CN105793778A - Photosensitive resin composition and photosensitive resin laminate - Google Patents
Photosensitive resin composition and photosensitive resin laminate Download PDFInfo
- Publication number
- CN105793778A CN105793778A CN201480064426.1A CN201480064426A CN105793778A CN 105793778 A CN105793778 A CN 105793778A CN 201480064426 A CN201480064426 A CN 201480064426A CN 105793778 A CN105793778 A CN 105793778A
- Authority
- CN
- China
- Prior art keywords
- mass
- divalent linker
- photosensitive polymer
- polymer combination
- phenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 46
- 239000011347 resin Substances 0.000 title claims abstract description 46
- 239000011342 resin composition Substances 0.000 title abstract 3
- 229920000642 polymer Polymers 0.000 claims abstract description 110
- 150000001875 compounds Chemical class 0.000 claims abstract description 89
- 239000000758 substrate Substances 0.000 claims abstract description 71
- 125000005647 linker group Chemical group 0.000 claims description 83
- 238000000034 method Methods 0.000 claims description 80
- 125000000217 alkyl group Chemical group 0.000 claims description 76
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 claims description 51
- 239000003795 chemical substances by application Substances 0.000 claims description 51
- 229920002120 photoresistant polymer Polymers 0.000 claims description 47
- 239000000203 mixture Substances 0.000 claims description 44
- 125000003118 aryl group Chemical group 0.000 claims description 43
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 36
- 229920002521 macromolecule Polymers 0.000 claims description 27
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 26
- 241001597008 Nomeidae Species 0.000 claims description 24
- 239000000178 monomer Substances 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 17
- 238000003475 lamination Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 125000000962 organic group Chemical group 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000000864 peroxy group Chemical group O(O*)* 0.000 claims description 2
- 239000003999 initiator Substances 0.000 abstract description 2
- -1 (methyl) benzyl Chemical group 0.000 description 88
- 239000002585 base Substances 0.000 description 58
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 54
- 239000010408 film Substances 0.000 description 45
- 239000001294 propane Substances 0.000 description 27
- 230000004304 visual acuity Effects 0.000 description 25
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 24
- 230000035945 sensitivity Effects 0.000 description 22
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 21
- 239000010410 layer Substances 0.000 description 20
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 19
- 229960003742 phenol Drugs 0.000 description 19
- 239000010409 thin film Substances 0.000 description 19
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 16
- 238000007747 plating Methods 0.000 description 15
- 239000011241 protective layer Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 15
- NPKSPKHJBVJUKB-UHFFFAOYSA-N N-phenylglycine Chemical compound OC(=O)CNC1=CC=CC=C1 NPKSPKHJBVJUKB-UHFFFAOYSA-N 0.000 description 14
- 238000013329 compounding Methods 0.000 description 14
- 239000000975 dye Substances 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 13
- 229920001451 polypropylene glycol Polymers 0.000 description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- 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 12
- 238000004519 manufacturing process Methods 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000004698 Polyethylene Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- 238000005530 etching Methods 0.000 description 10
- 229920000573 polyethylene Polymers 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 239000003513 alkali Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000002202 Polyethylene glycol Substances 0.000 description 7
- 230000006978 adaptation Effects 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229920001223 polyethylene glycol Polymers 0.000 description 7
- 150000003219 pyrazolines Chemical class 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000004973 liquid crystal related substance Substances 0.000 description 6
- 244000028419 Styrax benzoin Species 0.000 description 5
- 235000000126 Styrax benzoin Nutrition 0.000 description 5
- 235000008411 Sumatra benzointree Nutrition 0.000 description 5
- 229960002130 benzoin Drugs 0.000 description 5
- 239000012964 benzotriazole Substances 0.000 description 5
- 239000004305 biphenyl Substances 0.000 description 5
- 229940106691 bisphenol a Drugs 0.000 description 5
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 5
- 235000019382 gum benzoic Nutrition 0.000 description 5
- 150000002366 halogen compounds Chemical class 0.000 description 5
- 150000002460 imidazoles Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 238000009877 rendering Methods 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 238000000889 atomisation Methods 0.000 description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 238000000280 densification Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 229940059574 pentaerithrityl Drugs 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000013517 stratification Methods 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 3
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 3
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical class OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 description 3
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 150000008062 acetophenones Chemical class 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 3
- 125000005702 oxyalkylene group Chemical group 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 150000004053 quinones Chemical class 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- 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
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 2
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 2
- YYPNJNDODFVZLE-UHFFFAOYSA-N 3-methylbut-2-enoic acid Chemical compound CC(C)=CC(O)=O YYPNJNDODFVZLE-UHFFFAOYSA-N 0.000 description 2
- MTRFEWTWIPAXLG-UHFFFAOYSA-N 9-phenylacridine Chemical compound C1=CC=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 MTRFEWTWIPAXLG-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- OAZWDJGLIYNYMU-UHFFFAOYSA-N Leucocrystal Violet Chemical compound C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 OAZWDJGLIYNYMU-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- JUKUURGIXBLUTP-UHFFFAOYSA-N NC=C1C(=C2C(=NN=N2)C=C1)C(=O)O Chemical compound NC=C1C(=C2C(=NN=N2)C=C1)C(=O)O JUKUURGIXBLUTP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000205 computational method Methods 0.000 description 2
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- 239000013078 crystal Substances 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
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- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
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- NHOWDZOIZKMVAI-UHFFFAOYSA-N (2-chlorophenyl)(4-chlorophenyl)pyrimidin-5-ylmethanol Chemical compound C=1N=CN=CC=1C(C=1C(=CC=CC=1)Cl)(O)C1=CC=C(Cl)C=C1 NHOWDZOIZKMVAI-UHFFFAOYSA-N 0.000 description 1
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- QUDQABVGMBRGEA-UHFFFAOYSA-N 1,2,3,4,5,6,7,8-octaethylanthracene-9,10-dione Chemical compound CCC1=C(CC)C(CC)=C2C(=O)C3=C(CC)C(CC)=C(CC)C(CC)=C3C(=O)C2=C1CC QUDQABVGMBRGEA-UHFFFAOYSA-N 0.000 description 1
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- LMGYOBQJBQAZKC-UHFFFAOYSA-N 1-(2-ethylphenyl)-2-hydroxy-2-phenylethanone Chemical compound CCC1=CC=CC=C1C(=O)C(O)C1=CC=CC=C1 LMGYOBQJBQAZKC-UHFFFAOYSA-N 0.000 description 1
- YXZFFTJAHVMMLF-UHFFFAOYSA-N 1-bromo-3-methylbutane Chemical compound CC(C)CCBr YXZFFTJAHVMMLF-UHFFFAOYSA-N 0.000 description 1
- YZWKKMVJZFACSU-UHFFFAOYSA-N 1-bromopentane Chemical compound CCCCCBr YZWKKMVJZFACSU-UHFFFAOYSA-N 0.000 description 1
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- BTUGGGLMQBJCBN-UHFFFAOYSA-N 1-iodo-2-methylpropane Chemical compound CC(C)CI BTUGGGLMQBJCBN-UHFFFAOYSA-N 0.000 description 1
- BLXSFCHWMBESKV-UHFFFAOYSA-N 1-iodopentane Chemical compound CCCCCI BLXSFCHWMBESKV-UHFFFAOYSA-N 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- 125000004343 1-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C([H])([H])[H] 0.000 description 1
- UPQQXPKAYZYUKO-UHFFFAOYSA-N 2,2,2-trichloroacetamide Chemical compound OC(=N)C(Cl)(Cl)Cl UPQQXPKAYZYUKO-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
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- SHXOKQKTZJXHHR-UHFFFAOYSA-N n,n-diethyl-5-iminobenzo[a]phenoxazin-9-amine;hydrochloride Chemical compound [Cl-].C1=CC=C2C3=NC4=CC=C(N(CC)CC)C=C4OC3=CC(=[NH2+])C2=C1 SHXOKQKTZJXHHR-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000005026 oriented polypropylene Substances 0.000 description 1
- UHHKSVZZTYJVEG-UHFFFAOYSA-N oxepane Chemical compound C1CCCOCC1 UHHKSVZZTYJVEG-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- AYEFIAVHMUFQPZ-UHFFFAOYSA-N propane-1,2-diol;prop-2-enoic acid Chemical compound CC(O)CO.OC(=O)C=C AYEFIAVHMUFQPZ-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000001069 triethyl citrate Substances 0.000 description 1
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 1
- 235000013769 triethyl citrate Nutrition 0.000 description 1
- JEVGKYBUANQAKG-UHFFFAOYSA-N victoria blue R Chemical compound [Cl-].C12=CC=CC=C2C(=[NH+]CC)C=CC1=C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 JEVGKYBUANQAKG-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
- C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/02—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of acids, salts or anhydrides
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
-
- 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
-
- 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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
-
- 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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
-
- 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
- G03F7/075—Silicon-containing compounds
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
-
- 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
- G03F7/20—Exposure; Apparatus therefor
-
- 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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
-
- 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/05—Patterning and lithography; Masks; Details of resist
- H05K2203/0502—Patterning and lithography
- H05K2203/0514—Photodevelopable thick film, e.g. conductive or insulating paste
-
- 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
- H05K3/0011—Working of insulating substrates or insulating layers
- H05K3/0017—Etching of the substrate by chemical or physical means
- H05K3/0023—Etching of the substrate by chemical or physical means by exposure and development of a photosensitive insulating layer
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Engineering & Computer Science (AREA)
- Materials For Photolithography (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Abstract
A photosensitive resin composition including an alkali-soluble polymer (A), a compound (B) having an ethylenic unsaturated double bond, and a photopolymerization initiator (C). In a resist pattern obtained by forming a photosensitive resin layer comprising the photosensitive resin composition, upon a substrate surface and exposing and developing same, the difference is less than 15 [mu]m between: a pattern resolution (a) when the focal point is positioned on the substrate surface and the pattern is exposed; and a pattern resolution (b) obtained when the focal point position is displaced from the substrate surface by 300 [mu]m in the thickness direction of the substrate.
Description
Technical field
The present invention relates to photosensitive polymer combination etc..
Background technology
The electronic machine such as personal computer, portable phone, uses printed wiring board etc. for installation elements, quasiconductor etc..As manufacture opposing agent (resist) of printed wiring board etc., be used in supporting on thin film stacking photo-sensitive resin in the past so that on this photo-sensitive resin as required the photoresist duplexer of stacked guard thin film, the so-called photic opposing agent (below otherwise referred to as DF) of dry type film.As photo-sensitive resin, it is typically now use weak base aqueous solution as the photo-sensitive resin of the alkali developable of developer solution.In order to use DF to make printed wiring board etc., for instance via following operation.When DF has protective film, first peel off protective film.Then, use laminater etc. at the permanent circuit making such as copper-clad laminated board or flexible base board substrate overlaminate DF, be exposed by wiring pattern mask film etc..Peel off then according to needs and support thin film, by developer solution, the photo-sensitive resin of uncured portion (such as unexposed portion for minus) is dissolved or dispersion removal, substrate is formed and solidifies opposing agent pattern (being sometimes also only called opposing agent pattern below).
Opposing agent pattern forms rear, to form circuit technique and is roughly divided into two kinds of methods.First method, for by not by opposing agent pattern covers real estate (copper face of such as copper-clad laminated board) etching remove after, with the aqueous alkali stronger than developer solution will opposing agent pattern part remove method (etching method).Second method, after aforesaid substrate face being carried out to the plating of copper, scolding tin, nickel, stannum etc., opposing agent pattern part and then the method (plating method) that the real estate that will appear from (copper face of such as copper-clad laminated board) etches is removed in the same manner as first method.Etching uses copper chloride, iron chloride, cupric ammine complex solution etc..In recent years, along with miniaturization and the lightweight of electronic machine, the miniaturization of printed wiring board and densification progress, in above-mentioned manufacturing process, seek the high-performance DF that high resolution etc. is provided.As the technology realizing this high resolution, patent documentation 1 is described the photosensitive polymer combination being improved resolving power by specific thermoplastic resin, monomer and optical polymerism initiator.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2010-249884 publication
Summary of the invention
The problem that invention to solve
But, when the exposure method of the in recent years commonly used direct description etc. utilizing depicting pattern, resolving power is caused big impact by the position of focus.If such as owing to the position setting focus when bad problem etc. exposes of the warpage of substrate and deformation, exposure device offsets from substrate surface, resolving power is significantly deteriorated.Its result, produces short circuit problem when forming circuit by etching method, likely produces the problems such as shortcoming, open circuit, plating be bad when forming circuit by plating method.The technology of the record in above-mentioned patent documentation 1 considers the leeway that there is improvement further from this viewpoint.
Therefore, it is an object of the invention to, even if providing and also showing the photoresist duplexer of high resolution and for forming its photosensitive polymer combination during the focal shift when exposure, and provide the forming method of the opposing agent pattern employing this photoresist duplexer and the forming method of conductive pattern.
For solving the scheme of problem
The present inventor etc. carry out to solve the problems referred to above furtheing investigate, repeating experiment.It is found that by following technological means, can solve the problems referred to above.
That is, the present invention is as described below.
[1] a kind of photosensitive polymer combination, it contains (A) alkali-soluble macromolecule, (B) has compound and (C) Photoepolymerizationinitiater initiater of ethylenical unsaturated double bonds,
The photo-sensitive resin comprising this photosensitive polymer combination is being formed on substrate surface and is being exposed and in the opposing agent pattern that develops and obtain, this substrate surface is being directed at pattern resolution a when focal position carries out this exposure and to the difference of pattern resolution b when carrying out this exposure on the thickness direction of this substrate to the position alignment focal position of substrate offset inboard 300 μm from this substrate surface less than 15 μm.
[2] according to the photosensitive polymer combination described in [1], it contains by all solids composition quality benchmark of photosensitive polymer combination
Aforementioned (A) alkali-soluble macromolecule: 10 mass %～90 mass %；
Aforementioned (B) has the compound of ethylenical unsaturated double bonds: 5 mass %～70 mass %；With
Aforementioned (C) Photoepolymerizationinitiater initiater: 0.01 mass %～20 mass %.
[3] according to photosensitive polymer combination described in [2], its by all solids composition quality benchmark of photosensitive polymer combination possibly together with (D) phenol system derivant: 0.001 mass %～10 mass %.
[4] according to the photosensitive polymer combination described in [3], wherein, as (D) phenol system derivant, containing the compound shown in following formula (I),
In formula (I), R1Represent optionally substituted, straight chained alkyl, branched alkyl, aryl, cyclohexyl, the straight chained alkyl via divalent linker, the branched alkyl via divalent linker, the cyclohexyl via divalent linker or the aryl via divalent linker, multiple R1Optionally being mutually identical or different, m represents the integer of 0～4, and n represents the integer of more than 1, and when n is 1, A is monovalent organic group, and when n is more than 2, A represents the organic group of more than bivalence, singly-bound or the linking group comprising conjugated bonds.}.
[5] according to the photosensitive polymer combination described in [3] or [4], wherein, as (D) phenol system derivant, containing the compound shown in following formula (II),
In formula (II), R2Represent optionally substituted, straight chained alkyl, branched alkyl, aryl, cyclohexyl, the straight chained alkyl via divalent linker, the branched alkyl via divalent linker, the cyclohexyl via divalent linker or the aryl via divalent linker and R3、R4And R5Represent hydrogen or optionally substituted, straight chained alkyl, branched alkyl, aryl, cyclohexyl, the straight chained alkyl via divalent linker, the branched alkyl via divalent linker, the cyclohexyl via divalent linker or the aryl via divalent linker independently of one another.}.
[6] according to the photosensitive polymer combination described in [3] or [4], wherein, as (D) phenol system derivant, containing the compound shown in following formula (III),
In formula (III), R6And R7Represent optionally substituted, straight chained alkyl, branched alkyl, aryl, cyclohexyl, the straight chained alkyl via divalent linker, the branched alkyl via divalent linker, the cyclohexyl via divalent linker or the aryl via divalent linker, multiple R independently of one another6And R7Optionally being mutually identical or different, p and q represents the integer of 0～4 independently of one another, and B represents singly-bound or the linking group comprising conjugated bonds.}.
[7] a kind of photosensitive polymer combination, it contains by all solids composition quality benchmark of photosensitive polymer combination
(A) alkali-soluble macromolecule: 10 mass %～90 mass %；
(B) there is the compound of ethylenical unsaturated double bonds: 5 mass %～70 mass %；
(C) Photoepolymerizationinitiater initiater: 0.01 mass %～20 mass %；With
(D) phenol system derivant: 0.001 mass %～10 mass %,
As (D) phenol system derivant, containing at least one in the group that the choosing freely compound shown in following formula (II) and the compound shown in following formula (III) form,
In formula (II), R2Represent optionally substituted, straight chained alkyl, branched alkyl, aryl, cyclohexyl, the straight chained alkyl via divalent linker, the branched alkyl via divalent linker, the cyclohexyl via divalent linker or the aryl via divalent linker and R3、R4And R5Represent hydrogen or optionally substituted, straight chained alkyl, branched alkyl, aryl, cyclohexyl, the straight chained alkyl via divalent linker, the branched alkyl via divalent linker, the cyclohexyl via divalent linker or the aryl via divalent linker independently of one another.}
In formula (III), R6And R7Represent optionally substituted, straight chained alkyl, branched alkyl, aryl, cyclohexyl, the straight chained alkyl via divalent linker, the branched alkyl via divalent linker, the cyclohexyl via divalent linker or the aryl via divalent linker, multiple R independently of one another6And R7Optionally being mutually identical or different, p and q represents the integer of 0～4 independently of one another, and B represents singly-bound or the linking group comprising conjugated bonds.}.
[8] according to the photosensitive polymer combination described in [6] or [7], wherein, in previously described formula (III), B is singly-bound.
[9] according to the photosensitive polymer combination according to any one of [6]～[8], wherein, in previously described formula (III), p=q=0.
[10] according to the photosensitive polymer combination according to any one of [3]～[9], wherein, as (D) phenol system derivant, it is 20L mole containing the reaction rate constant with peroxy radical-1·sec-1Above compound.
[11] according to the photosensitive polymer combination according to any one of [1]～[10], wherein, the high molecular monomer component of (A) alkali-soluble has aromatic hydrocarbyl.
[12] according to the photosensitive polymer combination according to any one of [1]～[11], wherein, as (C) Photoepolymerizationinitiater initiater, containing acridine.
[13] a kind of photoresist duplexer, it is at the supporting layer upper strata stacked package photo-sensitive resin containing the photosensitive polymer combination according to any one of [1]～[12].
[14] a kind of forming method resisting agent pattern, it includes the photoresist duplexer described in [13] is laminated in the lamination process of substrate, the exposure process making the photo-sensitive resin of this photoresist duplexer expose and the developing procedure removed that developed in the unexposed portion of this photo-sensitive resin.
[15] forming method of the opposing agent pattern according to [14], wherein, for aforementioned exposure process, by utilizing the exposure method directly described of depicting pattern or making the exposure method that the image of photomask carries out projecting carry out by lens.
[16] forming method of the opposing agent pattern according to [15], wherein, for aforementioned exposure process, by utilizing the exposure method directly described of depicting pattern to carry out.
[17] according to the photosensitive polymer combination according to any one of [1]～[12], the forming method of its opposing agent pattern undertaken by utilizing the exposure method that depicting pattern is directly described for exposure process.
The effect of invention
Pass through the present invention, even if can providing and also showing the photoresist duplexer of high resolution and for forming its photosensitive polymer combination during the focal shift when exposure, and the forming method of the opposing agent pattern employing this photoresist duplexer and the forming method of conductive pattern can be provided.Its result, even if the position of focus when exposing due to the warpage of substrate and deformation, the bad problem etc. of setting of exposure device from substrate surface offset time, when forming circuit by etching method, short circuit problem can also be reduced, when forming circuit by plating method, it is also possible to reduce the problems such as shortcoming, open circuit, plating be bad.
Detailed description of the invention
Hereinafter the mode (hereinafter referred to as " embodiment ") of the illustration for implementing the present invention is described in detail.It should be noted that the present invention is not limited to following embodiment, it is possible to carry out various deformation in the scope of its purport and implement.
[photosensitive polymer combination]
In embodiment, photosensitive polymer combination has the feature that and is being formed on substrate surface by the photo-sensitive resin comprising this photosensitive polymer combination and is being exposed and in the opposing agent pattern that develops and obtain, this substrate surface is directed at pattern resolution a when focal position carries out this exposure and to the difference of pattern resolution b when carrying out this exposure on the thickness direction of this substrate to the position alignment focal position of substrate offset inboard 300 μm from this substrate surface less than 15 μm.Thus, even if the position of focus when exposing due to the warpage of substrate and deformation, the bad problem etc. of setting of exposure device from substrate surface offset time, it also is able to when forming circuit by etching method reduce short circuit problem, also is able to reduce the problems such as shortcoming, open circuit, plating be bad when forming circuit by plating method.The difference of pattern resolution a and pattern resolution b is preferably less than 12 μm, more preferably less than 10 μm.On the other hand, considering from viewpoints such as ease of manufacturing, sensitivity decrease are few, the difference of pattern resolution a and pattern resolution b is preferably more than 0 μm, more preferably more than 5 μm, more preferably more than 7 μm.It should be noted that for the various measured values in this specification, then measure into the method equal with it according to the method recorded in the item of [embodiment] of the disclosure or skilled artisans appreciate that unless otherwise specified.
Along with the miniaturization of electronic machine in recent years, slimming, the densification of wiring, flexible printing wiring board be suitable for so that the demand of multiple stratification improves.And along with multiple stratification is in progress, the fluctuating on surface increases, the adjoint variation of resolving power of focal shift when likely producing exposure, the variation of live width repeatability, the bad problem of its result poor short circuit, shortcoming, open circuit, plating, the problem that can not form desired copper cash become important day by day.The membrane thickness unevenness etc. in bad, the face of absorption for large substrate, during owing to being exposed, it is also possible to produce same problem.Consequently found that, it is conceived to pattern resolution a substrate surface being directed at when focal position is exposed and on the thickness direction of this substrate, is directed at the difference of focal position carry out this exposure time pattern resolution b to design photosensitive polymer combination to the position of substrate offset inboard 300 μm (reference value to set for very big side-play amount relative to the side-play amount of the focal positions such as the relief volume of aforementioned surfaces) with to from this substrate surface, be effective for solving the problems referred to above.Namely find, use by selecting the difference of pattern resolution a and pattern resolution b to be contained in a range of specific photosensitive polymer combination, even under the shapes such as wiring densification in recent years, multiple stratification, also it is effective for reducing the bad problem of poor short circuit, shortcoming, open circuit, plating, the problems such as desired copper cash can not be formed.
It should be noted that, it is in the means in above-mentioned particular range as the difference making pattern resolution a and pattern resolution b, it is not particularly limited, can list and such as the composition of photosensitive polymer combination is carried out various adjustment make each composition detailed content as described later.
In embodiment, photosensitive polymer combination contains (A) alkali-soluble macromolecule, (B) has the compound of ethylenical unsaturated double bonds and (C) Photoepolymerizationinitiater initiater.Photosensitive polymer combination, it is preferable that by all solids composition quality benchmark of this photosensitive polymer combination containing (A) alkali-soluble macromolecule: 10 mass %～90 mass %；(B) there is the compound of ethylenical unsaturated double bonds: 5 mass %～70 mass %；(C) Photoepolymerizationinitiater initiater: 0.01 mass %～20 mass %.Each composition is illustrated by next coming in order.
<(A) alkali-soluble macromolecule>
In the disclosure, (A) alkali-soluble macromolecule comprises the macromolecule being easily dissolved in alkaloid substance.More specifically, the amount of the carboxyl contained in (A) alkali-soluble macromolecule, is 100～600 by acid equivalent basis, it is preferred to 250～450.Acid equivalent refers to the quality (unit: gram) of the polymer of the carboxyl in this molecule with 1 equivalent.(A) photo-sensitive resin is provided developability and fissility for aqueous alkali by the carboxyl in alkali-soluble macromolecule is necessary.From the viewpoint of improve development patience, resolving power and adaptation, it is preferable that acid equivalent is set to more than 100.And acid equivalent is more preferably set to more than 250.On the other hand, from the viewpoint of improve developability and fissility, it is preferable that acid equivalent is set to less than 600.And acid equivalent is more preferably set to less than 450.In the disclosure, acid equivalent is the value using potential difference titration appratus, passing through to utilize the potential difference titration mensuration of the NaOH aqueous solution titration of 0.1 mole/L to obtain.
(A) the high molecular weight average molecular weight of alkali-soluble is preferably 5000～500000.From the viewpoint of improve resolving power and developability, it is preferable that weight average molecular weight is set to less than 500000.More preferably weight average molecular weight is set to less than 300000, it is preferred that be set to less than 200000.On the other hand, from the viewpoint of the character of edge-melting when controlling the character of development aggregation and form photoresist duplexer and the unexposed film such as chip, it is preferable that weight average molecular weight is set to more than 5000.More preferably weight average molecular weight is set to more than 10000, it is preferred that be set to more than 20000.Edge-melting refers to the degree that photo-sensitive resin when winding with web-like (namely comprising the layer of photosensitive polymer combination) is easily overflowed by the end face rolled up as photoresist duplexer.Chip refers to the degree that when being cut off by unexposed film, chip is easily splashed with cutting knife.If this chip is attached to the upper surface etc. of photoresist duplexer, exposure process thereafter etc. is transferred to mask and becomes the reason of defective work.
(A) alkali-soluble macromolecule is preferably the copolymer at least one derived above by least one above of the first monomer described later and second comonomer described later.
First monomer is carboxylic acid or the anhydride in molecule with a polymerism unsaturated group.First monomer is divided into first monomer with aromatic hydrocarbyl and first monomer without aromatic hydrocarbyl.As first monomer with aromatic hydrocarbyl, such as cinnamic acid etc. can be listed.As first monomer without aromatic hydrocarbyl, (methyl) acrylic acid, fumaric acid .beta.-methylacrylic acid, itaconic acid, maleic anhydride, acid half ester etc. can be listed such as.Particularly from the viewpoint of ease of manufacturing, developability are preferably (methyl) acrylic acid.In the disclosure, (methyl) acrylic acid refers to acrylic acid and/or methacrylic acid.Identical below.
Second comonomer is the monomer in nonacid and molecule with at least one polymerism unsaturated group.Second comonomer is divided into the second comonomer with aromatic hydrocarbyl and does not have the second comonomer of aromatic hydrocarbyl.As the second comonomer with aromatic hydrocarbyl, (methyl) benzyl acrylate, styrene, styrene derivative etc. can be listed such as.As the second comonomer without aromatic hydrocarbyl, (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) tert-butyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) 2-EHA, the esters of vinyl alcohol, such as vinyl acetate, (methyl) acrylonitrile etc. can be listed such as.Wherein, it is preferred to (methyl) acrylic acid methyl ester., (methyl) n-butyl acrylate, styrene, (methyl) 2-EHA and (methyl) benzyl acrylate.From the viewpoint of improve resolving power and the adaptation of opposing agent pattern, it is preferred to styrene and (methyl) benzyl acrylate.It addition, from the viewpoint of the difference of resolution during the position of focus during during the position of focus when reducing substrate surface alignment exposure and from substrate surface skew exposure, it is preferred to styrene and (methyl) benzyl acrylate.
(A) alkali-soluble macromolecule preferably comprises the monomer component with aromatic hydrocarbyl.Should the monomer component with aromatic hydrocarbyl in (A) alkali-soluble macromolecule containing ratio, when using the gross mass of whole monomer components as benchmark, it is preferably more than 10 mass %, it is more preferably more than 20 mass %, more preferably more than 30 mass %, it is particularly preferred to be more than 50 mass %.As the upper limit, it does not have be particularly limited to, it is preferred to below 95 mass %, more preferably below 80 mass %.
In preferred mode, (A) alkali-soluble macromolecule containing having the macromolecule being derived from (methyl) acrylic acid, (methyl) alkyl acrylate and cinnamic structure, and/or can have the macromolecule of the structure being derived from (methyl) acrylic acid, (methyl) benzyl acrylate and (methyl) alkyl acrylate.
The copolymerization ratio of the first monomer and second comonomer is by whole polymeric composition quality criterias, preferably the first monomer is 10 mass %～60 mass % and second comonomer is 40 mass %～90 mass %, and more preferably the first monomer is 15 mass %～35 mass % and second comonomer is 65 mass %～85 mass %.
(A) alkali-soluble macromolecule can be used alone one or mixes two or more use.When mixing two or more use, the alkali-soluble macromolecules mixing preferably containing the monomer component with aromatic hydrocarbyl by two kinds uses, or by the alkali-soluble macromolecule containing the monomer component with aromatic hydrocarbyl and the alkali-soluble macromolecule mixing use not containing the monomer component with aromatic hydrocarbyl.When the latter, contain the high molecular usage rate of alkali-soluble of the monomer component with aromatic hydrocarbyl relative to all (A) alkali-soluble macromolecules, it is preferably more than 50 mass %, it is more preferably more than 70 mass %, it is preferably more than 80 mass %, more preferably more than 90 mass %.
(A) the high molecular synthesis of alkali-soluble is preferably, by in the solution mixture of the first monomer and second comonomer diluted with acetone, butanone, isopropanol equal solvent, add the radical polymerization initiator such as benzoyl peroxide, azo isobutyronitrile in right amount and carry out heated and stirred and carry out.Sometimes synthesize while also a part for mixture being added drop-wise to reactant liquor.After reaction terminates, sometimes also add solvent further, adjust desired concentration.As synthesizing mean, except polymerisation in solution, it is possible to use polymerisation in bulk, suspension polymerisation or emulsion polymerization.
(A) alkali-soluble macromolecule is preferably in the scope of 10 mass %～90 mass % with the ratio of all solids composition quality of photosensitive polymer combination, more preferably 30 mass %～70 mass %, more preferably 40 mass %～60 mass %.From the viewpoint of control developing time, it is preferable that the ratio of (A) alkali-soluble macromolecule and photosensitive polymer combination is set to below 90 mass %.On the other hand, from the viewpoint of improve resistance to edge-melting, it is preferable that the ratio of (A) alkali-soluble macromolecule and photosensitive polymer combination is set to more than 10 mass %.
The compound of ethylenical unsaturated double bonds<(B) have>
(B) there is the compound of ethylenical unsaturated double bonds from the viewpoint of curable and with the high molecular compatibility of (A) alkali-soluble, it is preferable that containing the compound in molecule with (methyl) acryloyl group.(B) (methyl) the acryloyl radix in compound is more than 1.
As (B) compound with (methyl) acryloyl group; can list such as at the compound of a terminal addition (methyl) acrylic acid of polyoxyalkylene, or at a terminal addition (methyl) acrylic acid of polyoxyalkylene, by the compound etc. of another end alkyl etherificate or allyl etherization.
As this compound, can list such as:
By Polyethylene Glycol addition in (methyl) acrylate of the compound of phenyl, i.e. phenoxy group six ethylene glycol list (methyl) acrylate,
Addition is had the polypropylene glycol of the expoxy propane of average 2 moles and addition have average 7 moles oxirane Polyethylene Glycol addition in (methyl) acrylate of the compound of nonyl phenol, i.e. 4-n-nonyl phenoxy group seven ethylene glycol dipropylene glycol (methyl) acrylate,
Addition is had the polypropylene glycol of the expoxy propane of average 1 mole and addition have average 5 moles oxirane Polyethylene Glycol addition in (methyl) acrylate of the compound of nonyl phenol, i.e. 4-n-nonyl phenoxy group five ethylene glycol MPG (methyl) acrylate,
Addition is had the Polyethylene Glycol addition of oxirane of average 8 moles in the acrylate of the compound of nonyl phenol, i.e. 4-n-nonyl phenoxy group eight ethylene glycol (methyl) acrylate (such as East Asia synthesis (strain) system, M-114) etc..
As the compound in molecule with two (methyl) acryloyl groups, can list and such as at two ends of alkylene oxide base chain, there are two ends of the compound of (methyl) acryloyl group or the alkylene oxide base chain of or block bonding random at ethyleneoxy group chain and propylidene oxygen base chain there is the compound etc. of (methyl) acryloyl group.
As this compound, such as except TEG two (methyl) acrylate, five ethylene glycol two (methyl) acrylate, six ethylene glycol bisthioglycolates (methyl) acrylate, seven ethylene glycol bisthioglycolates (methyl) acrylate, eight ethylene glycol bisthioglycolates (methyl) acrylate, nine ethylene glycol bisthioglycolates (methyl) acrylate, ten ethylene glycol bisthioglycolates (methyl) acrylate, outside Polyethylene Glycol (methyl) acrylate such as the two ends compound with (methyl) acryloyl group at the ethyleneoxy group chain of 12 moles etc., also can list polypropylene glycol two (methyl) acrylate, polytetramethylene glycol two (methyl) acrylate etc..As polyoxyalkylene two (methyl) acrylate compounds containing ethyleneoxy group and propylidene oxygen base in compound, can list such as addition have average 12 moles expoxy propane polypropylene glycol two ends respectively further the dihydroxylic alcohols of the oxirane of average 3 moles of addition dimethylacrylate, have the dimethylacrylate etc. of the two ends dihydroxylic alcohols of the oxirane of average 15 moles of addition further respectively of the polypropylene glycol of the expoxy propane of average 18 moles in addition.
As the other example of the compound in molecule with two (methyl) acryloyl groups, there is the compound of (methyl) acryloyl group from the viewpoint of resolving power and adaptation are preferred by bisphenol-A carries out oxyalkylene modified at two ends.Oxyalkylene is modified exist ethylene-oxide-modified, epoxy pronane modification, epoxy butane modified, epoxypentane modified, oxepane is modified.Preferably by being carried out by bisphenol-A ethylene-oxide-modified, there is at two ends the compound of (methyl) acryloyl group.nullAs this compound，Such as 2 can be listed,Double; two (4-((methyl) acryloxy diethoxy) phenyl) propane (such as Xin Zhong village chemical industry (strain) NKEsterBPE-200 processed) of 2-、2,Double; two (4-((methyl) acryloxy triethoxy) phenyl) propane of 2-、2,Double; two (4-((methyl) acryloxy tetraethoxy) phenyl) propane of 2-、2,Double; two (4-((methyl) acryloxy five ethyoxyl) phenyl) propane (such as Xin Zhong village chemical industry (strain) NKEsterBPE-500 processed) of 2-、2,Double; two (4-((methyl) acryloxy six ethyoxyl) phenyl) propane of 2-、2,Double; two (4-((methyl) acryloxy seven ethyoxyl) phenyl) propane of 2-、2,Double; two (4-((methyl) acryloxy eight ethyoxyl) phenyl) propane of 2-、2,Double; two (4-((methyl) acryloxy nine ethyoxyl) phenyl) propane of 2-、2,Double; two (4-((methyl) acryloxy ten ethyoxyl) phenyl) propane of 2-、2,Double; two (4-((methyl) acryloxy 11 ethyoxyl) phenyl) propane of 2-、2,Double; two (4-((methyl) acryloxy ten diethoxy) phenyl) propane of 2-、2,Double; two (4-((methyl) acryloxy ten triethoxy) phenyl) propane of 2-、2,Double; two (4-((methyl) acryloxy ten tetraethoxy) phenyl) propane of 2-、2,Double; two (4-((methyl) acryloxy 15 ethyoxyl) phenyl) propane of 2-、2,Double; two (4-((methyl) acryloxy 16 ethyoxyl) phenyl) propane of 2-etc. 2,Double; two (4-((methyl) acryloxy polyethoxy) phenyl) propane of 2-etc..And then, be preferably also the poly alkylene glycol of the oxirane of the expoxy propane such as average 2 moles of the addition respectively of the two ends at bisphenol-A and average 6 moles two (methyl) acrylate or two (methyl) acrylate etc. of the expoxy propane of average 2 moles of the two ends of bisphenol-A addition respectively and the poly alkylene glycol of the oxirane of average 15 moles the compound of ethylene-oxide-modified and epoxy pronane modification.From the viewpoint of improve resolving power, adaptation and flexibility further, at two ends, there is the molal quantity of the oxirane in the compound of (methyl) acryloyl group be preferably more than 10 moles and less than 30 moles by bisphenol-A carries out oxyalkylene modified.
A part such as, has the compound more than 2 (methyl) acryloyl groups; as center framework; have in molecule more than 3 moles can the group of addition alkylene oxide base, obtain by making the alcohol obtained at alkylene oxide bases such as its addition ethyleneoxy group, propylidene oxygen base, butylene oxide bases form (methyl) acrylate.Now, as the compound that can form center framework, such as glycerol, trimethylolpropane, tetramethylolmethane, dipentaerythritol, isocyanurate ring etc. can be listed.
As this compound, the EO12 mole triacrylate etc. of oxirane (EO) the 3 mole triacrylate of such as trimethylolpropane, the EO6 mole triacrylate of trimethylolpropane, the EO9 mole triacrylate of trimethylolpropane, trimethylolpropane can be listed.nullAs this compound，The EO3 mole triacrylate (such as Xin Zhong village chemical industry (strain) A-GLY-3E processed) of such as glycerol can be listed、The EO9 mole triacrylate (such as Xin Zhong village chemical industry (strain) A-GLY-9E processed) of glycerol、EO6 mole of glycerol and expoxy propane (PO) 6 mole triacrylate (A-GLY-0606PE)、EO9 mole of PO9 mole triacrylate (A-GLY-0909PE) of glycerol、The 4EO of tetramethylolmethane modifiies tetraacrylate (such as SartomerJapanLtd.,SR-494 processed)、The 35EO of tetramethylolmethane modifiies tetraacrylate (such as Xin Zhong village chemical industry (strain) society NKEsterATM-35E) etc..
Except aforesaid compound, it is also possible to suitably use the compound etc. being exemplified below out.nullSuch as 1 can be listed,6-hexanediol two (methyl) acrylate、1,4-cyclohexane diol two (methyl) acrylate、2-bis-(p-hydroxybenzene) propane two (methyl) acrylate、2,Double; two [(4-(methyl) the acryloxy polytrimethylene oxygen base) phenyl] propane of 2-、2,Double; two [(4-(methyl) the acryloxy polybutylene oxygen base) phenyl] propane of 2-、Glycerol three (methyl) acrylate、Trimethylolpropane tris (methyl) acrylate、Polyoxy propyl group trimethylolpropane tris (methyl) acrylate、Dipentaerythritol five (methyl) acrylate、Trimethylolpropane tris glycidyl ether three (methyl) acrylate、Beta-hydroxy propyl group-β '-(acryloxy) propyl group phthalate ester、Nonylphenoxy polypropylene glycol (methyl) acrylate、Nonylphenoxy polytetramethylene glycol (methyl) acrylate、Polypropylene glycol list (methyl) acrylate etc..And then, it is possible to list following carbamate compounds.Such as hexamethylene diisocyanate, toluene di-isocyanate(TDI) or diisocyanate cpd (such as 2 can be listed; 2; 4-trimethyl hexamethylene diisocyanate), with the carbamate compounds of compound such as the acrylic acid 2-hydroxy propyl ester, low polypropylene glycol monomethacrylate in a part with hydroxyl and (methyl) acryloyl group.Specifically, there is the product of hexamethylene diisocyanate and low polypropylene glycol monomethacrylate (such as Nippon Yushi (Co., Ltd.), BlemmerPP1000).Additionally, it is possible to list two or three (methyl) acrylate etc. of the isocyanuric acid ester modified by polypropylene glycol or polycaprolactone.Additionally, it is possible to the end listing the carbamate compounds such as obtained as the addition polymers of diisocyanate and polyhydric alcohol reacts with the compound with ethylenical unsaturated double bonds and hydroxyl and the oligourethane etc. that obtains.
(B) ratio with the compound of ethylenical unsaturated double bonds and all solids composition quality of photosensitive polymer combination is preferably 5 mass %～70 mass %.From the viewpoint of sensitivity, resolving power and adaptation, it is preferable that this ratio is set to more than 5 mass %.More preferably this ratio is set to more than 20 mass %, it is preferred that be set to more than 30 mass %.On the other hand, from the viewpoint of suppress edge-melting and peeling off of solidification opposing agent to postpone, it is preferable that this ratio is set to below 70 mass %.More preferably this ratio is set to below 50 mass %.
<(C) Photoepolymerizationinitiater initiater>
As (C) Photoepolymerizationinitiater initiater, such as six aryl united imidazoles, N-aryl-alpha-amino acid compound, quinones, aromatic series ketone, acetophenones, acylphosphine oxide class, benzoin or benzoin ethers, dialkyl group ketal class, thioxanthene ketone, dialkylaminobenzoic acid esters class, oxime esters, acridine, pyrazoline derivative, the ester compounds of N-aryl amino acid, halogen compounds etc. can be listed.
nullAs six aryl united imidazoles，Such as 2-(Chloro-O-Phenyl)-4 can be listed,5-diphenyl bisglyoxaline、2,2’,5-tri--(Chloro-O-Phenyl)-4-(3,4-Dimethoxyphenyl)-4 ',5 '-diphenyl bisglyoxaline、2,4-pair-(Chloro-O-Phenyl)-5-(3,4-Dimethoxyphenyl)-diphenyl bisglyoxaline、2,4,5-tri--(Chloro-O-Phenyl)-diphenyl bisglyoxaline、2-(Chloro-O-Phenyl)-bis--4,5-(3,4-Dimethoxyphenyl)-bisglyoxaline、2,2 '-bis--(2-fluorophenyl)-4,4’,5,5 '-four-(3-methoxyphenyl)-bisglyoxalines、2,2 '-bis--(2,3-difluoromethyl phenyl)-4,4’,5,5 '-four-(3-methoxyphenyl)-bisglyoxalines、2,2 '-bis--(2,4-difluorophenyl)-4,4’,5,5 '-four-(3-methoxyphenyl)-bisglyoxalines、2,2 '-bis--(2,5-difluorophenyl)-4,4’,5,5 '-four-(3-methoxyphenyl)-bisglyoxalines、2,2 '-bis--(2,6-difluorophenyl)-4,4’,5,5 '-four-(3-methoxyphenyl)-bisglyoxalines、2,2 '-bis--(2,3,4-trifluorophenyl)-4,4’,5,5 '-four-(3-methoxyphenyl)-bisglyoxalines、2,2 '-bis--(2,3,5-trifluorophenyl)-4,4’,5,5 '-four-(3-methoxyphenyl)-bisglyoxalines、2,2 '-bis--(2,3,6-trifluorophenyl)-4,4’,5,5 '-four-(3-methoxyphenyl)-bisglyoxalines、2,2 '-bis--(2,4,5-trifluorophenyl)-4,4’,5,5 '-four-(3-methoxyphenyl)-bisglyoxalines、2,2 '-bis--(2,4,6-trifluorophenyl)-4,4’,5,5 '-four-(3-methoxyphenyl)-bisglyoxalines、2,2 '-bis--(2,3,4,5-tetrafluoro phenyl)-4,4’,5,5 '-four-(3-methoxyphenyl)-bisglyoxalines、2,2 '-bis--(2,3,4,6-tetrafluoro phenyl)-4,4’,5,5 '-four-(3-methoxyphenyl)-bisglyoxalines、2,2 '-bis--(2,3,4,5,6-pentafluorophenyl group)-4,4’,5,5 '-four-(3-methoxyphenyl)-bisglyoxalines etc..
As N-aryl-alpha-amino acid compound, such as N-phenylglycine, N-Methyl-N-phenyl glycine, N-ethyl, N-phenyl glycine etc. can be listed.Particularly N-phenylglycine is owing to effect of enhanced sensitivity is high preferably.
As quinones, can list such as 2-ethyl-anthraquinone, octaethyl anthraquinone, 1,2-benzo anthraquinone, 2,3-benzo anthraquinones, 2-phenyl anthraquinone, 2,3-diphenyl anthraquinones, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequione, 2-MNQ, 9,10-phenanthrenequione, 2-methyl isophthalic acid, 4-naphthoquinone, 2,3-dimethyl anthraquinones, 3-chloro-2-methyl anthraquinone etc..
As aromatic series ketone, such as benzophenone, Michler's keton [4 can be listed, 4 '-bis-(dimethylamino) benzophenone], 4,4 '-bis-(diethylamino) benzophenone, 4-methoxyl group-4 '-dimethylamino benzophenone etc..
As acetophenones, such as 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 1-(4-dodecylphenyl)-2-hydroxy-2-methyl propane-1-ketone, 4-(2-hydroxyl-oxethyl)-phenyl (2-hydroxyl-2-propyl group) ketone, 1-hydroxycyclohexylphenylketone, 2-benzyl-2-dimethylamino-1-(4-morpholino base phenyl)-butanone-1,2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino base-acetone-1 etc. can be listed.As the commercially available product of acetophenones, Irgacure-907, Irgacure-369 and the Irgacure-379 of such as CibaSpecialtyChemicalsInc. can be listed.
As acylphosphine oxide class, such as 2,4 can be listed; 6-trimethyl benzyl diphenyl phosphine oxide, double; two (2,4,6-trimethylbenzoyl)-phosphine oxide, double; two (2; 6-Dimethoxybenzoyl)-2,4,4-trimethyl-pentyl phosphine oxides etc..As the commercially available product of acylphosphine oxide class, the Irgacure-819 of LucirinTPO and the CibaSpecialtyChemicalsInc. system of such as BASF AG can be listed.
As benzoin or benzoin ethers, such as benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, ethyl benzoin etc. can be listed.
As dialkyl group ketal class, such as benzil dimethyl ketal, benzil diethyl ketal etc. can be listed.
As thioxanthene ketone, such as 2,4-diethyl thioxanthones, 2,4-diisopropylthioxanthone, CTX etc. can be listed.
As dialkylaminobenzoic acid esters class, such as dimethyl amino benzoate, diethylamino ethyl benzoate, ethyl-ESCAROL 507 ester, 2-ethylhexyl-4-(dimethylamino) benzoate etc. can be listed.
As oxime esters, such as 1-phenyl-1,2-pentanedione-2-O-benzoyl oximes, 1-phenyl-1,2-pentanedione-2-(O-ethoxy carbonyl) oxime etc. can be listed.As the commercially available product of oxime esters, CGI-325, Irgacure-OXE01 and the Irgacure-OXE02 of such as CibaSpecialtyChemicalsInc. can be listed.
nullAs acridine，Such as 1 can be listed,7-double; two (9,9 '-acridinyl) heptane、9-phenylacridine、9-methylacridine、9-ethyl acridine、9-chloroethyl acridine、9-methoxyacridine、9-ethyoxyl acridine、9-(4-aminomethyl phenyl) acridine、9-(4-ethylphenyl) acridine、9-(4-n-pro-pyl phenyl) acridine、9-(4-n-butylphenyl) acridine、9-(4-tert-butyl-phenyl) acridine、9-(4-methoxyphenyl) acridine、9-(4-ethoxyl phenenyl) acridine、9-(4-acetylphenyl) acridine、9-(4-dimethylaminophenyl) acridine、9-(4-chlorphenyl) acridine、9-(4-bromophenyl) acridine、9-(3-aminomethyl phenyl) acridine、9-(3-tert-butyl-phenyl) acridine、9-(3-acetylphenyl) acridine、9-(3-dimethylaminophenyl) acridine、9-(3-diethylamino phenyl) acridine、9-(3-chlorphenyl) acridine、9-(3-bromophenyl) acridine、9-(2-pyridine radicals) acridine、9-(3-pyridine radicals) acridine、9-(4-pyridine radicals) acridine etc..Among them, consider from sensitivity, resolving power, the viewpoint such as acquired, it is preferred to 1,7-double; two (9,9 '-acridinyl) heptane or 9-phenylacridine.
nullAs pyrazoline derivative，Such as 1-(4-tbutyl-phenyl)-3-styryl-5-phenyl-pyrazole quinoline can be listed、1-phenyl-3-(4-tert-butyl-styrene base)-5-(4-tbutyl-phenyl)-pyrazoline、1,5-pair-(4-tbutyl-phenyl)-3-(4-tert-butyl-styrene base)-pyrazoline、1-(4-t-octyl-phenyl)-3-styryl-5-phenyl-pyrazole quinoline、1-phenyl-3-(4-tert-butyl-styrene base)-5-(4-ethyoxyl-phenyl)-pyrazoline、1-phenyl-3-(4-t-octyl-styryl)-5-(4-t-octyl-phenyl)-pyrazoline、1,5-pair-(4-t-octyl-phenyl)-3-(4-t-octyl-styryl)-pyrazoline、1-(4-dodecyl-phenyl)-3-styryl-5-phenyl-pyrazole quinoline、1-phenyl-3-(4-dodecyl-styryl)-5-(4-dodecyl-phenyl)-pyrazoline、1-(4-dodecyl-phenyl)-3-(4-dodecyl-styryl)-5-(4-dodecyl-phenyl)-pyrazoline、1-(4-t-octyl-phenyl)-3-(4-tert-butyl-styrene base)-5-(4-tbutyl-phenyl)-pyrazoline、1-(4-tbutyl-phenyl)-3-(4-t-octyl-styryl)-5-(4-t-octyl-phenyl)-pyrazoline、1-(4-dodecyl-phenyl)-3-(4-tert-butyl-styrene base)-5-(4-tbutyl-phenyl)-pyrazoline、1-(4-tbutyl-phenyl)-3-(4-dodecyl-styryl)-5-(4-dodecyl-phenyl)-pyrazoline、1-(4-dodecyl-phenyl)-3-(4-t-octyl-styryl)-5-(4-t-octyl-phenyl)-pyrazoline、1-(4-t-octyl-phenyl)-3-(4-dodecyl-styryl)-5-(4-dodecyl-phenyl)-pyrazoline、1-(2,4-dibutyl-phenyl)-3-(4-dodecyl-styryl)-5-(4-dodecyl-phenyl)-pyrazoline etc..
nullAs pyrazoline derivative，And then，1-phenyl-3-(3 can be listed,5-di-t-butyl-styryl)-5-(3,5-di-t-butyl-phenyl)-pyrazoline、1-phenyl-3-(2,6-di-t-butyl-styryl)-5-(2,6-di-t-butyl-phenyl)-pyrazoline、1-phenyl-3-(2,5-di-t-butyl-styryl)-5-(2,5-di-t-butyl-phenyl)-pyrazoline、1-phenyl-3-(2,6-di-n-butyl-styryl)-5-(2,6-di-n-butyl-phenyl)-pyrazoline、1-(3,4-di-t-butyl-phenyl)-3-styryl-5-phenyl-pyrazole quinoline、1-(3,5-di-t-butyl-phenyl)-3-styryl-5-phenyl-pyrazole quinoline、1-(4-tbutyl-phenyl)-3-(3,5-di-t-butyl-phenyl)-5-phenyl-pyrazole quinoline、1-(3,5-di-t-butyl-phenyl)-3-(3,5-di-t-butyl-styryl)-5-(3,5-di-t-butyl-phenyl)-pyrazoline、1-(4-(5-butyl-benzoxazol-2-base) phenyl)-3-styryl-5-phenyl-pyrazole quinoline、1-(4-(benzothiazole-2-base) phenyl)-3-(4-tert-butyl-styrene base)-5-(4-tbutyl-phenyl)-pyrazoline、1-(4-(4-butyl-benzoxazol-2-base) phenyl)-3-(4-tert-butyl-styrene base)-5-(4-tbutyl-phenyl)-pyrazoline、1-(4-(5-t-octyl-benzothiazole-2-base) phenyl)-3-styryl-5-phenyl-pyrazole quinoline、1-(4-(benzothiazole-2-base) phenyl)-3-(4-t-octyl-styryl)-5-(4-t-octyl-phenyl)-pyrazoline、1-(4-(5-t-octyl-benzothiazole-2-base) phenyl)-3-(4-t-octyl-styryl)-5-(4-t-octyl-phenyl)-pyrazoline、1-(4-(5-dodecyl-benzothiazole-2-base) phenyl)-3-styryl-5-phenyl-pyrazole quinoline、1-(4-(benzothiazole-2-base) phenyl)-3-(4-dodecyl-styryl)-5-(4-dodecyl-phenyl)-pyrazoline、1-(4-(5-dodecyl-benzothiazole-2-base) phenyl)-3-(4-dodecyl-styryl)-5-(4-dodecyl-phenyl)-pyrazoline、1-(4-(5-t-octyl-benzothiazole-2-base) phenyl)-3-(4-tert-butyl-styrene base)-5-(4-tbutyl-phenyl)-pyrazoline etc..
nullAs pyrazoline derivative，And then，1-(4-(5-butyl-benzoxazol-2-base) phenyl)-3-(4-t-octyl-styryl)-5-(4-t-octyl-phenyl)-pyrazoline can be listed、1-(4-(5-dodecyl-benzothiazole-2-base) phenyl)-3-(4-tert-butyl-styrene base)-5-(4-tbutyl-phenyl)-pyrazoline、1-(4-(5-butyl-benzoxazol-2-base) phenyl)-3-(4-dodecyl-styryl)-5-(4-dodecyl-phenyl)-pyrazoline、1-(4-(5-dodecyl-benzothiazole-2-base) phenyl)-3-(4-t-octyl-styryl)-5-(4-t-octyl-phenyl)-pyrazoline、1-(4-(5-t-octyl-benzothiazole-2-base) phenyl)-3-(4-dodecyl-styryl)-5-(4-dodecyl-phenyl)-pyrazoline、1-(4-(4,6-dibutyl-benzothiazole-2-base) phenyl)-3-(4-dodecyl-styryl)-5-(4-dodecyl-phenyl)-pyrazoline、1-(4-(benzothiazole-2-base) phenyl)-3-(3,5-di-t-butyl styryl)-5-(3,5-di-t-butyl-phenyl)-pyrazoline、1-(4-(benzothiazole-2-base) phenyl)-3-(2,6-di-t-butyl-styryl)-5-(2,6-di-t-butyl-phenyl)-pyrazoline、1-(4-(benzothiazole-2-base) phenyl)-3-(2,5-di-t-butyl-styryl)-5-(2,5-di-t-butyl-phenyl)-pyrazoline、1-(4-(benzothiazole-2-base) phenyl)-3-(2,6-di-n-butyl-styryl)-5-(2,6-di-n-butyl-phenyl)-pyrazoline、1-(4-(4,6-di-t-butyl-benzothiazole-2-base) phenyl)-3-styryl-5-phenyl-pyrazole quinoline、1-(4-(5,7-di-t-butyl-benzothiazole-2-base) phenyl)-3-styryl-5-phenyl-pyrazole quinoline、1-(4-(5-butyl-benzoxazol-2-base) phenyl)-3-(3,5-di-t-butyl-styryl)-5-phenyl-pyrazole quinoline、1-(4-(4,6-di-t-butyl-benzothiazole-2-base) phenyl)-3-(3,5-di-t-butyl-styryl)-5-(3,5-di-t-butyl-phenyl)-pyrazoline、1-phenyl-3-(4-tert-butyl-styrene base)-5-(4-methanesulfonylamino-phenyl)-pyrazoline、1-phenyl-3-(4-tert-butyl-styrene base)-5-(4-N-Ethyl-phenyl)-pyrazoline、With 1-phenyl-3-(4-tert-butyl-styrene base)-5-(4-N,N-Diethyl-phenyl)-pyrazoline etc..
nullAs pyrazoline derivative，And then，1-phenyl-3-(4-xenyl)-5-(4-normal-butyl-phenyl)-pyrazoline can be listed、1-phenyl-3-(4-xenyl)-5-(4-tbutyl-phenyl)-pyrazoline、1-phenyl-3-(4-xenyl)-5-(4-isobutvl-phenyl)-pyrazoline、1-phenyl-3-(4-xenyl)-5-(4-n-pentyl-phenyl)-pyrazoline、1-phenyl-3-(4-xenyl)-5-(4-isopentyl-phenyl)-pyrazoline、1-phenyl-3-(4-xenyl)-5-(4-neopentyl-phenyl)-pyrazoline、1-phenyl-3-(4-xenyl)-5-(4-hexyl-phenyl)-pyrazoline、1-phenyl-3-(4-xenyl)-5-(4-heptyl-phenyl)-pyrazoline、1-phenyl-3-(4-xenyl)-5-(4-n-octyl-phenyl)-pyrazoline、1-phenyl-3-(4-xenyl)-5-(4-t-octyl-phenyl)-pyrazoline、1-phenyl-3-(4-xenyl)-5-(4-nonyl-phenyl)-pyrazoline、1-phenyl-3-(4-xenyl)-5-(4-decyl-phenyl)-pyrazoline、1-phenyl-3-(4-xenyl)-5-(4-undecyl-phenyl)-pyrazoline、1-phenyl-3-(4-xenyl)-5-(4-dodecyl-phenyl)-pyrazoline etc..
Among the above-mentioned pyrazoline derivative listed, from the viewpoint of the rectangularity of adaptation and opposing agent pattern, it is preferred to use select at least one in the group of free 1-phenyl-3-(4-tert-butyl-styrene base)-5-(4-tbutyl-phenyl)-pyrazoline, 1-phenyl-3-(4-xenyl)-5-(4-tbutyl-phenyl)-pyrazoline and 1-phenyl-3-(4-xenyl)-5-(4-t-octyl-phenyl)-pyrazoline composition.
As the ester compounds of N-aryl amino acid, the monooctyl ester etc. of the methyl ester of such as N-phenylglycine, the ethyl ester of N-phenylglycine, the n-propyl of N-phenylglycine, the isopropyl ester of N-phenylglycine, the 1-butyl ester of N-phenylglycine, the 2-butyl ester of N-phenylglycine, the tert-butyl ester of N-phenylglycine, the pentyl ester of N-phenylglycine, the own ester of N-phenylglycine, the pentyl ester of N-phenylglycine, N-phenylglycine can be listed.
As halogen compounds, can list such as amyl bromide, isoamyl bromide, brominated isobutylene, ethylene bromide, diphenyl methyl bromine, benzyl bromide a-bromotoluene, methylene bromide, trisbromomethyl phenyl sulfone, carbon tetrabromide, three (2,3-dibromopropyl) phosphate ester, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-tri-chloro-2,2-double; two (rubigan) ethane, chlorination triaizine compounds, diallyl iodine salt compounds etc., it is particularly preferred to for trisbromomethyl phenyl sulfone.
It is two or more that above-mentioned (C) Photoepolymerizationinitiater initiater listed can be used alone or combine use.Among these (C) Photoepolymerizationinitiater initiaters, consider from viewpoints such as the sensitivity of photosensitive polymer combination, resolving powers, at least one in the group of choosing freely six aryl united imidazoles, N-aryl-alpha-amino acid compound, quinones, acridine and pyrazoline derivative composition is preferably used, more preferably uses at least one in the group of choosing freely six aryl united imidazoles, N-aryl-alpha-amino acid compound and acridine composition.From viewpoints such as the sensitivity of photosensitive polymer combination, resolving powers, suppress the viewpoint that the resolution during focal shift when exposure is deteriorated, or the viewpoint suppressing the line-spacing part resisted between agent line the adjoined during focal shift when exposure narrowing considers, it is preferred that use acridine.
(C) Photoepolymerizationinitiater initiater is preferably 0.01 mass %～20 mass % with the ratio of all solids composition quality of photosensitive polymer combination.From the viewpoint of obtain good sensitivity, it is preferable that this ratio is set to more than 0.01 mass %.This ratio is more preferably set to more than 0.1 mass %, it is preferred that be set to more than 0.5 mass %.On the other hand, from the viewpoint of obtain high resolving power and suppress the aggregation in developer solution, it is preferable that this ratio is set to below 20 mass %.This ratio is more preferably set to below 10 mass %.
As (C) Photoepolymerizationinitiater initiater, when using six aryl united imidazoles, the content of this six aryl united imidazole is preferably 0.1 mass %～15 mass % relative to all solids composition quality of photosensitive polymer combination.From the viewpoint of obtain good sensitivity, it is preferable that this compounding amount is set to more than 0.1 mass %.This compounding amount is more preferably set to more than 1 mass %, it is particularly preferred to be set to more than 3 mass %.On the other hand, from the viewpoint of obtain high resolving power and suppress the aggregation in developer solution, it is preferable that this compounding amount is set to below 15 mass %.This compounding amount is more preferably set to below 10 mass %, it is particularly preferred to be set to below 6 mass %.
It addition, as (C) Photoepolymerizationinitiater initiater, when using N-aryl-alpha-amino acid compound, the content of this N-aryl-alpha-amino acid compound is preferably 0.001 mass %～5 mass % relative to all solids composition quality of photosensitive polymer combination.From the viewpoint of obtain good sensitivity, it is preferable that this compounding amount is set to more than 0.001 mass %.This compounding amount is more preferably set to more than 0.01 mass %, it is particularly preferred to be set to more than 0.1 mass %.On the other hand, from the viewpoint of obtain high resolving power and improve tone stability, it is preferable that this compounding amount is set to below 5 mass %.This compounding amount is more preferably set to below 1 mass %, it is particularly preferred to be set to below 0.5 mass %.
And then, as (C) Photoepolymerizationinitiater initiater, when using acridine, the content of acridine is preferably 0.01 mass %～5 mass % relative to all solids composition quality of photosensitive polymer combination.From the viewpoint of obtain good sensitivity, it is preferable that this compounding amount is set to more than 0.01 mass %.This compounding amount is more preferably set to more than 0.1 mass %, it is particularly preferred to be set to more than 0.2 mass %.On the other hand, from the viewpoint of obtain the opposing agent shape of rectangle and improve tone stability, it is preferable that this compounding amount is set to below 5 mass %.This compounding amount is more preferably set to below 3 mass %, it is particularly preferred to be set to below 2 mass %.It addition, from the viewpoint of the difference of resolution during the position of focus during during the position of focus when reducing substrate surface alignment exposure and from substrate surface skew exposure, it is also preferred that be set to the compounding amount of above-mentioned scope.
<(D) phenol system derivant>
In embodiment, photosensitive polymer combination is preferably possibly together with (D) phenol system derivant.Wherein, photosensitive polymer combination preferably comprises the compound shown in following formula (I) as (D) phenol system derivant.
In formula (I), R1That expression can be replaced, straight chained alkyl, branched alkyl, aryl, cyclohexyl, the straight chained alkyl via divalent linker, the branched alkyl via divalent linker, the cyclohexyl via divalent linker or the aryl via divalent linker, multiple R1Can being mutually identical or different, m represents the integer of 0～4, and n represents the integer of more than 1, and when n is 1, A represents monovalent organic group, and when n is more than 2, A represents the organic group of more than bivalence, singly-bound or the linking group comprising conjugated bonds }.From the viewpoint of suppress the viewpoint of sensitivity decrease of photosensitive polymer combination and focusing position not to impact and maintain good resolution, the compound shown in formula (I) is excellent.From the same viewpoint, n is preferably the integer of more than 2.
As the compound shown in formula (I), preferably comprise at least one in the group of the choosing freely compound shown in following formula (II) and the composition of the compound shown in following formula (III), more preferably contain the compound shown in formula (III).It should be noted that as the compound shown in formula (II), do not include the compound meeting the compound shown in formula (III).
In formula (II), R2That expression can be replaced, straight chained alkyl, branched alkyl, aryl, cyclohexyl, the straight chained alkyl via divalent linker, the branched alkyl via divalent linker, the cyclohexyl via divalent linker or the aryl via divalent linker, and R3、R4And R5Represent independently of one another hydrogen or can be replaced, straight chained alkyl, branched alkyl, aryl, cyclohexyl, the straight chained alkyl via divalent linker, the branched alkyl via divalent linker, the cyclohexyl via divalent linker or the aryl via divalent linker
In formula (III), R6And R7Represent that can be replaced, straight chained alkyl, branched alkyl, aryl, cyclohexyl, the straight chained alkyl via divalent linker, the branched alkyl via divalent linker, the cyclohexyl via divalent linker or the aryl via divalent linker, multiple R independently of one another6And R7Can being mutually identical or different, p and q represents the integer of 0～4 independently of one another, and B represents singly-bound or the linking group comprising conjugated bonds }.
Compound shown in formula (II) and the compound shown in formula (III) respectively from the viewpoint of improve the viewpoint of the resolving power of photosensitive polymer combination, the focal shift that suppresses when exposure time resolving power be deteriorated viewpoint, suppress when exposure focal shift time opposing agent line and opposing agent line between the narrowing viewpoint of line-spacing part and suppress sensitivity decrease excellence especially.
From the viewpoint of improve the viewpoint of the resolving power of photosensitive polymer combination, the focal shift that suppresses when exposure time resolving power be deteriorated viewpoint, suppress when exposure focal shift time opposing agent line and opposing agent line between the narrowing viewpoint of line-spacing part and suppress sensitivity decrease, R in the compound preferred formula (II) shown in formula (II)2、R3、R4And R5In at least one there is aromatic rings.From the same viewpoint, the compound shown in formula (II) preferably has two or more phenol nucleus.
From the same viewpoint, the hydroxyl concentration of the compound shown in formula (II) is preferably 0.10 mole/100g～0.75 mole/100g.It addition, from the same viewpoint, in above-mentioned formula (II), R2In at least one is preferably straight or branched alkyl, benzyl, 1-phenylethyl or 2-phenylethyl or the thiophenyl for being replaced by hydroxyl or alkyl.And as preferred alkyl, such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group etc. can be listed.
From the same viewpoint, the molecular weight of the compound shown in formula (II) is preferably from about 130～about 1000, more preferably about 130～about 600, and more preferably about 130～about 400, it is particularly preferred to for about 180～about 400.From the same viewpoint, compound shown in formula (II) preferably has the proportion of about 1.02～about 1.12 or the fusing point of more than about 155 DEG C (such as more than about 208 DEG C), or for water for slightly solubility and for the organic solvents such as methanol, acetone, toluene for ease of solubility, or be solid (such as powder, crystal etc.) or liquid when using.
As the compound shown in formula (II), such as 4 can be listed, 4 '-sulfenyl double; two (the 6-tert-butyl group-metacresol), 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol), 1,1,3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, styrenated phenol (such as Kawaguchi's chemical industry (strain) system, ANTAGESP), tribenzyl phenol (such as Kawaguchi's chemical industry (strain) system, TBP, there is the phenol of 1～3 benzyl) etc..
In compound shown in formula (III), B represents singly-bound or the linking group comprising conjugated bonds.The linking group comprising conjugated bonds is preferably the binding affinity linking group of conjugation that formed by C, N, O, S etc., more preferably the groups such as the combination of alkenylene, alkynylene, arlydene, O divalent aromatic heterocycle, azo and imines and more than one and N in them.
Compound shown in formula (III), from the viewpoint of improve the viewpoint of the resolving power of photosensitive polymer combination, the focal shift that suppresses when exposure time resolving power be deteriorated viewpoint, suppress when exposure focal shift time opposing agent line and opposing agent line between the narrowing viewpoint of line-spacing part and suppress sensitivity decrease, it is preferable that in formula (III), B is singly-bound.
From the same viewpoint, p=q=0 in the compound preferred formula (III) shown in formula (III), it is particularly preferred to for xenol.
In embodiment, as (D) phenol system derivant, it is possible to possibly together with the compound beyond the compound that formula (II) and formula (III) are respectively shown in.nullAs the compound beyond the compound that formula (II) and formula (III) are respectively shown in，Such as 2 can be listed,6-di-t-butyl-4-methylphenol、2,5-bis--tertiary pentyl hydroquinone、2,5-di-t-butyl hydroquinone、2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert-butylphenol)、Double; two (the 2-hydroxyl-3-tert-butyl group-5-ethylphenyl) methane、2,2'-ethylenedioxybis(ethanol) .-bis-[3-(the 3-tert-butyl group-5-methyl-4-hydroxy phenyl) propionic ester]、1,6-hexanediol-bis-[3-(3,5-di-t-butyl-4-hydroxy phenyl) propionic ester]、Tetramethylolmethane four [3-(3,5-di-t-butyl-4-hydroxy phenyl) propionic ester]、2,2-sulfenyl-di ethylene bis [3-(3,5-di-t-butyl-4-hydroxy phenyl) propionic ester]、Octadecyl-3-(3,5-di-t-butyl-4-hydroxy phenyl) propionic ester、N,N '-hexa-methylene double; two (3,5-di-t-butyl-4-hydroxy-hydrocineamide)、3,5-di-t-butyl-4-hydroxybenzylphosphaonate-diethyl ester、1,3,5-trimethyl-2,4,6-tri-(3,5-di-t-butyl-4-hydroxybenzyl) benzene、Three-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanuric acid ester etc..
The reaction rate constant with peroxy radical as (D) phenol system derivant in embodiment, it is preferred to 20L mole-1·sec-1(it is more preferably 30L mole above-1·sec-1Above, more preferably 40L mole-1·sec-1Compound above), it is preferred to 500L mole-1·sec-1(it is more preferably 300L mole below-1·sec-1Below, more preferably 200L mole-1·sec-1Compound below).
At this, select above-mentioned (D) phenol system derivant, whether the value for pattern resolution a Yu the difference of pattern resolution b impacts, even and then under the shapes such as wiring densification in recent years, multiple stratification, also reduce the bad problem of poor short circuit, shortcoming, open circuit, plating, can not be formed the problems such as desired copper cash photosensitive polymer combination choose whether impact, although its detailed mechanism is unclear, but it is believed that as described below.
For the antioxidation of phenol system derivant, from the reactive aspect of free radical kind and with the reaction of free radical kind after the stability aspect of phenoxyl radicals that generates consider, it is believed that there is most suitable point.Such as the OH base of phenol, the more big then phenoxyl radicals of the substituent group at ortho position is more stable.On the other hand, if the steric hindrance of this ortho-substituent is excessive, with the reactive reduction of free radical kind.It addition, the most suitable value of the degree of steric hindrance is different according to characteristic (easily the degree of the oxidation) difference of oxidized chemical seed.
At this, owing to the photosensitive polymer combination in embodiment is optical free radical polymerism, therefore to catch the peroxy radical of factor being likely to become so that resolution is deteriorated, the high reactivity with free radical kind is required for (D) phenol system derivant.
When comprehensively considering any of the above key element, as (D) phenol system derivant, it is preferably the compound shown in formula (I), more preferably selects at least one in the group of the compound shown in free formula (II) and the composition of the compound shown in formula (III).Compound shown in formula (II), owing to adjusting most suitable by the steric hindrance of ortho-substituent, it is believed that excellent with both the stability of the reactivity of peroxy radical and phenoxyl radicals.It is additionally contemplated that, in the compound shown in formula (III), if the steric hindrance of ortho-substituent is little, with the reactive height of peroxy radical, biphenyl phenolic phenoxyl radicals is many and stabilized by the resonant structure of phenoxyl radicals.
About the above-mentioned middle compound as shown in the concrete example of the compound shown in formula (II) or formula (III), to meet above-mentioned reaction rate constant scope, such as 1,1,3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, for 45.4L mole-1·sec-1, for 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol), for 48.6L mole-1·sec-1。
The γ-value (gamma value) being derived from residual film ratio of photosensitive polymer combination is preferably more than 0.5, more preferably more than 1.0, and more preferably more than 2.0, it is particularly preferred to be more than 5.0.The γ-value (gamma value) being derived from the response rate of C=C double bond is preferably more than 0.18, more preferably more than 0.19, more preferably more than 0.20, it is particularly preferred to be more than 0.25.
(D) phenol system derivant is preferably 0.001 mass %～10 mass % with the ratio of all solids composition quality of photosensitive polymer combination.From the viewpoint of improve photosensitive polymer combination resolving power viewpoint, suppress exposure time focal shift time resolving power be deteriorated viewpoint and suppress exposure time focal shift time opposing agent line and opposing agent line between line-spacing part narrowing, this ratio is preferably more than 0.001 mass %, it is more preferably more than 0.01 mass %, more preferably more than 0.1 mass %, it is particularly preferably more than 0.2 mass %, it is most preferred that be more than 0.5 mass %.On the other hand, from the viewpoint of the few viewpoint of sensitivity decrease and improve resolving power, this ratio is preferably below 10 mass %, it is more preferably below 5 mass %, more preferably below 3 mass %, it is particularly preferred to be below 2 mass %, it is most preferred that be below 1.5 mass %.
<additive>
(dyestuff and coloring material)
In embodiment, photosensitive polymer combination as required can possibly together with at least one in the group selecting free dyestuff (such as leuco dye, fluoran dyes etc.) and coloring material composition.
As coloring material, such as magenta, phthalocyanine green, auramine, paramagenta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, peacock green (such as HodogayaChemicalCo. can be listed, Ltd. Aizen processed (registered trade mark) MALACHITEGREEN), alkali blue 20, diamond green (such as HodogayaChemicalCo., Ltd. Aizen (registered trade mark) DIAMONDGREENGH).For the content of the coloring material in photosensitive polymer combination, when all solids composition quality of photosensitive polymer combination is set to 100 mass %, it is preferred to 0.001 mass %～1 mass %.From the viewpoint of improve the operability of photosensitive polymer combination, it is preferable that this content is set to more than 0.001 mass %.On the other hand, from the viewpoint of maintain the storage stability of photosensitive polymer combination, it is preferable that this content is set to below 1 mass %.
Photosensitive polymer combination is owing to developing the color by the exposed portion containing dyestuff, from the viewpoint of visual preferred, it addition, when verifiers etc. read the alignment mark for exposing, when exposure portion is big with the contrast in unexposed portion, it is easy to identify, be advantageous for.Consider preferred dyestuff as from this viewpoint, leuco dye and fluoran dyes can be listed.
As leuco dye, three (4-dimethylaminophenyl) methane [leuco crystal violet], double; two (4-dimethylaminophenyl) phenylmethane [leucomalachite greens] etc. can be listed.Particularly from the viewpoint of contrast is good, as leuco dye, it is preferred to use leuco crystal violet.For the content of the leuco dye in photosensitive polymer combination, it is preferably 0.1 mass %～10 mass % relative to all solids composition quality of photosensitive polymer combination.From the viewpoint of make exposed portion good with the contrast of unexposed portion, it is preferable that this content is set to more than 0.1 mass %.This content is more preferably more than 0.2 mass %, it is particularly preferred to be more than 0.4 mass %.On the other hand, from the viewpoint of maintain storage stability, it is preferable that this content is set to below 10 mass %.This content is more preferably below 5 mass %, it is particularly preferred to be below 2 mass %.
It addition, from the viewpoint of by adaptation and contrast most appropriate, it is preferable that leuco dye is used by photosensitive polymer combination with aforesaid halogen compounds combination in (C) Photoepolymerizationinitiater initiater.When leuco dye is used with the combination of this halogen compounds, content for this halogen compounds in photosensitive polymer combination, when all solids composition quality of photosensitive polymer combination is set to 100 mass %, from the viewpoint of the storage stability of the tone maintained in photosensitive layer, it is preferred to 0.01 mass %～3 mass %.
(other additive)
In order to improve heat stability and storage stability, photosensitive polymer combination can possibly together with at least one compound in the group selecting free radical polymerization inhibitor, benzotriazole and carboxyl benzotriazole class composition.
As radical polymerization inhibitor, can list such as p-methoxyphenol, hydroquinone, 1,2,3,-thrihydroxy-benzene, naphthylamine, tert-butyl catechol, Cu-lyt., 2,6-di-t-butyl-paracresol, 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert-butylphenol), 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), nitroso-group phenylhydroxylamine aluminium salt, diphenyl nitroso-amines etc..In order to not damage the sensitivity of photosensitive polymer combination, it is preferred to nitroso-group phenylhydroxylamine aluminium salt.
As benzotriazole, such as 1,2,3-benzotriazole, 1-chloro-1 can be listed, 2,3-benzotriazole, double; two (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, double; two (N-2-ethylhexyl) aminomethylene-1,2,3-tolyl-triazole, double; two (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole etc..
As carboxyl benzotriazole class, such as 4-carboxyl-1 can be listed, 2,3-benzotriazole, 5-carboxyl-1,2,3-benzotriazole, N-(N, N-bis--2-ethylhexyl) aminomethylene carboxyl benzotriazole, N-(N, N-bis--2-hydroxyethyl) aminomethylene carboxyl benzotriazole, N-(N, N-bis--2-ethylhexyl) aminoethylene carboxyl benzotriazole etc..
Total content for radical polymerization inhibitor, benzotriazole and carboxyl benzotriazole class, when all solids composition quality of photosensitive polymer combination is set to 100 mass %, it is preferably 0.01 mass %～3 mass %, more preferably 0.05 mass %～1 mass %.From the viewpoint of give storage stability to photosensitive polymer combination, it is preferable that this content is set to more than 0.01 mass %.On the other hand, from the viewpoint of maintain the decolouring of sensitivity, suppression dyestuff, it is preferable that this content is set to below 3 mass %.
In embodiment, photosensitive polymer combination can possibly together with the epoxide class of bisphenol-A.As the epoxide class of bisphenol-A, can list and such as modify, with polypropylene glycol, the compound etc. that end-rings is aoxidized by bisphenol-A.
In embodiment, photosensitive polymer combination can possibly together with plasticizer.As plasticizer, such as phthalate (such as ethyl phthalate etc.), o-toluene sulfonic acid amide, p-methyl benzenesulfonic acid amide, tributyl citrate, triethyl citrate, CitroflexA-2, acetyl citrate three n-propyl, acetyl tributyl citrate, Polyethylene Glycol, polypropylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether etc. can be listed.nullAdditionally，Also ADEKANOLSDX-1569 can be listed、ADEKANOLSDX-1570、ADEKANOLSDX-1571、ADEKANOLSDX-479 (above rising sun electrification (strain) system)、NewpolBP-23P、NewpolBP-3P、NewpolBP-5P、NewpolBPE-20T、NewpolBPE-60、NewpolBPE-100、NewpolBPE-180 (above Sanyo chemical conversion (strain) system)、UNIOLDB-400、UNIOLDAB-800、UNIOLDA-350F、UNIOLDA-400、UNIOLDA-700 (above Nippon Yushi (Co., Ltd.))、BA-P4UGlycol、BA-P8Glycol (above Japan's emulsifying agent (strain) system) etc. has the compound of bisphenol backbone.
For the content of the plasticizer in photosensitive polymer combination, relative to all solids composition quality of photosensitive polymer combination, it is preferred to 1 mass %～50 mass %, more preferably 1 mass %～30 mass %.From the viewpoint of suppress postponing and giving flexibility to cured film of developing time, it is preferable that this content is set to more than 1 mass %.On the other hand, from the viewpoint of suppress to solidify insufficient and cold deformation, it is preferable that this content is set to below 50 mass %.
[solvent]
Photosensitive polymer combination can be dissolved in solvent and with the manufacture for photoresist duplexer of the form of photosensitive polymer combination modulating liquid.As solvent, ketone, alcohols etc. can be listed.Aforementioned ketone is with butanone (MEK) for representative.Aforementioned alcohols is with methanol, ethanol and isopropanol for representative.Solvent preferably with when manufacturing photoresist duplexer, the photosensitive polymer combination modulating liquid coated on supporting layer at 25 DEG C time viscosity be 500mPa s～4000mPa s amount make an addition to photosensitive polymer combination.
[photoresist duplexer]
In embodiment, it is provided that the photo-sensitive resin comprising above-mentioned photosensitive polymer combination is laminated in the photoresist duplexer on supporting layer (such as supporting thin film etc.).As required, photoresist duplexer can have protective layer on the surface with opposition side, supporting layer side of photo-sensitive resin.
As supporting layer, it is preferred to through the transparent support thin film of the light radiated by exposure light source.As this support thin film, such as pet film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer thin film, polyvinylidene chloride film, vinylidene chloride copolymerization thin film, polymethyl methacrylate copolymer thin film, polystyrene film, polyacrylonitrile thin film, styrol copolymer thin film, polyamide film, cellulose derivative film etc. can be listed.These thin film can also use the thin film being stretched as required.Support thin film and be preferably the support thin film of mist degree less than 5.The thickness of thin film is more thin, more favourable for improving image formative and economy, but in order to maintain the intensity of photoresist duplexer, it is preferred to use the thin film of 10 μm～30 μm.
For in photoresist duplexer use protective layer key property for, with the closing force of photo-sensitive resin compared with supporting layer fully little, it is possible to be easily peeled off.Such as polyethylene film or polypropylene film can be preferably used as protective layer.Alternatively, it is also possible to use the thin film of the fissility excellence shown in Japanese Laid-Open Patent Publication 59-202457 publication.The thickness of protective layer is preferably 10 μm～100 μm, more preferably 10 μm～50 μm.
The gel being referred to as flake is there may exist on polyethylene film surface.Have flake polyethylene film be used as protective layer when, this flake is likely transferred to photo-sensitive resin.If flake is transferred to photo-sensitive resin, likely it is involved in air during lamination and forms space, cause the defect of opposing agent pattern.From the viewpoint of prevent flake, as the material of protective layer, it is preferred to oriented polypropylene.As concrete example, Oji Paper (strain) ALPHANE-200A processed can be listed.
The thickness of the photo-sensitive resin in photoresist duplexer is different according to purposes difference, but is preferably 5 μm～100 μm, more preferably 7 μm～60 μm.The thickness of photo-sensitive resin is more thin, and resolution more improves, and additionally more thick, film-strength more improves.
Then, the manufacture method of photoresist duplexer is illustrated.
As stacking gradually supporting layer and photo-sensitive resin and the method to make photoresist duplexer of the protective layer as required, it is possible to adopt known method.Such as the photosensitive polymer combination used in photo-sensitive resin is mixed with the solvent dissolving it, forms uniform solution, first, bar coater or roll coater is used to coat on supporting layer, then it is dried and removes aforementioned solvents, thus can at the supporting layer upper strata stacked package photo-sensitive resin containing photosensitive polymer combination.Then according to requiring at photo-sensitive resin overlaminate protective layer, it is possible to make photoresist duplexer.
<forming method of opposing agent pattern>
Then, an example of the method that the photoresist duplexer using present embodiment manufactures opposing agent pattern illustrates.The method may include that the lamination process that photoresist duplexer is laminated in substrate, make the photo-sensitive resin of this photoresist duplexer expose exposure process and the developing procedure removed that developed in the unexposed portion of this photo-sensitive resin.As opposing agent pattern, such as printed wiring board, semiconductor element, galley, display panels, flexible base board, leadframe substrate, COF (chip on film) substrate, base plate for encapsulating semiconductor, liquid crystal transparency electrode, liquid crystal TFT wiring, PDP (plasma display) pattern of electrode etc. can be listed.As an example, the manufacture method of printed wiring board is described as described below.
Printed wiring board is through following each operation manufacture.
(1) lamination process
In this operation, while being peeled off by the protective layer of photoresist duplexer (when there is protective layer), use hot-roll lamination device that photoresist duplexer is sealed on the substrate such as copper-clad laminated board, flexible base board.
(2) exposure process
In this operation, by making the mask film with desired wiring pattern be sealed on supporting layer, use the exposure method that activity light source carries out, utilize the exposure method directly described of the depicting pattern as desired wiring pattern, or utilization is by the exposure method of the image of lens projects photomask so that photo-sensitive resin exposes.The advantage of the photosensitive polymer combination of embodiment, utilize depicting pattern the exposure method directly described or by the exposure method of the image of lens projects photomask in more notable, particularly significant in the exposure method directly described utilize depicting pattern.
(3) developing procedure
In this operation, after exposure, peeling off the supporting layer on photo-sensitive resin, the development of unexposed portion is removed by the developer solution being then used by aqueous alkali, is thus formed on substrate by opposing agent pattern.
As aqueous alkali, use Na2CO3Or K2CO3Aqueous solution.Aqueous alkali meets the characteristic of photo-sensitive resin and suitably selects, it is preferred to the Na of the concentration of about 0.2 mass %～about 2 mass % and about 20 DEG C～about 40 DEG C2CO3Aqueous solution.
Each operation through above-mentioned (1)～(3), it is possible to obtain opposing agent pattern.After these operations, the heating process of about 100 DEG C～about 300 DEG C can also be carried out as required further.By implementing this heating process, it is possible to improve chemical reagent resistance further.Heating can use the heating furnace of hot blast, infrared ray or far infrared mode.
(4) etching work procedure or plating process
The substrate surface (copper face of such as copper-clad laminated board) exposed by developing is etched or plating, manufactures conductive pattern.
(5) stripping process
Then, the aqueous solution with the alkalescence stronger than developer solution is utilized to be resisted agent pattern by strippable substrate.Aqueous alkali for peeling off is not particularly limited, it is preferred to the aqueous solution of NaOH or KOH of the temperature of the concentration of about 2 mass %～about 5 mass % and about 40 DEG C～about 70 DEG C.Stripper can also add a small amount of water-soluble solvent.
The photoresist duplexer of present embodiment is the photoresist duplexer of the manufacture of the conductive pattern being suitable to printed wiring board, flexible base board, leadframe substrate, COF substrate, base plate for encapsulating semiconductor, liquid crystal transparency electrode, liquid crystal TFT wiring, PDP electrode etc..
It should be noted that for above-mentioned various parameters, then measure into the method equal with it according to the assay method in embodiment described later or skilled artisans appreciate that unless otherwise specified.
Embodiment
Then, list embodiment and present embodiment is specifically described by comparative example.But, then do not limited by below example as long as present embodiment is not departed from by its purport.Physical property in embodiment measures by the following method.
<sensitivity evaluation>
Firstly, for the copper-clad laminated board thick for 0.4mm being laminated with 35 μm of rolled copper foils, use removing material (JapanCarlitCo., Ltd. system, SAKURUNDUMR (registered trade mark #220)) with atomisation pressure 0.2MPa, carry out jet polishing.
Then; while peeling off the polyethylene film (protective layer) of photoresist duplexer; at the copper-clad laminated board being preheating to 60 DEG C, utilize hot-roll lamination device (Asahi Chemical Industry's (strain) society system, AL-700), with 105 DEG C of laminated photosensitive laminated resin bodies of roll temperature.Air pressure is set to 0.35MPa, laminate speed is set to 1.5m/ minute.
Then, utilize direct rendering style exposure device (OrbotechLtd. system, Paragon-Ultra100), using Stouffer21 level exposure guide rule (steptablet) as mask, be exposed with various light exposures.The position of focus time now, to substrate surface alignment exposure.
And then after peeling off pet film (supporting layer), use alkali developing machine (FUJIKIKOCO., LTD. system, dry type film developing machine), with 1 mass %Na of stipulated time spraying 30 DEG C2CO3Aqueous solution, dissolves removal with the times of the 2 of minimum developing time times by the unexposed portion of photo-sensitive resin.Now, the photo-sensitive resin of unexposed portion is completely dissolved required minimum time as minimum developing time.
By above operation, obtain solidifying opposing agent pattern.Obtain the light exposure that residual film limit progression is 7 grades after development.
<resolution evaluation (generally)>
Firstly, for the copper-clad laminated board thick for 0.4mm being laminated with 35 μm of rolled copper foils, use removing material (JapanCarlitCo., Ltd. system, SAKURUNDUMR (registered trade mark #220)) with atomisation pressure 0.2MPa, carry out jet polishing.
Then; while peeling off the polyethylene film (protective layer) of photoresist duplexer; at the copper-clad laminated board being preheating to 60 DEG C, utilize hot-roll lamination device (Asahi Chemical Industry's (strain) society system, AL-700), with 105 DEG C of laminated photosensitive laminated resin bodies of roll temperature.Air pressure is set to 0.35MPa, laminate speed is set to 1.5m/ minute.
Then, direct rendering style exposure device (OrbotechLtd. system, Paragon-Ultra100) is utilized so that unexposed portion forms the pattern exposure of line (line-spacing).Exposure now, is exposed aforesaid Stouffer21 level exposure guide rule (steptablet) as mask, and the light exposure that the highest residual film progression during to develop is 7 grades is exposed.The position of focus time now, to substrate surface alignment exposure.And then after peeling off pet film (supporting layer), develop with the developing time of the 2 of minimum developing time times.Now, the value of the line in unexposed portion and the minimum feature of line-spacing is normally formed as pattern resolution a.
In the disclosure, the photo-sensitive resin of unexposed portion is completely dissolved required minimum time as minimum developing time.It should be noted that to solidifying in opposing agent pattern, do not remain opposing agent at the substrate surface of unexposed portion, substrate surface exposes, also without as by the opposing projection of agent composition solidifying opposing agent wire drawing, line rectilinearity also good, be evaluated also without the closely sealed minimum feature normally formed solidified between opposing agent.As the value of resolution, 30 μm of every 2 μm of depicting pattern obtained used below are exposed, and 30 μm of every 5 μm of depicting pattern obtained used above are exposed.
<resolution evaluation (focal shift)>
The position of focus during exposure from substrate surface on the thickness direction of this substrate to substrate offset inboard 300 μm.In addition identical with above-mentioned resolution evaluation (generally).Now, the value of minimum feature of the line (line-spacing) in unexposed portion is normally formed as pattern resolution b.
<difference of resolution>
The position of the focus during position of focus during to substrate surface alignment exposure and during exposure from substrate surface offset 300 μm time the difference of resolution, the value of the pattern resolution a by being deducted<resolution evaluation (generally)>by the value of the pattern resolution b of above-mentioned<resolution evaluation (focal shift)>is obtained.
<difference of line-spacing width>
Firstly, for the copper-clad laminated board thick for 0.4mm being laminated with 35 μm of rolled copper foils, use removing material (JapanCarlitCo., Ltd. system, SAKURUNDUMR (registered trade mark #220)) with atomisation pressure 0.2MPa, carry out jet polishing.
Then; while peeling off the polyethylene film (protective layer) of photoresist duplexer; at the copper-clad laminated board being preheating to 60 DEG C, utilize hot-roll lamination device (Asahi Chemical Industry's (strain) society system, AL-700), with 105 DEG C of laminated photosensitive laminated resin bodies of roll temperature.Air pressure is set to 0.35MPa, laminate speed is set to 1.5m/ minute.
Then, direct rendering style exposure device (OrbotechLtd. system, Paragon-Ultra100) is utilized so that the pattern exposure of the ratio that respective width is 2:1 in exposure portion and unexposed portion.Exposure now, is exposed aforesaid Stouffer21 level exposure guide rule (steptablet) as mask, and the light exposure that the highest residual film progression during to develop is 7 grades is exposed.And then after peeling off pet film (supporting layer), develop with the developing time of the 2 of minimum developing time times.For the part that line (line-spacing) width is 40 μm in the unexposed portion in obtained pattern, by this line-spacing width of microscope practical measurement.For the sample of each duplexer, the position of the focus when situation of the position of focus when carrying out substrate surface alignment exposure and exposure is formed to situation both patterns of substrate offset inboard 300 μm on the thickness direction of this substrate from substrate surface.
The position of the focus during position of focus during to substrate surface alignment exposure and during exposure from substrate surface offset 300 μm time the difference of line-spacing width, the line-spacing width when position of focus when deducting exposure by line-spacing width during by the position of focus during to substrate surface alignment exposure is from substrate surface to substrate offset inboard 300 μm is obtained.
<weight average molecular weight>
By Japan's light splitting (strain) gel permeation chromatography processed (GPC) [pump: Gulliver, PU-1580 type, chromatographic column: 4 series connection of Showa electrician (strain) Shodex processed (registered trade mark) (KF-807, KF-806M, KF-806M, KF-802.5), eluting layer solvent: oxolane, use utilize the standard curve that polystyrene standard sample (Showa electrician (strain) ShodexSTANDARDSM-105 processed) obtains], obtain weight average molecular weight with polystyrene conversion value.
<reaction rate constant with peroxy radical>
Based on J.Macromol.Sci.Chem., A11 (10), the method recorded in p1975 (1977).
<being derived from the γ-value (gamma value) of residual film ratio>
Firstly, for the copper-clad laminated board thick for 0.4mm being laminated with 35 μm of rolled copper foils, use removing material (JapanCarlitCo., Ltd. system, SAKURUNDUMR (registered trade mark #220)) with atomisation pressure 0.2MPa, carry out jet polishing.
Then; while peeling off the polyethylene film (protective layer) of photoresist duplexer; at the copper-clad laminated board being preheating to 60 DEG C, utilize hot-roll lamination device (Asahi Chemical Industry's (strain) society system, AL-700), with 105 DEG C of laminated photosensitive laminated resin bodies of roll temperature.Air pressure is set to 0.35MPa, laminate speed is set to 1.5m/ minute.
Then, utilize direct rendering style exposure device (OrbotechLtd. system, Paragon-Ultra100), using Stouffer41 level exposure guide rule (steptablet) as mask, be exposed with various light exposures.The position of focus time now, to substrate surface alignment exposure.
And then, after peeling off pet film (supporting layer), use alkali developing machine (FUJIKIKOCO., LTD. system, dry type film developing machine), with 1 mass %Na of stipulated time spraying 30 DEG C2CO3Aqueous solution, dissolves removal with the times of the 2 of minimum developing time times by the unexposed portion of photo-sensitive resin.
For the thickness solidifying opposing agent pattern obtained by above operation, utilize surface roughness profile measuring machine ((strain) Tokyo precision system, SURFCOM575A) to be measured, this thickness obtain residual film ratio.It addition, calculated essence light exposure by the transmitance of light exposure and Stouffer41 level exposure guide rule (steptablet).γ-value is obtained based on this residual film ratio and essence light exposure.It should be noted that the computational methods of γ-value can by " by the photoresist (first か ら ぶ photonasty fat) of primary learning, P.60, Zhang Yanshui open country, Ikeda crystalline substance well work, the census of manufacturing meeting " in record method obtain.
<being derived from the γ-value (gamma value) of the response rate of C=C double bond>
Direct rendering style exposure device (OrbotechLtd. system, Paragon-Ultra100) is utilized by pet film (supporting layer) side of photoresist duplexer, using Stouffer41 level exposure guide rule (steptablet) as mask, it is exposed with various light exposures.The position of focus time now, to opposing agent bottom alignment exposure.
The response rate solidifying the C=C double bond resisting agent pattern obtained by operation above is obtained by FT-IR (ThermoSCIENTIFIC system, NICOLET380).It should be noted that C=C double bond measures 810cm-1Peak height.It addition, calculated essence light exposure by the transmitance of light exposure and Stouffer41 level exposure guide rule (steptablet).Response rate based on this C=C double bond obtains γ-value together with essence light exposure.It should be noted that the computational methods of γ-value are same as described above.
<the tone stability of photosensitive polymer combination modulating liquid>
The transmitance of 600nm and the 630nm of photoresist duplexer uses ultraviolet-visible light (UV-Vis) determinator (HitachiHigh-TechnologiesCorporation system, U-3010 shape spectrophotometer) mensuration as described below:
I the transmitance of 600nm and 630nm is peeled off, measured to the polyethylene film of photoresist duplexer by ().
(ii) the photosensitive polymer combination modulating liquid after preserving 3 days at using 40 DEG C makes photoresist duplexer, peels off the polyethylene film of this photoresist duplexer, measures the transmitance of 600nm and 630nm.
The change of tone is obtained by the calculating of the transmitance of transmitance-(i) of (ii).
[embodiment 1～11 and comparative example 1～15]
The photosensitive polymer combination of composition (wherein, the numeral of each composition is denoted as the compounding amount (mass parts) of solid constituent) shown in table 1 and 2 and solvent (butanone and ethanol) are sufficiently stirred for, are mixed to get the photosensitive polymer combination modulating liquid solution of 55 mass % (photosensitive polymer combination be).As supporting layer, prepare the pet film (TeijinDuPontFilmsJapanLimited (strain) system, GR-16) of 16 μ m-thick, bar coater photosensitive resin coating compositions modulating liquid equably is used on the surface of this thin film, the exsiccator of 95 DEG C dries 4 minutes, forms photo-sensitive resin.The thickness of photo-sensitive resin is 35 μm.
Then, the polyethylene film (TamapolyCo., Ltd. system, GF-18) of 19 μ m-thick fitted on the surface not having stacking pet film of photo-sensitive resin as protective layer, obtain photoresist duplexer.Various evaluation is carried out for obtained photoresist duplexer.Result collects and is shown in table 1.It addition, the result of the difference of line-spacing width, be-5.9 μm in embodiment 1, in embodiment 3 for-5.2 μm, in example 4 for-5.6 μm, in embodiment 5 for-6.0 μm, in comparative example 1 for-7.5 μm, in comparative example 2 for-9.5 μm.It addition, be derived from the result of the γ-value (gamma value) of residual film ratio, it be 1.3 in example 4, be 0.6 in embodiment 5.It is derived from the result of the γ-value (gamma value) of the response rate of C=C double bond, is 0.192 in embodiment 3, is 0.177 in comparative example 1.
Utilizing the circuit pattern etching L/S=60/60 μm carried out to make repetition 8 times, attempt stacking, the fluctuating of result most surface is about 30 μm.In the circuit pattern of most surface now, for the composition of comparative example 1, it was observed that the short circuit of copper cash, but for the composition of embodiment 3, it does not have observe short circuit, thus it is speculated that bad problem can be reduced.
[embodiment 12]
The H-1 (1 mass parts) of the embodiment 1 shown in table 1 is replaced into 1,1,3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane (with peroxy radical reaction rate constant=45.4L mole-1·sec-1) (1 mass parts), in addition similarly to Example 1.Its result, sensitivity (necessary light exposure) is 21mJ/cm2, resolution (generally) be 18 μm, resolution (focal shift) be 30 μm, the difference of resolution be 12 μm.
[comparative example 16]
The H-1 (1 mass parts) of the embodiment 1 shown in table 1 is replaced into H-4 (1 mass parts), in addition similarly to Example 1.Its result, sensitivity (necessary light exposure) is 80mJ/cm2, resolution (generally) be 45 μm.
The result of the tone stability of photosensitive polymer combination modulating liquid, embodiment 1 is 1% when 600nm, it is 5% when 630nm, embodiment 3 is 0% when 600nm, it is 5% when 630nm, embodiment 12 is 2% when 600nm, it is 7% when 630nm, comparative example 1 is 0% when 600nm, it is 5% when 630nm, comparative example 2 is-21% when 600nm, it is 3% when 630nm, comparative example 8 is 5% when 600nm, it is 11% when 630nm, comparative example 9 is 11% when 600nm, it is 27% when 630nm, comparative example 16 is-41% when 600nm, it is-8% when 630nm.For comparative example 13,14,15, owing to when the transmitance of common (i), decolouring is very big, if being obtained by the calculating of the transmitance of (i) of the transmitance-comparative example 1 of (ii), comparative example 13 is 12% when 600nm, is 30% when 630nm, comparative example 14 is 16% when 600nm, is 37% when 630nm, and comparative example 15 is 16% when 600nm, is 37% when 630nm.
One of the composition of table 1. photosensitive composite and evaluation result (whole four)
(table 1. has follow-up)
The composition of table 1. photosensitive composite and evaluation result (the two of whole four)
(table 1. has follow-up)
The composition of table 1. photosensitive composite and evaluation result (the three of whole four)
(table 1. has follow-up)
The composition of table 1. photosensitive composite and evaluation result (the four of whole four)
(table 1. terminates)
Table 2. uses composition guide look one of (whole three)
(table 2. has follow-up)
Table 2. uses composition guide look (the two of whole three)
(table 2. has follow-up)
Table 2. uses composition guide look (the three of whole three)
(table 2. terminates)
By the known herein below of result of table 1 and 2.
If by the contrast of embodiment and comparative example it can be seen that use the photosensitive polymer combination of present embodiment, high resolution can be shown, even if during focal shift particularly when exposure, it is also possible to show high resolution.And then, it is also possible to maintain high sensitivity.By using this photosensitive polymer combination, even if be applicable to multilayer wiring, it also is able to when forming circuit by etching method suppress short circuit problem.
Industrial applicability
The photoresist duplexer of present embodiment can show high sensitivity and high resolution, even if particularly exposure time focal shift time also be able to show high resolution, even if the position of focus when therefore exposing due to the warpage of substrate and deformation, the bad problem etc. of setting of exposure device from substrate surface offset time, it is also possible to prevent short circuit problem when forming circuit by etching method, is also possible to prevent the problems such as shortcoming, open circuit, plating be bad when forming circuit by plating method.Therefore, this photoresist duplexer can be suitably used for the manufacture of printed wiring board, flexible base board, leadframe substrate, COF (chip on film) substrate, base plate for encapsulating semiconductor, liquid crystal transparency electrode, liquid crystal TFT wiring, PDP (plasma display) conductive pattern of electrode etc..
Claims (17)
1. a photosensitive polymer combination, it contains (A) alkali-soluble macromolecule, (B) has the compound of ethylenical unsaturated double bonds and (C) Photoepolymerizationinitiater initiater,
The photo-sensitive resin comprising this photosensitive polymer combination is being formed on substrate surface and is being exposed and in the opposing agent pattern that develops and obtain, this substrate surface is being directed at pattern resolution a when focal position carries out this exposure and to the difference of pattern resolution b when carrying out this exposure on the thickness direction of this substrate to the position alignment focal position of substrate offset inboard 300 μm from this substrate surface less than 15 μm.
2. photosensitive polymer combination according to claim 1, it contains by all solids composition quality benchmark of photosensitive polymer combination
Described (A) alkali-soluble macromolecule: 10 mass %～90 mass %；
Described (B) has the compound of ethylenical unsaturated double bonds: 5 mass %～70 mass %；With
Described (C) Photoepolymerizationinitiater initiater: 0.01 mass %～20 mass %.
3. photosensitive polymer combination according to claim 2, its by all solids composition quality benchmark of photosensitive polymer combination possibly together with (D) phenol system derivant: 0.001 mass %～10 mass %.
4. photosensitive polymer combination according to claim 3, wherein, as (D) phenol system derivant, containing the compound shown in following formula (I),
In formula (I), R1Represent optionally substituted, straight chained alkyl, branched alkyl, aryl, cyclohexyl, the straight chained alkyl via divalent linker, the branched alkyl via divalent linker, the cyclohexyl via divalent linker or the aryl via divalent linker, multiple R1Optionally being mutually identical or different, m represents the integer of 0～4, and n represents the integer of more than 1, and when n is 1, A is monovalent organic group, and when n is more than 2, A represents the organic group of more than bivalence, singly-bound or the linking group comprising conjugated bonds.
5. the photosensitive polymer combination according to claim 3 or 4, wherein, as (D) phenol system derivant, containing the compound shown in following formula (II),
In formula (II), R2Represent optionally substituted, straight chained alkyl, branched alkyl, aryl, cyclohexyl, the straight chained alkyl via divalent linker, the branched alkyl via divalent linker, the cyclohexyl via divalent linker or the aryl via divalent linker and R3、R4And R5Represent hydrogen or optionally substituted, straight chained alkyl, branched alkyl, aryl, cyclohexyl, the straight chained alkyl via divalent linker, the branched alkyl via divalent linker, the cyclohexyl via divalent linker or the aryl via divalent linker independently of one another.
6. the photosensitive polymer combination according to claim 3 or 4, wherein, as (D) phenol system derivant, containing the compound shown in following formula (III),
In formula (III), R6And R7Represent optionally substituted, straight chained alkyl, branched alkyl, aryl, cyclohexyl, the straight chained alkyl via divalent linker, the branched alkyl via divalent linker, the cyclohexyl via divalent linker or the aryl via divalent linker, multiple R independently of one another6And R7Optionally being mutually identical or different, p and q represents the integer of 0～4 independently of one another, and B represents singly-bound or the linking group comprising conjugated bonds.
7. a photosensitive polymer combination, it contains by all solids composition quality benchmark of photosensitive polymer combination
(A) alkali-soluble macromolecule: 10 mass %～90 mass %；
(B) there is the compound of ethylenical unsaturated double bonds: 5 mass %～70 mass %；
(C) Photoepolymerizationinitiater initiater: 0.01 mass %～20 mass %；With
(D) phenol system derivant: 0.001 mass %～10 mass %,
As (D) phenol system derivant, containing at least one in the group that the choosing freely compound shown in following formula (II) and the compound shown in following formula (III) form,
In formula (II), R2Represent optionally substituted, straight chained alkyl, branched alkyl, aryl, cyclohexyl, the straight chained alkyl via divalent linker, the branched alkyl via divalent linker, the cyclohexyl via divalent linker or the aryl via divalent linker and R3、R4And R5Represent hydrogen or optionally substituted, straight chained alkyl, branched alkyl, aryl, cyclohexyl, the straight chained alkyl via divalent linker, the branched alkyl via divalent linker, the cyclohexyl via divalent linker or the aryl via divalent linker independently of one another
In formula (III), R6And R7Represent optionally substituted, straight chained alkyl, branched alkyl, aryl, cyclohexyl, the straight chained alkyl via divalent linker, the branched alkyl via divalent linker, the cyclohexyl via divalent linker or the aryl via divalent linker, multiple R independently of one another6And R7Optionally being mutually identical or different, p and q represents the integer of 0～4 independently of one another, and B represents singly-bound or the linking group comprising conjugated bonds.
8. the photosensitive polymer combination according to claim 6 or 7, wherein, in described formula (III), B is singly-bound.
9. the photosensitive polymer combination according to any one of claim 6～8, wherein, in described formula (III), p=q=0.
10. the photosensitive polymer combination according to any one of claim 3～9, wherein, as (D) phenol system derivant, is 20L mole containing the reaction rate constant with peroxy radical-1Second-1Above compound.
11. the photosensitive polymer combination according to any one of claim 1～10, wherein, the high molecular monomer component of (A) alkali-soluble has aromatic hydrocarbyl.
12. the photosensitive polymer combination according to any one of claim 1～11, wherein, as (C) Photoepolymerizationinitiater initiater, containing acridine.
13. a photoresist duplexer, it is at the supporting layer upper strata stacked package photo-sensitive resin containing the photosensitive polymer combination according to any one of claim 1～12.
14. resist a forming method for agent pattern, it includes the photoresist duplexer described in claim 13 is laminated in the lamination process of substrate, the exposure process making the photo-sensitive resin of this photoresist duplexer expose and the developing procedure removed that developed in the unexposed portion of this photo-sensitive resin.
15. the forming method of opposing agent pattern according to claim 14, wherein, for described exposure process, by utilizing the exposure method directly described of depicting pattern or making the exposure method that the image of photomask carries out projecting carry out by lens.
16. the forming method of opposing agent pattern according to claim 15, wherein, for described exposure process, by utilizing the exposure method directly described of depicting pattern to carry out.
17. the photosensitive polymer combination according to any one of claim 1～12, the forming method of its opposing agent pattern undertaken by utilizing the exposure method that depicting pattern is directly described for exposure process.
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Also Published As
| Publication number | Publication date |
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| JP6320425B2 (en) | 2018-05-09 |
| TW201922805A (en) | 2019-06-16 |
| JP6666944B2 (en) | 2020-03-18 |
| WO2015099137A1 (en) | 2015-07-02 |
| TW201533526A (en) | 2015-09-01 |
| CN105793778B (en) | 2021-02-09 |
| KR102248976B1 (en) | 2021-05-06 |
| JPWO2015099137A1 (en) | 2017-03-23 |
| TW201727369A (en) | 2017-08-01 |
| TWI721371B (en) | 2021-03-11 |
| TW201616234A (en) | 2016-05-01 |
| KR20210049995A (en) | 2021-05-06 |
| JP2018120242A (en) | 2018-08-02 |
| KR20160070801A (en) | 2016-06-20 |
| KR102437195B1 (en) | 2022-08-26 |
| TWI592748B (en) | 2017-07-21 |
| TWI674478B (en) | 2019-10-11 |
| CN111596526B (en) | 2023-07-25 |
| KR20180021226A (en) | 2018-02-28 |
| CN111596526A (en) | 2020-08-28 |
| TWI541596B (en) | 2016-07-11 |
| MY174577A (en) | 2020-04-28 |
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