JP2005301101A - Photosensitive resin composition and its use - Google Patents
Photosensitive resin composition and its use Download PDFInfo
- Publication number
- JP2005301101A JP2005301101A JP2004119974A JP2004119974A JP2005301101A JP 2005301101 A JP2005301101 A JP 2005301101A JP 2004119974 A JP2004119974 A JP 2004119974A JP 2004119974 A JP2004119974 A JP 2004119974A JP 2005301101 A JP2005301101 A JP 2005301101A
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- JP
- Japan
- Prior art keywords
- photosensitive resin
- mass
- resin composition
- film
- meth
- 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
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- 239000011342 resin composition Substances 0.000 title claims abstract description 31
- 229920005989 resin Polymers 0.000 claims abstract description 79
- 239000011347 resin Substances 0.000 claims abstract description 79
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- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 239000004020 conductor Substances 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 239000011230 binding agent Substances 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 38
- 239000000758 substrate Substances 0.000 claims description 37
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 29
- 239000011889 copper foil Substances 0.000 claims description 15
- 229920000620 organic polymer Polymers 0.000 claims description 14
- 238000007747 plating Methods 0.000 claims description 11
- 238000005530 etching Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000000539 dimer Substances 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 50
- -1 polyethylene terephthalate Polymers 0.000 description 30
- 238000010030 laminating Methods 0.000 description 23
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 21
- 230000018109 developmental process Effects 0.000 description 20
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- 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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000000975 dye Substances 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
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- 239000002904 solvent Substances 0.000 description 7
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 238000004040 coloring Methods 0.000 description 5
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- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- NNBFNNNWANBMTI-UHFFFAOYSA-M brilliant green Chemical compound OS([O-])(=O)=O.C1=CC(N(CC)CC)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](CC)CC)C=C1 NNBFNNNWANBMTI-UHFFFAOYSA-M 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000004071 soot Substances 0.000 description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 3
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 229920001515 polyalkylene glycol Polymers 0.000 description 3
- 229920006267 polyester film Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- NSWNXQGJAPQOID-UHFFFAOYSA-N 2-(2-chlorophenyl)-4,5-diphenyl-1h-imidazole Chemical class ClC1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 NSWNXQGJAPQOID-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- NREFJJBCYMZUEK-UHFFFAOYSA-N 2-[2-[4-[2-[4-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]phenyl]propan-2-yl]phenoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound C1=CC(OCCOCCOC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCCOCCOC(=O)C(C)=C)C=C1 NREFJJBCYMZUEK-UHFFFAOYSA-N 0.000 description 2
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 2
- LYCNQAIOLGIAFA-UHFFFAOYSA-N 4-[bis[4-(dimethylamino)-2-methylphenyl]methyl]-n,n,3-trimethylaniline Chemical compound CC1=CC(N(C)C)=CC=C1C(C=1C(=CC(=CC=1)N(C)C)C)C1=CC=C(N(C)C)C=C1C LYCNQAIOLGIAFA-UHFFFAOYSA-N 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
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
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- 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
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
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- 239000002585 base Substances 0.000 description 2
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- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 2
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- 150000002366 halogen compounds Chemical class 0.000 description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 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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- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
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- SDTXSEXYPROZSZ-UHFFFAOYSA-N 1,2-dibromo-2-methylpropane Chemical compound CC(C)(Br)CBr SDTXSEXYPROZSZ-UHFFFAOYSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- ATOUXIOKEJWULN-UHFFFAOYSA-N 1,6-diisocyanato-2,2,4-trimethylhexane Chemical compound O=C=NCCC(C)CC(C)(C)CN=C=O ATOUXIOKEJWULN-UHFFFAOYSA-N 0.000 description 1
- IKCJPNPQDRZXHN-UHFFFAOYSA-N 1-[4-(butylamino)phenyl]ethanone Chemical compound CCCCNC1=CC=C(C(C)=O)C=C1 IKCJPNPQDRZXHN-UHFFFAOYSA-N 0.000 description 1
- HUDYANRNMZDQGA-UHFFFAOYSA-N 1-[4-(dimethylamino)phenyl]ethanone Chemical compound CN(C)C1=CC=C(C(C)=O)C=C1 HUDYANRNMZDQGA-UHFFFAOYSA-N 0.000 description 1
- YXZFFTJAHVMMLF-UHFFFAOYSA-N 1-bromo-3-methylbutane Chemical compound CC(C)CCBr YXZFFTJAHVMMLF-UHFFFAOYSA-N 0.000 description 1
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- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
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- RNIPJYFZGXJSDD-UHFFFAOYSA-N 2,4,5-triphenyl-1h-imidazole Chemical group C1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 RNIPJYFZGXJSDD-UHFFFAOYSA-N 0.000 description 1
- DXUMYHZTYVPBEZ-UHFFFAOYSA-N 2,4,6-tris(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 DXUMYHZTYVPBEZ-UHFFFAOYSA-N 0.000 description 1
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- SNFCQJAJPFWBDJ-UHFFFAOYSA-N 2-(4-methoxyphenyl)-4,5-diphenyl-1h-imidazole Chemical class C1=CC(OC)=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 SNFCQJAJPFWBDJ-UHFFFAOYSA-N 0.000 description 1
- QRHHZFRCJDAUNA-UHFFFAOYSA-N 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=CC(OC)=CC=C1C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 QRHHZFRCJDAUNA-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Materials For Photolithography (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
Description
本発明は感光性樹脂組成物、ならびにその用途に関し、詳しくはチップオンフィルム用配線板の製造に適した感光性樹脂積層体、ならびにそれを用いたレジストパターンの形成方法、及びチップオンフィルム用配線板の製造方法に関する。さらに詳しくは、導体幅が３０μｍ以下の微細なパターンを有するチップオンフィルム用配線板の製造方法に関する。 The present invention relates to a photosensitive resin composition and use thereof, and more specifically, a photosensitive resin laminate suitable for manufacturing a chip-on-film wiring board, a resist pattern forming method using the same, and a chip-on-film wiring The present invention relates to a method for manufacturing a plate. More specifically, the present invention relates to a method for manufacturing a chip-on-film wiring board having a fine pattern with a conductor width of 30 μm or less.
本発明においてチップオンフィルム即ちＣＯＦ（Ｃｈｉｐ Ｏｎ Ｆｉｌｍの略称、以下ＣＯＦと略す）とは、半導体ＩＣ（Ｃｈｉｐ）をフィルム状の微細配線板（Ｆｉｌｍ）の上に搭載した複合部品のことである。多くの場合、このようなＣＯＦはさらに大きなリジッド配線板やディスプレイ板に接続して使用されており、電子機器の微細化をさらに進める上で、近年特に注目されている実装形態である。
ここで用いられるフィルム状の微細配線板、即ちＣＯＦ用配線板は、ポリイミド、ポリエステル等の有機ポリマーフィルムと銅箔を積層したフレキシブル基板を材料として作られることから、フレキシブルプリント配線板の一種と言うことができ、特に、回路が微細な点が特徴とされる。
In the present invention, a chip-on-film, that is, COF (abbreviation of Chip On Film, hereinafter abbreviated as COF) is a composite part in which a semiconductor IC (Chip) is mounted on a film-like fine wiring board (Film). In many cases, such a COF is used by being connected to a larger rigid wiring board or display board, and is a mounting form that has been particularly attracting attention in recent years for further miniaturization of electronic devices.
The film-like fine wiring board used here, that is, the wiring board for COF is a kind of flexible printed wiring board because it is made of a flexible substrate obtained by laminating an organic polymer film such as polyimide and polyester and copper foil. In particular, it is characterized by a fine circuit.
また、ＴＡＢ（Ｔａｐｅ Ａｕｔｏｍａｔｅｄ Ｂｏｎｄｉｎｇ）という名称の実装形態があるが、フィルム状の微細配線板に半導体ＩＣを搭載しているという点や、その配線板がさらに別の配線板やディスプレイ板等に接続される等の共通点から、ＣＯＦの一種あるいは別の呼び方と言えるので、本発明では、ＴＡＢも含めた意味で、一括してＣＯＦという表現を採用する。
ＣＯＦ用配線板は、一般的なプリント配線板の場合と同様の製造方法により製造される。
In addition, there is a mounting form called TAB (Tape Automated Bonding), but the fact that a semiconductor IC is mounted on a film-like fine wiring board, and that wiring board is connected to another wiring board, display board, etc. Since it can be said that it is a kind of COF or another way of calling it from the common point such as being used, in the present invention, the expression COF is collectively adopted in the sense including TAB.
The COF wiring board is manufactured by the same manufacturing method as that of a general printed wiring board.
即ち、フレキシブル基板の銅面上に感光性樹脂層を積層し、所望の導体パターンに対応した露光を行い、必要な部分の感光性樹脂を光硬化させる。次に現像により、未露光部分の感光性樹脂を除去した後、エッチングにより硬化レジストに覆われていない基板の被覆銅層を除去したり、またはめっきにより硬化レジストに覆われていない部分にめっき金属を析出させる。最後に、剥離により、硬化レジストを除去して、所望の導体パターンを有する配線板を得る。 That is, a photosensitive resin layer is laminated on the copper surface of the flexible substrate, exposure corresponding to a desired conductor pattern is performed, and a necessary portion of the photosensitive resin is photocured. Next, after the photosensitive resin in the unexposed part is removed by development, the coated copper layer of the substrate not covered with the cured resist is removed by etching, or the plated metal is applied to the part not covered with the cured resist by plating. To precipitate. Finally, the cured resist is removed by peeling to obtain a wiring board having a desired conductor pattern.
フレキシブル基板の銅面上に感光性樹脂を積層する方法としては、液状レジストを塗布、乾燥する方法が多く用いられてきたが、最近リジッド配線板の場合と同様に、生産性や膜厚均一性、品質の点で、感光性樹脂積層体をラミネートする方法が使われ始めた。
感光性樹脂積層体は、支持層と保護層の間に１〜１００μｍの厚みの感光性樹脂層を挟み込んだ積層フィルムである。これをフレキシブル基板にラミネートする際には、保護層を剥離した上で、感光性樹脂層とフレキシブル基板の銅面とが接着する重ね方で、上下1 対のホットロールの間を通すことにより圧着させる。フレキシブル基板の両面に銅が積層されている両面板の場合、1 枚のフレキシブル基板に対して、２枚の感光性樹脂積層体を用いて、両面ラミネートされる。
As a method of laminating a photosensitive resin on the copper surface of a flexible substrate, a method of applying and drying a liquid resist has been used in many cases, but recently, as in the case of rigid wiring boards, productivity and film thickness uniformity are used. In terms of quality, a method of laminating a photosensitive resin laminate has begun to be used.
The photosensitive resin laminate is a laminated film in which a photosensitive resin layer having a thickness of 1 to 100 μm is sandwiched between a support layer and a protective layer. When laminating this on a flexible board, the protective layer is peeled off, and the photosensitive resin layer and the copper surface of the flexible board are bonded together, and then crimped by passing between a pair of upper and lower hot rolls. Let In the case of a double-sided board in which copper is laminated on both sides of the flexible substrate, the double-sided lamination is performed on one flexible substrate using two photosensitive resin laminates.
ラミネ−トにより積層された感光性樹脂層は、露光、現像工程を経て、レジストパタ−ンを形成し、さらにエッチングまたはめっき処理を行い、上述のごとく最終的には硬化レジストを除去して導体パタ−ンを得る。この際、現像後において硬化レジストとフレキシブル基板との境界部分にスソ（硬化レジストフット部）と呼ばれる半硬化レジストが発生することがある。このスソは特にＣＯＦ用のフレキシブル基板や金属スパッタリング基材（多くが銅スパッタリング）上でレジストパターンを形成する時に発生しやすい。このスソが大きく、特に導体ライン幅が３０μｍ以下のファインパターンになると隣同士のスソが接すると解像度不足となり導体パターンのショ−ト不良につながる。また、このスソが部分的に脱落することにより次工程のエッチング工程後、導体パターンのガタツキという問題が発生する。 The photosensitive resin layer laminated by lamination is subjected to exposure and development processes to form a resist pattern, and further subjected to etching or plating treatment, and finally the cured resist is removed as described above to form a conductor pattern. -Get At this time, a semi-cured resist called a soot (cured resist foot portion) may be generated at the boundary between the cured resist and the flexible substrate after development. This soot is particularly likely to occur when a resist pattern is formed on a flexible substrate for COF or a metal sputtering base (mostly copper sputtering). When the width of the conductor is large, especially in a fine pattern with a conductor line width of 30 μm or less, if the adjacent edges contact each other, the resolution becomes insufficient, leading to a short circuit of the conductor pattern. In addition, since the sushi is partially removed, there is a problem that the conductive pattern is not smooth after the next etching process.
プリント配線板製造やパッケージ基板製造の分野においては、感光性樹脂組成物が多数提案されているが（例えば、特許文献１、２、及び３参照）、解像度の観点から微細配線形成用のＣＯＦ用配線板製造用には適さないものであった。また、ＣＯＦ用配線板製造用の感光性樹脂組成物及びプロセスも提案されているが（特許文献４参照）、前述の現像後のスソ抑制という観点では不充分なものであった。
本発明は、現像後の解像性、及び密着性が良好で、且つ、可とう性に優れ、特に、現像後のスソの切れが良いレジストパターンを形成し、ショート不良やガタツキ等の無い良好な導体パターンを形成するために好適な感光性樹脂組成物、及び該組成物からなる感光性樹脂層を有する感光性樹脂積層体を提供すること、ならびに、該積層体を用いたレジストパターンの形成方法、及び微細配線を有する配線板、特にＣＯＦ用配線板の製造方法を提供することを目的とする。 The present invention has a good resolution and adhesion after development, and is excellent in flexibility, and in particular, forms a resist pattern with good severance after development, and is excellent in that there is no short-circuit failure or rattling. A photosensitive resin composition suitable for forming a conductive pattern, a photosensitive resin laminate having a photosensitive resin layer comprising the composition, and formation of a resist pattern using the laminate It is an object of the present invention to provide a method and a method for manufacturing a wiring board having fine wiring, particularly a wiring board for COF.
上記課題を解決するため検討した結果、特定の感光性樹脂組成物を用いることにより、解像性及び密着性が良好でかつ現像後のスソの切れがよいレジストパターンを形成し、良好な導体パターンを形成することが可能なことを見出し、本発明に至った。
即ち、本発明は、以下の感光性樹脂組成物、感光性樹脂積層体、レジストパタ−ン形成方法、及びチップオンフィルム用配線板の製造方法の発明である。
（１）（ａ）カルボキシル基含有量が酸当量で１００〜６００であり、共重合成分としてベンジル（メタ）アクリレートを含有し、かつ、重量平均分子量が５０００〜５０００００であるバインダ−用樹脂：２０〜９０質量％、（ｂ）下記一般式（Ｉ）又は（ＩＩ）で表される化合物群から選択される少なくとも一種の光重合可能な不飽和化合物：３〜７０質量％、ならびに（ｃ）光重合開始剤：０．１〜２０質量％を含有することを特徴とする感光性樹脂組成物。
As a result of studying to solve the above-mentioned problems, by using a specific photosensitive resin composition, a resist pattern having good resolution and adhesion and having good severance after development is formed. The inventors have found that it is possible to form the present invention, and have reached the present invention.
That is, this invention is invention of the manufacturing method of the following photosensitive resin composition, the photosensitive resin laminated body, the resist pattern formation method, and the wiring board for chip-on-film.
(1) (a) Resin for binder having a carboxyl group content of 100 to 600 in terms of acid equivalent, containing benzyl (meth) acrylate as a copolymerization component, and having a weight average molecular weight of 5,000 to 500,000: 20 -90 mass%, (b) at least one photopolymerizable unsaturated compound selected from the group of compounds represented by the following general formula (I) or (II): 3-70 mass%, and (c) light Polymerization initiator: The photosensitive resin composition characterized by containing 0.1-20 mass%.
（式中、Ｒ１及びＲ２はＨ又はＣＨ３であり、これらは同一であっても相違してもよく、ｎ１、ｎ２及びｎ３は３〜２０の整数である。） (In the formula, R 1 and R 2 are H or CH 3 , which may be the same or different, and n 1 , n 2, and n 3 are integers of 3 to 20)
（式中、Ｒ３、Ｒ４はＨ又はＣＨ３であり、これらは同一であっても相違してもよく、ＡはＣ２Ｈ４、ＢはＣＨ２ＣＨ（ＣＨ３）を意味し、ｍ１＋ｍ２は２〜３０の整数、ｍ３＋ｍ４は０〜３０の整数、ｍ１及びｍ２はそれぞれ独立に１〜２９の整数、ｍ３及びｍ４はそれぞれ独立に０〜２９の整数である。なお、−（Ａ−Ｏ）−、及び−（Ｂ−Ｏ）−の繰り返し単位の配列は、ランダムであってもブロックであってもよく、−（Ａ−Ｏ）−、及び−（Ｂ−Ｏ）−の順序は、何れがビスフェニル基側であってもよい。） (Wherein R 3 and R 4 are H or CH 3 , which may be the same or different, A means C 2 H 4 , B means CH 2 CH (CH 3 ), m 1 + m 2 is an integer of 2 to 30, m 3 + m 4 is an integer of 0 to 30, m 1 and m 2 are each independently an integer of 1 to 29, and m 3 and m 4 are each independently 0 to 29. Note that the arrangement of the repeating units of-(A-O)-and-(B-O)-may be random or block,-(A-O)-, and Any order of-(B-O)-may be on the bisphenyl group side.)
（２）（ｃ）光重合開始剤として、下記一般式（ＩＩＩ）で表される２，４，５−トリアリ−ルイミダゾ−ル二量体を含有することを特徴とする上記（１）記載の感光性樹脂組成物。 (2) (c) The 2,4,5-triary imidazole dimer represented by the following general formula (III) is contained as a photopolymerization initiator: Photosensitive resin composition.
（式中、Ｘ、Ｙ、及びＺはそれぞれ独立に水素、アルキル基、アルコキシ基、及びハロゲン基のいずれかを表し、ｐ、ｑ、及びｒはそれぞれ独立に１〜５の整数である。） (In the formula, X, Y, and Z each independently represent any of hydrogen, an alkyl group, an alkoxy group, and a halogen group, and p, q, and r are each independently an integer of 1 to 5).
（３）有機ポリマーフィルムからなる支持層上に上記（１）又は（２）記載の感光性樹脂組成物からなる感光性樹脂層を設けた感光性樹脂積層体。
（４）上記（３）記載の感光性樹脂積層体を用いて、厚みが１０〜１００μｍのフィルムに銅箔を積層したフレキシブル基板に
（Ａ）感光性樹脂積層体をラミネートし、
（Ｂ）所望の導体パターンに対応した露光を行い、露光された部分の感光性樹脂層を光硬化させて硬化レジストを得、
（Ｃ）現像により、未露光部分の感光性樹脂層を除去する
工程を含むレジストパタ−ンの形成方法。
(3) The photosensitive resin laminated body which provided the photosensitive resin layer which consists of a photosensitive resin composition of the said (1) or (2) description on the support layer which consists of an organic polymer film.
(4) Using the photosensitive resin laminate described in (3) above, (A) the photosensitive resin laminate is laminated on a flexible substrate obtained by laminating a copper foil on a film having a thickness of 10 to 100 μm,
(B) The exposure corresponding to a desired conductor pattern is performed, the photosensitive resin layer of the exposed part is photocured, and a cured resist is obtained,
(C) A resist pattern forming method including a step of removing a photosensitive resin layer in an unexposed portion by development.
（５）上記（３）記載の感光性樹脂積層体を用いて、厚みが１０〜１００μｍのフィルムに銅箔を積層したフレキシブル基板に
（Ａ）感光性樹脂積層体をラミネートし、
（Ｂ）所望の導体パターンに対応した露光を行い、露光された部分の感光性樹脂層を光硬化させて硬化レジストを得、
（Ｃ）現像により、未露光部分の感光性樹脂層を除去し、
（Ｄ）エッチングによりフレキシブル基板の硬化レジストに覆われていない部分の銅箔層を除去するか、または、めっきにより硬化レジストに覆われていない部分にめっき金属を析出させた後、
（Ｅ）剥離により、硬化レジストを除去する
工程を含むチップオンフィルム用配線板の製造方法。
(5) Using the photosensitive resin laminate described in (3) above, (A) the photosensitive resin laminate is laminated on a flexible substrate in which a copper foil is laminated on a film having a thickness of 10 to 100 μm,
(B) The exposure corresponding to a desired conductor pattern is performed, the photosensitive resin layer of the exposed part is photocured, and a cured resist is obtained,
(C) The photosensitive resin layer in the unexposed part is removed by development,
(D) After removing the copper foil layer of the portion not covered with the cured resist of the flexible substrate by etching or depositing the plating metal on the portion not covered with the cured resist by plating,
(E) The manufacturing method of the wiring board for chip-on-film including the process of removing a hardening resist by peeling.
本発明により、現像後の解像性、密着性が良好で、且つ、可とう性に優れ、特に、現像後のスソの切れが良いレジストパターンを形成し、ショート不良やガタツキ等の無い良好な導体パターンを形成するために好適な感光性樹脂組成物、及び該組成物からなる感光性樹脂層を有する感光性樹脂積層体を提供することができる。また、該積層体を用いたレジストパターンの形成方法、及び微細配線を有する配線板、特にＣＯＦ用配線板の製造方法を提供することができる。 According to the present invention, the resolution and adhesion after development are good and the flexibility is excellent, and in particular, a resist pattern having good severance after development is formed, and there is no short circuit or rattling. A photosensitive resin composition suitable for forming a conductor pattern and a photosensitive resin laminate having a photosensitive resin layer made of the composition can be provided. In addition, a method of forming a resist pattern using the laminate and a method of manufacturing a wiring board having fine wiring, particularly a COF wiring board can be provided.
以下、本発明について具体的に説明する。本発明で用いられるフレキシブル基板は、ポリイミド、ポリエステル等の有機ポリマーフィルムに銅箔を積層した基板であり、該有機ポリマーフィルムの具体例としては、カプトン（登録商標、東レ・デュポン社製）、ユーピレックス（登録商標、宇部興産製）などのポリイミドからなる有機ポリマーフィルム、並びにポリエチレンテレフタレート、ポリブチレンテレフタレート、及びポリエチレンナフタレート等からなる有機ポリマーフィルムが挙げられる。 Hereinafter, the present invention will be specifically described. The flexible substrate used in the present invention is a substrate obtained by laminating copper foil on an organic polymer film such as polyimide or polyester. Specific examples of the organic polymer film include Kapton (registered trademark, manufactured by Toray DuPont), Upilex. Examples thereof include organic polymer films made of polyimide such as (registered trademark, manufactured by Ube Industries), and organic polymer films made of polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and the like.
有機ポリマーフィルムに銅箔を積層する方法としては、めっき法、キャスティング法、及びラミネート法等が挙げられる。キャスティング法は、銅箔上にポリマー液を塗布した後、乾燥、及び／又は熱反応させることでフレキシブル基板を作製する方法であり、ラミネート法は、銅箔と有機ポリマーフィルムを接着層を介して貼り合わせて作製する方法である。これらの２つの方法は、あらかじめ製造された銅箔を用いることで共通しており、この銅箔の種類により、フレキシブル基板のもともとの銅表面形状が決定される。めっき法は有機ポリマーフィルムにシード層として金属（クロム、銅等）をスパッタリングで作製し、その後、電解めっきにより銅層形成を行う方法である。 Examples of the method for laminating the copper foil on the organic polymer film include a plating method, a casting method, and a laminating method. The casting method is a method of preparing a flexible substrate by applying a polymer solution on a copper foil and then drying and / or heat-reacting. The laminating method is a method of laminating a copper foil and an organic polymer film through an adhesive layer. This is a method of bonding. These two methods are common by using a copper foil manufactured in advance, and the original copper surface shape of the flexible substrate is determined by the type of the copper foil. The plating method is a method in which a metal (chromium, copper, etc.) is formed as a seed layer on an organic polymer film by sputtering, and then a copper layer is formed by electrolytic plating.
ＣＯＦ用配線板のためのフレキシブル基板は、有機ポリマーフィルムの厚みが１０〜１００μｍであり、銅箔の厚みは、１〜３５μｍであることが好ましく、特に好ましくは３〜１８μｍである。
本発明で用いられる感光性樹脂積層体は、支持層と保護層の間に感光性樹脂層を挟み込んだ積層フィルム、又は該積層フィルムから保護層を剥離したものであり、感光性エレメント、感光性フィルム、ドライフィルム（レジスト）あるいはＤＦＲと呼ばれることもある。
In the flexible substrate for the wiring board for COF, the thickness of the organic polymer film is 10 to 100 μm, and the thickness of the copper foil is preferably 1 to 35 μm, particularly preferably 3 to 18 μm.
The photosensitive resin laminate used in the present invention is a laminated film in which a photosensitive resin layer is sandwiched between a support layer and a protective layer, or a protective layer is peeled off from the laminated film. Sometimes called film, dry film (resist) or DFR.
感光性樹脂層の厚みは、高解像度の観点から１〜２０μｍが好ましく、特に好ましくは３〜１５μｍ、さらに好ましくは３〜１０μｍである。感光性樹脂組成物の支持層へのコーティングを容易にするために１μｍ以上が好ましく、感光性樹脂積層体の保管中に該積層体の端面から感光性樹脂層が染み出すエッジフューズ性を抑えて且つ、３０μｍ以下の導体ライン幅の回路を得る上で２０μｍ以下が好ましい。 The thickness of the photosensitive resin layer is preferably 1 to 20 μm, particularly preferably 3 to 15 μm, and more preferably 3 to 10 μm from the viewpoint of high resolution. In order to facilitate the coating of the photosensitive resin composition on the support layer, it is preferably 1 μm or more, and the edge fuse property that the photosensitive resin layer oozes out from the end face of the laminate during storage of the photosensitive resin laminate is suppressed. Moreover, in order to obtain a circuit having a conductor line width of 30 μm or less, 20 μm or less is preferable.
支持層には、平滑性が高く、露光に用いられる活性光線に対して透過性が高い有機ポリマーフィルムが用いられる。支持層のヘ−ズは５．０以下が好ましい。支持層の厚みは、５〜２０μｍが好ましく、特に好ましくは、９〜１６μｍである。支持層としての強度を保つ上で５μｍ以上が好ましく、微細な配線を作るために感光性樹脂の解像性を良好に保つ上で２０μｍ以下が好ましい。
このような支持層に用いられる有機ポリマーフィルムの例としては、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリビニルアルコール、ポリ塩化ビニル、塩化ビニル共重合体、ポリ塩化ビニリデン、塩化ビニリデン共重合体、ポリメタクリル酸メチル共重合体、ポリスチレン、ポリアクリロニトリル、スチレン共重合体、ポリアミド、セルロース誘導体等のフィルムが挙げられる。好ましくは、ポリエチレンテレフタレートフィルムが用いられる。
For the support layer, an organic polymer film having high smoothness and high transparency to actinic rays used for exposure is used. The haze of the support layer is preferably 5.0 or less. The thickness of the support layer is preferably 5 to 20 μm, particularly preferably 9 to 16 μm. 5 μm or more is preferable for maintaining the strength as the support layer, and 20 μm or less is preferable for maintaining good resolution of the photosensitive resin in order to make fine wiring.
Examples of the organic polymer film used in such a support layer include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyvinyl alcohol, polyvinyl chloride, vinyl chloride copolymer, polyvinylidene chloride, vinylidene chloride copolymer, Examples of the film include polymethyl methacrylate copolymer, polystyrene, polyacrylonitrile, styrene copolymer, polyamide, and cellulose derivative. Preferably, a polyethylene terephthalate film is used.
保護層には、平滑性が高く支持層より感光性樹脂層との密着性が低い有機ポリマーフィルムが用いられる。厚みは２５〜６０μｍが好ましく、特に好ましくは３０〜５０μｍである。保護層自体の平滑性を保つ上で２５μｍ以上が好ましく、感光性樹脂積層体のフィルムとしての操作性を保つ上で６０μｍ以下が好ましい。
保護層に用いられるフィルムの例としては、ポリエチレンやポリプロピレン等のポリオレフィンやポリエステルあるいはシリコーン処理又はアルキッド処理により剥離性を向上させたポリエステル等のフィルムが挙げられる。好ましくはポリエチレンが用いられる。
For the protective layer, an organic polymer film having high smoothness and lower adhesion to the photosensitive resin layer than the support layer is used. The thickness is preferably 25 to 60 μm, particularly preferably 30 to 50 μm. In order to maintain the smoothness of the protective layer itself, it is preferably 25 μm or more, and in order to maintain the operability as a film of the photosensitive resin laminate, it is preferably 60 μm or less.
Examples of the film used for the protective layer include polyolefin films such as polyethylene and polypropylene, polyester films, and polyester films whose peelability is improved by silicone treatment or alkyd treatment. Preferably, polyethylene is used.
本発明に用いられる（ａ）バインダ−用樹脂に含まれるカルボキシル基の量は、酸当量で１００〜６００が好ましく、より好ましくは３００〜４５０である。酸当量とは、その中に１当量のカルボキシル基を有する線状重合体の質量を言う。
バインダ−用樹脂中のカルボキシル基は、感光性樹脂層にアルカリ水溶液に対する現像性や剥離性を与えるために必要である。酸当量は、現像耐性、解像性および密着性の観点から１００以上が好ましく、現像性および剥離性の観点から６００以下が好ましい。
The amount of the carboxyl group contained in the binder resin (a) used in the present invention is preferably 100 to 600, more preferably 300 to 450, in terms of acid equivalent. An acid equivalent means the mass of the linear polymer which has a 1 equivalent carboxyl group in it.
The carboxyl group in the binder resin is necessary to give the photosensitive resin layer developability and releasability with respect to an alkaline aqueous solution. The acid equivalent is preferably 100 or more from the viewpoint of development resistance, resolution, and adhesion, and is preferably 600 or less from the viewpoint of developability and peelability.
本発明に用いられる（ａ）バインダ−用樹脂の重量平均分子量は、５０００〜５０００００であることが好ましい。バインダ−用樹脂の重量平均分子量は、解像性の観点から５０００００以下が好ましく、エッジフューズの観点から５０００以上が好ましい。本発明の効果をさらに良く発揮するためには、バインダ−用樹脂の重量平均分子量は、５０００〜１０００００であることがより好ましく、さらに好ましくは５０００〜６００００である。分散度（分子量分布と呼ぶこともある）は下記式の重量平均分子量と数平均分子量の比で表される。
（分散度）＝（重量平均分子量）／（数平均分子量）。
分散度は１〜６程度のものが用いられ好ましくは１〜４である。
The weight average molecular weight of the (a) binder resin used in the present invention is preferably 5,000 to 500,000. The weight average molecular weight of the binder resin is preferably 500000 or less from the viewpoint of resolution, and 5000 or more is preferable from the viewpoint of edge fuse. In order to better exhibit the effects of the present invention, the weight average molecular weight of the binder resin is more preferably 5,000 to 100,000, and still more preferably 5,000 to 60,000. The degree of dispersion (sometimes referred to as molecular weight distribution) is represented by the ratio of the weight average molecular weight to the number average molecular weight of the following formula.
(Dispersity) = (weight average molecular weight) / (number average molecular weight).
The degree of dispersion is about 1 to 6, preferably 1 to 4.
なお、酸当量の測定は、平沼産業（株）製平沼自動滴定装置（ＣＯＭ−５５５）を使用し、０．１ｍｏｌ／Ｌの水酸化ナトリウム水溶液を用いて電位差滴定法により行われる。
分子量は、日本分光（株）製ゲルパ−ミエ−ションクロマトグラフィ−（ＧＰＣ）（ポンプ：Ｇｕｌｌｉｖｅｒ、ＰＵ−１５８０型、カラム：昭和電工（株）製Ｓｈｏｄｅｘ（登録商標）（ＫＦ−８０７、ＫＦ−８０６Ｍ、ＫＦ−８０６Ｍ、ＫＦ−８０２．５）４本直列、移動層溶媒：テトラヒドロフラン、ポリスチレン標準サンプルによる検量線使用）により重量平均分子量（ポリスチレン換算）として求められる。
The acid equivalent is measured by a potentiometric titration method using a Hiranuma automatic titration apparatus (COM-555) manufactured by Hiranuma Sangyo Co., Ltd., and using a 0.1 mol / L sodium hydroxide aqueous solution.
The molecular weight was measured by Gel Permeation Chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko KK (KF-807, KF-806M). , KF-806M, KF-802.5) 4 in series, moving bed solvent: tetrahydrofuran, use of calibration curve with polystyrene standard sample), as a weight average molecular weight (polystyrene conversion).
本発明に用いられる（ａ）バインダー用樹脂は、下記の２種類の単量体の中より、各々一種又はそれ以上の単量体を共重合させることにより得られる。
第一の単量体は、分子中に重合性不飽和基を一個有するカルボン酸又は酸無水物である。例えば、（メタ）アクリル酸、フマル酸、ケイ皮酸、クロトン酸、イタコン酸、マレイン酸無水物、マレイン酸半エステル等が挙げられる。
The resin for binder (a) used in the present invention is obtained by copolymerizing one or more monomers from the following two types of monomers.
The first monomer is a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule. Examples include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid half ester, and the like.
第二の単量体は、非酸性で、分子中に重合性不飽和基を一個有する化合物である。該化合物は、感光性樹脂層の現像性、エッチング及びめっき工程での耐性、硬化膜の可とう性等の種々の特性を保持するように選ばれる。該化合物としては、例えば、メチル（メタ）アクリレ−ト、エチル（メタ）アクリレ−ト、ブチル（メタ）アクリレ−ト、２−エチルヘキシル（メタ）アクリレ−ト等のアルキル（メタ）アクリレ−ト、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、（メタ）アクリロニトリル、ベンジル（メタ）アクリレート、メトキシベンジル（メタ）アクリレート、クロロベンジル（メタ）アクリレート、フルフリル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェニル（メタ）アクリレート、クレジル（メタ）アクリレート、ナフチル（メタ）アクリレートなどのアリール（メタ）アクリレート、フェニル基を有するビニル化合物（例えば、スチレン）等を用いることができる。 The second monomer is a non-acidic compound having one polymerizable unsaturated group in the molecule. The compound is selected so as to maintain various properties such as developability of the photosensitive resin layer, resistance in etching and plating processes, and flexibility of the cured film. Examples of the compound include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like. 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylonitrile, benzyl (meth) acrylate, methoxybenzyl (meth) acrylate, chlorobenzyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydro Aryl (meth) acrylates such as furfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyl (meth) acrylate, cresyl (meth) acrylate, naphthyl (meth) acrylate, vinyl compounds having a phenyl group For example, styrene), or the like can be used.
現像後のスソの切れがよい（スソ無し、もしくは極小）という観点から、ベンジル（メタ）アクリレートを上記第二の単量体として用いることが好ましい。ベンジル（メタ）アクリレートはバインダー用樹脂１分子中に１０質量％〜９５質量％共重合されることが好ましい。現像後のスソ低減の観点から１０質量％以上が好ましく、現像性の観点から９５質量％以下が好ましい。より好ましくは２０質量％以上９０質量％以下である。
本発明に用いられる（ａ）バインダ−用樹脂は、上記第一の単量体と第二の単量体との混合物を、アセトン、メチルエチルケトン、又はイソプロパノ−ル等の溶剤で希釈した溶液に、過酸化ベンゾイル、アゾイソブチロニトリル等のラジカル重合開始剤を適量添加し、過熱攪拌することにより合成を行うことが好ましい。混合物の一部を反応液に滴下しながら合成を行う場合もある。反応終了後、さらに溶剤を加えて、所望の濃度に調整する場合もある。合成手段としては、溶液重合以外に、塊状重合、懸濁重合、又は乳化重合を用いてもよい。
From the viewpoint of good cutting after development (no or minimum), it is preferable to use benzyl (meth) acrylate as the second monomer. It is preferable that 10% by mass to 95% by mass of benzyl (meth) acrylate is copolymerized in one molecule of the binder resin. 10 mass% or more is preferable from a viewpoint of the soot reduction after image development, and 95 mass% or less is preferable from a developability viewpoint. More preferably, it is 20 mass% or more and 90 mass% or less.
The resin for binder (a) used in the present invention is a solution obtained by diluting a mixture of the first monomer and the second monomer with a solvent such as acetone, methyl ethyl ketone, or isopropanol. It is preferable to carry out the synthesis by adding an appropriate amount of a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile and stirring with heating. In some cases, the synthesis is performed while a part of the mixture is dropped into the reaction solution. After completion of the reaction, a solvent may be further added to adjust to a desired concentration. As a synthesis means, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.
本発明に用いられる（ａ）バインダ−用樹脂の感光性樹脂組成物全体に対する割合は、２０〜９０質量％の範囲であり、好ましくは３０〜７０質量％である。露光、現像によって形成されるレジストパターンが、レジストとしての特性、例えば、テンティング、エッチング及び各種めっき工程において十分な耐性等を有するという観点から２０質量％以上９０質量％以下が好ましい。
本発明において、（ｂ）下記一般式（Ｉ）又は（ＩＩ）で表される化合物群から選択される少なくとも１種の光重合可能な不飽和化合物を含有していることは、高解像度の観点から好ましい。
The ratio of the (a) binder resin used in the present invention to the entire photosensitive resin composition is in the range of 20 to 90% by mass, preferably 30 to 70% by mass. The resist pattern formed by exposure and development is preferably 20% by mass or more and 90% by mass or less from the viewpoint that the resist pattern has sufficient resistance as a resist, for example, tenting, etching, and various plating processes.
In the present invention, (b) containing at least one photopolymerizable unsaturated compound selected from the group of compounds represented by the following general formula (I) or (II) is a high resolution viewpoint. To preferred.
（式中、Ｒ１及びＲ２はＨ又はＣＨ３であり、これらは同一であっても相違してもよく、ｎ１、ｎ２、及びｎ３はそれぞれ独立に３〜２０の整数である。） (Wherein R 1 and R 2 are H or CH 3 , which may be the same or different, and n 1 , n 2 , and n 3 are each independently an integer of 3-20. .)
（式中、Ｒ３及びＲ４はＨ又はＣＨ３であり、これらは同一であっても相違してもよく、ＡはＣ２Ｈ４、ＢはＣＨ２ＣＨ（ＣＨ３）を意味し、ｍ１＋ｍ２は２〜３０の整数、ｍ３＋ｍ４は０〜３０の整数、ｍ１及びｍ２はそれぞれ独立に１〜２９の整数、ｍ３及びｍ４はそれぞれ独立に０〜２９の整数である。なお、−（Ａ−Ｏ）−、及び−（Ｂ−Ｏ）−の繰り返し単位の配列は、ランダムであってもブロックであってもよく、−（Ａ−Ｏ）−、及び−（Ｂ−Ｏ）−の順序は、何れがビスフェニル基側であってもよい。） (Wherein R 3 and R 4 are H or CH 3 , which may be the same or different, A means C 2 H 4 , B means CH 2 CH (CH 3 ), m 1 + m 2 is an integer of 2 to 30, m 3 + m 4 is an integer of 0 to 30, m 1 and m 2 are each independently an integer of 1 to 29, and m 3 and m 4 are each independently 0 to 29. Note that the arrangement of the repeating units of-(A-O)-and-(B-O)-may be random or block,-(A-O)-, and Any order of-(B-O)-may be on the bisphenyl group side.)
一般式（Ｉ）で表される化合物は、沸点、臭気の観点から、ｎ１、ｎ２、及びｎ３が、３以上であることが好ましい。単位質量あたりの光活性部位の濃度に起因する感度の観点からｎ１、ｎ２、及びｎ３が、２０以下であることが好ましい。本発明に用いられる一般式（Ｉ）で表される化合物の具体例としては、例えば、平均１２モルのプロピレンオキサイドを付加したポリプロピレングリコ−ルの両端にエチレンオキサイドをそれぞれ平均３モルずつ付加したグリコ−ルのジメタクリレ−トが好ましいものとして挙げられる。 In the compound represented by the general formula (I), n 1 , n 2 , and n 3 are preferably 3 or more from the viewpoints of boiling point and odor. From the viewpoint of sensitivity due to the concentration of the photoactive site per unit mass, n 1 , n 2 , and n 3 are preferably 20 or less. Specific examples of the compound represented by the general formula (I) used in the present invention include, for example, a glycol having an average of 3 moles of ethylene oxide added to both ends of polypropylene glycol having an average of 12 moles of propylene oxide added. -Dimethacrylate of benzene is preferred.
一般式（ＩＩ）で表される化合物は感度の観点からｍ１＋ｍ２及びｍ３＋ｍ４が３０以下が好ましい。
本発明に用いられる一般式（ＩＩ）で表される化合物の具体例としては、ビスフェノ−ルＡの両端にそれぞれ平均２モルずつのプロピレンオキサイドと平均６モルずつのエチレンオキサイドを付加したポリアルキレングリコ−ルのジメタクリレ−トや、ビスフェノ−ルＡの両端にそれぞれ平均５モルずつのエチレンオキサイドを付加したポリエチレングリコ−ルのジメタクリレ−ト（新中村化学工業（株）製ＮＫエステルＢＰＥ−５００）及びビスフェノ−ルＡの両端にそれぞれ平均２モルのエチレンオキサイドを付加したポリエチレングリコ−ルのジメタクリレ−ト（新中村化学工業（株）製ＮＫエステルＢＰＥ−２００）がある。
In the compound represented by the general formula (II), m 1 + m 2 and m 3 + m 4 are preferably 30 or less from the viewpoint of sensitivity.
Specific examples of the compound represented by the general formula (II) used in the present invention include polyalkylene glycols each having an average of 2 moles of propylene oxide and an average of 6 moles of ethylene oxide added to both ends of bisphenol A. Dimethacrylate of polyethylene, dimethacrylate of polyethylene glycol with an average of 5 moles of ethylene oxide added to each end of bisphenol A (NK ester BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.) and There is a polyethylene glycol dimethacrylate (NK ester BPE-200 manufactured by Shin-Nakamura Chemical Co., Ltd.) having an average of 2 moles of ethylene oxide added to both ends of bisphenol A.
（ｂ）前記一般式（Ｉ）又は（ＩＩ）で表される化合物群から選択される少なくとも１種の光重合可能な不飽和化合物においては、解像度と密着性との両立の観点から一般式（Ｉ）で表される化合物と一般式（ＩＩ）で表される化合物とを同時に用いることが好ましい。 (B) In at least one photopolymerizable unsaturated compound selected from the group of compounds represented by the general formula (I) or (II), the general formula ( It is preferable to use the compound represented by I) and the compound represented by the general formula (II) at the same time.
本発明の感光性樹脂組成物には、（ｂ）前記一般式（Ｉ）又は（ＩＩ）で表される化合物群から選択される少なくとも１種の光重合可能な不飽和化合物以外に、下記に示される光重合可能な不飽和化合物を同時に併用することもできる。例えば、１，６−ヘキサンジオ−ルジ（メタ）アクリレート、１，４−シクロヘキサンジオ−ルジ（メタ）アクリレート、ポリプロピレングリコ−ルジ（メタ）アクリレート、ポリエチレングリコ−ルジ（メタ）アクリレート、２−ジ（ｐ−ヒドロキシフェニル）プロパンジ（メタ）アクリレート、グリセロ−ルトリ（メタ）アクリレート、トリメチロ−ルプロパントリ（メタ）アクリレート、ポリオキシプロピルトリメチロ−ルプロパントリ（メタ）アクリレート、ポリオキシエチルトリメチロ−ルプロパントリアクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリト−ルペンタ（メタ）アクリレート、トリメチロ−ルプロパントリグリシジルエ−テルトリ（メタ）アクリレート、ビスフェノ−ルＡジグリシジルエ−テルジ（メタ）アクリレート、β−ヒドロキシプロピル−β’−（アクリロイルキシ）プロピルフタレート、フェノキシポリエチレングリコ−ル（メタ）アクリレート、ノニルフェノキシポリエチレングリコール（メタ）アクリレート、ノニルフェノキシポリアルキレングリコール（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート等が挙げられる。 In addition to at least one photopolymerizable unsaturated compound selected from the group of compounds represented by (b) the general formula (I) or (II), the photosensitive resin composition of the present invention includes: The photopolymerizable unsaturated compounds shown can also be used in combination. For example, 1,6-hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2-di (p -Hydroxyphenyl) propane di (meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyoxypropyltrimethylolpropane tri (meth) acrylate, polyoxyethyltrimethylolpropane triacrylate, penta Erythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl ether tertri (meth) acrylate, bisphenol A jigly Dilether-terdi (meth) acrylate, β-hydroxypropyl-β ′-(acryloyloxy) propyl phthalate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyalkylene glycol (meth) Examples thereof include acrylate and polypropylene glycol mono (meth) acrylate.
また、ウレタン化合物も挙げられる。ウレタン化合物としては、例えば、ヘキサメチレンジイソシアネ−ト、トリレンジイソシアネ−ト、又は２，２，４−トリメチルヘキサメチレンジイソシアネ−ト等のジイソシアネ−ト化合物と、一分子中にヒドロキシル基と（メタ）アクリル基を有する化合物（２−ヒドロキシプロピルアクリレート、オリゴプロピレングリコ−ルモノメタクリレ−ト等）との反応で得られるウレタン化合物等が挙げられる。具体的には、ヘキサメチレンジイソシアネ−トとオリゴプロピレングリコ−ルモノメタクリレート（日本油脂（株）製、ブレンマ−ＰＰ１０００）との反応物がある。 Moreover, a urethane compound is also mentioned. Examples of the urethane compound include a diisocyanate compound such as hexamethylene diisocyanate, tolylene diisocyanate, or 2,2,4-trimethylhexamethylene diisocyanate, and hydroxyl group in one molecule. And urethane compounds obtained by reaction of a group with a compound having a (meth) acryl group (such as 2-hydroxypropyl acrylate and oligopropylene glycol monomethacrylate). Specifically, there is a reaction product of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (manufactured by NOF Corporation, Bremma-PP1000).
（ｂ）前記一般式（Ｉ）又は（ＩＩ）で表される化合物群から選択される少なくとも１種の光重合可能な不飽和化合物の、感光性樹脂組成物全体に対する割合は、３〜７０質量％の範囲である。解像度の観点から３質量％以上であり、ＣＯＦやフレキシブル配線板用としてのレジストパターンの可とう性の観点から７０質量％以下である。より好ましくは３質量％以上、３０質量％以下である。また（ｂ）成分を含めた光重合性不飽和化合物全体の感光性樹脂組成物全体に対する割合は、感度の観点から３質量％以上が好ましく、エッジフューズの観点から７０質量％以下が好ましい。より好ましくは１０〜６０質量％、さらに好ましくは１５〜５５質量％である。
本発明において、（ｃ）光重合開始剤として、下記一般式（ＩＩＩ）で表される２，４，５−トリアリ−ルイミダゾ−ル二量体を含むことは高解像度の観点から好ましい実施態様である。
(B) The ratio of the at least one photopolymerizable unsaturated compound selected from the compound group represented by the general formula (I) or (II) to the entire photosensitive resin composition is 3 to 70 masses. % Range. It is 3% by mass or more from the viewpoint of resolution, and 70% by mass or less from the viewpoint of the flexibility of the resist pattern for COF and flexible wiring boards. More preferably, it is 3 mass% or more and 30 mass% or less. Further, the ratio of the entire photopolymerizable unsaturated compound including the component (b) to the entire photosensitive resin composition is preferably 3% by mass or more from the viewpoint of sensitivity, and preferably 70% by mass or less from the viewpoint of edge fuse. More preferably, it is 10-60 mass%, More preferably, it is 15-55 mass%.
In the present invention, (c) a 2,4,5-triarylimidazole dimer represented by the following general formula (III) as a photopolymerization initiator is a preferred embodiment from the viewpoint of high resolution. is there.
（式中、Ｘ、Ｙ、及びＺはそれぞれ独立に水素、アルキル基、アルコキシ基及びハロゲン基のいずれかを表し、ｐ、ｑ、及びｒはそれぞれ独立に１〜５の整数である。）
上記一般式（ＩＩＩ）で表される化合物においては、２個のロフィン基を結合する共有結合は、１，１’−、１，２’−、１，４’−、２，２’−、２，４’−又は４，４’−位についているが、１，２’−位についている化合物が好ましい。
２，４，５−トリアリ−ルイミダゾ−ル二量体には、例えば、２−（ｏ−クロロフェニル）−４，５−ジフェニルイミダゾ−ル二量体、２−（ｏ−クロロフェニル）−４，５−ビス−（ｍ−メトキシフェニル）イミダゾ−ル二量体、２−（ｐ−メトシキフェニル）−４，５−ジフェニルイミダゾ−ル二量体等があるが、特に、２−（ｏ−クロロフェニル）−４，５−ジフェニルイミダゾ−ル二量体が好ましい。
(In the formula, X, Y, and Z each independently represent any of hydrogen, an alkyl group, an alkoxy group, and a halogen group, and p, q, and r are each independently an integer of 1-5.)
In the compound represented by the general formula (III), the covalent bond for bonding two lophine groups is 1,1′-, 1,2′-, 1,4′-, 2,2′-, Although it is in the 2,4′- or 4,4′-position, a compound in the 1,2′-position is preferred.
Examples of 2,4,5-triarylimidazole dimers include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5. -Bis- (m-methoxyphenyl) imidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, etc., and in particular, 2- (o-chlorophenyl) ) -4,5-diphenylimidazole dimer is preferred.
本発明に用いられる（ｃ）光重合開始剤としては、前記した一般式（ＩＩＩ）で表される２，４，５−トリアリ−ルイミダゾ−ル二量体とｐ−アミノフェニルケトンを併用する系が好ましい。ｐ−アミノフェニルケトンとしては、例えば、ｐ−アミノベンゾフェノン、ｐ−ブチルアミノアセトフェノン、ｐ−ジメチルアミノアセトフェノン、ｐ−ジメチルアミノベンゾフェノン、ｐ，ｐ’−ビス（エチルアミノ）ベンゾフェノン、ｐ，ｐ’−ビス（ジメチルアミノ）ベンゾフェノン［ミヒラーズケトン］、ｐ，ｐ’−ビス（ジエチルアミノ）ベンゾフェノン、ｐ，ｐ’−ビス（ジブチルアミノ）ベンゾフェノン等があげられる。 (C) The photopolymerization initiator used in the present invention is a system in which 2,4,5-triary-imidazole dimer represented by the general formula (III) and p-aminophenyl ketone are used in combination. Is preferred. Examples of p-aminophenyl ketone include p-aminobenzophenone, p-butylaminoacetophenone, p-dimethylaminoacetophenone, p-dimethylaminobenzophenone, p, p'-bis (ethylamino) benzophenone, p, p'- Bis (dimethylamino) benzophenone [Michler's ketone], p, p′-bis (diethylamino) benzophenone, p, p′-bis (dibutylamino) benzophenone, and the like.
また、上記で示された化合物以外に、他の光重合開始剤との併用も可能である。ここでの光重合開始剤とは、各種の活性光線、例えば紫外線等により活性化され、重合を開始する化合物である。
他の光重合開始剤としては、例えば、２−エチルアントラキノン、２−ｔｅｒｔ−ブチルアントラキノン等のキノン類、ベンゾフェノン等の芳香族ケトン類、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル等のベンゾインエーテル類、９−フェニルアクリジン等のアクリジン化合物、ベンジルジメチルケタ−ル、ベンジルジエチルケタ−ル等がある。
In addition to the compounds shown above, other photopolymerization initiators can be used in combination. Here, the photopolymerization initiator is a compound that is activated by various actinic rays, for example, ultraviolet rays, and starts polymerization.
Other photopolymerization initiators include, for example, quinones such as 2-ethylanthraquinone and 2-tert-butylanthraquinone, aromatic ketones such as benzophenone, benzoin ethers such as benzoin, benzoin methyl ether and benzoin ethyl ether, Examples include acridine compounds such as 9-phenylacridine, benzyldimethylketal, and benzyldiethylketal.
また、例えば、チオキサントン、２，４−ジエチルチオキサントン、２−クロロチオキサントン等のチオキサントン類と、ジメチルアミノ安息香酸アルキルエステル化合物等の三級アミン化合物との組み合わせもある。
また、１−フェニル−１、２−プロパンジオン−２−Ｏ−ベンゾイルオキシム、１−フェニル−１、２−プロパンジオン−２−（Ｏ−エトキシカルボニル）オキシム等のオキシムエステル類等がある。また、Ｎ−アリ−ル−α−アミノ酸化合物も用いることも可能であり、これらの中では、Ｎ−フェニルグリシンが特に好ましい。
Further, for example, there are combinations of thioxanthones such as thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and tertiary amine compounds such as dimethylaminobenzoic acid alkyl ester compounds.
Further, there are oxime esters such as 1-phenyl-1,2-propanedione-2-O-benzoyloxime and 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime. Further, N-aryl-α-amino acid compounds can also be used, and among these, N-phenylglycine is particularly preferable.
本発明の感光性樹脂組成物において、（ｃ）光重合開始剤の割合は、０．１質量％〜２０質量％である必要がある。この割合が０．１質量％未満であると十分な感度が得られない。また、この割合が２０質量％を超えると、露光時にフォトマスクを通した光の回折によるかぶりが発生しやすくなり、その結果として解像性が悪化する。 In the photosensitive resin composition of the present invention, the ratio of the (c) photopolymerization initiator needs to be 0.1% by mass to 20% by mass. If this ratio is less than 0.1% by mass, sufficient sensitivity cannot be obtained. On the other hand, when the ratio exceeds 20% by mass, fogging due to diffraction of light passing through the photomask at the time of exposure tends to occur, and as a result, resolution is deteriorated.
本発明における感光性樹脂組成物には、染料、顔料等の着色物質を含有させることもできる。用いられる着色物質としては、例えば、フクシン、フタロシアニングリ−ン、オ−ラミン塩基、カルコキシドグリ−ンＳ，パラマジエンタ、クリスタルバイオレット、メチルオレンジ、ナイルブル−２Ｂ、ビクトリアブル−、マラカイトグリ−ン（保土ヶ谷化学（株）製 アイゼン（登録商標） ＭＡＬＡＣＨＩＴＥ ＧＲＥＥＮ）、ベイシックブル−２０、ダイアモンドグリ−ン（保土ヶ谷化学（株）製 アイゼン（登録商標） ＤＩＡＭＯＮＤ ＧＲＥＥＮ ＧＨ）等が挙げられる。 The photosensitive resin composition in the present invention may contain coloring substances such as dyes and pigments. Examples of the coloring substance used include fuchsin, phthalocyanine green, olamine base, chalcoxide green S, paramadienta, crystal violet, methyl orange, Nile Bull-2B, Victoria Bull, Malachite Green (Hodogaya Chemical ( Eisen (registered trademark) MALACHITE GREEN), Basic Bull-20, Diamond Green (Hozengaya Chemical Co., Ltd. Eisen (registered trademark) DIAMOND GREEN GH), and the like.
本発明における感光性樹脂組成物には、光照射により発色する発色系染料を含有させることもできる。用いられる発色系染料としては、例えば、ロイコ染料又はフルオラン染料と、ハロゲン化合物の組み合わせがある。
ロイコ染料としては、例えば、トリス（４−ジメチルアミノ−２−メチルフェニル）メタン［ロイコクリスタルバイオレット］、トリス（４−ジメチルアミノ−２−メチルフェニル）メタン［ロイコマラカイトグリ−ン］等が挙げられる。
ハロゲン化合物としては、臭化アミル、臭化イソアミル、臭化イソブチレン、臭化エチレン、臭化ジフェニルメチル、臭化ベンザル、臭化メチレン、トリブロモメチルフェニルスルフォン、四臭化炭素、トリス（２，３−ジブロモプロピル）ホスフェ−ト、トリクロロアセトアミド、ヨウ化アミル、ヨウ化イソブチル、１，１，１−トリクロロ−２，２−ビス（ｐ−クロロフェニル）エタン、ヘキサクロロエタン、トリアジン化合物等が挙げられる。該トリアジン化合物としては、２，４，６−トリス（トリクロロメチル）−ｓ−トリアジン、２−（４−メトキシフェニル）−４，６−ビス（トリクロロメチル）−ｓ−トリアジンが挙げられる。
The photosensitive resin composition in the present invention may contain a coloring dye that develops color when irradiated with light. Examples of the coloring dye used include a combination of a leuco dye or a fluorane dye and a halogen compound.
Examples of the leuco dye include tris (4-dimethylamino-2-methylphenyl) methane [leuco crystal violet], tris (4-dimethylamino-2-methylphenyl) methane [leucomalachite green], and the like. .
Halogen compounds include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2,3 -Dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, hexachloroethane, triazine compounds and the like. Examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine and 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine.
このような発色系染料の中でも、トリブロモメチルフェニルスルフォンとロイコ染料との組み合わせや、トリアジン化合物とロイコ染料との組み合わせが有用である。
本発明における感光性樹脂組成物の熱安定性、保存安定性を向上させるために、感光性樹脂組成物にラジカル重合禁止剤を含有させることは好ましいことである。
このようなラジカル重合禁止剤としては、例えば、ｐ−メトキシフェノ−ル、ハイドロキノン、ピロガロ−ル、ナフチルアミン、ｔｅｒｔ−ブチルカテコ−ル、塩化第一銅、２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾ−ル、２，２’−メチレンビス（４−エチル−６−ｔｅｒｔ−ブチルフェノ−ル）、２，２’−メチレンビス（４−メチル−６−ｔｅｒｔ−ブチルフェノ−ル）、ジフェニルニトロソアミン等が挙げられる。
Among such coloring dyes, a combination of tribromomethylphenylsulfone and a leuco dye or a combination of a triazine compound and a leuco dye is useful.
In order to improve the thermal stability and storage stability of the photosensitive resin composition in the present invention, it is preferable that the photosensitive resin composition contains a radical polymerization inhibitor.
Examples of such radical polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p- Examples include cresol, 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), diphenylnitrosamine and the like. .
また、本発明の感光性樹脂組成物に、必要に応じて可塑剤等の添加剤を含有させることもできる。そのような添加剤としては、例えば、ジエチルフタレ−ト等のフタル酸エステル類やｐ−トルエンスルホンアミド、ポリプロピレングリコ−ル、ポリエチレングリコ−ルモノアルキルエ−テル等が挙げられる。
感光性樹脂積層体を得るには、上記感光性樹脂組成物をメチルエチルケトン等の適当な溶媒に溶解し、前述の支持層上に塗工し乾燥工程を経て溶媒を除去し、支持層面とは反対側の感光性樹脂層表面に、前述の保護層を積層して得られる。支持層よりも保護層の方が感光性樹脂層との密着力が充分小さく、容易に剥離できることがこの保護層としての重要な特性である。
Moreover, the photosensitive resin composition of this invention can also be made to contain additives, such as a plasticizer, as needed. Examples of such additives include phthalic acid esters such as diethyl phthalate, p-toluenesulfonamide, polypropylene glycol, polyethylene glycol monoalkyl ether, and the like.
In order to obtain a photosensitive resin laminate, the above photosensitive resin composition is dissolved in a suitable solvent such as methyl ethyl ketone, coated on the above-mentioned support layer, the solvent is removed through a drying step, and the surface opposite to the support layer surface is obtained. It is obtained by laminating the above protective layer on the surface of the photosensitive resin layer on the side. An important characteristic of this protective layer is that the protective layer has a sufficiently lower adhesion to the photosensitive resin layer than the support layer and can be easily peeled off.
次に、レジストパターンの形成方法、及びＣＯＦ用配線板の製造方法の具体的な例を説明する。
（Ａ）ラミネート工程：感光性樹脂積層体の保護層を剥がしながら感光性樹脂層とフレキシブル基板の銅面とが接着する重ね方で、上下１対のラミネートロールの間を通すことにより圧着させる。
該ラミネートロールの温度は５０〜１２０℃、ラミネート速度は０．１〜６ｍ／分であることが好ましい。上下１対の該ラミネートロールは、エアーシリンダー、あるいはばねによりピンチされており、圧力はラミネートロールの単位長さ当たりの圧力として、０．１〜１ＭＰａ／ｃｍが好ましく、０．２〜０．５ＭＰａ／ｃｍがより好ましい。
Next, specific examples of a resist pattern forming method and a COF wiring board manufacturing method will be described.
(A) Laminating step: In a method of laminating the photosensitive resin laminate and the copper surface of the flexible substrate while peeling off the protective layer of the photosensitive resin laminate, pressure bonding is performed by passing between a pair of upper and lower laminating rolls.
The temperature of the laminating roll is preferably 50 to 120 ° C., and the laminating speed is preferably 0.1 to 6 m / min. The pair of upper and lower laminating rolls are pinched by an air cylinder or a spring, and the pressure is preferably 0.1-1 MPa / cm as the pressure per unit length of the laminating roll, 0.2-0.5 MPa. / Cm is more preferable.
ラミネーターとしては、１対のラミネートロールを用いる１段式ラミネーター、２対以上のラミネートロールを用いる多段式ラミネーター、ラミネートする部分を容器で密閉した上で真空ポンプで減圧あるいは真空にする真空ラミネーター等が使用される。ラミネート時のエアーの混入を抑制する上で、真空ラミネーターが好ましい。
また、感光性樹脂積層体をフレキシブル基板にラミネートする前に、該基板との密着性を高めるために種々の処理（前処理）をすることがある。例えば、銅を腐食させる能力を持つ酸性液を前処理液として使用し、必要に応じ、２５〜５０℃に加温して、浸漬法やスプレー法でフレキシブル基板を処理する。
Laminators include a one-stage laminator that uses a pair of laminate rolls, a multi-stage laminator that uses two or more pairs of laminate rolls, a vacuum laminator that seals the part to be laminated with a container and then depressurizes or evacuates it with a vacuum pump, etc. used. A vacuum laminator is preferable in order to suppress air mixing during lamination.
In addition, before laminating the photosensitive resin laminate on the flexible substrate, various treatments (pretreatment) may be performed in order to improve the adhesion to the substrate. For example, an acidic liquid having the ability to corrode copper is used as a pretreatment liquid, heated to 25 to 50 ° C. as necessary, and the flexible substrate is treated by an immersion method or a spray method.
該前処理液の成分としては、硫酸と過酸化水素水の混合液、過硫酸アンモニウムや過硫酸ナトリウムの水溶液、過硫酸アンモニウムや過硫酸ナトリウムの水溶液と硫酸の混合液、硝酸と硝酸金属塩と有機酸の混合物水溶液、酢酸金属塩と有機酸の混合物水溶液等が挙げられ、該有機酸としては、ギ酸、酢酸、リンゴ酸、アクリル酸、グリコール酸、マレイン酸、イタコン酸、無水マレイン酸等が挙げられる。
化学研磨剤、ソフトエッチング剤あるいは表面粗化剤として市販されている薬液も上記成分を含むものであれば使用できる。例としては、ＣＰＥ−９００、ＣＰＥ−５００（いずれも三菱ガス化学製、商品名）、ＣＺ−８１００、ＣＢ−８０１（いずれもメック製、商品名）が挙げられる。
The components of the pretreatment liquid include a mixed solution of sulfuric acid and hydrogen peroxide, an aqueous solution of ammonium persulfate or sodium persulfate, a mixed solution of an aqueous solution of ammonium persulfate or sodium persulfate and sulfuric acid, nitric acid, metal nitrate and organic acid. Examples of the organic acid include formic acid, acetic acid, malic acid, acrylic acid, glycolic acid, maleic acid, itaconic acid, maleic anhydride, and the like. .
A chemical solution commercially available as a chemical abrasive, a soft etching agent or a surface roughening agent can be used as long as it contains the above components. Examples include CPE-900, CPE-500 (both manufactured by Mitsubishi Gas Chemical Co., Ltd., trade names), CZ-8100, and CB-801 (both manufactured by MEC, trade names).
（Ｂ）露光工程：所望の導体パターンを活性光線を用いて露光する。該活性光線としては、紫外線が好ましい。露光方法としては、導体パターンが描画されたフォトマスクを、フレキシブル基板に圧着された感光性樹脂積層体の支持層上に微小なギャップを介して乗せた状態、あるいは密着させた状態で露光する。また、投影レンズを用いてフォトマスク像を該感光性樹脂積層体の感光性樹脂層に結像させて露光する方法でもよい。フォトマスク像を投影して露光する場合は、該積層体から支持層を剥離して露光しても良いし、支持層がついたまま露光しても良い。紫外線光源としては、高圧水銀灯、超高圧水銀灯、紫外線蛍光灯、カーボンアーク灯、キセノンランプなどが挙げられる。より微細なレジストパターンを得るためには平行光光源を用いるのが好ましい。 (B) Exposure process: A desired conductor pattern is exposed using actinic rays. As the actinic ray, ultraviolet rays are preferable. As an exposure method, exposure is performed in a state in which a photomask on which a conductor pattern is drawn is placed on or in close contact with a support layer of a photosensitive resin laminate that is pressure-bonded to a flexible substrate. Alternatively, a photomask image may be formed on the photosensitive resin layer of the photosensitive resin laminate using a projection lens and exposed. In the case of exposing by projecting a photomask image, the support layer may be peeled off from the laminate, and the exposure may be performed with the support layer attached. Examples of the ultraviolet light source include a high pressure mercury lamp, an ultra high pressure mercury lamp, an ultraviolet fluorescent lamp, a carbon arc lamp, and a xenon lamp. In order to obtain a finer resist pattern, it is preferable to use a parallel light source.
（Ｃ）現像工程：支持層が残っている場合は、感光性樹脂積層体から支持層を剥離した後、アルカリ現像液を用いて感光性樹脂層の未露光部分を溶解または分散除去して、硬化レジストパターンをフレキシブル基板上に形成する。
現像工程で用いられるアルカリ現像液としては、炭酸ナトリウム、炭酸カリウム、水酸化ナトリウム、水酸化カリウム等の水溶液が挙げられる。最も一般的には、０．２〜２質量％の炭酸ナトリウム水溶液が用いられる。
現像後の水洗水は、レジストパターンの密着性、解像度、裾引きの観点から脱イオン化していない水が好ましい。例えば水道水があげられる。ここまででの工程でフレキシブル基板上にレジストパターンを形成することができるが、ＣＯＦ用配線板を製造する場合は、さらに以下の工程を実施する。
(C) Development step: When the support layer remains, after peeling the support layer from the photosensitive resin laminate, the unexposed portion of the photosensitive resin layer is dissolved or dispersed and removed using an alkali developer, A cured resist pattern is formed on the flexible substrate.
Examples of the alkaline developer used in the development step include aqueous solutions of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and the like. Most commonly, a 0.2 to 2% by weight aqueous sodium carbonate solution is used.
The washing water after development is preferably water that has not been deionized from the viewpoints of resist pattern adhesion, resolution, and tailing. An example is tap water. Although the resist pattern can be formed on the flexible substrate by the steps up to here, the following steps are further performed when manufacturing the wiring board for COF.
（Ｄ）回路（導体パターン）形成工程：フレキシブル基板上に形成された硬化レジストパターン上からエッチング液を用いて該硬化レジストパターンに覆われていない銅面をエッチングする、またはレジストパターンによって覆われていない銅面に銅、はんだ、ニッケルおよび錫等のめっき処理を行う。 (D) Circuit (conductor pattern) forming step: Etching the copper surface not covered with the cured resist pattern from the cured resist pattern formed on the flexible substrate using an etching solution, or covered with the resist pattern Plating treatment of copper, solder, nickel, tin, etc. on a copper surface that is not present.
（Ｅ）剥離工程：レジストパターンをアルカリ剥離液を用いて基板から除去する。
剥離工程で用いられるアルカリ剥離液としては、現像で用いたアルカリ現像液よりもさらに強いアルカリ性の水溶液が好ましく、水酸化ナトリウム、水酸化カリウム、有機アミン化合物等の水溶液が挙げられる。最も一般的には１〜５質量％の水酸化ナトリウムまたは水酸化カリウムの水溶液が用いられる。
以下、実施例により本発明の実施の形態の例をさらに詳しく説明する。
(E) Stripping step: The resist pattern is removed from the substrate using an alkali stripping solution.
The alkaline stripping solution used in the stripping step is preferably an alkaline aqueous solution that is stronger than the alkaline developer used in the development, and examples thereof include aqueous solutions of sodium hydroxide, potassium hydroxide, organic amine compounds, and the like. Most commonly, an aqueous solution of 1-5% by weight sodium hydroxide or potassium hydroxide is used.
Hereinafter, examples of the embodiment of the present invention will be described in more detail by way of examples.
１）感光性樹脂積層体の調製
表１の実施例および比較例に示す感光性樹脂組成物を溶媒（メチルエチルケトン）に溶解させて支持層上にバ−コ−タ−を用いて均一に塗布し、９５℃の乾燥機中で１分間乾燥して、５μｍ厚みの感光性樹脂層を形成した。さらに該感光性樹脂層の上に保護層を張り合わせて感光性樹脂積層体を得た。尚、溶媒は感光性樹脂組成物には含まない。
支持層には、Ｒ３４０Ｇ（三菱化学ポリエステルフィルム株式会社製、ポリエチレンテレフタレート、１６μｍ厚み）、保護層にはＴ１−Ａ７４２Ａ（タマポリ社製、ポリエチレン、３５μｍ厚み）を用いた。
また、表１において略号（Ｐ−１〜Ｂ−４）で表した感光性樹脂組成物を構成する成分を後記する＜記号説明＞に示す。
1) Preparation of photosensitive resin laminate The photosensitive resin compositions shown in the Examples and Comparative Examples in Table 1 were dissolved in a solvent (methyl ethyl ketone) and uniformly applied onto the support layer using a bar coater. And dried for 1 minute in a dryer at 95 ° C. to form a photosensitive resin layer having a thickness of 5 μm. Further, a protective layer was laminated on the photosensitive resin layer to obtain a photosensitive resin laminate. In addition, a solvent is not contained in the photosensitive resin composition.
R340G (Mitsubishi Chemical Polyester Film Co., Ltd., polyethylene terephthalate, 16 μm thickness) was used for the support layer, and T1-A742A (Tamapoly, polyethylene, 35 μm thickness) was used for the protective layer.
In addition, components constituting the photosensitive resin composition represented by abbreviations (P-1 to B-4) in Table 1 are shown in <Symbol Explanation> below.
２）配線板作製
（ラミネート）
ラミネーターＡＬ−７０（旭化成製、商品名）を用いて、フレキシブル基板に上記保護層を剥離した感光性樹脂積層体をラミネートした。その条件は、ラミネート速度：１．０ｍ／分、ラミネートロール温度：１０５℃、ラミネート圧力：０．３５ＭＰａ／ｃｍとした。
なお、フレキシブル基板として、エスパーフレックス（登録商標、住友金属鉱山製）を用いた。このフレキシブル基板は、２５μｍ厚みのポリイミドフィルムに９μｍ厚みの銅箔を積層したものである。
2) Wiring board production (laminate)
Laminator AL-70 (manufactured by Asahi Kasei, trade name) was used to laminate a photosensitive resin laminate from which the protective layer was peeled off on a flexible substrate. The conditions were laminating speed: 1.0 m / min, laminating roll temperature: 105 ° C., laminating pressure: 0.35 MPa / cm.
In addition, Esperflex (registered trademark, manufactured by Sumitomo Metal Mining) was used as the flexible substrate. This flexible substrate is obtained by laminating a 9 μm thick copper foil on a 25 μm thick polyimide film.
（露光）
クロムガラスフォトマスクを用いて、超高圧水銀ランプを有する露光機（プロジェクション露光装置ＵＸ２００３ＳＭ−ＭＳ０４：ウシオ電機株式会社製）により、１５０ｍＪ／ｃｍ2 の露光量で感光性樹脂層をプロジェクション露光した。ここで露光された部分は、硬化レジストとなる。
（現像）
支持層を除去し、０．４質量％炭酸ナトリウム水溶液をアルカリ現像液として、３０℃で、スプレー圧が０．１５ＭＰａで２０秒間スプレー現像することにより、感光性樹脂層の未露光部を除去し、水道水で水洗後乾燥してレジストパターンを得た。実施例１〜７にて得られるレジストパターンはＣＯＦ用配線板の屈曲性に充分対応できる可とう性を有している。
(exposure)
Using a chromium glass photomask, the photosensitive resin layer was subjected to projection exposure at an exposure amount of 150 mJ / cm 2 using an exposure machine having an ultra-high pressure mercury lamp (projection exposure apparatus UX2003SM-MS04: manufactured by USHIO INC.). The part exposed here becomes a cured resist.
(developing)
The support layer is removed, and an unexposed portion of the photosensitive resin layer is removed by spray development at 30 ° C. and a spray pressure of 0.15 MPa for 20 seconds using an aqueous 0.4 mass% sodium carbonate solution as an alkaline developer. Then, it was washed with tap water and dried to obtain a resist pattern. The resist patterns obtained in Examples 1 to 7 have flexibility that can sufficiently cope with the flexibility of the wiring board for COF.
［解像度評価］
フレキシブル基板にラミネ−トされた感光性樹脂積層体を、各種の幅のラインに対してラインとスペ−スが１：１であるパターンを有するクロムガラスフォトマスクを通して露光し、現像した。得られたレジストパタ−ンの分離し得る最小ライン幅を解像度とした。
◎：解像度が１０μｍ未満
○：解像度が１０〜１５μｍ未満
△：解像度が１５〜２０μｍ未満
×：解像度が２０μｍ以上
[Resolution evaluation]
The photosensitive resin laminate laminated on the flexible substrate was exposed and developed through a chromium glass photomask having a pattern of 1: 1 lines and spaces with respect to various width lines. The resolution was defined as the minimum line width at which the obtained resist pattern could be separated.
A: Resolution is less than 10 μm ○: Resolution is less than 10-15 μm Δ: Resolution is less than 15-20 μm x: Resolution is 20 μm or more
［密着性評価］
フレキシブル基板にラミネ−トされた感光性樹脂積層体に、各種の幅の独立したラインからなるパターンを有するクロムガラスフォトマスクを通して露光し、現像した。剥離せずに得られる独立したレジストパタ−ンの最小ライン幅を密着性とした。
◎：密着性が１０μｍ未満
○：密着性が１０〜１５μｍ未満
△：密着性が１５〜２０μｍ未満
×：密着性が２０μｍ以上
[Adhesion evaluation]
The photosensitive resin laminate laminated on the flexible substrate was exposed and developed through a chromium glass photomask having patterns composed of independent lines of various widths. The minimum line width of an independent resist pattern obtained without peeling was defined as adhesion.
A: Adhesion is less than 10 μm B: Adhesion is less than 10-15 μm Δ: Adhesion is less than 15-20 μm X: Adhesion is 20 μm or more
［レジスト形状］
フレキシブル基板にラミネ−トされた感光性樹脂積層体に、クロムガラスフォトマスクを通して露光し、現像した。得られたレジストパタ−ンの１５μｍラインの形状を下記によりランク付けした。スソ引きは硬化レジストパターンのフット部の縁（ふち）幅を測定した。
〇：硬化レジストのフット部の切れは良好でスソ引きが無い。
△：硬化レジストのフット部に３μｍ以下のスソ引きが認められる。
×：硬化レジストのフット部に３μｍを超えるスソ引きが認められる。
[Resist shape]
The photosensitive resin laminate laminated on the flexible substrate was exposed and developed through a chromium glass photomask. The shapes of 15 μm lines of the obtained resist patterns were ranked according to the following. As for the pulling, the edge (edge) width of the foot portion of the cured resist pattern was measured.
◯: The cut portion of the cured resist has a good cut and there is no sooting.
(Triangle | delta): The soot pull of 3 micrometers or less is recognized by the foot part of a cured resist.
X: Soo pulling exceeding 3 μm is observed in the foot portion of the cured resist.
＜記号説明＞
Ｐ−１：ベンジルメタクリレート８０質量％、メタクリル酸２０質量％の２元共重合体の
メチルエチルケトン溶液（固形分濃度５０％、重量平均分子量２．５万、酸当量 ４３０、分散度２．７）
Ｐ−２：ベンジルメタクリレート８０質量％、メタクリル酸２０質量％の２元共重合体の
メチルエチルケトン溶液（固形分濃度５０％、重量平均分子量５．６万、酸当量
４３０、分散度３．６）
Ｐ−３：メタクリル酸メチル５０質量％、メタクリル酸２５質量％、スチレン２５質量％ の三元共重合体のメチルエチルケトン溶液（固形分濃度３５％、重量平均分子量 ５万、酸当量３４４、分散度３．１）
Ｐ−４：メタクリル酸メチル６５質量％、メタクリル酸２５質量％、ノルマルブチルアク リレート１０質量％の三元共重合体のメチルエチルケトン溶液（固形分濃度５０
％、重量平均分子量３万、酸当量３４４、分散度３．７）
<Symbol explanation>
P-1: Methyl ethyl ketone solution of binary copolymer of benzyl methacrylate 80% by mass and methacrylic acid 20% by mass (solid content concentration 50%, weight average molecular weight 25,000, acid equivalent 430, dispersity 2.7)
P-2: Methyl ethyl ketone solution of binary copolymer of 80% by mass of benzyl methacrylate and 20% by mass of methacrylic acid (solid concentration 50%, weight average molecular weight 56,000, acid equivalent 430, dispersity 3.6)
P-3: Methyl ethyl ketone solution of a terpolymer of 50% by weight of methyl methacrylate, 25% by weight of methacrylic acid and 25% by weight of styrene (solid content concentration 35%, weight average molecular weight 50,000, acid equivalent 344, dispersity 3 .1)
P-4: Methyl ethyl ketone solution of 65% by weight of methyl methacrylate, 25% by weight of methacrylic acid, and 10% by weight of normal butyl acrylate (solid content: 50%)
%, Weight average molecular weight 30,000, acid equivalent 344, dispersity 3.7)
Ｍ−１：平均１２モルのプロピレンオキサイドを付加したポリプロピレングリコ−ルにエ チレンオキサイドをさらに両端にそれぞれ平均３モルずつ付加したポリアルキレ ングリコ−ルのジメタクリレ−ト
Ｍ−２：ビスフェノ−ルＡの両端にそれぞれ平均２モルずつのプロピレンオキサイドと平 均６モルずつのエチレンオキサイドを付加したポリアルキレングリコ−ルのジメ タクリレ−ト
Ｍ−３：ビスフェノ−ルＡの両端にそれぞれ平均２モルずつのエチレンオキサイドを付加 したポリエチレングリコ−ルのジメタクリレ−ト（新中村化学工業（株）製ＮＫ エスエルＢＰＥ−２００）
Ｍ−４：ビスフェノ−ルＡの両端にそれぞれ平均５モルずつのエチレンオキサイドを付加 したポリエチレングリコ−ルのジメタクリレ−ト（新中村化学工業（株）製ＮＫ エスエルＢＰＥ−５００）
Ｍ−５：ヘキサメチレンジイソシアネ−トとオリゴプロピレングリコ−ルモノメタクリレ
ート（日本油脂（株）製、ブレンマ−ＰＰ１０００）との反応物であるウレタン
ポリプロピレングリコールジメタクリレート
Ｍ−６：トリメチロ−ルプロパントリアクリレ−ト
Ｍ−７：トリメチロ−ルプロパントリメタクリレ−ト
Ｍ−８：トリオキシエチルトリメチロ−ルプロパントリアクリレ−ト（新中村化学工業 （株）製 ＮＫエステルＡ−ＴＭＰＴ−３ＥＯ）
Ｍ−９：ノナエチレングリコ−ルジアクリレ−ト
M-1: Polyalkylene glycol dimethacrylate with an average of 3 moles of ethylene oxide added to both ends of polypropylene glycol with an average of 12 moles of propylene oxide added M-2: Both ends of bisphenol A Polyalkylene glycol dimethacrylate M-3 with an average of 2 moles of propylene oxide and an average of 6 moles of ethylene oxide respectively added to both ends of bisphenol A at an average of 2 moles of ethylene oxide. Polyethylene glycol dimethacrylate with NP (NSK SL BPE-200 manufactured by Shin-Nakamura Chemical Co., Ltd.)
M-4: Polyethylene glycol dimethacrylate with an average of 5 moles of ethylene oxide added to both ends of bisphenol A (NSK SPE BPE-500, Shin-Nakamura Chemical Co., Ltd.)
M-5: Urethane polypropylene glycol dimethacrylate M-6: trimethylo-reaction product of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (Nippon Yushi Co., Ltd., Bremma PP1000) Rupropanetriacrylate M-7: Trimethylolpropane trimethacrylate M-8: Trioxyethyltrimethylolpropane triacrylate (NK ester A- from Shin-Nakamura Chemical Co., Ltd.) TMPT-3EO)
M-9: Nonaethylene glycol diacrylate
Ａ−１：４，４’−ビス（ジエチルアミノ）ベンゾフェノン
Ａ−２：２−（ｏ−クロロフェニル）−４、５−ジフェニルイミダゾ−ル二量体
Ｂ−１：ダイアモンドグリ−ン（保土ヶ谷化学（株）製 アイゼン（登録商標）
ＤＩＡＭＯＮＤ ＧＲＥＥＮ ＧＨ）
Ｂ−２：ロイコクリスタルバイオレット
DIAMOND GREEN GH)
B-2: Leuco Crystal Violet
本発明はフレキシブル基板を用いた微細配線形成用のＣＯＦ用基板製造用に好適に用いられ、特に導体幅が３０μｍ以下の微細配線用に有用である。 The present invention is suitably used for manufacturing a substrate for COF for forming fine wiring using a flexible substrate, and is particularly useful for fine wiring having a conductor width of 30 μm or less.
Claims (5)
（Ａ）感光性樹脂積層体をラミネートし、
（Ｂ）所望の導体パターンに対応した露光を行い、露光された部分の感光性樹脂層を光硬化させて硬化レジストを得、
（Ｃ）現像により、未露光部分の感光性樹脂層を除去する
工程を含むレジストパタ−ンの形成方法。 Using the photosensitive resin laminate according to claim 3, (A) the photosensitive resin laminate is laminated on a flexible substrate in which a copper foil is laminated on a film having a thickness of 10 to 100 μm.
(B) The exposure corresponding to a desired conductor pattern is performed, the photosensitive resin layer of the exposed part is photocured, and a cured resist is obtained,
(C) A resist pattern forming method including a step of removing a photosensitive resin layer in an unexposed portion by development.
（Ａ）感光性樹脂積層体をラミネートし、
（Ｂ）所望の導体パターンに対応した露光を行い、露光された部分の感光性樹脂層を光硬化させて硬化レジストを得、
（Ｃ）現像により、未露光部分の感光性樹脂層を除去し、
（Ｄ）エッチングによりフレキシブル基板の硬化レジストに覆われていない部分の銅箔層を除去するか、または、めっきにより硬化レジストに覆われていない部分にめっき金属を析出させた後、
（Ｅ）剥離により、硬化レジストを除去する
工程を含むチップオンフィルム用配線板の製造方法。 Using the photosensitive resin laminate according to claim 3, (A) the photosensitive resin laminate is laminated on a flexible substrate in which a copper foil is laminated on a film having a thickness of 10 to 100 μm.
(B) The exposure corresponding to a desired conductor pattern is performed, the photosensitive resin layer of the exposed part is photocured, and a cured resist is obtained,
(C) The photosensitive resin layer in the unexposed part is removed by development,
(D) After removing the copper foil layer of the portion not covered with the cured resist of the flexible substrate by etching or depositing the plating metal on the portion not covered with the cured resist by plating,
(E) The manufacturing method of the wiring board for chip-on-film including the process of removing a hardening resist by peeling.
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| WO2006059534A1 (en) * | 2004-12-01 | 2006-06-08 | Fujifilm Corporation | Pattern forming material and pattern forming method |
| JP2007052392A (en) * | 2005-07-22 | 2007-03-01 | Fujifilm Corp | Pattern forming material, pattern forming apparatus and pattern forming method |
| JP2008039978A (en) * | 2006-08-03 | 2008-02-21 | Asahi Kasei Electronics Co Ltd | Photosensitive resin composition and laminate |
| JP2011081391A (en) * | 2005-07-22 | 2011-04-21 | Fujifilm Corp | Material, apparatus and method for forming pattern |
| CN102778815A (en) * | 2011-05-10 | 2012-11-14 | 日立化成工业株式会社 | Photosensitive resin composition, photosensitive element, method of forming anti-corrosion pattern and method of manufacturing pcb |
| US10104781B2 (en) | 2013-12-27 | 2018-10-16 | Hitachi Chemical Company, Ltd. | Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board |
| WO2019145833A1 (en) * | 2018-01-29 | 2019-08-01 | 3M Innovative Properties Company | Curable composition for plating mask, mask material and removing method of plating |
| CN110615861A (en) * | 2019-08-28 | 2019-12-27 | 苏州欧纳克纳米科技有限公司 | Chloroacetate resin-based benzophenone macromolecular photoinitiator and preparation method thereof |
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| JP2005215342A (en) * | 2004-01-29 | 2005-08-11 | Fuji Photo Film Co Ltd | Light-sensitive transfer sheet, light-sensitive laminate, image pattern forming method and wiring pattern forming method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH09101619A (en) * | 1995-10-04 | 1997-04-15 | Asahi Chem Ind Co Ltd | New photosetting resin composition |
| JP2005215342A (en) * | 2004-01-29 | 2005-08-11 | Fuji Photo Film Co Ltd | Light-sensitive transfer sheet, light-sensitive laminate, image pattern forming method and wiring pattern forming method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006059534A1 (en) * | 2004-12-01 | 2006-06-08 | Fujifilm Corporation | Pattern forming material and pattern forming method |
| JP2007052392A (en) * | 2005-07-22 | 2007-03-01 | Fujifilm Corp | Pattern forming material, pattern forming apparatus and pattern forming method |
| JP4651524B2 (en) * | 2005-07-22 | 2011-03-16 | 富士フイルム株式会社 | Pattern forming material, pattern forming apparatus and pattern forming method |
| JP2011081391A (en) * | 2005-07-22 | 2011-04-21 | Fujifilm Corp | Material, apparatus and method for forming pattern |
| JP2008039978A (en) * | 2006-08-03 | 2008-02-21 | Asahi Kasei Electronics Co Ltd | Photosensitive resin composition and laminate |
| JP2012252320A (en) * | 2011-05-10 | 2012-12-20 | Hitachi Chem Co Ltd | Photosensitive resin composition, photosensitive element, method for forming resist pattern and method for manufacturing printed wiring board |
| CN102778815A (en) * | 2011-05-10 | 2012-11-14 | 日立化成工业株式会社 | Photosensitive resin composition, photosensitive element, method of forming anti-corrosion pattern and method of manufacturing pcb |
| US10104781B2 (en) | 2013-12-27 | 2018-10-16 | Hitachi Chemical Company, Ltd. | Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board |
| WO2019145833A1 (en) * | 2018-01-29 | 2019-08-01 | 3M Innovative Properties Company | Curable composition for plating mask, mask material and removing method of plating |
| JP2019131836A (en) * | 2018-01-29 | 2019-08-08 | スリーエム イノベイティブ プロパティズ カンパニー | Curable composition for plating mask, mask material and removal method of plating |
| CN111655902A (en) * | 2018-01-29 | 2020-09-11 | 3M创新有限公司 | Curable composition for plating mask, mask material, and method for removing plating layer |
| JP7008517B2 (en) | 2018-01-29 | 2022-01-25 | スリーエム イノベイティブ プロパティズ カンパニー | Curing composition for plating mask, mask material and method for removing plating |
| CN111655902B (en) * | 2018-01-29 | 2022-09-02 | 3M创新有限公司 | Curable composition for plating mask, mask material, and method for removing plating layer |
| CN110615861A (en) * | 2019-08-28 | 2019-12-27 | 苏州欧纳克纳米科技有限公司 | Chloroacetate resin-based benzophenone macromolecular photoinitiator and preparation method thereof |
| CN110615861B (en) * | 2019-08-28 | 2021-07-02 | 常州格林感光新材料有限公司 | Chloroacetate resin-based benzophenone macromolecular photoinitiator and preparation method thereof |
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