JP7557262B2 - 感光性樹脂組成物 - Google Patents
感光性樹脂組成物 Download PDFInfo
- Publication number
- JP7557262B2 JP7557262B2 JP2019159653A JP2019159653A JP7557262B2 JP 7557262 B2 JP7557262 B2 JP 7557262B2 JP 2019159653 A JP2019159653 A JP 2019159653A JP 2019159653 A JP2019159653 A JP 2019159653A JP 7557262 B2 JP7557262 B2 JP 7557262B2
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- resin composition
- photosensitive resin
- alkylene oxide
- component
- oxide chain
- Prior art date
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- 239000011256 inorganic filler Substances 0.000 claims description 19
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- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 7
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- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000007964 xanthones Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- C08F265/04—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 esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- 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
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
- C08F290/144—Polymers containing more than one epoxy group per molecule
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
- C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- 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
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- 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
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- 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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- 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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
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- 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
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/282—Applying non-metallic protective coatings for inhibiting the corrosion of the circuit, e.g. for preserving the solderability
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- 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
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
- H05K3/3452—Solder masks
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- Microelectronics & Electronic Packaging (AREA)
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- Architecture (AREA)
- Structural Engineering (AREA)
- Materials For Photolithography (AREA)
- Polymerisation Methods In General (AREA)
- Epoxy Resins (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
[1] (A)エチレン性不飽和基とカルボキシル基とを含有する樹脂、
(B)エポキシ樹脂、
(C)光重合性モノマー、及び
(D)光重合開始剤、を含有する感光性樹脂組成物であって、
(A)成分、(B)成分、及び(C)成分のいずれかには、アルキレンオキシド鎖を含み、下記式(1)で示されるパラメーターXが、4以上25以下である、感光性樹脂組成物。
[2] さらに、(E)無機充填材を含む、[1]に記載の感光性樹脂組成物。
[3] アルキレンオキシド鎖は、(B)成分及び(C)成分のいずれかに含む、[1]又は[2]に記載の感光性樹脂組成物。
[4] (A)成分が、酸変性不飽和エポキシエステル樹脂を含む、[1]~[3]のいずれかに記載の感光性樹脂組成物。
[5] (A)成分が、酸変性エポキシ(メタ)アクリレートを含む、[1]~[4]のいずれかに記載の感光性樹脂組成物。
[6] (A)成分が、酸変性ナフタレン骨格含有エポキシ(メタ)アクリレート、及び酸変性ビスフェノール骨格含有エポキシ(メタ)アクリレートのいずれかを含む、[1]~[5]のいずれかに記載の感光性樹脂組成物。
[7] 酸変性ビスフェノール骨格含有エポキシ(メタ)アクリレートが、ビスフェノールA骨格及びビスフェノールF骨格のいずれかを有する、[6]に記載の感光性樹脂組成物。
[8] (B)成分が、ビフェニル骨格を有する、[1]~[7]のいずれかに記載の感光性樹脂組成物。
[9] (D)成分が、オキシムエステル系光重合開始剤を含む、[1]~[8]のいずれかに記載の感光性樹脂組成物。
[10] [1]~[9]のいずれかに記載の感光性樹脂組成物を含有する、感光性フィルム。
[11] 支持体と、該支持体上に設けられた、[1]~[9]のいずれかに記載の感光性樹脂組成物を含む感光性樹脂組成物層と、を有する支持体付き感光性フィルム。
[12] [1]~[9]のいずれかに記載の感光性樹脂組成物の硬化物により形成された絶縁層を含むプリント配線板。
[13] 絶縁層が、ソルダーレジストである、[12]に記載のプリント配線板。
[14] [12]又は[13]に記載のプリント配線板を含む、半導体装置。
本発明の感光性樹脂組成物は、(A)エチレン性不飽和基とカルボキシル基とを含有する樹脂、(B)エポキシ樹脂、(C)光重合性モノマー、及び(D)光重合開始剤、を含有する感光性樹脂組成物であって、(A)成分、(B)成分、及び(C)成分のいずれかには、アルキレンオキシド鎖を含み、下記式(1)で示されるパラメーターXが、4以上25以下である。
感光性樹脂組成物は、(A)成分として、エチレン性不飽和基とカルボキシル基とを含有する樹脂を含有する。(A)成分を感光性樹脂組成物に含有させることにより現像性を向上させることができる。
式:A(b)=10×Vf×56.1/(Wp×I)
1/Tg=(W1/Tg1)+(W2/Tg2)+・・・+(Wm/Tgm)
W1+W2+・・・+Wm=1
Wmは(A)成分を構成する各モノマーの含有量(質量%)を表し、Tgmは、(A)成分を構成する各モノマーのガラス転移温度(K)を表す。
感光性樹脂組成物は、(B)成分としてエポキシ樹脂を含有する。(B)成分を含有させることにより、絶縁信頼性を向上させることができる。但し、ここでいう(B)成分は、エチレン性不飽和基及びカルボキシル基を含有するエポキシ樹脂は含めない。
樹脂の重量平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)法により、ポリスチレン換算の値として測定できる。
感光性樹脂組成物は、(C)成分として、光重合性モノマーを含有する。但し、(C)成分には(A)成分及び(B)成分は含めない。(C)光重合性モノマーを感光性樹脂組成物に含有させることで、光反応性を向上させることができる。(C)成分としては、例えば、1分子中に1個以上の(メタ)アクリロイル基を有する室温で液体、固体又は半固形の感光性(メタ)アクリレート化合物が使用できる。室温とは、25℃程度を表す。
感光性樹脂組成物は、(D)成分として、光重合開始剤を含有する。(D)光重合開始剤を感光性樹脂組成物に含有させることにより、感光性樹脂組成物を効率的に光硬化させることができる。これらは1種単独で用いてもよく、2種以上を組み合わせて用いてもよい。
感光性樹脂組成物は、上述した成分以外に、任意の成分として、更に(E)成分として無機充填材を含有してもよい。
感光性樹脂組成物は、上述した成分以外に、任意の成分として、更に(F)溶剤を含有していてもよい。(F)溶剤を含有させることによりワニス粘度を調整できる。(F)溶剤としては、有機溶剤が挙げられる。
感光性樹脂組成物は、本発明の目的を阻害しない程度に、(G)その他の添加剤を更に含有してもよい。(G)その他の添加剤としては、例えば、熱可塑性樹脂、有機充填材、メラミン、有機ベントナイト等の微粒子、フタロシアニンブルー、フタロシアニングリーン、アイオディン・グリーン、ジアゾイエロー、クリスタルバイオレット、酸化チタン、カーボンブラック、ナフタレンブラック等の着色剤、ハイドロキノン、フェノチアジン、メチルハイドロキノン、ハイドロキノンモノメチルエーテル、カテコール、ピロガロール等の重合禁止剤、ベントン、モンモリロナイト等の増粘剤、シリコーン系、フッ素系、ビニル樹脂系の消泡剤、臭素化エポキシ化合物、酸変性臭素化エポキシ化合物、アンチモン化合物、リン系化合物、芳香族縮合リン酸エステル、含ハロゲン縮合リン酸エステル等の難燃剤、フェノール系硬化剤、シアネートエステル系硬化剤等の熱硬化樹脂、等の各種添加剤を添加することができる。
感光性樹脂組成物は、(A)成分、(B)成分、及び(C)成分のいずれかにアルキレンオキシド鎖を含む。このとき、下記式(1)で示されるパラメーターXが4以上25以下である。式(1)を満たすことで、屈曲性及び絶縁性に優れる硬化物を得ることが可能となる。
本発明の感光性樹脂組成物は、樹脂ワニス状態で支持基板上に塗布し、有機溶剤を乾燥させることで感光性樹脂組成物層を形成して、感光性フィルムとすることができる。また、予め支持体上に形成された感光性フィルムを支持基板に積層して用いることもできる。感光性フィルムは様々な支持基板に積層させることができる。支持基板としては主に、ガラスエポキシ基板、金属基板、ポリエステル基板、ポリイミド基板、BTレジン基板、熱硬化型ポリフェニレンエーテル基板等の基板が挙げられる。
本発明の感光性樹脂組成物は、感光性樹脂組成物層が支持体上に層形成された支持体付き感光性フィルムの形態で好適に使用することができる。つまり、支持体付き感光性フィルムは、支持体と、該支持体上に設けられた、本発明の感光性樹脂組成物で形成された感光性樹脂組成物層を含む。
感光性樹脂組成物は、数回に分けて塗布してもよいし、1回で塗布してもよく、また異なる方式を複数組み合わせて塗布してもよい。中でも、均一塗工性に優れる、ダイコート方式が好ましい。また、異物混入等をさけるために、クリーンルーム等の異物発生の少ない環境で塗布工程を実施することが好ましい。
本発明のプリント配線板は、本発明の感光性樹脂組成物の硬化物により形成された絶縁層を含む。該絶縁層は、ソルダーレジストとして使用することが好ましい。
感光性樹脂組成物を樹脂ワニス状態で直接的に回路基板上に塗布し、有機溶剤を乾燥させることにより、回路基板上に感光性フィルムを形成する。
また、支持体付き感光性フィルムを用いる場合には、感光性樹脂組成物層側を、真空ラミネーターを用いて回路基板の片面又は両面にラミネートする。ラミネート工程において、支持体付き感光性フィルムが保護フィルムを有している場合には該保護フィルムを除去した後、必要に応じて支持体付き感光性フィルム及び回路基板をプレヒートし、感光性樹脂組成物層を加圧及び加熱しながら回路基板に圧着する。支持体付き感光性フィルムにおいては、真空ラミネート法により減圧下で回路基板にラミネートする方法が好適に用る。
塗布及び乾燥工程、あるいはラミネート工程により、回路基板上に感光性フィルムが設けられた後、次いで、マスクパターンを通して、感光性樹脂組成物層の所定部分に活性光線を照射し、照射部の感光性樹脂組成物層を光硬化させる露光工程を行う。活性光線としては、例えば、紫外線、可視光線、電子線、X線等が挙げられ、特に紫外線が好ましい。紫外線の照射量はおおむね10mJ/cm2~1000mJ/cm2である。露光方法にはマスクパターンをプリント配線板に密着させて行う接触露光法と、密着させずに平行光線を使用して露光する非接触露光法とがあるが、どちらを用いてもかまわない。また、感光性樹脂組成物層上に支持体が存在している場合は、支持体上から露光してもよいし、支持体を剥離後に露光してもよい。
露光工程後、感光性樹脂組成物層上に支持体が存在している場合にはその支持体を除去した後、ウエット現像又はドライ現像で、光硬化されていない部分(未露光部)を除去して現像することにより、パターンを形成することができる。
上記現像工程終了後、熱硬化(ポストベーク)工程を行い、ソルダーレジストを形成する。ポストベーク工程としては、高圧水銀ランプによる紫外線照射工程やクリーンオーブンを用いた加熱工程等が挙げられる。紫外線を照射させる場合は必要に応じてその照射量を調整することができ、例えば0.05J/cm2~10J/cm2程度の照射量で照射を行うことができる。また加熱の条件は、感光性樹脂組成物中の樹脂成分の種類、含有量などに応じて適宜選択すればよいが、好ましくは150℃~220℃で20分間~180分間の範囲、より好ましくは160℃~200℃で30分間~120分間の範囲で選択される。
プリント配線板は、ソルダーレジストを形成後、さらに穴あけ工程、デスミア工程を含んでもよい。これらの工程は、プリント配線板の製造に用いられる、当業者に公知の各種方法に従って実施してよい。
本発明の半導体装置は、プリント配線板を含む。本発明の半導体装置は、本発明のプリント配線板を用いて製造することができる。
4口フラスコに、ビスフェノールA 60.8部(0.26mol)、ビスフェノールA型エポキシ化合物(YD8125、新日鐵化学社製)43.4部(0.11mol)、ポリエチレングリコールジグリシジルエーテル(EX861、ナガセケムテックス社製)145.8部(0.13mol)、触媒としてトリフェニルホスフィン1.25部、N,N-ジメチルベンジルアミン1.25部、溶剤としてトルエン250部を仕込み、窒素気流下、撹拌しながら110℃に昇温し8時間反応させ、ヒドロキシル基含有樹脂を得た。次に、酸無水物として無水コハク酸(リカシッドSA、新日本理化社製)49.8部(0.48mol)を投入し、110℃のまま4時間反応させた。FT-IR測定にて酸無水物基の吸収消失を確認後、室温まで冷却した。次に、攪拌しながらグリシジルメタクリレート(GMA、日油社製)41.1部(0.29mol)、重合禁止剤としてヒドロキノン0.17部を投入し、80℃で8時間反応させた。反応終了後、酸無水物としてリカシッドSA(新日本理化株式会社製:無水コハク酸)26.0部(0.25mol)を投入し、80℃のまま4時間反応させた。FT-IR測定にて酸無水物基の吸収が消失しているのを確認後、室温まで冷却した。この溶液にメチルエチルケトンを加えて固形分が50%になるように調整した。得られた樹脂(A-1)の重量平均分子量は20000、樹脂固形分の酸価は70mgKOH/gであった。
アルキレンオキシド鎖を有するモノマーはポリエチレングリコールジグリシジルエーテル(EX861)である。EX861の分子量は1098であるから式(2)中のAは1098である。また、アルキレンオキシド鎖の分子量は968であるから、式(2)中のAAOは968である。
樹脂(A-1)は、ビスフェノールA、ビスフェノールA型エポキシ化合物、ポリエチレングリコールジグリシジルエーテル、無水コハク酸、及びグリシジルメタクリレートの共重合体である。アルキレンオキシド鎖を含むモノマーはポリエチレングリコールジリシジルエーテルであるから、式(2)中のBAOは0.13となる。また、式(2)中のBは0.26+0.11+0.13+0.48+0.29+0.25=1.52となる。
よって、式(2)は、(968/1098)×(0.13/1.52)≒0.08となる。
4口フラスコに、プロピレングリコールモノメチルエーテルアセテート510g、メチルメタクリレート50g、ブチルメタクリレート90g、ヒドロキシエチルメタクリレート60gおよびアゾビスイソブチロニリル2gを加え、窒素ガスを吹き込みながら、80℃で6時間加熱した。得られたポリマー1の重量平均分子量は40000であった。
・(A-1):合成例1で合成した樹脂(A-1)、固形分50%のメチルエチルケトン溶液、MAO×100=8
・ZFR-1491H:bis-F骨格含有酸変性エポキシアクリレート、日本化薬社製、EDGAc(エチルジグリコールアセテート)カット、固形分70%、MAO×100=0
・ZAR-2000:bis-A骨格含有酸変性エポキシアクリレート、日本化薬社製、EDGAcカット、固形分70%、MAO×100=0
・EX-821:ポリエチレングリコールジグリシジルエーテル、n=4、エポキシ当量185、ナガセケムテックス社製、MAO×100=58
・EX-920:ポリプロピレングリコールジグリシジルエーテル、n=3、エポキシ当量176、ナガセケムテックス社製)MAO×100=57
・NC3000H:ビフェニル型エポキシ樹脂(日本化薬社製、エポキシ当量約272)、MAO×100=0
・R-551:EO変性bisフェノールA型アクリレート、日本化薬社製、MAO×100=34
・A-PTMG-65:ポリテトラメチレングリコール#650ジアクリレート、新中村化学工業社製、MAO×100=83
・1.9ND-A:1.9-ノナンジオールジアクリレート、共栄社化学社製、MAO×100=0
・NCI-831:オキシムエステル系光重合開始剤、ADEKA社製、
・EP4-A:アミノシラン処理を施した水酸化マグネシウム(神島化学社製)
・MEK:メチルエチルケトン、純正化学社製
・ポリマー1:合成例2で合成したポリマー1、固形分25%のプロピレングリコールモノメチルエーテルアセテート溶液、MAO×100=8
X={(2.5÷55)×58}+{(7÷55)×34}+{(3÷55)×83}≒11.5
支持体としてアルキド樹脂系離型剤(リンテック社製「AL-5」)で離型処理したPETフィルム(東レ社製「ルミラーT6AM」、厚み38μm、軟化点130℃、「離型PET」)を用意した。調製した樹脂ワニスをかかる離型PETに乾燥後の感光性樹脂組成物層の厚みが25μmになるよう、ダイコーターにて均一に塗布し、80℃から120℃で乾燥することにより、支持体付き感光性フィルムを得た。
厚さ18μmの銅層をパターニングした回路が形成されているガラスエポキシ基板(銅張積層板)の銅層に対して、有機酸を含む表面処理剤(CZ8100、メック社製)による処理にて粗化を施した。次に実施例、比較例により得られた支持体付き感光性フィルムの感光性樹脂組成物層が銅層の表面と接するように配置し、真空ラミネーター(ニッコー・マテリアルズ社製、VP160)を用いて積層し、前記銅張積層板と、前記感光性樹脂組成物層と、前記支持体とがこの順に積層された積層体を形成した。圧着条件は、真空引きの時間30秒間、圧着温度80℃、圧着圧力0.7MPa、加圧時間30秒間とした。該積層体を室温30分以上静置し、該積層体の支持体上から、丸穴パターンを用いパターン形成装置を用いて、紫外線で露光を行った。露光パターンは開口:50μm/60μm/70μm/80μm/90μm/100μmの丸穴(ビア)、L/S(ライン/スペース):50μm/50μm、60μm/60μm、70μm/70μm、80μm/80μm、90μm/90μm、100μm/100μmのラインアンドスペース、1cm×2cmの四角形を描画させる石英ガラスマスクを使用した。室温にて30分間静置した後、前記積層体から支持体を剥がし取った。該積層体上の絶縁層の全面に、現像液として30℃の1質量%炭酸ナトリウム水溶液をスプレー圧0.2MPaにて2分間のスプレー現像を行った。スプレー現像後、1J/cm2の紫外線照射を行い、さらに180℃、30分間の加熱処理を行い、開口部を有する絶縁層を該積層体上に形成した。これを評価用積層体とした。
評価用積層体で形成した100μmの丸穴において、以下の基準で評価した。
○:残渣がない。
×:残渣が観察される、もしくは膜が剥離又は樹脂が一部溶解している。
実施例、比較例で得られた支持体付き感光性フィルムの感光性樹脂組成物層に全面露光、現像、加熱処理を実施した。露光、現像、加熱処理の条件は評価用積層体の形成条件と同様とした。支持体を剥離し、硬化物フィルムを得た。この硬化物フィルムを15mm×110mmに裁断し、MIT耐折疲労試験機(東洋精機社製)を用いて屈曲性を評価した。試験はJIS P8115に準拠して行い、張力:500g、試験速度:175回/分、折り曲げ角度:135°、折り曲げクランプのR:0.38mmとした。破断までの折り曲げ回数をカウントし、3回の屈曲回数の平均を以下の基準で評価した。
◎:300回以上
○:100回以上300回未満
×:100回未満
10%の硫酸にて洗浄と乾燥を実施した圧延銅箔(JX日鉱日石金属社製、BHY-22B-T、厚さ18μm)を用意した。圧延銅箔の光沢面に、支持体付き感光性フィルムを貼り合わせ、全面露光、現像、加熱処理を実施し、基板を得た。露光、現像、及び加熱処理の条件は屈曲性の評価と同様とした。得られた基板の絶縁層側とガラスエポキシ基板を接合し、銅箔の引きはがし強度を、日本工業規格(JIS C6481)に準拠した引っ張り試験機(TSE社製、「AC-50C-SL」)を用いて測定し、以下の基準で評価した。
○:密着強度が0.5kgf以上
×:密着強度が0.5kgf未満
支持体付き感光性フィルムの支持体上から、L(配線幅)/S(間隔)=20μm/20μmの櫛型配線パターンを用いて、紫外線で全面露光、現像、及び加熱処理を実施した。全面露光、現像、及び加熱処理の条件は評価用積層体の形成条件と同様とした。櫛型配線パターンの両側に電極として銅線を半田付けし、85℃、85%RHで50Vの電圧を印加して、500時間後に抵抗値(Ω)を測定し、7箇所分の抵抗値から、平均値を算出し、以下の基準で評価した。
○:抵抗値の平均値が108Ω以上
×:抵抗値の平均値が108Ω未満
Claims (15)
- (A)エチレン性不飽和基とカルボキシル基とを含有する樹脂、
(B)エポキシ樹脂、
(C)光重合性モノマー、及び
(D)光重合開始剤、を含有する感光性樹脂組成物であって、
(A)成分の重量平均分子量が、2000以上50000以下であり、
(A)成分が、酸変性不飽和エポキシエステル樹脂を含み、
(A)成分、(B)成分、及び(C)成分のいずれかには、下記式(a)で表されるアルキレンオキシド鎖を含み、下記式(1)で示されるパラメーターXが、4以上25以下である、感光性樹脂組成物。
- (A)エチレン性不飽和基とカルボキシル基とを含有する樹脂、
(B)エポキシ樹脂、
(C)光重合性モノマー、及び
(D)光重合開始剤、を含有する感光性樹脂組成物であって、
(A)成分の重量平均分子量が、2000以上50000以下であり、
(B)成分が、ビフェニル骨格を有するエポキシ樹脂を含み、
(A)成分、(B)成分、及び(C)成分のいずれかには、下記式(a)で表されるアルキレンオキシド鎖を含み、下記式(1)で示されるパラメーターXが、4以上25以下である、感光性樹脂組成物。
- (A)成分が、酸変性不飽和エポキシエステル樹脂を含む、請求項2に記載の感光性樹脂組成物。
- (A)成分が、酸変性エポキシ(メタ)アクリレートを含む、請求項1~3のいずれか1項に記載の感光性樹脂組成物。
- (A)成分が、酸変性ナフタレン骨格含有エポキシ(メタ)アクリレート、及び酸変性ビスフェノール骨格含有エポキシ(メタ)アクリレートのいずれかを含む、請求項1~4のいずれか1項に記載の感光性樹脂組成物。
- 酸変性ビスフェノール骨格含有エポキシ(メタ)アクリレートが、ビスフェノールA骨格及びビスフェノールF骨格のいずれかを有する、請求項5に記載の感光性樹脂組成物。
- さらに、(E)無機充填材を含む、請求項1~6のいずれか1項に記載の感光性樹脂組成物。
- アルキレンオキシド鎖は、(B)成分及び(C)成分のいずれかに含む、請求項1~7のいずれか1項に記載の感光性樹脂組成物。
- (D)成分が、オキシムエステル系光重合開始剤を含む、請求項1~8のいずれか1項に記載の感光性樹脂組成物。
- (C)成分の含有量が、感光性樹脂組成物の固形分全体を100質量%とした場合、0.5質量%以上10質量%以下である、請求項1~9のいずれか1項に記載の感光性樹脂組成物。
- 請求項1~10のいずれか1項に記載の感光性樹脂組成物を含有する、感光性フィルム。
- 支持体と、該支持体上に設けられた、請求項1~10のいずれか1項に記載の感光性樹脂組成物を含む感光性樹脂組成物層と、を有する支持体付き感光性フィルム。
- 請求項1~10のいずれか1項に記載の感光性樹脂組成物の硬化物により形成された絶縁層を含むプリント配線板。
- 絶縁層が、ソルダーレジストである、請求項13に記載のプリント配線板。
- 請求項13又は14に記載のプリント配線板を含む、半導体装置。
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