminopropylacrylamide, a copolymer of at least two of these, a copolymer containing at least 10% or more of the above heptad units, or at least one of aminoacetal, pyridine aldehyde, and dimethylaminobenzaldehyde. Polyvinyl alcohol or polyethyleneimine having a degree of polymerization of 500 to 4,000 is preferable.
感光性成分としては、ビニル基、アリル基、アクリル基
またはメタクリル基を持ち、かつ三級アミンまたは二級
アミンのうち少なくとも一種を有する感光性成分が好ま
しく、具体的にはビニルピロリドン、ビニルピリジン、
ビニルイミダゾール、Ｎ、Ｎ−ジメチルアクリルアミド
、Ｎ、Ｎ−ジメチルアミノエチルアクリレート、Ｎ、Ｎ
−ジメチルアミノプロピルアクリルアミド、テトラグリ
シジルアミノジフェニルメタンテトラアクリレート、ト
リグリシジル−パラアミノフェノールトリアクリレート
、トリグリシジル−メタアミノフェノールトリアクリレ
ート、ジグリシジルアニリンジアクリレート。As the photosensitive component, a photosensitive component having a vinyl group, an allyl group, an acrylic group, or a methacrylic group and at least one of a tertiary amine or a secondary amine is preferable, and specifically, vinyl pyrrolidone, vinyl pyridine,
Vinylimidazole, N,N-dimethylacrylamide, N,N-dimethylaminoethyl acrylate, N,N
-dimethylaminopropylacrylamide, tetraglycidylaminodiphenylmethanetetraacrylate, triglycidyl-para-aminophenol triacrylate, triglycidyl-methaminophenol triacrylate, diglycidylaniline diacrylate.
ジグリシジルトルイジンジアクリレート、テトラグリシ
ジルメタキシリレンジアミン、テトラアクリレート、ジ
グリシジルトリブロムアニリンジアクリレート、テトラ
グリシジルビスアミノメチルシクロヘキサンテトラアク
リレート、ジメチル−１゜３−グリシジルヒダントイン
ジアクリレート、メチルエチル−１，３−グリシジルヒ
ダントインジアクリレート、ペンタメチレン−１，３−
グリシジルヒダントインジアクリレート、アクリレート
変性またはメタクリレート変性ポリグリシジルアミンな
どが好ましい。Diglycidyl toluidine diacrylate, tetraglycidyl metaxylylene diamine, tetraacrylate, diglycidyl tribromoaniline diacrylate, tetraglycidyl bisaminomethyl cyclohexane tetraacrylate, dimethyl-1°3-glycidylhydantoin diacrylate, methyl ethyl-1,3 -Glycidylhydantoin diacrylate, pentamethylene-1,3-
Glycidylhydantoin diacrylate, acrylate-modified or methacrylate-modified polyglycidylamine, etc. are preferred.
この発明の感光性樹脂組成物はこれ等の成分の他、用途
によってはさらに光重合開始剤１着色剤、溶剤、色素、
レベリング剤、消泡剤などを含有してもよく、これらを
混合または混練して用いられる。In addition to these components, the photosensitive resin composition of the present invention may further include a photopolymerization initiator, a coloring agent, a solvent, a pigment,
It may contain a leveling agent, an antifoaming agent, etc., and these are used by mixing or kneading.
この発明の感光性樹脂組成物としては、例えばバインダ
ー成分５〜３０重量％、感光性成分１０〜８０重量％、
光重合開始剤０．１〜１０重量％、残部溶剤のものがあ
る。The photosensitive resin composition of the present invention includes, for example, 5 to 30% by weight of the binder component, 10 to 80% by weight of the photosensitive component,
There is one containing 0.1 to 10% by weight of photopolymerization initiator and the remainder being solvent.
光重合開始剤としては例えば、２．２−ジェトキシアセ
トフェノン、アントラキノン、２−メチルアントラキノ
ン、２−ｔ−ブチルアントラキノン、ベンジルメチルケ
タール、ベンジル−β−メトキシエチルアセタール、１
−フェニル１，２−プロパンジオン−２−（０−エトキ
シカルボニル）オキシム、ベンゾフェノン、０−ベンゾ
イン安息香酸メチル、ミヒラーズケトン、４，４′−ビ
スジエチルアミノベンゾフェノン、４．４′−ジクロロ
ベンゾフェノン、ベンジル、２−フェニル−２−ヒドロ
キシアセトフェノン、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、Ｐ−ジメチルアミノ安息
香酸、ｐ−ジメチルアミノ安息香酸エチル、４−ジメチ
ルアミノ安息香酸−２−エチルヘキシル、ｐ−ジメチル
安息香酸イソアミル、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、ベンゾインアルキル
エーテル、４′−イソプロピル−２−ヒドロキシ−２−
メチル−プロピオフェノン、ｐ−ジメチルアミノアセト
フェノン、 ｐ−ｔ−ブチルトリクロロアセトフェノン
、ｐ−ｔ−ブチルジクロロアセトフェノン、チオキサン
トン、２−メチルチオキサントン、クロロチオキサント
ン、２−イソプロピルチオキサントン、ジベンゾスベロ
ン、２，５−ビス−（４′−ジエチルアミノベンザル）
シクロペンタノン、１−アセチルアミノ−４−ニトロナ
フタレン、５−ニトロアセナフテン、１−二トロピレン
、α、α−ジクロロー４−フェノキシアセトフェノン、
１−ヒドロキシシクロへキシルフェニルケトンなどがあ
り、これらのうち一種または二種以上の混合物を用いる
ことができる。Examples of the photopolymerization initiator include 2.2-jethoxyacetophenone, anthraquinone, 2-methylanthraquinone, 2-t-butylanthraquinone, benzyl methyl ketal, benzyl-β-methoxyethyl acetal, 1
-Phenyl 1,2-propanedione-2-(0-ethoxycarbonyl)oxime, benzophenone, 0-benzoin methyl benzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, benzyl, 2 -Phenyl-2-hydroxyacetophenone, benzoin methyl ether, benzoin isopropyl ether, P-dimethylaminobenzoic acid, ethyl p-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, isoamyl p-dimethylbenzoate, benzoin -n-butyl ether, benzoin isobutyl ether, benzoin alkyl ether, 4'-isopropyl-2-hydroxy-2-
Methyl-propiophenone, p-dimethylaminoacetophenone, p-t-butyltrichloroacetophenone, p-t-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, chlorothioxanthone, 2-isopropylthioxanthone, dibenzosuberone, 2,5 -bis-(4'-diethylaminobenzal)
Cyclopentanone, 1-acetylamino-4-nitronaphthalene, 5-nitroacenaphthene, 1-nitropylene, α,α-dichloro-4-phenoxyacetophenone,
Examples include 1-hydroxycyclohexylphenyl ketone, and one type or a mixture of two or more of these can be used.
上記の感光性樹脂組成物は分子内に三級アミンまたは二
級アミンのうち少なくとも一種を有するポリマーに、分
子内にビニル基、アリル基、アクリル基、メタクリル基
のいずれかを持ち、しかも三級アミンまたは二級アミン
のうち少なくとも一種を有する化合物を加え、有機溶剤
に相溶させて得られる。The above-mentioned photosensitive resin composition has a polymer having at least one of tertiary amine or secondary amine in the molecule, a vinyl group, allyl group, acrylic group, or methacrylic group in the molecule, and a tertiary amine. It is obtained by adding a compound having at least one type of amine or secondary amine and dissolving it in an organic solvent.
この発明の感光性樹脂組成物は１例えばガラスエポキシ
積層板、ガラスポリイミド積層板等のプリント基板製造
に使用される基板上に塗布し、ネガマスクを密着あるい
は塗布剤より少し離して置いて紫外光を照射し、有機溶
剤水溶液または水で現像を行い、次いで充分な露光を行
った後、無電解メッキ浴に浸し、配線パターンを析出さ
せた後。The photosensitive resin composition of the present invention is applied to a substrate used for manufacturing printed circuit boards, such as a glass epoxy laminate or a glass polyimide laminate, and exposed to ultraviolet light by applying a negative mask or placing it a little apart from the coating agent. After irradiation, development with an organic solvent aqueous solution or water, and then sufficient exposure, immersion in an electroless plating bath to deposit a wiring pattern.
有機溶剤または酸性水溶液でパターニングされた感光性
樹脂を除去し、基板上に無電解鋼パターンを形成する。The patterned photosensitive resin is removed using an organic solvent or acidic aqueous solution to form an electroless steel pattern on the substrate.
すなわち上記のようにして得られた感光性樹脂組成物を
、例えばスピンコード、ディップコート、ローラーコー
ト、スクリーン印刷等の方法により、ガラスエポキシ積
層板、ガラスポリイミド積層板など各種基板上に塗布す
るか、あるいはあらかじめドライフィルムを形成し、熱
圧着して基板に貼り付ける。基板とレジスト膜の密着性
を向上させるためには、溶剤や機械的研磨によって基板
表面の粗化を行うことが望ましい。That is, the photosensitive resin composition obtained as described above is coated on various substrates such as glass epoxy laminates and glass polyimide laminates by methods such as spin cording, dip coating, roller coating, and screen printing. Alternatively, a dry film is formed in advance and attached to the substrate by thermocompression bonding. In order to improve the adhesion between the substrate and the resist film, it is desirable to roughen the substrate surface using a solvent or mechanical polishing.
上記の感光性樹脂組成物を塗布した基板は、所定の温度
１時間でプリベークを行い、溶剤の大部分を蒸着させ、
表面をタックフリーの状態にした後、マスクを密着させ
、紫外線で露光する。一方。The substrate coated with the above photosensitive resin composition is prebaked at a predetermined temperature for 1 hour to vapor-deposit most of the solvent.
After the surface is made tack-free, a mask is applied and exposed to ultraviolet light. on the other hand.
ドライフィルムの場合は圧着後３０分程度室温に放置し
、ベースフィルムの上からマスクを密着させ。In the case of dry film, leave it at room temperature for about 30 minutes after pressure bonding, and then fit the mask tightly over the base film.
紫外線で露光した後、ベースフィルムをはがす。After exposure to UV light, peel off the base film.
この後重合を促進させるため二者ともに室温〜８０℃下
で１０〜３０分間放置した後、メタノール、エタノール
、水、アセトン、ジメチルホルムアミド、ジメチルアセ
トアミド、Ｎ−メチルピロリドン等の溶剤またはこれ等
の混合溶剤に必要に応じて塩化アンモニウム、硫酸アン
モニウムなどの塩を添加した溶剤で現像を行う。After this, in order to promote polymerization, both are left for 10 to 30 minutes at room temperature to 80°C, and then a solvent such as methanol, ethanol, water, acetone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, or a mixture thereof is used. Development is performed using a solvent to which a salt such as ammonium chloride or ammonium sulfate is added as necessary.
この後水洗と乾燥を行い、 ２ Ｊ／ｃ＋ｅ”程度の照
射量で後露光を行い、さらに１３０℃程度の温度下に３
０分〜１時間放置することによって完全硬化を行う。形
成されたレジストパターンは、５０μ腸までの解像度を
有しており、ｐＨ１２，５，７０〜８０℃の無電解鋼メ
ッキ洛中で１８時間以上放置しても変化は見られず、十
分な耐無電解メッキ浴性を有している。After this, it was washed with water and dried, and then post-exposed at a dose of about 2 J/c+e'', and then exposed to light at a temperature of about 130°C for 3 hours.
Complete curing is performed by leaving it for 0 minutes to 1 hour. The formed resist pattern has a resolution of up to 50 μm, and no change was observed even if it was left in an electroless steel plating tank at pH 12, 5, and 70 to 80°C for more than 18 hours, and it has sufficient resistance to corrosion. It has electrolytic plating bath properties.
さらに１０％Ｈ２ＳＯ，メタノール溶液、１５％ＩＩ、
Ｓｏ４水溶液などの酸性溶液に基板を浸した後、ブラシ
などで表面を軽くこするとレジストパターンは基板から
容易に除去でき、基板上に銅パターンが得られる。Further 10% H2SO, methanol solution, 15% II,
After immersing the substrate in an acidic solution such as an aqueous So4 solution, the resist pattern can be easily removed from the substrate by lightly rubbing the surface with a brush or the like, and a copper pattern can be obtained on the substrate.
この発明の感光性樹脂組成物は系中に三級アミンまたは
二級アミンを含んでいるためアルカリ性溶液に耐性を示
し、かつ酸性溶液中で膨潤しやすく、しかも光硬化可能
な成分を含んでいるため写真製版によりパターニングが
できる。この結果、ρ旧２以上の強いアルカリ性を示す
無電解メッキ浴に対し優れた耐性を持ち、しかも酸性溶
液で簡単に除去できる微細レジストパターンが得られる
。The photosensitive resin composition of the present invention contains a tertiary amine or a secondary amine in the system, so it is resistant to alkaline solutions, easily swells in acidic solutions, and contains a photocurable component. Therefore, patterning can be done by photolithography. As a result, a fine resist pattern can be obtained which has excellent resistance to electroless plating baths exhibiting strong alkalinity of ρ<2> and which can be easily removed with an acidic solution.
以上の通り、この発明の感光性樹脂組成物は三級アミン
または二級アミンを有するポリマーを含んでいるので、
基板に塗布し光で硬化した後はアルカリ性水溶液に対し
優れた耐性を示し、かつ酸性溶液で容易に基板から除去
できる。As mentioned above, since the photosensitive resin composition of the present invention contains a polymer having a tertiary amine or a secondary amine,
After being applied to a substrate and cured with light, it exhibits excellent resistance to alkaline aqueous solutions and can be easily removed from the substrate with acidic solutions.
以下、この発明の実施例について説明する。 Examples of the present invention will be described below.
実施例１
ポリビニルピリジン５０ｇ（床束化学（株）製分子嚢１
００００）を１００ｇのジメチルホルムアミドに溶解し
。Example 1 50 g of polyvinylpyridine (Molecular capsule 1 manufactured by Tokonshu Kagaku Co., Ltd.)
0000) was dissolved in 100 g of dimethylformamide.
これにメタクリレート化ポリグリシジルアミン（分子量
約１０００） １００ｇ、ジグリシジルトリブロモアニ
リンジメタクリレート５０ｇを加えて加熱溶解する。次
にミヒラーズケトン５ｇ、ベンゾフェノン１０ｇを加え
て溶解させ、感光性樹脂組成物１を得た。To this were added 100 g of methacrylated polyglycidylamine (molecular weight approximately 1000) and 50 g of diglycidyl tribromoaniline dimethacrylate and dissolved by heating. Next, 5 g of Michler's ketone and 10 g of benzophenone were added and dissolved to obtain photosensitive resin composition 1.
実施例２
ポリビニルピロリドン（東京化成（株）製分子嚢１００
００） ５０ｇを１００ｇのジメチルホルムアミドに溶
解し、これにメタクリレート化ポリグリシジルアミン１
００ｇ、ジグリシジルトリブロモアニリンジメタクリレ
ート５０ｇを加えて加熱溶解する０次にミヒラーズケト
ン５ｇ、ベンゾフェノンｔｏｇを加えて溶解させ、感光
性樹脂組成物２を得た。Example 2 Polyvinylpyrrolidone (Molecular capsule 100 manufactured by Tokyo Kasei Co., Ltd.)
00) Dissolve 50g in 100g of dimethylformamide and add methacrylated polyglycidylamine 1
Next, 5 g of Michler's ketone and benzophenone TOG were added and dissolved to obtain a photosensitive resin composition 2.
実施例３
ピリジン−４−アルデヒドを用いて６０％アセタール化
したポリビニルアルコール（重合度２０００） ｓｏｇ
を１００ｇのジメチルホルムアミドに溶解し、これにメ
タクリレート化ポリグリシジルアミン１００ｇ、ジグリ
シジルトリブロモアニリンジメタクリレート７０ｇを加
えて加熱溶解する０次にミヒラーズケトン５ｇ、ベンゾ
フェノン１０ｇを加えて溶解させ、感光性樹脂組成物３
を得た。Example 3 Polyvinyl alcohol acetalized 60% using pyridine-4-aldehyde (degree of polymerization 2000) sog
was dissolved in 100 g of dimethylformamide, 100 g of methacrylated polyglycidylamine and 70 g of diglycidyl tribromoaniline dimethacrylate were added thereto and dissolved by heating. Next, 5 g of Michler's ketone and 10 g of benzophenone were added and dissolved to form a photosensitive resin composition. Thing 3
I got it.
実施例４
常法によりラジカル重合したポリジメチルアクリルアミ
ド（分子量５ Ｘ １０’）３０ｇ、ジメチル１，３グ
リシジルヒダントインジアクリレ一ト７０ｇ、ビニルピ
ロリドンＬｏｇを１００ｇのジメチルホルムアミドに溶
解し、さらにミヒラーズケトン５Ｋ、ベンゾフェノンｔ
ｏｇを加えて溶解し、感光性樹脂組成物４を得た。Example 4 30 g of polydimethylacrylamide (molecular weight 5 x 10') radically polymerized by a conventional method, 70 g of dimethyl 1,3 glycidylhydantoin diacrylate, and vinylpyrrolidone Log were dissolved in 100 g of dimethylformamide, and further, Michler's ketone 5K, benzophenone t
og was added and dissolved to obtain a photosensitive resin composition 4.
実施例５
常法によりラジカル重合したポリ４−ビニルイミダゾー
ル（分子量２ ｘ １０’）２０ｇ、４−ビニルイミダ
ゾール５ｇ、ポリグリシジルアミンアクリレート２０ｇ
、ビニルピロリドン５ｇを１００ｇのジメチルホルムア
ミドに溶解し、さらにミヒラーズケトン５ｇ、ベンゾフ
ェノンＬｏｇを加えて溶解し、感光性樹脂組成物５を得
た。Example 5 20 g of poly-4-vinylimidazole (molecular weight 2 x 10'), 5 g of 4-vinylimidazole, and 20 g of polyglycidylamine acrylate, which were radically polymerized by a conventional method.
, 5 g of vinyl pyrrolidone was dissolved in 100 g of dimethylformamide, and 5 g of Michler's ketone and benzophenone Log were further added and dissolved to obtain photosensitive resin composition 5.
比較例１
ビスフェノールＡエポキシジアクリレート（ＶＲ−６０
、昭和高分子（株）製）５０ｇ、トリメチロールプロパ
ントリアクリレート５ｇ、テトラビスフェノールＡエチ
レンオキサイド付加物アクリレート（ＧＸ６０９４第−
工業製薬Ｃ株）ｉｌ） １０ｇをセロソルブアセテート
５０ｇに溶解し、さらにミヒラーズケトン５ｇ、ベンゾ
フェノン１０ｇを加えて溶解させ比較試料１を得た。Comparative Example 1 Bisphenol A epoxy diacrylate (VR-60
, manufactured by Showa Kobunshi Co., Ltd.) 50 g, trimethylolpropane triacrylate 5 g, tetrabisphenol A ethylene oxide adduct acrylate (GX6094 No.
Comparative sample 1 was obtained by dissolving 10 g of Kogyo Seiyaku C Co., Ltd. il) in 50 g of cellosolve acetate, and further adding and dissolving 5 g of Michler's ketone and 10 g of benzophenone.
比較例２
グリシジルアクリレートを用いて６０％アクリレート化
したポリアクリル酸５０ｇ、ポリエチレングリコールジ
メタクリレート（ＮＫエステル２３Ｇ、新中村化学工業
（株）製） １０ｇ、ＥＯ変性フェノキシ化リン酸アク
リレート（ＡＲ−２６０、大人化学（株）製）１０ｇを
トルエン５０ｇに溶解し、さらにミヒラーズケトン５ｇ
、ベンゾフェノンＬｏｇを加えて溶解させ比較試料２を
得た。Comparative Example 2 50 g of polyacrylic acid 60% acrylated using glycidyl acrylate, 10 g of polyethylene glycol dimethacrylate (NK Ester 23G, manufactured by Shin-Nakamura Chemical Co., Ltd.), EO-modified phenoxylated phosphoric acid acrylate (AR-260, (manufactured by Otona Kagaku Co., Ltd.) was dissolved in 50 g of toluene, and then 5 g of Michler's ketone was added.
, benzophenone Log was added and dissolved to obtain Comparative Sample 2.
試験例
２００ｍ＋ｅ Ｘ ２５０ｍｍ Ｘ １ 、６ｍｍのガ
ラスエポキシ積層板にメッキ核を付着させた基板に４０
μｍのバーコーターを用いてレジスト試料を塗布し、７
５℃で３０〜６０分間乾燥させる０次に塗布面にマスク
を密着させ、高圧水銀灯（５００１）を用いて所ｔの光
量を照射した後、 ６０℃下に３０分間基板を放置する
０次に４定の現像液で現像し、水洗した後高圧水銀灯（
１，５ｋ１１）を用いて２ Ｊ／ｃｏ”の光量を照射し
、１３０℃で３０分間アフターベイクする。基板を放冷
後下記の無電解銅メッキ液に浸漬し、空気攪拌を行いな
がら７２℃で１８時間メッキを行い、厚さ約３２μ■の
導体回路を形成した。Test example 200m+e x 250mm
Coat the resist sample using a μm bar coater, and
Dry at 5℃ for 30 to 60 minutes Next, place a mask tightly on the coated surface and irradiate the substrate with a certain amount of light using a high-pressure mercury lamp (5001), then leave the substrate at 60℃ for 30 minutes. After developing with 4 constant developer and washing with water, use a high pressure mercury lamp (
1.5k11) with a light intensity of 2 J/co" and after-baking at 130°C for 30 minutes. After cooling the board, it was immersed in the following electroless copper plating solution and heated to 72°C with air agitation. Plating was carried out for 18 hours to form a conductor circuit with a thickness of approximately 32 μm.
ＣｕＳＯ４・５Ｈ２Ｑ ｌ
Ｏｇエチレンジアミン四酢酸 ３０ｇホ
ルマリン（３７％） ３ｇポ
リエチレングリコール（分子量６００） ２０ｇ
２．２′−ジピリジル ０．０３
ｇＮａ０１ｌ
ｌ１ｇ水 全量１０００Ｉ
ｌＩＱになる量次に基板を水洗、乾燥し、所定の酸性剥
離液に浸漬した後表面をナイロンブラシでこすり、膨潤
したレジストを除去して水洗し、炭酸アンモニウム５％
水溶液で洗った後、再び水洗、乾燥し、銅パターンを肉
眼あるいは光学顕微鏡を用いて観察した。CuSO4・5H2Q l
Og ethylenediaminetetraacetic acid 30g formalin (37%) 3g polyethylene glycol (molecular weight 600) 20g
2.2'-dipyridyl 0.03
gNa01l
l1g water total amount 1000I
After washing the substrate with water and drying it, immersing it in a specified acidic stripping solution, rub the surface with a nylon brush to remove the swollen resist, wash it with water, and remove 5% ammonium carbonate.
After washing with an aqueous solution, the copper pattern was washed again with water and dried, and the copper pattern was observed with the naked eye or using an optical microscope.
上記の評価方法による評価結果を表１に示す。Table 1 shows the evaluation results according to the above evaluation method.
表１から明らかなように、感光性樹脂組成物工ないし５
、比較試料１および２は全て５０μ墓のラインアンドス
ペースをバターニングすることができたが、比較試料２
は耐アルカリ性が乏しく、無電解メッキ洛中で加水分解
を起こし、ファインな銅配線パターンが得られなかった
。また比較試料１は銅配線パターンの形成は可能である
が、パターニングしたレジストを基板より除去すること
ができなかった。As is clear from Table 1, photosensitive resin compositions
, Comparative Samples 1 and 2 were all able to pattern the lines and spaces of the 50μ grave, but Comparative Sample 2
has poor alkali resistance and undergoes hydrolysis during electroless plating, making it impossible to obtain fine copper wiring patterns. Furthermore, although it was possible to form a copper wiring pattern in Comparative Sample 1, the patterned resist could not be removed from the substrate.
一方、感光性樹脂組成物工ないし５はいずれも耐無電解
メッキ浴性に優れており、ファインな銅配線パターンが
得られた。また１０％）１２ｓＯ４メタノール溶液に１
〜２分間浸漬することにより、レジストパターンが著し
く膨潤し、ナイロンブラシでこすったところ容易に除去
できた。On the other hand, photosensitive resin compositions Nos. 1 to 5 all had excellent electroless plating bath resistance, and fine copper wiring patterns were obtained. 10%) 12sO4 methanol solution
By dipping for ~2 minutes, the resist pattern swelled significantly and could be easily removed by rubbing with a nylon brush.
以上説明したとおり、この発明によれば、分子内に少な
くとも一種類の三級アミンまたは二級アミンを有するポ
リマーからなるバインダー成分を含有するため、光硬化
後、無電解鋼メッキ浴に対し優れた耐性を有し、しかも
容易に除去可能で、フォトレジストとしての機能を持ち
、基板上に銅ファイン配線パターンが得られる効果があ
る。As explained above, according to the present invention, since it contains a binder component made of a polymer having at least one type of tertiary amine or secondary amine in its molecule, it has excellent properties against electroless steel plating baths after photocuring. It has durability, is easily removable, functions as a photoresist, and has the effect of providing a fine copper wiring pattern on a substrate.
Claims (5)
アミンまたは二級アミンを有するポリマーからなるバイ
ンダー成分とを含有することを特徴とする感光性樹脂組
成物。(1) A photosensitive resin composition containing a photosensitive component and a binder component made of a polymer having at least one type of tertiary amine or secondary amine in the molecule.
リル基またはメタクリル基を持ち、かつ少なくとも一種
の三級アミンまたは二級アミンを持つ化合物を含むこと
を特徴とする特許請求の範囲第１項記載の感光性樹脂組
成物。(2) The photosensitive component includes a compound having a vinyl group, allyl group, acrylic group, or methacrylic group in the molecule and at least one type of tertiary amine or secondary amine. The photosensitive resin composition according to item 1.
、ビニルイミダゾール、ポリグリシジルアミンアクリレ
ートまたはグリシジルヒダントインアクリレートである
ことを特徴とする特許請求の範囲第１項記載の感光性樹
脂組成物。(3) The photosensitive resin composition according to claim 1, wherein the photosensitive component is vinylpyrrolidone, vinylpyridine, vinylimidazole, polyglycidylamine acrylate, or glycidylhydantoin acrylate.
ゾール、ビニルピロリドン、Ｎ，Ｎ−ジメチルアクリル
アミド、Ｎ，Ｎ−ジメチルアミノエチルアクリレートも
しくはＮ，Ｎ−ジメチルアミノプロピルアクリルアミド
のホモポリマーまたは二種以上の共重合体であることを
特徴とする特許請求の範囲第１項ないし第３項のいずれ
かに記載の感光性樹脂組成物。(4) Homopolymer or copolymer of two or more binder components of vinylpyridine, vinylimidazole, vinylpyrrolidone, N,N-dimethylacrylamide, N,N-dimethylaminoethyl acrylate, or N,N-dimethylaminopropylacrylamide The photosensitive resin composition according to any one of claims 1 to 3, characterized in that:
含むアルデヒドによりアセタール化された重合度５００
〜４０００のポリビニルアルコールであることを特徴と
する特許請求の範囲第１項ないし第３項のいずれかに記
載の感光性樹脂組成物。(5) Polymerization degree of 500 when the binder component is acetalized with an aldehyde containing a tertiary amine or a secondary amine
The photosensitive resin composition according to any one of claims 1 to 3, wherein the photosensitive resin composition is polyvinyl alcohol having a molecular weight of 4,000 to 4,000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27127886A JPS63124046A (en) | 1986-11-14 | 1986-11-14 | Photosensitive resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27127886A JPS63124046A (en) | 1986-11-14 | 1986-11-14 | Photosensitive resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63124046A true JPS63124046A (en) | 1988-05-27 |
Family
ID=17497845
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27127886A Pending JPS63124046A (en) | 1986-11-14 | 1986-11-14 | Photosensitive resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63124046A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006285035A (en) * | 2005-04-01 | 2006-10-19 | Jsr Corp | Negative radiation sensitive resin composition |
| JP2008035602A (en) * | 2006-07-27 | 2008-02-14 | Denso Corp | Method and device for manufacturing rotor of rotary electric machine |
-
1986
- 1986-11-14 JP JP27127886A patent/JPS63124046A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006285035A (en) * | 2005-04-01 | 2006-10-19 | Jsr Corp | Negative radiation sensitive resin composition |
| JP2008035602A (en) * | 2006-07-27 | 2008-02-14 | Denso Corp | Method and device for manufacturing rotor of rotary electric machine |
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