TWI706222B - Photosensitive resin composition - Google Patents

Photosensitive resin composition Download PDF

Info

Publication number
TWI706222B
TWI706222B TW108122448A TW108122448A TWI706222B TW I706222 B TWI706222 B TW I706222B TW 108122448 A TW108122448 A TW 108122448A TW 108122448 A TW108122448 A TW 108122448A TW I706222 B TWI706222 B TW I706222B
Authority
TW
Taiwan
Prior art keywords
photosensitive resin
compound
resin composition
mass
meth
Prior art date
Application number
TW108122448A
Other languages
Chinese (zh)
Other versions
TW201947323A (en
Inventor
国松真一
松田隆之
山田有里
筒井大和
藤原晶
Original Assignee
日商旭化成股份有限公司
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 日商旭化成股份有限公司 filed Critical 日商旭化成股份有限公司
Publication of TW201947323A publication Critical patent/TW201947323A/en
Application granted granted Critical
Publication of TWI706222B publication Critical patent/TWI706222B/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • 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
    • 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
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • 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
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—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 end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

本發明之感光性樹脂組合物包含鹼溶性高分子、具有乙烯性不飽和鍵之化合物、及光聚合起始劑，並且於基板表面上形成包含該感光性樹脂組合物之感光性樹脂層，並進行曝光及顯影所獲得之抗蝕圖案利用用以評價耐藥液性之藥液進行處理後，硬化抗蝕劑線之最小線寬為17 μm以下。The photosensitive resin composition of the present invention contains an alkali-soluble polymer, a compound having an ethylenically unsaturated bond, and a photopolymerization initiator, and a photosensitive resin layer containing the photosensitive resin composition is formed on the surface of a substrate, and After the resist pattern obtained by exposure and development is processed with a chemical solution for evaluating drug resistance, the minimum line width of the hardened resist line is 17 μm or less.

Description

感光性樹脂組合物Photosensitive resin composition

本發明係關於一種感光性樹脂組合物等。The present invention relates to a photosensitive resin composition and the like.

先前，印刷配線板通常係藉由光微影法而製造。於光微影法中，首先，對積層於基板上之感光性樹脂組合物層進行圖案曝光。感光性樹脂組合物之曝光部進行聚合硬化(負型之情形時)或對於顯影液可溶(正型之情形時)。其次，利用顯影液去除未曝光部(負型之情形時)或曝光部(正型之情形時)而於基板上形成抗蝕圖案。進而，於實施蝕刻或鍍敷處理而形成導體圖案後，自基板上剝離去除抗蝕圖案。藉由經過該等步驟，於基板上形成導體圖案。 於光微影法中，通常，於將感光性樹脂組合物塗佈於基板上之時，使用如下方法之任一種：將感光性樹脂組合物之溶液塗佈於基板並使之乾燥之方法；或將藉由依序積層支持體、包含感光性樹脂組合物之層(以下，亦稱為「感光性樹脂層」)、及視需要之保護層而獲得之感光性樹脂積層體(以下，亦稱為「乾膜抗蝕劑」)積層於基板之方法。於印刷配線板之製造中大多使用後者。 隨著近年來之印刷配線板之配線間隔之微細化，對乾膜抗蝕劑不斷要求各種特性。例如，為了提高抗蝕圖案之密接性及解像性，且於顯影步驟前為止之階段中，使覆蓋通孔之抗蝕圖案不易斷裂，業界提出有如下感光性樹脂組合物，其分別包含具有源自二季戊四醇之骨架之(甲基)丙烯酸酯化合物作為具有乙烯性不飽和鍵之化合物，且含有吡唑啉化合物作為光敏劑(專利文獻1)。 為了提高抗蝕圖案之密接性及解像性，且於顯影步驟中抑制抗蝕圖案底部之殘渣之產生，業界亦提出有如下感光性樹脂組合物，其分別包含具有源自二季戊四醇之骨架之(甲基)丙烯酸酯化合物、及具有雙酚A型骨架及環氧烷鏈之二(甲基)丙烯酸酯化合物(專利文獻2)。 於對形成有抗蝕圖案之基板進行蝕刻或鍍敷之導體圖案形成步驟中，或於該步驟前，存在利用脫脂液等藥液洗淨抗蝕圖案及基板之情形。於與藥液之接觸前後之比較中，要求抑制抗蝕圖案形狀之變化。 然而，就抗蝕圖案之耐化學品性等觀點而言，專利文獻1及2中所記述之感光性樹脂組合物尚具有改良之餘地。 進而，為了提高抗蝕劑之特性，業界提出有各種感光性樹脂組合物(專利文獻3～6)。 於專利文獻3中，就抗蝕圖案之下擺部形狀、解像性及殘膜率之觀點而言，業界正研究如下感光性樹脂組合物，其包含季戊四醇聚烷氧基四甲基丙烯酸酯作為具有乙烯性不飽和鍵之化合物。 於專利文獻4中，就抗蝕圖案之下擺部形狀、解像性、密接性、最小顯影時間及滲出性之觀點而言，作為感光性樹脂組合物中之單體，業界正研究進行環氧乙烷改性而成之季戊四醇四(甲基)丙烯酸酯、使雙酚A進行環氧烷改性而成之二(甲基)丙烯酸酯、及二季戊四醇(甲基)丙烯酸酯之組合。 於專利文獻5及6中，記述有如下感光性樹脂組合物，其包含具有超過106℃之玻璃轉移溫度之鹼溶性高分子。 然而，於印刷配線板等之製造中，於硬化抗蝕劑之硬度過高之情形時，因顯影處理中或搬送中之物理衝擊而抗蝕圖案折斷，作為結果有配線圖案之產率變差之虞。因此，為了維持對基材之密接，而對硬化抗蝕劑期待柔軟性良好。又，乾膜抗蝕劑雖然存在捲取為卷狀而保管之情形，但若干膜抗蝕劑之構成成分因滲出而附著於支持膜表面，則存在難以進行穩定之配線圖案生產之情形。 然而，關於專利文獻3～6中所記述之感光性樹脂組合物，就改善抗蝕圖案之柔軟性而提高密接性，且抑制乾膜抗蝕劑之構成成分之滲出之觀點而言，尚具有改良之餘地。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開2012-048202號公報 [專利文獻2]國際公開第2015/012272號 [專利文獻3]日本專利特開2013-156369號公報 [專利文獻4]日本專利特開2014-081440號公報 [專利文獻5]日本專利特開2013-117716號公報 [專利文獻6]日本專利特開2014-191318號公報Previously, printed wiring boards were usually manufactured by photolithography. In the photolithography method, first, pattern exposure is performed on the photosensitive resin composition layer laminated on the substrate. The exposed part of the photosensitive resin composition is polymerized and cured (in the case of a negative type) or is soluble in the developer (in the case of a positive type). Next, the unexposed part (in the case of the negative type) or the exposed part (in the case of the positive type) is removed with a developer to form a resist pattern on the substrate. Furthermore, after performing an etching or a plating process to form a conductor pattern, it peels and removes a resist pattern from a board|substrate. Through these steps, a conductor pattern is formed on the substrate. In the photolithography method, generally, when the photosensitive resin composition is applied to the substrate, any one of the following methods is used: a method of applying a solution of the photosensitive resin composition to the substrate and drying it; Or a photosensitive resin laminate obtained by sequentially laminating a support, a layer containing a photosensitive resin composition (hereinafter, also referred to as "photosensitive resin layer"), and a protective layer as needed (hereinafter also referred to as It is a method of laminating "dry film resist") on a substrate. The latter is mostly used in the manufacture of printed wiring boards. With the miniaturization of the wiring spacing of printed wiring boards in recent years, various characteristics have been continuously required for dry film resists. For example, in order to improve the adhesion and resolution of the resist pattern and prevent the resist pattern covering the through holes from being easily broken during the stage before the development step, the industry has proposed the following photosensitive resin compositions, which respectively include The (meth)acrylate compound derived from the skeleton of dipentaerythritol is a compound having an ethylenically unsaturated bond, and contains a pyrazoline compound as a photosensitizer (Patent Document 1). In order to improve the adhesion and resolution of the resist pattern, and to suppress the generation of residues at the bottom of the resist pattern during the development step, the industry has also proposed the following photosensitive resin compositions, which respectively contain a skeleton derived from dipentaerythritol A (meth)acrylate compound, and a di(meth)acrylate compound having a bisphenol A type skeleton and an alkylene oxide chain (Patent Document 2). In the conductor pattern forming step of etching or plating the substrate on which the resist pattern is formed, or before this step, there are cases in which the resist pattern and the substrate are washed with a chemical solution such as a degreasing solution. In the comparison before and after contact with the chemical solution, it is required to suppress the change of the resist pattern shape. However, the photosensitive resin composition described in Patent Documents 1 and 2 still has room for improvement in terms of the chemical resistance of the resist pattern and the like. Furthermore, in order to improve the characteristics of the resist, various photosensitive resin compositions have been proposed in the industry (Patent Documents 3 to 6). In Patent Document 3, from the viewpoints of the shape, resolution, and residual film rate of the resist pattern, the industry is studying the following photosensitive resin composition, which contains pentaerythritol polyalkoxytetramethacrylate as Compounds with ethylenically unsaturated bonds. In Patent Document 4, from the viewpoints of the shape of the lower part of the resist pattern, the resolution, the adhesion, the minimum development time, and the exudation, the industry is studying epoxy resin as a monomer in the photosensitive resin composition. A combination of pentaerythritol tetra(meth)acrylate modified by ethane, di(meth)acrylate modified by bisphenol A with alkylene oxide, and dipentaerythritol (meth)acrylate. Patent Documents 5 and 6 describe a photosensitive resin composition containing an alkali-soluble polymer having a glass transition temperature exceeding 106°C. However, in the manufacture of printed wiring boards, etc., when the hardness of the hardened resist is too high, the resist pattern is broken due to physical impact during the development process or during transportation. As a result, the yield of wiring patterns deteriorates. The fear. Therefore, in order to maintain close contact with the substrate, the cured resist is expected to have good flexibility. In addition, although the dry film resist may be wound in a roll shape and stored, some components of the film resist adhere to the surface of the support film due to bleed out, and it may be difficult to produce stable wiring patterns. However, with regard to the photosensitive resin compositions described in Patent Documents 3 to 6, in terms of improving the flexibility of the resist pattern and improving the adhesion, and suppressing the bleeding of the constituent components of the dry film resist, there are Room for improvement. [Prior Technical Literature] [Patent Literature] [Patent Document 1] Japanese Patent Laid-Open No. 2012-048202 [Patent Document 2] International Publication No. 2015/012272 [Patent Document 3] Japanese Patent Laid-Open No. 2013-156369 [Patent Document 4] Japanese Patent Laid-Open No. 2014-081440 [Patent Document 5] Japanese Patent Laid-Open No. 2013-117716 [Patent Document 6] Japanese Patent Laid-Open No. 2014-191318

[發明所欲解決之問題] 本發明係針對上述中所說明之背景技術而成者，本發明所欲解決之問題在於提供一種密接性、解像性及保存穩定性之至少一者優異之感光性樹脂組合物。 [解決問題之技術手段] 本發明者發現，藉由以下之技術方法可解決上述課題。 [1] 一種感光性樹脂組合物，其係包含如下成分者： (A)鹼溶性高分子； (B)具有乙烯性不飽和鍵之化合物；及 (C)光聚合起始劑；並且 於基板表面上形成包含該感光性樹脂組合物之感光性樹脂層，並進行曝光及顯影所獲得之抗蝕圖案利用耐藥液性評價之藥液進行處理後，硬化抗蝕劑線之最小線寬為17 μm以下。 [2] 如[1]中所記載之感光性樹脂組合物，其中於上述基板表面上形成上述感光性樹脂層，以斯圖費(Stouffer)41段格階段式曝光表作為光罩而進行曝光，繼而，以進行顯影時之最高殘膜段格數成為15段格之曝光量，對該感光性樹脂層進行曝光時， 於FT-IR(Fourier Transform Infrared Radiation，傅立葉變換紅外光譜)測定中，於將曝光前之波數810 cm-1 下之波峰高度設為P，將進行上述曝光後之上述(B)具有乙烯性不飽和鍵之化合物中之乙烯性雙鍵之反應率設為Q，將上述感光性樹脂層之膜厚設為R之情形時之P×Q/R之值為0.21以上。 [3] 如[1]或[2]中所記載之感光性樹脂組合物，其中上述(A)鹼溶性高分子之玻璃轉移溫度Tg之重量平均值Tgtotal 為110℃以下。 [4] 如[1]至[3]中任一項所記載之感光性樹脂組合物，其中上述(B)具有乙烯性不飽和鍵之化合物之重量平均分子量為760以上。 [5] 如[1]至[4]中任一項所記載之感光性樹脂組合物，其中上述(B)具有乙烯性不飽和鍵之化合物中之甲基丙烯醯基之濃度為0.20 mol/100 g以上。 [6] 如[1]至[5]中任一項所記載之感光性樹脂組合物，其中上述(B)具有乙烯性不飽和鍵之化合物中之環氧乙烷單元之濃度為0.80 mol/100 g以上。 [7] 如[1]至[6]中任一項所記載之感光性樹脂組合物，其包含六芳基雙咪唑化合物作為上述(C)光聚合起始劑。 [8] 一種上述感光性樹脂組合物，其包括如下成分： (A)鹼溶性高分子； (B)具有乙烯性不飽和鍵之化合物；及 (C)光聚合起始劑；並且 上述(A)鹼溶性高分子之玻璃轉移溫度Tg之重量平均值Tgtotal 為110℃以下，且 包含具有3個以上乙烯性不飽和鍵之(甲基)丙烯酸酯化合物作為上述(B)具有乙烯性不飽和鍵之化合物。 [9] 如[8]中所記載之感光性樹脂組合物，其包含具有5個以上乙烯性不飽和鍵，且具有環氧烷鏈之(甲基)丙烯酸酯化合物作為上述(B)具有乙烯性不飽和鍵之化合物。 [10] 如[8]或[9]中所記載之感光性樹脂組合物，其中上述(A)鹼溶性高分子具有100～600之酸當量及5,000～500,000之重量平均分子量，且於其側鏈具有芳香族基。 [11] 如[8]至[10]中任一項所記載之感光性樹脂組合物，其包含具有5個以上乙烯性不飽和鍵，且具有環氧乙烷鏈之(甲基)丙烯酸酯化合物作為上述(B)具有乙烯性不飽和鍵之化合物。 [12] 如[8]至[11]中任一項所記載之感光性樹脂組合物，其包含具有環氧乙烷鏈與二季戊四醇骨架之(甲基)丙烯酸酯化合物作為上述(B)具有乙烯性不飽和鍵之化合物。 [13] 如[8]至[12]中任一項所記載之感光性樹脂組合物，其進而包含下述通式(II)所表示之化合物作為上述(B)具有乙烯性不飽和鍵之化合物， [化1]

Figure 02_image001
{式中，R1 及R2 分別獨立表示氫原子或甲基，A為C2 H4 ，B為C3 H6 ，n1 及n3 分別獨立為1～39之整數，且n1 ＋n3 為2～40之整數，n2 及n4 分別獨立為0～29之整數，且n2 ＋n4 為0～30之整數，-(A-O)-及-(B-O)-之重複單元之排列可為無規亦可為嵌段，於嵌段之情形時，-(A-O)-與-(B-O)-之任一者亦可為聯苯基側}。 [14] 如[8]至[13]中任一項所記載之感光性樹脂組合物，其進而包含下述通式(I)所表示之化合物作為上述(B)具有乙烯性不飽和鍵之化合物， [化2]
Figure 02_image003
{式中，R3 ～R6 分別獨立表示碳數1～4之烷基，X表示碳數2～6之伸烷基，m1 、m2 、m3 及m4 分別獨立為0～40之整數，m1 ＋m2 ＋m3 ＋m4 為1～40，於m1 ＋m2 ＋m3 ＋m4 為2以上之情形時，複數個X可相互相同或不同}。 [15] 如[8]至[14]中任一項所記載之感光性樹脂組合物，其包含六芳基雙咪唑化合物作為上述(C)光聚合起始劑。 [16] 如[8]至[15]中任一項所記載之感光性樹脂組合物，其包含吡唑啉化合物作為上述(C)光聚合起始劑。 [17] 如[8]至[16]中任一項所記載之感光性樹脂組合物，其係直接成像曝光用。 [18] 如[8]中所記載之感光性樹脂組合物，其中上述(A)鹼溶性高分子之玻璃轉移溫度Tg之重量平均值Tgtotal 為105℃以下，並且 於相對於上述感光性樹脂組合物之固形物成分總量超過0質量%且為16質量%以下之範圍內包含(b1)具有至少3個甲基丙烯醯基之化合物作為上述(B)具有乙烯性不飽和鍵之化合物，且 上述(B)具有乙烯性不飽和鍵之化合物中之70質量%以上為具有500以上之重量平均分子量之化合物。 [19] 如[18]中所記載之感光性樹脂組合物，其中上述(b1)具有至少3個甲基丙烯醯基之化合物具有500以上之重量平均分子量。 [20] 如[18]或[19]中所記載之感光性樹脂組合物，其包含(b2)具有環氧丁烷鏈與1個或2個(甲基)丙烯醯基之化合物作為上述(B)具有乙烯性不飽和鍵之化合物。 [21] 如[20]中所記載之感光性樹脂組合物，其中上述(b2)具有環氧丁烷鏈與1個或2個(甲基)丙烯醯基之化合物具有500以上之重量平均分子量。 [發明之效果] 根據本發明，可提供一種密接性、解像性及保存穩定性之至少一者優異之感光性樹脂組合物。[Problems to be Solved by the Invention] The present invention is based on the background art described above. The problem to be solved by the present invention is to provide a photosensitive film with excellent adhesion, resolution, and storage stability.性resin composition. [Technical Means to Solve the Problem] The inventor found that the above-mentioned problems can be solved by the following technical methods. [1] A photosensitive resin composition comprising: (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated bond; and (C) a photopolymerization initiator; and on a substrate A photosensitive resin layer containing the photosensitive resin composition is formed on the surface, and the resist pattern obtained by exposing and developing is treated with a chemical solution for drug resistance evaluation. The minimum line width of the hardened resist line is Below 17 μm. [2] The photosensitive resin composition as described in [1], wherein the photosensitive resin layer is formed on the surface of the substrate, and exposure is performed using a Stouffer 41-segment stepwise exposure meter as a photomask Then, when the photosensitive resin layer is exposed to the maximum number of remaining film segments at the time of development, it is measured in FT-IR (Fourier Transform Infrared Radiation) measurement. Set the peak height under the wave number 810 cm -1 before exposure to P, and set the reaction rate of the ethylenic double bond in the compound with ethylenically unsaturated bond (B) after the above exposure to Q, When the film thickness of the photosensitive resin layer is R, the value of P×Q/R is 0.21 or more. [3] The photosensitive resin composition as described in [1] or [2], wherein the weight average Tg total of the glass transition temperature Tg of the alkali-soluble polymer (A) is 110° C. or less. [4] The photosensitive resin composition as described in any one of [1] to [3], wherein the weight average molecular weight of the compound having an ethylenically unsaturated bond (B) is 760 or more. [5] The photosensitive resin composition as described in any one of [1] to [4], wherein the concentration of the methacrylic acid group in the compound having an ethylenically unsaturated bond (B) is 0.20 mol/ More than 100 g. [6] The photosensitive resin composition according to any one of [1] to [5], wherein the concentration of the ethylene oxide unit in the compound having an ethylenically unsaturated bond (B) is 0.80 mol/ More than 100 g. [7] The photosensitive resin composition as described in any one of [1] to [6], which contains a hexaarylbisimidazole compound as the (C) photopolymerization initiator. [8] A photosensitive resin composition as described above, comprising the following components: (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated bond; and (C) a photopolymerization initiator; and the above (A) ) The weight average Tg total of the glass transition temperature Tg of the alkali-soluble polymer is 110°C or less, and contains a (meth)acrylate compound having 3 or more ethylenic unsaturated bonds as the above (B) having ethylenic unsaturation The compound of the bond. [9] The photosensitive resin composition as described in [8], which contains a (meth)acrylate compound having 5 or more ethylenic unsaturated bonds and an alkylene oxide chain as the above (B) having ethylene Compounds with unsaturated bonds. [10] The photosensitive resin composition as described in [8] or [9], wherein the (A) alkali-soluble polymer has an acid equivalent of 100 to 600 and a weight average molecular weight of 5,000 to 500,000, and is on its side The chain has an aromatic group. [11] The photosensitive resin composition as described in any one of [8] to [10], which contains a (meth)acrylate having 5 or more ethylenically unsaturated bonds and an ethylene oxide chain The compound is a compound having an ethylenically unsaturated bond in (B). [12] The photosensitive resin composition as described in any one of [8] to [11], which contains a (meth)acrylate compound having an ethylene oxide chain and a dipentaerythritol skeleton as the above (B) Compounds with ethylenically unsaturated bonds. [13] The photosensitive resin composition as described in any one of [8] to [12], which further contains a compound represented by the following general formula (II) as the above-mentioned (B) having an ethylenically unsaturated bond Compound, [化1]
Figure 02_image001
{In the formula, R 1 and R 2 each independently represent a hydrogen atom or a methyl group, A is C 2 H 4 , B is C 3 H 6 , n 1 and n 3 are each independently an integer of 1 to 39, and n 1 + n 3 is an integer from 2 to 40, n 2 and n 4 are each independently an integer from 0 to 29, and n 2 + n 4 is an integer from 0 to 30, arrangement of repeating units of -(AO)- and -(BO)- It may be random or block. In the case of block, either of -(AO)- and -(BO)- may be biphenyl side}. [14] The photosensitive resin composition as described in any one of [8] to [13], which further comprises a compound represented by the following general formula (I) as the above (B) having an ethylenically unsaturated bond Compound, [化2]
Figure 02_image003
{In the formula, R 3 to R 6 each independently represent an alkyl group having 1 to 4 carbon atoms, X represents an alkylene group having 2 to 6 carbon atoms, and m 1 , m 2 , m 3 and m 4 are each independently 0-40 The integer of m 1 + m 2 + m 3 + m 4 is 1-40. When m 1 + m 2 + m 3 + m 4 is 2 or more, a plurality of Xs may be the same or different from each other}. [15] The photosensitive resin composition as described in any one of [8] to [14], which contains a hexaarylbisimidazole compound as the (C) photopolymerization initiator. [16] The photosensitive resin composition as described in any one of [8] to [15], which contains a pyrazoline compound as the (C) photopolymerization initiator. [17] The photosensitive resin composition as described in any one of [8] to [16], which is used for direct image exposure. [18] The photosensitive resin composition as described in [8], wherein the weight average Tg total of the glass transition temperature Tg of the alkali-soluble polymer (A) is 105° C. or less, and is relative to the photosensitive resin The composition contains (b1) a compound having at least 3 methacrylic acid groups as the above-mentioned (B) compound having an ethylenically unsaturated bond within a range where the total solid content of the composition exceeds 0% by mass and is 16% by mass or less, In addition, 70% by mass or more of the compound having an ethylenically unsaturated bond (B) is a compound having a weight average molecular weight of 500 or more. [19] The photosensitive resin composition as described in [18], wherein the compound (b1) having at least 3 methacrylic groups has a weight average molecular weight of 500 or more. [20] The photosensitive resin composition as described in [18] or [19], which comprises (b2) a compound having a butylene oxide chain and one or two (meth)acryloyl groups as the ( B) Compounds with ethylenically unsaturated bonds. [21] The photosensitive resin composition as described in [20], wherein the compound (b2) having a butylene oxide chain and one or two (meth)acrylic groups has a weight average molecular weight of 500 or more . [Effects of the Invention] According to the present invention, it is possible to provide a photosensitive resin composition excellent in at least one of adhesion, resolution, and storage stability.

以下，對用以實施本發明之形態(以下，簡稱為「本實施形態」)具體地進行說明。 ＜感光性樹脂組合物＞ 於本實施形態中，感光性樹脂組合物包含(A)鹼溶性高分子、(B)具有乙烯性不飽和鍵之化合物、及(C)光聚合起始劑。感光性樹脂組合物視需要可進而含有(D)添加劑等其他成分。 本發明之第一態樣係一種感光性樹脂組合物，其係以如下方式進行設計：於基板表面上形成包含感光性樹脂組合物之感光性樹脂層，並進行曝光及顯影所獲得之抗蝕圖案利用耐藥液性評價之藥液進行處理後，硬化抗蝕劑線之最小線寬為17 μm以下。藉由使用此種感光性樹脂組合物，於藉由鍍敷形成配線圖案時，可抑制短路。又，藉由亦抑制鍍敷鑽入，可獲得直線性優異之配線圖案。即，本發明之感光性樹脂組合物係密接性及/或解像性優異者。硬化抗蝕劑線之最小線寬較佳為16 μm以下，更佳為15 μm以下，進而較佳為12 μm以下，尤佳為10 μm以下，最佳為8 μm以下。硬化抗蝕劑線之最小線寬之測定方法及條件係於實施例之耐藥液性評價中進行說明。 本發明之第二態樣係一種感光性樹脂組合物，其中(A)鹼溶性高分子之玻璃轉移溫度Tg之重量平均值Tgtotal 為110℃以下，且包含具有3個以上乙烯性不飽和鍵之(甲基)丙烯酸酯化合物作為(B)具有乙烯性不飽和鍵之化合物。藉由包含Tgtotal 為110℃以下之(A)鹼溶性高分子及具有3個以上乙烯性不飽和鍵之(甲基)丙烯酸酯化合物，可提高反應率，又，由於呈現交聯密度上升之傾向，並且未反應之(B)成分不易殘留，故而其結果為，呈現感光性樹脂組合物提供一種密接性、解像性及保存穩定性之至少一者優異之抗蝕圖案之傾向。 於基板表面上形成包含本實施形態之感光性樹脂組合物之感光性樹脂層，以斯圖費41段格階段式曝光表作為光罩而進行曝光，繼而，以進行顯影時之最高殘膜段格數成為15段格之曝光量，對感光性樹脂層進行曝光時，感光性樹脂層較佳為滿足由下述式所表示之關係， P×Q/R≧0.21 {式中，關於感光性樹脂層，於FT-IR測定中，P表示曝光前之波數810 cm-1 下之波峰高度，Q表示(B)具有乙烯性不飽和鍵之化合物中之乙烯性雙鍵於曝光後之反應率，且R表示膜厚}。 上述中所說明之式P×Q/R所表示之值更佳為0.22以上、0.23以上、0.24以上、0.25以上、或0.27以上。式P×Q/R所表示之值之測定方法及條件係於實施例中進行說明。 (A)鹼溶性高分子 (A)鹼溶性高分子係可溶解於鹼性物質中之高分子。於本實施形態中，就鹼性顯影性之觀點而言，感光性樹脂組合物較佳為具有羧基，更佳為包含含羧基之單體作為共聚合成分之共聚物。 於本實施形態中，關於感光性樹脂組合物，就抗蝕圖案之高解像性及下擺部形狀之觀點而言，進而就抗蝕圖案之耐化學品性之觀點而言，作為(A)鹼溶性高分子，較佳為包含具有芳香族基之共聚物，尤佳為包含側鏈具有芳香族基之共聚物。再者，作為此種芳香族基，例如可列舉：經取代或未經取代之苯基、或經取代或未經取代之芳烷基。 作為具有芳香族基之共聚物於(A)成分中所占之比率，較佳為50質量%以上，較佳為60質量%以上，較佳為70質量%以上，較佳為80質量%以上，較佳為90質量%以上，亦可為100質量%。 又，就抗蝕圖案之高解像性及下擺部形狀之觀點而言，進而就抗蝕圖案之耐化學品性之觀點而言，作為具有芳香族基之共聚物中之具有芳香族基之共聚單體之共聚合比率，較佳為20質量%以上，較佳為30質量%以上，較佳為40質量%以上，較佳為50質量%以上，較佳為60質量%以上，較佳為70質量%以上，較佳為80質量%以上。作為共聚合比率之上限，並無特別限制，就維持鹼溶性之觀點而言，較佳為95質量%以下，更佳為90質量%以下。 作為上述具有芳香族基之共聚單體，例如可列舉：具有芳烷基之單體、苯乙烯、及可進行聚合之苯乙烯衍生物(例如甲基苯乙烯、乙烯基甲苯、第三丁氧基苯乙烯、乙醯氧基苯乙烯、4-乙烯基苯甲酸、苯乙烯二聚物、苯乙烯三聚物等)。其中，較佳為具有芳烷基之單體、或苯乙烯，更佳為具有芳烷基之單體。 作為芳烷基，可列舉：經取代或未經取代之苯基烷基(苄基除外)、或經取代或未經取代之苄基等，較佳為經取代或未經取代之苄基。 作為具有苯基烷基之共聚單體，可列舉：(甲基)丙烯酸苯基乙酯等。 作為具有苄基之共聚單體，可列舉：具有苄基之(甲基)丙烯酸酯、例如(甲基)丙烯酸苄酯、(甲基)丙烯酸氯苄酯等；具有苄基之乙烯基單體、例如乙烯基苄基氯、乙烯基苄醇等。其中，較佳為(甲基)丙烯酸苄酯。 側鏈具有芳香族基(尤佳為苄基)之共聚物較佳為藉由使具有芳香族基之單體與下述第一單體之至少1種及/或下述第二單體之至少1種進行聚合而獲得。 側鏈具有芳香族基之共聚物以外之(A)鹼溶性高分子較佳為藉由使下述第一單體之至少1種進行聚合而獲得，更佳為藉由使第一單體之至少1種與下述第二單體之至少1種進行共聚合而獲得。 第一單體係分子中具有羧基之單體。作為第一單體，例如可列舉：(甲基)丙烯酸、反丁烯二酸、肉桂酸、丁烯酸、伊康酸、4-乙烯基苯甲酸、順丁烯二酸酐、順丁烯二酸半酯等。該等之中，較佳為(甲基)丙烯酸。 再者，於本說明書中所謂「(甲基)丙烯酸」係指丙烯酸或甲基丙烯酸，所謂「(甲基)丙烯醯基」係指丙烯醯基或甲基丙烯醯基，且所謂「(甲基)丙烯酸酯」係指「丙烯酸酯」或「甲基丙烯酸酯」。 第一單體之共聚合比率以全部單體成分之合計質量作為基準，較佳為10～50質量%。就表現出良好之顯影性之觀點、控制邊緣熔融性等觀點而言，較佳為將該共聚合比率設為10質量%以上。就抗蝕圖案之高解像性及下擺部形狀之觀點而言，進而就抗蝕圖案之耐化學品性之觀點而言，較佳為將該共聚合比率設為50質量%以下，於該等觀點中，更佳為30質量%以下，進而較佳為25質量%以下，尤佳為22質量%以下，最佳為20質量%以下。 第二單體為非酸性，且係分子中具有至少1個聚合性不飽和基之單體。作為第二單體，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸2-乙基己酯等(甲基)丙烯酸酯類；乙酸乙烯酯等乙烯醇之酯類；以及(甲基)丙烯腈等。其中，較佳為(甲基)丙烯酸甲酯、(甲基)丙烯酸2-乙基己酯、及(甲基)丙烯酸正丁酯。 於本實施形態中，(A)鹼溶性高分子可藉由如下方法而製備：使上述中所說明之單數或複數個單體藉由已知之聚合法、較佳為加成聚合、更佳為自由基聚合而進行聚合。 就抗蝕圖案之耐化學品性、密接性、高解像性、或下擺部形狀之觀點而言，較佳為具有芳烷基之單體、及或含有苯乙烯作為單體，例如，較佳為包含甲基丙烯酸、甲基丙烯酸苄酯及苯乙烯之共聚物、包含甲基丙烯酸、甲基丙烯酸甲酯、甲基丙烯酸苄酯及苯乙烯之共聚物等。 就抗蝕圖案之耐化學品性、密接性、高解像性、或下擺部形狀之觀點而言，藉由Fox式求出之(A)鹼溶性高分子之玻璃轉移溫度(於(A)成分包含複數種共聚物之情形時，係關於該混合物整體之玻璃轉移溫度Tg、即，玻璃轉移溫度之重量平均值Tgtotal )較佳為110℃以下，更佳為107℃以下、105℃以下、100℃以下、95℃以下、90℃以下或80℃以下。(A)鹼溶性高分子之玻璃轉移溫度(Tg)之下限值並無限定，就控制邊緣熔融性之觀點而言，較佳為30℃以上，更佳為50℃以上，進而較佳為60℃以上。 關於(A)鹼溶性高分子之酸當量(於(A)成分包含複數種共聚物之情形時，係關於該混合物整體之酸當量)，就感光性樹脂層之耐顯影性、以及抗蝕圖案之解像性及密接性之觀點而言，較佳為100以上，就感光性樹脂層之顯影性及剝離性之觀點而言，較佳為600以下。(A)鹼溶性高分子之酸當量更佳為200～500，進而較佳為250～450。 (A)鹼溶性高分子之重量平均分子量(於(A)成分包含複數種共聚物之情形時，係關於該混合物整體之重量平均分子量)較佳為5,000～500,000。關於(A)鹼溶性高分子之重量平均分子量，就均勻地維持乾膜抗蝕劑之厚度，獲得對於顯影液之耐性之觀點而言，較佳為5,000以上，就維持乾膜抗蝕劑之顯影性之觀點、抗蝕圖案之高解像性及下擺部形狀之觀點、進而抗蝕圖案之耐化學品性之觀點而言，較佳為500,000以下。(A)鹼溶性高分子之重量平均分子量更佳為10,000～200,000，進而較佳為20,000～130,000，尤佳為30,000～100,000，最佳為40,000～70,000。(A)鹼溶性高分子之分散度較佳為1.0～6.0。 於本實施形態中，感光性樹脂組合物中之(A)鹼溶性高分子之含量以感光性樹脂組合物之固形物成分總量作為基準(以下，只要未特別明示，則於各含有成分中同樣)，較佳為10質量%～90質量%，更佳為20質量%～80質量%，進而較佳為40質量%～60質量%之範圍內。關於(A)鹼溶性高分子之含量，就維持感光性樹脂層之鹼性顯影性之觀點而言，較佳為10質量%以上，就藉由曝光形成之抗蝕圖案充分地發揮作為抗蝕劑材料之性能之觀點、抗蝕圖案之高解像性及下擺部形狀之觀點、進而抗蝕圖案之耐化學品性之觀點而言，較佳為90質量%以下，更佳為70質量%以下，進而較佳為60質量%以下。 (B)具有乙烯性不飽和鍵之化合物 (B)具有乙烯性不飽和鍵之化合物係藉由在其結構中具有乙烯性不飽和基而具有聚合性之化合物。 就抗蝕圖案之耐化學品性、密接性、高解像性或下擺部形狀之觀點而言，本實施形態之感光性樹脂組合物較佳為包含具有3個以上乙烯性不飽和鍵之(甲基)丙烯酸酯化合物作為(B)具有乙烯性不飽和鍵之化合物。於該情形時，乙烯性不飽和鍵更佳為源自甲基丙烯醯基。 具有3個以上乙烯性不飽和鍵之(甲基)丙烯酸酯化合物例如係作為具有環氧乙烷鏈與二季戊四醇骨架之(甲基)丙烯酸酯化合物、或(b1)具有至少3個甲基丙烯醯基之化合物而於下文中進行說明。 就抗蝕圖案之耐化學品性、密接性、高解像性或下擺部形狀之觀點而言，本實施形態之感光性樹脂組合物較佳為包含具有5個以上乙烯性不飽和鍵，且具有環氧烷鏈之(甲基)丙烯酸酯化合物作為(B)具有乙烯性不飽和鍵之化合物。於該情形時，乙烯性不飽和鍵更佳為源自甲基丙烯醯基，並且環氧烷鏈更佳為環氧乙烷鏈。 具有5個以上乙烯性不飽和鍵，且具有環氧烷鏈之(甲基)丙烯酸酯化合物例如係作為具有環氧乙烷鏈與二季戊四醇骨架之(甲基)丙烯酸酯化合物而於下文中進行說明。 就抗蝕圖案之耐化學品性、密接性、高解像性或下擺部形狀之觀點而言，(B)具有乙烯性不飽和鍵之化合物中之甲基丙烯醯基之濃度較佳為0.20 mol/100 g以上，更佳為0.30 mol/100 g以上，進而較佳為0.35 mol/100 g以上，尤佳為0.40 mol/100 g以上。甲基丙烯醯基之濃度之上限值只要確保聚合性及鹼性顯影性，則並無特別限定，例如可為0.90 mol/100 g以下或0.80 mol/100 g以下。 就同樣之觀點而言，(B)具有乙烯性不飽和鍵之化合物中之甲基丙烯醯基之濃度/(甲基丙烯醯基之濃度＋丙烯醯基之濃度)之值較佳為0.50以上，更佳為0.60以上，進而較佳為0.80以上，尤佳為0.90以上，最佳為0.95以上。 就抗蝕圖案之耐化學品性、密接性、高解像性或下擺部形狀之觀點而言，(B)具有乙烯性不飽和鍵之化合物中之環氧乙烷單元之濃度較佳為0.80 mol/100 g以上，更佳為0.90 mol/100 g以上，進而較佳為1.00 mol/100 g以上，尤佳為1.10 mol/100 g以上。關於環氧乙烷單元之濃度之上限值，只要確保抗蝕圖案之耐化學品性、密接性及解像性，則並無特別限定，例如可為1.60 mol/100 g以下、1.50 mol/100 g以下、1.45 mol/100 g以下或1.40 mol/100 g以下。 於本實施形態中，就抗蝕圖案之耐化學品性、密接性、高解像性或下擺部形狀之觀點而言，感光性樹脂組合物較佳為包含具有環氧烷鏈與二季戊四醇骨架之(甲基)丙烯酸酯化合物作為(B)具有乙烯性不飽和鍵之化合物。作為環氧烷鏈，例如可列舉：環氧乙烷鏈、環氧丙烷鏈、環氧丁烷鏈、環氧戊烷鏈、環氧己烷鏈等。於感光性樹脂組合物包含複數個環氧烷鏈之情形時，該等相互可相同亦可不同。就上述觀點而言，作為環氧烷鏈，更佳為環氧乙烷鏈、環氧丙烷鏈、或環氧丁烷鏈，進而較佳為環氧乙烷鏈、或環氧丙烷鏈，尤佳為環氧乙烷鏈。 於感光性樹脂組合物中，藉由併用(A)鹼溶性高分子與具有環氧烷鏈及二季戊四醇骨架之(甲基)丙烯酸酯化合物，有保持抗蝕圖案之耐化學品性、密接性及解像性之平衡性之傾向。 所謂具有環氧烷鏈及二季戊四醇骨架之(甲基)丙烯酸酯化合物，係指利用伸烷基氧基將複數個羥基之至少一個改性而成之二季戊四醇化合物與(甲基)丙烯酸之酯。二季戊四醇骨架之6個羥基亦可利用伸烷基氧基進行改性。酯一分子中之酯鍵之數量可為1～6，較佳為6。 作為具有環氧烷鏈及二季戊四醇骨架之(甲基)丙烯酸酯化合物，例如可列舉於二季戊四醇上加成有環氧烷平均4～30莫耳、平均6～24莫耳、或平均10～14莫耳之六(甲基)丙烯酸酯。 具體而言，作為具有環氧烷鏈及二季戊四醇骨架之(甲基)丙烯酸酯化合物，就抗蝕圖案之耐化學品性、密接性、高解像性或下擺部形狀之觀點而言，較佳為下述通式(III)所表示之化合物， [化3]

Figure 02_image005
{式中，R分別獨立表示氫原子或甲基，且n為0～30之整數，且所有n之合計值為1以上}。 於通式(III)中，較佳為所有n之平均值為4以上，或n分別為1以上。作為R，較佳為甲基。 就抗蝕圖案之耐化學品性之觀點而言，感光性樹脂組合物中之具有環氧烷鏈及二季戊四醇骨架之(甲基)丙烯酸酯化合物之含量較佳為1質量%～50質量%，更佳為5質量%～40質量%，進而較佳為7質量%～30質量%之範圍內。 於本實施形態中，為了抑制乾膜抗蝕劑之構成成分之滲出而提高保存穩定性，將(B)具有乙烯性不飽和鍵之化合物之固形物成分總量作為基準，(B)具有乙烯性不飽和鍵之化合物中之70質量%以上、較佳為80質量%以上、更佳為90質量%以上、進而較佳為100質量%係具有500以上之重量平均分子量之化合物。就抑制滲出及抗蝕圖案之耐化學品性之觀點而言，(B)具有乙烯性不飽和鍵之化合物之重量平均分子量較佳為760以上，更佳為800以上，進而較佳為830以上，尤佳為900以上。(B)具有乙烯性不飽和鍵之化合物之重量平均分子量係藉由實施例中所記載之方法而進行測定。 為了改善抗蝕圖案之柔軟性而提高密接性，且抑制乾膜抗蝕劑之構成成分之滲出，感光性樹脂組合物較佳為包含(b1)具有至少3個甲基丙烯醯基之化合物作為(B)具有乙烯性不飽和鍵之化合物。 就抑制滲出之觀點而言，(b1)具有至少3個甲基丙烯醯基之化合物具有較佳為500以上、更佳為700以上、進而較佳為900以上之重量平均分子量。 關於(b1)具有至少3個甲基丙烯醯基之化合物，甲基丙烯醯基之數量較佳為4以上、5以上或6以上。具有至少3個甲基丙烯醯基之化合物亦可具有環氧烷鏈、例如環氧乙烷鏈、環氧丙烷鏈、或該等之組合。 作為(b1)具有至少3個甲基丙烯醯基之化合物，可列舉：三甲基丙烯酸酯、例如乙氧基化甘油三甲基丙烯酸酯、乙氧基化異三聚氰酸三甲基丙烯酸酯、季戊四醇三甲基丙烯酸酯、三羥甲基丙烷三甲基丙烯酸酯(例如，就柔軟性、密接性、及抑制滲出之觀點而言，較佳為於三羥甲基丙烷上加成有平均21莫耳之環氧乙烷之三甲基丙烯酸酯、或於三羥甲基丙烷上加成有平均30莫耳之環氧乙烷之三甲基丙烯酸酯)等；四甲基丙烯酸酯、例如二-三羥甲基丙烷四甲基丙烯酸酯、季戊四醇四甲基丙烯酸酯、二季戊四醇四甲基丙烯酸酯等；五甲基丙烯酸酯、例如二季戊四醇五甲基丙烯酸酯等；六甲基丙烯酸酯、例如二季戊四醇六甲基丙烯酸酯等。該等之中，較佳為四、五或六甲基丙烯酸酯。 作為四甲基丙烯酸酯，較佳為季戊四醇四甲基丙烯酸酯。季戊四醇四甲基丙烯酸酯可為於季戊四醇之4個末端加成有合計1～40莫耳之環氧烷之四甲基丙烯酸酯等。 四甲基丙烯酸酯更佳為下述通式(I)所表示之四甲基丙烯酸酯化合物， [化4]
Figure 02_image007
{式中，R3 ～R6 分別獨立表示碳數1～4之烷基，X表示碳數2～6之伸烷基，m1 、m2 、m3 及m4 分別獨立為0～40之整數，m1 ＋m2 ＋m3 ＋m4 為1～40，於m1 ＋m2 ＋m3 ＋m4 為2以上之情形時，複數個X可相互相同或不同}。 雖然並不期望侷限於理論，但認為，通式(I)所表示之四甲基丙烯酸酯化合物藉由具有基R3 ～R6 ，與具有H2 C＝CH-CO-O-部分之四丙烯酸酯相比，抑制於鹼性溶液中之水解性。就提高抗蝕圖案之解像性、詳細而言，線形狀、更詳細而言，線之下擺部形狀、以及抗蝕劑之密接性之觀點而言，較佳為使用包含通式(I)所表示之四甲基丙烯酸酯化合物之感光性樹脂組合物。 於通式(I)中，較佳為基R3 ～R6 之至少一個為甲基，並且更佳為基R3 ～R6 之全部為甲基。 關於抗蝕圖案，就獲得所需之解像性、下擺部形狀及殘膜率之觀點而言，於通式(I)中，X較佳為-CH2 -CH2 -。 關於抗蝕圖案，就獲得所需之解像性、下擺部形狀及殘膜率之觀點而言，於通式(I)中，m1 、m2 、m3 及m4 較佳為分別獨立為1～20之整數，更佳為2～10之整數。進而，於通式(I)中，m1 ＋m2 ＋m3 ＋m4 較佳為1～36或4～36。 作為通式(I)所表示之化合物，例如可列舉季戊四醇(聚)烷氧基四甲基丙烯酸酯等。又，於本說明書中，「季戊四醇(聚)烷氧基四甲基丙烯酸酯」包括於上述通式(I)中，m1 ＋m2 ＋m3 ＋m4 ＝1之「季戊四醇烷氧基四甲基丙烯酸酯」及m1 ＋m2 ＋m3 ＋m4 ＝2～40之「季戊四醇聚烷氧基四甲基丙烯酸酯」之兩者。作為通式(I)所表示之化合物，可列舉日本專利特開2013-156369號公報中所列舉之化合物、例如季戊四醇(聚)烷氧基四甲基丙烯酸酯等。 作為六甲基丙烯酸酯化合物，較佳為於二季戊四醇之6個末端加成有合計1～24莫耳之環氧乙烷之六甲基丙烯酸酯、於二季戊四醇之6個末端加成有合計1～10莫耳之ε-己內酯之六甲基丙烯酸酯。 相對於感光性樹脂組合物之固形物成分總量，(b1)具有至少3個甲基丙烯醯基之化合物之含量較佳為超過0質量%且為16質量%以下。若該含量超過0質量%，則有解像度提高之傾向，若為16質量%以下，則有硬化抗蝕劑之柔軟性得到改善，且剝離時間縮短之傾向。該含量更佳為2質量%以上且15質量%以下，進而較佳為4質量%以上且12質量%以下。 感光性樹脂組合物較佳為包含(b2)具有環氧丁烷鏈與1個或2個(甲基)丙烯醯基之化合物作為(B)具有乙烯性不飽和鍵之化合物。 就抑制滲出之觀點而言，(b2)具有環氧丁烷鏈與1個或2個(甲基)丙烯醯基之化合物具有較佳為500以上、更佳為700以上、進而較佳為1000以上之分子量。 作為(b2)具有環氧丁烷鏈與1個或2個(甲基)丙烯醯基之化合物，可列舉：聚四亞甲基二醇(甲基)丙烯酸酯、聚四亞甲基二醇二(甲基)丙烯酸酯等。 具體而言，(b2)具有環氧丁烷鏈與1個或2個(甲基)丙烯醯基之化合物係具有較佳為1～20個、更佳為4～15個、進而較佳為6～12個C4 H8 O之(甲基)丙烯酸酯或二(甲基)丙烯酸酯。 相對於感光性樹脂組合物之固形物成分總量，(b2)具有環氧丁烷鏈與1個或2個(甲基)丙烯醯基之化合物之含量較佳為超過0質量%且為20質量%以下。 感光性樹脂組合物可含有(b3)具有芳香環及乙烯性不飽和鍵之化合物作為(B)具有乙烯性不飽和鍵之化合物。 (b3)具有芳香環及乙烯性不飽和鍵之化合物亦可進而具有環氧烷鏈。芳香環較佳為作為源自雙酚A之二價骨架、源自萘之二價骨架、伸苯基、甲基伸苯基等二價芳香族基而組入至化合物中。環氧烷鏈可為環氧乙烷鏈、環氧丙烷鏈、或該等之組合。乙烯性不飽和鍵較佳為作為(甲基)丙烯醯基而組入至化合物中。 具體而言，作為(b3)具有芳香環及乙烯性不飽和鍵之化合物，可使用下述通式(II)所表示之化合物， [化5]
Figure 02_image009
{式中，R1 及R2 分別獨立表示氫原子或甲基，A為C2 H4 ，B為C3 H6 ，n1 及n3 分別獨立為1～39之整數，且n1 ＋n3 為2～40之整數，n2 及n4 分別獨立為0～29之整數，且n2 ＋n4 為0～30之整數，-(A-O)-及-(B-O)-之重複單元之排列可為無規亦可為嵌段，於嵌段之情形時，-(A-O)-與-(B-O)-之任一者亦可為聯苯基側}。 就解像性、及密接性之觀點而言，例如較佳為於雙酚A之兩端分別加成有平均各5莫耳之環氧乙烷之聚乙二醇之二甲基丙烯酸酯、於雙酚A之兩端分別加成有平均各2莫耳之環氧乙烷之聚乙二醇之二甲基丙烯酸酯、於雙酚A之兩端分別加成有平均各1莫耳之環氧乙烷之聚乙二醇之二甲基丙烯酸酯等。 又，作為上述具有芳香環、環氧烷鏈及乙烯性不飽和鍵之化合物，亦可使用上述通式(II)中之芳香環具有雜原子及/或取代基之化合物。 作為雜原子，例如可列舉鹵素原子等，並且作為取代基，可列舉：碳數1～20之烷基、碳數3～10之環烷基、碳數6～18之芳基、苯甲醯甲基、胺基、碳數1～10之烷基胺基、碳數2～20之二烷基胺基、硝基、氰基、羰基、巰基、碳數1～10之烷基巰基、芳基、羥基、碳數1～20之羥基烷基、羧基、烷基之碳數為1～10之羧基烷基、烷基之碳數為1～10之醯基、碳數1～20之烷氧基、碳數1～20之烷氧基羰基、碳數2～10之烷基羰基、碳數2～10之烯基、碳數2～10之N-烷基胺甲醯基或包含雜環之基、或經該等取代基取代之芳基等。該等取代基亦可形成縮合環、或該等取代基中之氫原子經鹵素原子等雜原子取代。於通式(II)中之芳香環具有複數個取代基之情形時，複數個取代基可相同或不同。 相對於感光性樹脂組合物之固形物成分總量，(b3)具有芳香環及乙烯性不飽和鍵之化合物之含量較佳為超過0質量%且為50質量%以下。若該含量超過0質量%，則有改善解像度及密接性之傾向，就顯影時間及邊緣熔融之觀點而言，較佳為50質量%以下。 上述中所說明之具有環氧烷鏈及二季戊四醇骨架之(甲基)丙烯酸酯化合物、以及(b1)～(b3)化合物可分別獨立使用或進行組合而使用。感光性樹脂組合物不僅可含有具有環氧烷鏈及二季戊四醇骨架之(甲基)丙烯酸酯化合物以及(b1)～(b3)化合物作為(B)具有乙烯性不飽和鍵之化合物，亦可含有其他化合物作為(B)具有乙烯性不飽和鍵之化合物。 作為其他化合物，可列舉：具有至少1個(甲基)丙烯醯基之丙烯酸酯化合物、具有胺基甲酸酯鍵之(甲基)丙烯酸酯、使α,β-不飽和羧酸與多元醇進行反應而獲得之化合物、使α,β-不飽和羧酸與含縮水甘油基之化合物進行反應而獲得之化合物、鄰苯二甲酸系化合物等。其中，就解像度、密接性及剝離時間之觀點而言，較佳為具有至少2個(甲基)丙烯醯基之丙烯酸酯化合物。具有至少2個(甲基)丙烯醯基之丙烯酸酯化合物可為二、三、四、五、六(甲基)丙烯酸酯等。就柔軟性、解像性、密接性等觀點而言，例如較佳為聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、具有環氧乙烷與聚環氧丙烷兩者之二(甲基)丙烯酸酯(例如「FA-023M、FA-024M、FA-027M，製品名，日立化成工業製造」)。 又，就剝離性或硬化膜柔軟性之觀點而言，較佳為包含4-正壬基苯氧基八乙二醇丙烯酸酯、4-正壬基苯氧基四乙二醇丙烯酸酯、鄰苯二甲酸γ-氯-β-羥基丙基-β'-甲基丙烯醯氧乙酯之類的具有1個乙烯性不飽和鍵之化合物，就感度、解像性、或密接性之觀點而言，亦較佳為包含鄰苯二甲酸γ-氯-β-羥基丙基-β'-甲基丙烯醯氧乙酯。 於本實施形態中，就提高抗蝕圖案之密接性，且抑制抗蝕圖案之硬化不良、顯影時間之延遲、冷流或滲出或硬化抗蝕劑之剝離延遲之觀點而言，感光性樹脂組合物中之所有(B)具有乙烯性不飽和鍵之化合物之總含量較佳為1質量%～70質量%，更佳為2質量%～60質量%，進而較佳為4質量%～50質量%之範圍內。 (C)光聚合起始劑 (C)光聚合起始劑係藉由光使單體進行聚合之化合物。感光性樹脂組合物包含本技術領域中通常已知之化合物作為(C)光聚合起始劑。 感光性樹脂組合物中之(C)光聚合起始劑之總含量較佳為0.01～20質量%，更佳為0.05質量%～10質量%，進而較佳為0.1質量%～7質量%，尤佳為0.1質量%～6質量%之範圍內。關於(C)光聚合起始劑之總含量，就獲得充分之感度之觀點而言較佳為0.01質量%以上，就使光充分地透過至抗蝕劑底面，而獲得良好之高解像性之觀點而言，較佳為20質量%以下。 作為(C)光聚合起始劑，可列舉：醌類、芳香族酮類、苯乙酮類、醯基氧化膦類、安息香或安息香醚類、二烷基縮酮類、9-氧硫𠮿
Figure 108122448-xxxx-3
類、二烷基胺基苯甲酸酯類、肟酯類、吖啶類(就感度、解像性、及密接性之觀點而言，例如較佳為9-苯基吖啶、雙吖啶基庚烷、9-(對甲基苯基)吖啶、9-(間甲基苯基)吖啶)，進而可列舉：六芳基聯咪唑、吡唑啉化合物、蒽化合物(就感度、解像性、及密接性之觀點而言，例如較佳為9,10-二丁氧基蒽、9,10-二乙氧基蒽、9,10-二苯基蒽)、香豆素化合物(就感度、解像性、及密接性之觀點而言，例如較佳為7-二乙基胺基-4-甲基香豆素)、N-芳基胺基酸或其酯化合物(就感度、解像性、及密接性之觀點而言，例如較佳為N-苯基甘胺酸)、及鹵化合物(例如三溴甲基苯基碸)等。該等可單獨使用一種或組合兩種以上而使用。除此以外，亦可使用2,2-二甲氧基-1,2-二苯基乙烷-1-酮、2-甲基-1-(4-甲基噻吩基)-2-嗎啉基丙烷-1-酮、2,4,6-三甲基苯甲醯基-二苯基氧化膦、三苯基氧化膦等。 作為芳香族酮類，例如可列舉：二苯甲酮、米其勒酮[4,4'-雙(二甲基胺基)二苯甲酮]、4,4'-雙(二乙基胺基)二苯甲酮、4-甲氧基-4'-二甲基胺基二苯甲酮。該等可單獨使用一種或組合兩種以上而使用。該等之中，就密接性之觀點而言，較佳為4,4'-雙(二乙基胺基)二苯甲酮。進而，就透過率之觀點而言，感光性樹脂組合物中之芳香族酮類之含量較佳為0.01質量%～0.5質量%，進而較佳為0.02質量%～0.3質量%之範圍內。 作為六芳基聯咪唑之例，可列舉：2-(鄰氯苯基)-4,5-二苯基聯咪唑、2,2',5-三-(鄰氯苯基)-4-(3,4-二甲氧基苯基)-4',5'-二苯基聯咪唑、2,4-雙-(鄰氯苯基)-5-(3,4-二甲氧基苯基)-二苯基聯咪唑、2,4,5-三-(鄰氯苯基)-二苯基聯咪唑、2-(鄰氯苯基)-雙-4,5-(3,4-二甲氧基苯基)-聯咪唑、2,2'-雙-(2-氟苯基)-4,4',5,5'-四-(3-甲氧基苯基)-聯咪唑、2,2'-雙-(2,3-二氟甲基苯基)-4,4',5,5'-四-(3-甲氧基苯基)-聯咪唑、2,2'-雙-(2,4-二氟苯基)-4,4',5,5'-四-(3-甲氧基苯基)-聯咪唑、2,2'-雙-(2,5-二氟苯基)-4,4',5,5'-四-(3-甲氧基苯基)-聯咪唑、2,2'-雙-(2,6-二氟苯基)-4,4',5,5'-四-(3-甲氧基苯基)-聯咪唑、2,2'-雙-(2,3,4-三氟苯基)-4,4',5,5'-四-(3-甲氧基苯基)-聯咪唑、2,2'-雙-(2,3,5-三氟苯基)-4,4',5,5'-四-(3-甲氧基苯基)-聯咪唑、2,2'-雙-(2,3,6-三氟苯基)-4,4',5,5'-四-(3-甲氧基苯基)-聯咪唑、2,2'-雙-(2,4,5-三氟苯基)-4,4',5,5'-四-(3-甲氧基苯基)-聯咪唑、2,2'-雙-(2,4,6-三氟苯基)-4,4',5,5'-四-(3-甲氧基苯基)-聯咪唑、2,2'-雙-(2,3,4,5-四氟苯基)-4,4',5,5'-四-(3-甲氧基苯基)-聯咪唑、2,2'-雙-(2,3,4,6-四氟苯基)-4,4',5,5'-四-(3-甲氧基苯基)-聯咪唑、及2,2'-雙-(2,3,4,5,6-五氟苯基)-4,4',5,5'-四-(3-甲氧基苯基)-聯咪唑等，該等可單獨使用一種或組合兩種以上而使用。就高感度、解像性及密接性之觀點而言，較佳為2-(鄰氯苯基)-4,5-二苯基咪唑二聚物。 於本實施形態中，就提高感光性樹脂層之剝離特性及/或感度之觀點而言，感光性樹脂組合物中之六芳基雙咪唑化合物之含量較佳為0.05質量%～7質量%，更佳為0.1質量%～6質量%，進而較佳為1質量%～4質量%之範圍內。 就感光性樹脂層之剝離特性、感度、解像性、或密接性之觀點而言，感光性樹脂組合物較佳為亦包含吡唑啉化合物作為光敏劑。 作為吡唑啉化合物，就上述觀點而言，例如較佳為1-苯基-3-(4-第三丁基-苯乙烯基)-5-(4-第三丁基-苯基)-吡唑啉、1-(4-(苯并
Figure 108122448-A0304-12-0015-1
唑-2-基)苯基)-3-(4-第三丁基-苯乙烯基)-5-(4-第三丁基-苯基)-吡唑啉、1-苯基-3-(4-聯苯基)-5-(4-第三丁基-苯基)-吡唑啉、1-苯基-3-(4-聯苯基)-5-(4-第三辛基-苯基)-吡唑啉、1-苯基-3-(4-異丙基苯乙烯基)-5-(4-異丙基苯基)-吡唑啉、1-苯基-3-(4-甲氧基苯乙烯基)-5-(4-甲氧基苯基)-吡唑啉、1-苯基-3-(3,5-二甲氧基苯乙烯基)-5-(3,5-二甲氧基苯基)-吡唑啉、1-苯基-3-(3,4-二甲氧基苯乙烯基)-5-(3,4-二甲氧基苯基)-吡唑啉、1-苯基-3-(2,6-二甲氧基苯乙烯基)-5-(2,6-二甲氧基苯基)-吡唑啉、1-苯基-3-(2,5-二甲氧基苯乙烯基)-5-(2,5-二甲氧基苯基)-吡唑啉、1-苯基-3-(2,3-二甲氧基苯乙烯基)-5-(2,3-二甲氧基苯基)-吡唑啉、1-苯基-3-(2,4-二甲氧基苯乙烯基)-5-(2,4-二甲氧基苯基)-吡唑啉等，更佳為1-苯基-3-(4-聯苯基)-5-(4-第三丁基-苯基)-吡唑啉。 感光性樹脂組合物可含有一種或兩種以上之吡唑啉化合物作為光敏劑。 於本實施形態中，就提高感光性樹脂層之剝離特性及/或感度之觀點而言，感光性樹脂組合物中之光敏劑之含量較佳為0.05質量%～5質量%，更佳為0.1質量%～3質量%之範圍內。 (D)添加劑 感光性樹脂組合物視需要可含有染料、塑化劑、抗氧化劑、穩定劑等添加劑。例如可使用日本專利特開2013-156369號公報中所列舉之添加劑。 就著色性、色相穩定性及曝光對比度之觀點而言，感光性樹脂組合物較佳為包含三(4-二甲基胺基苯基)甲烷[隱色結晶紫]及/或鑽石綠(Hodogaya化學股份有限公司製造之Aizen(註冊商標)DIAMOND GREEN GH)作為染料。 於本實施形態中，感光性樹脂組合物中之染料之含量較佳為0.001質量%～3質量%，更佳為0.01質量%～2質量%，進而較佳為0.02質量%～1質量%之範圍內。關於染料之含量，就獲得良好之著色性之觀點而言，較佳為0.001質量%以上，就維持感光性樹脂層之感度之觀點而言，較佳為3質量%以下。 就感光性樹脂組合物之熱穩定性或保存穩定性之觀點而言，感光性樹脂組合物較佳為包含選自由自由基聚合抑制劑、例如亞硝基苯基羥基胺鋁鹽、對甲氧基苯酚、4-第三丁基鄰苯二酚、4-乙基-6-第三丁基苯酚等；苯并三唑類、例如1-(2-二-正丁基胺基甲基)-5-羧基苯并三唑與1-(2-二-正丁基胺基甲基)-6-羧基苯并三唑之1：1混合物等；羧基苯并三唑類、例如4-羧基-1,2,3-苯并三唑、5-羧基-1,2,3-苯并三唑、6-羧基-1,2,3-苯并三唑等；及具有縮水甘油基之環氧烷化合物、例如新戊二醇二縮水甘油基醚等所組成之群中之至少一者作為穩定劑。除此以外，亦可含有2-巰基苯并咪唑、1H-四唑、1-甲基-5-巰基-1H-四唑、2-胺基-5-巰基-1,3,4-噻二唑、3-胺基-5-巰基-1,2,4-三唑、3-巰基-1,2,4-三唑、3-巰基三唑、4,5-二苯基-1,3-二唑-2-基、5-胺基-1H-四唑等。 於本實施形態中，感光性樹脂組合物中之所有穩定劑之總含量較佳為0.001質量%～3質量%，更佳為0.01質量%～1質量%，進而較佳為0.05質量%～0.7質量%之範圍內。關於穩定劑之總含量，就對感光性樹脂組合物賦予良好之保存穩定性之觀點而言，較佳為0.001質量%以上，就維持感光性樹脂層之感度之觀點而言，較佳為3質量%以下。 上述中所說明之添加劑可單獨使用一種或組合兩種以上而使用。 ＜感光性樹脂組合物調合液＞ 於本實施形態中，藉由向感光性樹脂組合物中添加溶劑，可形成感光性樹脂組合物調合液。作為適宜之溶劑，可列舉：酮類、例如甲基乙基酮(MEK)等；及醇類、例如甲醇、乙醇、異丙醇等。較佳為以感光性樹脂組合物調合液之黏度於25℃下成為500 mPa・sec～4000 mPa・sec之方式，將溶劑添加至感光性樹脂組合物中。 ＜感光性樹脂積層體＞ 於本實施形態中，可提供一種感光性樹脂積層體，其具有支持體、及積層於支持體上之包含上述感光性樹脂組合物之感光性樹脂層。感光性樹脂積層體視需要可於感光性樹脂層之與支持體側相反之側具有保護層。 作為支持體，並無特別限定，較佳為使自曝光光源發射之光透過之透明者。作為此種支持體，例如可列舉：聚對苯二甲酸乙二酯膜、聚乙烯醇膜、聚氯乙烯膜、氯乙烯共聚物膜、聚偏二氯乙烯膜、偏二氯乙烯共聚合膜、聚甲基丙烯酸甲酯共聚物膜、聚苯乙烯膜、聚丙烯腈膜、苯乙烯共聚物膜、聚醯胺膜、及纖維素衍生物膜。該等膜視需要亦可經延伸。霧度較佳為0.01%～5.0%，更佳為0.01%～2.5%，進而較佳為0.01%～1.0%。關於膜之厚度，雖然膜越薄於圖像形成性及經濟性之方面越有利，但因維持強度之需求，較佳為10 μm～30 μm。 又，感光性樹脂積層體中所使用之保護層之重要之特性如下：關於與感光性樹脂層之密接力，保護層小於支持體，可容易地剝離。作為保護層，例如，較佳為聚乙烯膜、聚丙烯膜等。例如可使用日本專利特開昭59-202457號公報中所記載之剝離性優異之膜。保護層之膜厚較佳為10 μm～100 μm，更佳為10 μm～50 μm。 於本實施形態中，感光性樹脂積層體中之感光性樹脂層之厚度較佳為5 μm～100 μm，更佳為7 μm～60 μm。感光性樹脂層之厚度越小，抗蝕圖案之解像性越提高，另一方面，感光性樹脂層之厚度越大硬化膜之強度越提高，因此可根據用途加以選擇。 作為依序積層支持體、感光性樹脂層、及視需要之保護層，而製作感光性樹脂積層體之方法，可使用已知之方法。 例如，製備上述感光性樹脂組合物調合液，其次使用棒式塗佈機或輥式塗佈機塗佈於支持體上並使之乾燥，於支持體上積層包含感光性樹脂組合物調合液之感光性樹脂層。進而，視需要於感光性樹脂層上積層保護層，藉此可製作感光性樹脂積層體。 ＜抗蝕圖案形成方法＞ 抗蝕圖案之形成方法較佳為依序包括如下步驟：層壓步驟，其於支持體上積層包含上述感光性樹脂組合物之感光性樹脂層；曝光步驟，其對感光性樹脂層進行曝光；及顯影步驟，其將經曝光之感光性樹脂層進行顯影。於本實施形態中，將形成抗蝕圖案之具體方法之一例示於以下。 首先，於層壓步驟中，使用貼合機於基板上形成感光性樹脂層。具體而言，於感光性樹脂積層體具有保護層之情形時，於剝離保護層後，利用貼合機將感光性樹脂層加熱壓接於基板表面而進行層壓。作為基板之材料，例如可列舉：銅、不鏽鋼(SUS)、玻璃、氧化銦錫(ITO)等。 於本實施形態中，感光性樹脂層亦可僅於基板表面之單面進行層壓、或視需要於雙面進行壓。層壓時之加熱溫度通常為40℃～160℃。又，藉由進行2次以上層壓時之加熱壓接，可提高所獲得之抗蝕圖案對於基板之密接性。於加熱壓接時，使用具備兩根輥之二段式貼合機，或者亦可藉由使基板與感光性樹脂層之積層物重複數次通過輥而進行壓接。 其次，於曝光步驟中，使用曝光機使感光性樹脂組層曝光於活性光下。曝光視需要可於剝離支持體後進行。於利用光罩進行曝光之情形時，曝光量係根據光源照度及曝光時間而決定，亦可使用光量計進行測定。於曝光步驟中，亦可進行直接成像曝光。於直接成像曝光中，不使用光罩而利用直接繪圖裝置於基板上進行曝光。作為光源，可使用波長350 nm～410 nm之半導體雷射或超高壓水銀燈。於利用電腦控制繪圖圖案之情形時，曝光量係根據曝光光源之照度及基板之移動速度而決定。亦可藉由使光罩之像通過透鏡進行投影而進行曝光。 其次，於顯影步驟中，使用顯影裝置利用顯影液去除曝光後之感光性樹脂層之未曝光部或曝光部。曝光後，於在感光性樹脂層上存在支持體之情形時，將其去除。繼而使用包含鹼性水溶液之顯影液，將未曝光部或曝光部顯影去除，而獲得抗蝕劑圖像。 作為鹼性水溶液，較佳為Na2 CO3 、K2 CO3 等之水溶液。鹼性水溶液係根據感光性樹脂層之特性而加以選擇，通常使用0.2質量%～2質量%之濃度之Na2 CO3 水溶液。於鹼性水溶液中，亦可混合表面活性劑、消泡劑、用以促進顯影之少量之有機溶劑等。顯影步驟中之顯影液之溫度較佳為於20℃～40℃之範圍內保持為固定。 藉由上述步驟可獲得抗蝕圖案，視需要亦可進而於100℃～300℃下進行加熱步驟。藉由實施該加熱步驟，可提高抗蝕圖案之耐化學品性。加熱步驟中可使用利用熱風、紅外線、或遠紅外線之方式之加熱爐。 本實施形態之感光性樹脂組合物可適宜地用以形成印刷基板之電路。通常，作為印刷基板之電路形成方法，使用減成法及半加成法(SAP)。 減成法係藉由蝕刻自配置於基板整個面之導體僅去除非電路部分而形成電路之方法。 SAP係於配置於基板整個面之導體籽晶層上之非電路部分形成抗蝕劑後，藉由鍍敷僅形成電路部分之方法。 於本實施形態中，感光性樹脂組合物更佳為用於SAP。 ＜感光性樹脂組合物之硬化物＞ 於本實施形態中，為了改善抗蝕圖案之柔軟性，感光性樹脂組合物之硬化物之伸長率較佳為1 mm以上，更佳為2 mm以上，進而較佳為3 mm以上。 硬化物之伸長率係藉由如下方法而進行測定：使利用感光性樹脂組合物所製作之感光性樹脂積層體通過5 mm×40 mm之長方形之光罩而進行曝光，進而以最小顯影時間之2倍之時間進行顯影，利用拉伸試驗機(Orientec股份有限公司製造之RTM-500)以100 mm/min之速度拉伸所獲得之硬化抗蝕劑。 於本實施形態中，就抗蝕圖案之解像性與柔軟性之觀點而言，感光性樹脂組合物之硬化物之楊氏模數較佳為1.5 GPa以上且未達8 GPa之範圍內。於本說明書中，「楊氏模數」可使用Toyo Technica股份有限公司製造之奈米壓痕儀(nanoindenter)DCM並藉由奈米壓痕法進行測定。具體而言，「楊氏模數」係將測定對象樹脂組合物層壓於基板上，進行曝光並進行顯影，對所獲得之基板上之感光性樹脂組合物表面使用Toyo Technica股份有限公司製造之奈米壓痕儀DCM進行測定。作為測定之方法，使用DCM Basic Hardness, Modulus, Tip Cal, Load Control. msm(MultiLoad Unload Method, MultiLoad Method)，壓入試驗之參數係設為卸載百分比(Percent To Unload)＝90%、最大負載(Maximum Load)＝1 gf、負載率與卸載率之比(Load Rate Multiple For Unload Rate)＝1、負載時間編號(Number Of Times to Load)＝5、峰值保持時間(Peak Hold time)＝10 s、負載時間(Time To Load)＝15 s、柏鬆比(Poisson's ratio)＝0.25。楊氏模數係設為「Modulas At Max Load」之值。 ＜導體圖案之製造方法＞ 導體圖案之製造方法較佳為依序包括如下步驟：層壓步驟，於金屬板、金屬皮膜絕緣板等基板上積層包含上述感光性樹脂組合物之感光性樹脂層；曝光步驟，其對感光性樹脂層進行曝光；顯影步驟，藉由利用顯影液去除經曝光之感光性樹脂層之未曝光部或曝光部，而獲得形成有抗蝕圖案之基板；及導體圖案形成步驟，其對形成有抗蝕圖案之基板進行蝕刻或鍍敷。 於本實施形態中，導體圖案之製造方法係藉由使用金屬板或金屬皮膜絕緣板作為基板，於藉由上述抗蝕圖案形成方法形成抗蝕圖案後，經過形成導體圖案步驟而進行。於導體圖案形成步驟中，於藉由顯影而露出之基板表面(例如銅面)上使用已知之蝕刻法或鍍敷法而形成導體圖案。 進而，本發明例如適宜地應用於以下之用途。 ＜配線板之製造方法＞ 於藉由導體圖案之製造方法而製造導體圖案後，進而進行利用具有強於顯影液之鹼性之水溶液而自基板上剝離抗蝕圖案之剝離步驟，藉此可獲得具有所需之配線圖案之配線板(例如印刷配線板)。 於配線板之製造中，作為基板，使用絕緣樹脂層與銅層之積層體、或可撓性基板。為了進行SAP，較佳為使用絕緣樹脂層與銅層之積層體。關於SAP，銅層較佳為包含鈀作為觸媒之無電解鍍銅層。關於SAP，亦較佳為藉由已知之鍍敷法進行導體圖案形成步驟。為了進行改良型半加成法(MSAP)，基板較佳為絕緣樹脂層與銅箔之積層體，更佳為銅箔積層板。 關於剝離用之鹼性水溶液(以下，亦稱為「剝離液」)，並無特別限制，通常使用2質量%～5質量%之濃度之NaOH或KOH之水溶液、或者有機胺系剝離液。於剝離液中可添加少量之水溶性溶劑。作為水溶性溶劑，例如可列舉醇等。剝離步驟中之剝離液之溫度較佳為40℃～70℃之範圍內。 為了進行SAP，配線板之製造方法較佳為進而包括自所獲得之配線板去除鈀之步驟。 ＜引線框架之製造＞ 使用銅、銅合金、或鐵系合金等金屬板作為基板，藉由抗蝕圖案形成方法而形成抗蝕圖案後，經過以下之步驟，藉此可製造引線框架。首先，進行對藉由顯影而露出之基板進行蝕刻而形成導體圖案之步驟。其後，進行藉由與配線板之製造方法相同之方法而剝離抗蝕圖案之剝離步驟，從而可獲得所需之引線框架。 ＜具有凹凸圖案之基材之製造＞ 藉由抗蝕圖案形成方法而形成之抗蝕圖案可用作藉由噴砂方法對基板實施加工時之保護光罩構件。於該情形時，作為基板，例如可列舉：玻璃、矽晶圓、非晶質矽、多晶矽、陶瓷、藍寶石、金屬材料等。於該等基板上，藉由與抗蝕圖案形成方法相同之方法，形成抗蝕圖案。其後，可進行自所形成之抗蝕圖案上吹送噴砂材，並切削至目標深度之噴砂處理步驟；及利用鹼性剝離液等自基板上去除殘留於基板上之抗蝕圖案部分之剝離步驟，而製造於基板上具有微細之凹凸圖案之基材。 於噴砂處理步驟中，可使用公知之噴砂材，例如通常使用包含SiC、SiO2 、Al2 O3 、CaCO3 、ZrO、玻璃、不鏽鋼等之粒徑2 μm～100 μm之微粒子。 ＜半導體封裝之製造＞ 使用大規模積體化電路(LSI)之形成結束之晶圓作為基板，於藉由抗蝕圖案形成方法於晶圓上形成抗蝕圖案後，經過以下之步驟，藉此可製造半導體封裝。首先，進行對藉由顯影而露出之開口部實施銅、焊料等之柱狀鍍敷，而形成導體圖案之步驟。其後，進行藉由與配線板之製造方法相同之方法而剝離抗蝕圖案之剝離步驟，進而，進行藉由蝕刻去除柱狀鍍層以外之部分之較薄之金屬層之步驟，藉此可獲得所需之半導體封裝。 於本實施形態中，感光性樹脂組合物可用於印刷配線板之製造；IC(Integrated Circuit，積體電路)晶片搭載用引線框架製造；金屬掩膜製造等金屬箔精密加工；球柵陣列(BGA)、晶片尺寸封裝(CSP)等封裝之製造；薄膜覆晶(COF)、捲帶式自動接合(TAB)等捲帶基板之製造；半導體凸塊之製造；及ITO電極、定址電極、電磁波遮罩等平板顯示器之間隔壁之製造。 再者，關於上述各參數之值，只要無特別說明，則依據下述實施例中之測定方法而進行測定。 [實施例] 說明高分子之物性值之測定、高分子之玻璃轉移溫度之計算、以及實施例及比較例之評價用樣品之製作方法，繼而，示出針對所獲得之樣品之評價方法及其評價結果。 (1)物性值之測定或計算 ＜高分子之重量平均分子量或數量平均分子量之測定＞ 高分子之重量平均分子量或數量平均分子量係藉由日本分光股份有限公司製造之凝膠滲透層析儀(GPC)(泵：Gulliver、PU-1580型、管柱：昭和電工股份有限公司製造之Shodex(註冊商標)(KF-807、KF-806M、KF-806M、KF-802.5)4根串聯、流動層溶劑：四氫呋喃、使用利用聚苯乙烯標準樣品(昭和電工股份有限公司製造之Shodex STANDARD SM-105)之校準曲線)，以聚苯乙烯換算之形式求出。 進而，高分子之分散度係以重量平均分子量相對於數量平均分子量之比(重量平均分子量/數量平均分子量)之形式而算出。 ＜酸當量＞ 於本說明書中，所謂酸當量係指於分子中具有1當量之羧基之聚合物之質量(克)。使用平沼產業股份有限公司製造之平沼自動滴定裝置(COM-555)，使用0.1 mol/L之氫氧化鈉水溶液並藉由電位差滴定法測定酸當量。 ＜玻璃轉移溫度＞ 鹼溶性高分子之玻璃轉移溫度係根據下述式(Fox式)求出之值， [數1]
Figure 02_image011
{式中，Wi 係構成鹼溶性高分子之共聚單體各自之質量， Tgi 係構成鹼溶性高分子之共聚單體之各者為均聚物之情形時之玻璃轉移溫度， Wtotal 係鹼溶性高分子之合計質量，並且 n係構成鹼溶性高分子之共聚單體之種類之數量}。 此處，於求出玻璃轉移溫度Tgi 時，作為包含形成相對應之鹼溶性高分子之共聚單體之均聚物之玻璃轉移溫度，係設為使用Brandrup, J. Immergut, E. H. 編輯「Polymer handbook, Third edition, John wiley ＆ sons, 1989, p. 209 Chapter VI 『Glass transition temperatures of polymers』」所表示之值者。再者，將於實施例中計算所使用之包含各共聚單體之均聚物之Tgi 示於表1。 ＜(B)具有乙烯性不飽和鍵之化合物之重量平均分子量＞ 於實施例I-1～I-16及比較例I-1～I-3中，根據(B)具有乙烯性不飽和鍵之化合物之分子結構進行計算，藉此求出分子量。於存在複數種(B)具有乙烯性不飽和鍵之化合物之情形時，藉由對各化合物之分子量利用含量進行加權平均而求出。 又，於實施例II-1～II-6及比較例II-1～II-5中，具有乙烯性不飽和鍵之化合物之重量平均分子量係藉由日本分光股份有限公司製造之凝膠滲透層析儀(GPC)(泵：Gulliver、PU-1580型、管柱：昭和電工股份有限公司製造之Shodex(註冊商標)(K-801、K-801、K-802、KF-802.5)4根串聯、流動層溶劑：四氫呋喃、使用利用聚苯乙烯標準樣品(Tosoh股份有限公司製造之TSK standard POLYSTYRENE)之校準曲線)，以聚苯乙烯換算之形式求出。 ＜(B)具有乙烯性不飽和鍵之化合物中之甲基丙烯醯基之濃度＞ 藉由計算甲基丙烯醯基相對於(B)具有乙烯性不飽和鍵之化合物100 g之莫耳數而求出。 ＜B)具有乙烯性不飽和鍵之化合物中之環氧乙烷(EO)單元之濃度＞ 藉由計算環氧乙烷(EO)單元相對於(B)具有乙烯性不飽和鍵之化合物100 g之莫耳數而求出。 (2)評價用樣品之製作方法 評價用樣品係以如下方式製作。 ＜感光性樹脂積層體之製作＞ 將下述表2～5中所示之成分(其中，各成分之數字表示以固形物成分計之調配量(質量份))及溶劑充分地攪拌、混合，而獲得感光性樹脂組合物調合液。將於表2及4中縮寫所表示之成分之名稱分別示於下述表3及5。使用16 μm厚之聚對苯二甲酸乙二酯膜(Toray股份有限公司製造之FB-40)作為支持膜，使用棒式塗佈機，將該調合液均勻地塗佈於其表面，於95℃之乾燥機中進行2.5分鐘乾燥，而形成感光性樹脂組合物層。感光性樹脂組合物層之乾燥厚度為25 μm。 繼而，於感光性樹脂組合物層之未積層聚對苯二甲酸乙二酯膜之側之表面上，貼合19 μm厚之聚乙烯膜(Tamapoly股份有限公司製造之GF-818)作為保護層而獲得感光性樹脂積層體。 ＜基板整面＞ 於實施例I-1～I-16及比較例I-1～I-3中，作為感度、圖像性、密接性及耐藥液性之評價基板，利用軟蝕刻劑(菱江化學股份有限公司製造之CPE-900)對積層有35 μm壓延銅箔之0.4 mm厚之銅箔積層板進行處理，並利用10質量%H2 SO4 洗淨基板表面。 又，於實施例II-1～II-6及比較例II-1～II-5中，使用研削材(日本Carlit股份有限公司製造之Sakurundum R(註冊商標＃220))，對積層有35 μm壓延銅箔之0.4 mm厚之銅箔積層板於噴霧壓0.2 MPa下進行噴砂沖洗研磨，藉此製作評價用基板。 ＜層壓＞ 一面剝離感光性樹脂積層體之聚乙烯膜，一面對表面進行清潔修整而於預熱至60℃之銅箔積層板上，利用加熱輥貼合機(旭化成股份有限公司製造之AL-700)，將感光性樹脂積層體於輥溫度105℃下進行層壓而獲得試片。氣壓係設為0.35 MPa，層壓速度係設為1.5 m/min。 ＜曝光＞ 於實施例I-1～I-16及比較例I-1～I-3中，利用直接繪圖曝光機(日立Via Mechanics股份有限公司製造，DE-1DH，光源：GaN藍紫二極體，主波長405±5 nm)，使用斯圖費41段格階段式曝光表或特定之直接成像(DI)曝光用之光罩圖案，於照度85 mW/cm2 之條件下進行曝光。曝光係以將上述斯圖費41段格階段式曝光表作為光罩而進行曝光、顯影時之最高殘膜段格數成為15段格之曝光量進行。 又，於實施例II-1～II-6及比較例II-1～II-5中，使用鉻玻璃光罩，利用平行光曝光機(Oak股份有限公司製作所公司製造之HMW-801)，以表4所示之曝光量進行曝光。 ＜顯影＞ 於實施例I-1～I-16及比較例I-1～I-3中，剝離經曝光之評價基板之聚對苯二甲酸乙二酯膜後，使用鹼性顯影機(FUJI KIKO製造之乾膜用顯影機)，將30℃之1質量%Na2 CO3 水溶液噴霧特定時間，而將感光性樹脂層之未曝光部分溶解去除。此時，歷經最小顯影時間之2倍之時間進行顯影，而製作硬化抗蝕圖案。再者，所謂最小顯影時間，係指未曝光部分之感光性樹脂層完全溶解所需之最少之時間。 又，於實施例II-1～II-6及比較例II-1～II-5中，於自感光性樹脂積層體剝離聚對苯二甲酸乙二酯膜後，使用FUJI KIKO股份有限公司製造之顯影裝置，利用全錐(full cone)型之噴嘴，於顯影噴霧壓0.15 MPa下，將30℃之1質量%Na2 CO3 水溶液噴霧特定時間並進行顯影，而將感光性樹脂層之未曝光部分溶解去除。此時，將未曝光部分之感光性樹脂層完全溶解所需之最少之時間設為最小顯影時間而進行測定，以最小顯影時間之2倍之時間進行顯影而製作抗蝕圖案。此時，水洗步驟係利用平板型之噴嘴，於水洗噴霧壓0.15 MPa下，進行與顯影步驟相同時間之處理。 (3)樣品之評價方法 ＜感度評價＞ 使層壓後經過15分鐘之感度評價用基板通過斯圖費41段格階段式曝光表之光罩而進行曝光。以最小顯影時間之2倍之時間進行顯影，以最高殘膜段格數成為15段格之曝光量藉由以下之基準進行分級。 ○(良好)：最高殘膜段格數成為15段格之曝光量未達70 mJ/cm2 。 ×(不良)：最高殘膜段格數成為15段格之曝光量為70 mJ/cm2 以上。 ＜解像性＞ 對層壓後經過15分鐘之解像性評價用基板，使用具有曝光部與未曝光部之寬度為1：1之比率之線圖案之繪圖資料而進行曝光。以最小顯影時間之2倍之顯影時間進行顯影，而形成硬化抗蝕劑線。 於實施例I-1～I-16及比較例I-1～I-3中，將正常形成硬化抗蝕劑線之最小線寬設為解像度之值並藉由以下之基準進行分級。 ○(良好)：解像度之值為12 μm以下。 △(容許)：解像度之值超過12 μm且為17 μm以下。 ×(不良)：解像度之值超過17 μm。 又，於實施例II-1～II-6及比較例II-1～II-5中，將正常形成硬化抗蝕劑線之最小線寬設為解像度之值並藉由以下之基準進行分級。 ◎(極良好)：解像度之值為7.5 μm以下。 ○(良好)：解像度之值超過7.5 μm且為9 μm以下。 △(容許)：解像度之值超過9 μm。 ＜FT-IR測定＞ 於剝離感光性樹脂積層體之聚乙烯膜後，進行FT-IR(Thermo SCIENTIFIC製造之NICOLET 380)測定。 波數810 cm-1 下之波峰高度P係藉由在曝光前利用FT-IR測定吸光度而求出。於該波峰與其他波峰重疊之情形時，利用線連接該波峰之兩側之上升點彼此，並測量距該線之最高高度。 乙烯性雙鍵之反應率Q係藉由以下之方法求出。自感光性樹脂積層體之聚對苯二甲酸乙二酯膜(支持層)側使用直接繪圖曝光機(日立Via Mechanics股份有限公司製造，DE-1DH，光源：GaN藍紫二極體(主波長405±5 nm))，進行曝光。曝光時之照度係設為85 mW/cm2 。關於此時之曝光量，藉由上述方法以斯圖費41段格階段式曝光表作為光罩而進行曝光，繼而以進行顯影時之最高殘膜段格數成為15段格之曝光量進行。對藉由以上之操作而獲得之硬化抗蝕劑之乙烯性雙鍵之反應率Q，根據波數810 cm-1 之曝光前後之波峰高度算出乙烯性雙鍵基之消失率(%)，並求出反應率Q(%)。 R為感光性樹脂層之膜厚(μm)，藉由計算求出P×Q/R。 ＜密接性＞ 於實施例I-1～I-16及比較例I-1～I-3中，對層壓後經過15分鐘之解像性評價用基板，使用具有曝光部與未曝光部之寬度為1：400之比率之線圖案之繪圖資料而進行曝光。以最小顯影時間之2倍之顯影時間進行顯影，將正常形成硬化抗蝕劑線之最小線寬設為密接性之值，並藉由以下之基準進行分級。 ○(極良好)：密接性之值為12 μm以下。 ○△(良好)：密接性之值超過12 μm且為13 μm以下。 △(容許)：密接性之值超過13 μm且為15 μm以下。 ×(不良)：密接性之值超過15 μm。 又，於實施例II-1～II-6及比較例II-1～II-5中，使層壓後經過15分鐘之評價用基板通過具有曝光部與未曝光部之寬度為1：100之比率之線圖案之鉻玻璃光罩而進行曝光。以最小顯影時間之2倍之時間進行顯影，將正常形成硬化抗蝕劑線之最小線寬設為密接性之值，並以如下方法進行分級。 ◎(極良好)：密接性之值為7.5 μm以下。 ○(良好)：密接性之值超過7.5 μm且為9 μm以下。 △(容許)：密接性之值超過9 μm且未達10 μm。 ×(不良)：密接性之值為10 μm以上。 ＜耐藥液性評價＞ 將Atotech Japan股份有限公司製造之CupraPro S2 100 mL、98%硫酸60 mL及純水840 mL混合，而製作藥液。對層壓後經過15分鐘之解像性評價用基板，使用具有曝光部與未曝光部之寬度為1：400之比率之線圖案之繪圖資料而進行曝光。以最小顯影時間之2倍之顯影時間進行顯影，並於燒杯中於加熱至40℃之藥液中浸漬5分鐘。浸漬後，利用純水進行洗淨，將正常形成硬化抗蝕劑線之最小線寬設為耐藥液性之值而獲得。再者，於表2中，僅將耐藥液性之值超過17 μm之情形表示為「×(不良)」。 ＜滲出性＞ 將捲取為卷狀之感光性樹脂積層體於23℃、遮光條件下保管，對因滲出而於支持膜表面(其中輥之最外層除外)產生黏性前之時間以如下方式進行分級，並評價滲出性。 ○(良好)：於支持膜表面產生黏性前之時間為1個月以上 ×(不良)：於支持膜表面產生黏性前之時間未達1個月 (4)評價結果 將評價結果示於下述表2～5。以耐藥液性評價為17 μm以下之方式設計之感光性樹脂組合物之抗蝕圖案之密接性、解像性、或下擺部形狀之平衡性亦優異。又，藉由使用此種感光性樹脂組合物，於藉由鍍敷形成配線圖案時，可抑制短路。於耐藥液性評價之後進行鍍銅，結果藉由比較例I-1之組成，於硬化抗蝕劑之線寬15 μm之部分觀察到短路，但藉由實施例I-1之組成，未觀察到短路，而推測不良有可能減少。 [表1]
Figure 108122448-A0304-0001
 [表2]
Figure 108122448-A0304-0002
 [表3]
Figure 108122448-A0304-0003
 [表4]
Figure 108122448-A0304-0004
 [表5]
Figure 108122448-A0304-0005
 Hereinafter, a mode for implementing the present invention (hereinafter referred to as "this embodiment") will be specifically described. <Photosensitive resin composition> In this embodiment, the photosensitive resin composition contains (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator. The photosensitive resin composition may further contain other components, such as (D) additives, as needed. The first aspect of the present invention is a photosensitive resin composition, which is designed in the following manner: a photosensitive resin layer containing the photosensitive resin composition is formed on the surface of the substrate, and the resulting resist is exposed and developed. After the pattern is processed with the chemical solution for the evaluation of chemical resistance, the minimum line width of the hardened resist line is 17 μm or less. By using such a photosensitive resin composition, when a wiring pattern is formed by plating, a short circuit can be suppressed. In addition, by also suppressing plating penetration, a wiring pattern with excellent linearity can be obtained. That is, the photosensitive resin composition of the present invention is one having excellent adhesiveness and/or resolution. The minimum line width of the hardened resist line is preferably 16 μm or less, more preferably 15 μm or less, still more preferably 12 μm or less, particularly preferably 10 μm or less, and most preferably 8 μm or less. The method and conditions for measuring the minimum line width of the hardened resist line are described in the evaluation of chemical resistance in the examples. The second aspect of the present invention is a photosensitive resin composition, wherein (A) the weight average Tg total of the glass transition temperature Tg of the alkali-soluble polymer is 110° C. or less, and contains three or more ethylenically unsaturated bonds The (meth)acrylate compound is (B) a compound having an ethylenically unsaturated bond. By including (A) alkali-soluble polymer with Tg total of 110℃ or less and (meth)acrylate compound with 3 or more ethylenic unsaturated bonds, the reaction rate can be increased, and the crosslinking density can be increased. As a result, the photosensitive resin composition tends to provide a resist pattern excellent in at least one of adhesion, resolution and storage stability, and the unreacted component (B) is unlikely to remain. A photosensitive resin layer containing the photosensitive resin composition of the present embodiment is formed on the surface of the substrate, and exposure is carried out using a Stufer 41-segment step-type exposure meter as a mask, and then the highest residual film section during development The number of grids becomes the exposure amount of 15 grids. When the photosensitive resin layer is exposed, the photosensitive resin layer preferably satisfies the relationship expressed by the following formula: P×Q/R≧0.21 {where, regarding the sensitivity In the resin layer, in the FT-IR measurement, P represents the peak height under the wave number 810 cm -1 before exposure, and Q represents (B) the reaction of the ethylenic double bond in the compound with ethylenic unsaturated bond after exposure Rate, and R represents the film thickness}. The value represented by the formula P×Q/R explained above is more preferably 0.22 or more, 0.23 or more, 0.24 or more, 0.25 or more, or 0.27 or more. The method and conditions for measuring the value represented by the formula P×Q/R are described in the examples. (A) Alkali-soluble polymers (A) Alkali-soluble polymers are polymers that can be dissolved in alkaline substances. In this embodiment, from the viewpoint of alkaline developability, the photosensitive resin composition preferably has a carboxyl group, and more preferably a copolymer containing a carboxyl group-containing monomer as a copolymerization component. In this embodiment, the photosensitive resin composition is referred to as (A) from the viewpoint of the high resolution of the resist pattern and the shape of the hem portion, and further from the viewpoint of the chemical resistance of the resist pattern The alkali-soluble polymer preferably includes a copolymer having an aromatic group, and particularly preferably includes a copolymer having an aromatic group in the side chain. Furthermore, as such an aromatic group, for example, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted aralkyl group can be cited. As the ratio of the aromatic group-containing copolymer in the component (A), it is preferably 50% by mass or more, more preferably 60% by mass or more, preferably 70% by mass or more, and preferably 80% by mass or more , Preferably 90% by mass or more, and may also be 100% by mass. In addition, from the viewpoint of the high resolution of the resist pattern and the shape of the bottom part, and from the viewpoint of the chemical resistance of the resist pattern, the copolymer having an aromatic group has an aromatic group The copolymerization ratio of the comonomer is preferably 20% by mass or more, more preferably 30% by mass or more, preferably 40% by mass or more, preferably 50% by mass or more, preferably 60% by mass or more, more preferably It is 70% by mass or more, preferably 80% by mass or more. The upper limit of the copolymerization ratio is not particularly limited, but from the viewpoint of maintaining alkali solubility, it is preferably 95% by mass or less, and more preferably 90% by mass or less. As the above-mentioned comonomer having an aromatic group, for example, a monomer having an aralkyl group, styrene, and polymerizable styrene derivatives (such as methyl styrene, vinyl toluene, tertiary butoxy Styrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.). Among them, a monomer having an aralkyl group or styrene is preferred, and a monomer having an aralkyl group is more preferred. As the aralkyl group, a substituted or unsubstituted phenylalkyl group (except for the benzyl group), or a substituted or unsubstituted benzyl group, etc. can be mentioned, and a substituted or unsubstituted benzyl group is preferred. Examples of the comonomer having a phenylalkyl group include phenylethyl (meth)acrylate and the like. Examples of comonomers having a benzyl group include: (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate, chlorobenzyl (meth)acrylate, etc.; vinyl monomers having a benzyl group , Such as vinyl benzyl chloride, vinyl benzyl alcohol and the like. Among them, benzyl (meth)acrylate is preferred. The copolymer having an aromatic group (especially a benzyl group) in the side chain is preferably obtained by combining a monomer having an aromatic group with at least one of the following first monomers and/or the following second monomers At least one is obtained by polymerization. The (A) alkali-soluble polymer other than the copolymer having an aromatic group in the side chain is preferably obtained by polymerizing at least one of the following first monomers, and more preferably by making the first monomer It is obtained by copolymerizing at least one type with at least one type of the following second monomer. A monomer having a carboxyl group in the first single system molecule. As the first monomer, for example, (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, maleic acid Acid half ester and so on. Among them, (meth)acrylic acid is preferred. Furthermore, in this specification, "(meth)acrylic acid" refers to acrylic acid or methacrylic acid, and "(meth)acrylic acid group" refers to acrylic acid group or methacrylic acid group, and the so-called "(former "Acrylate" means "acrylate" or "methacrylate". The copolymerization ratio of the first monomer is based on the total mass of all monomer components, and is preferably 10 to 50% by mass. From the viewpoint of expressing good developability and controlling edge meltability, it is preferable to set the copolymerization ratio to 10% by mass or more. From the viewpoint of the high resolution of the resist pattern and the shape of the bottom part, and from the viewpoint of the chemical resistance of the resist pattern, it is preferable to set the copolymerization ratio to 50% by mass or less. From other viewpoints, it is more preferably 30% by mass or less, still more preferably 25% by mass or less, particularly preferably 22% by mass or less, and most preferably 20% by mass or less. The second monomer is non-acidic and is a monomer having at least one polymerizable unsaturated group in the molecule. As the second monomer, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-(meth)acrylate Butyl ester, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid ring (Meth)acrylates such as hexyl ester and 2-ethylhexyl (meth)acrylate; vinyl alcohol esters such as vinyl acetate; and (meth)acrylonitrile. Among them, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-butyl (meth)acrylate are preferred. In this embodiment, the (A) alkali-soluble polymer can be prepared by the following method: the singular or plural monomers described above are prepared by a known polymerization method, preferably addition polymerization, more preferably The polymerization proceeds by radical polymerization. From the viewpoints of the chemical resistance, adhesion, high resolution, or shape of the hem portion of the resist pattern, a monomer having an aralkyl group or a monomer containing styrene is preferred, for example, more It is preferably a copolymer containing methacrylic acid, benzyl methacrylate and styrene, a copolymer containing methacrylic acid, methyl methacrylate, benzyl methacrylate and styrene, etc. From the viewpoint of chemical resistance, adhesiveness, high resolution, or shape of the hem of the resist pattern, the glass transition temperature of (A) alkali-soluble polymer (in (A) When the component contains a plurality of copolymers, the glass transition temperature Tg of the whole mixture, that is, the weight average value of the glass transition temperature Tg total ) is preferably 110°C or less, more preferably 107°C or less, 105°C or less , Below 100℃, below 95℃, below 90℃ or below 80℃. (A) The lower limit of the glass transition temperature (Tg) of the alkali-soluble polymer is not limited. From the viewpoint of controlling the edge meltability, it is preferably 30°C or higher, more preferably 50°C or higher, and still more preferably Above 60°C. Regarding the acid equivalent of (A) alkali-soluble polymer (when the component (A) contains a plurality of copolymers, it is related to the acid equivalent of the entire mixture), the development resistance of the photosensitive resin layer and the resist pattern From the viewpoint of resolution and adhesion, it is preferably 100 or more, and from the viewpoint of developability and peelability of the photosensitive resin layer, it is preferably 600 or less. (A) The acid equivalent of the alkali-soluble polymer is more preferably 200-500, and still more preferably 250-450. (A) The weight average molecular weight of the alkali-soluble polymer (when the component (A) contains a plurality of copolymers, it is the weight average molecular weight of the entire mixture) is preferably 5,000 to 500,000. Regarding the weight average molecular weight of (A) alkali-soluble polymer, from the viewpoint of maintaining the thickness of the dry film resist uniformly and obtaining the resistance to the developer, it is preferably 5,000 or more. From the viewpoint of developability, the viewpoint of the high resolution of the resist pattern and the shape of the bottom part, and the viewpoint of the chemical resistance of the resist pattern, it is preferably 500,000 or less. (A) The weight average molecular weight of the alkali-soluble polymer is more preferably 10,000 to 200,000, more preferably 20,000 to 130,000, particularly preferably 30,000 to 100,000, and most preferably 40,000 to 70,000. (A) The dispersion degree of the alkali-soluble polymer is preferably 1.0 to 6.0. In this embodiment, the content of (A) alkali-soluble polymer in the photosensitive resin composition is based on the total solid content of the photosensitive resin composition (hereinafter, unless otherwise specified, it is included in each component Similarly), it is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and still more preferably in the range of 40% by mass to 60% by mass. Regarding the content of (A) alkali-soluble polymer, from the viewpoint of maintaining the alkali developability of the photosensitive resin layer, it is preferably 10% by mass or more, since the resist pattern formed by exposure fully functions as a resist From the viewpoint of the performance of the agent material, the high resolution of the resist pattern and the shape of the bottom part, and the viewpoint of the chemical resistance of the resist pattern, it is preferably 90% by mass or less, more preferably 70% by mass Hereinafter, it is more preferably 60% by mass or less. (B) The compound having an ethylenically unsaturated bond (B) The compound having an ethylenically unsaturated bond is a compound having polymerizable properties by having an ethylenically unsaturated group in its structure. From the viewpoint of the chemical resistance, adhesiveness, high resolution of the resist pattern, or the shape of the hem portion, the photosensitive resin composition of the present embodiment preferably contains the one having three or more ethylenically unsaturated bonds ( The meth)acrylate compound is (B) a compound having an ethylenically unsaturated bond. In this case, the ethylenic unsaturated bond is more preferably derived from a methacrylic acid group. The (meth)acrylate compound having 3 or more ethylenically unsaturated bonds is, for example, a (meth)acrylate compound having an ethylene oxide chain and a dipentaerythritol skeleton, or (b1) having at least 3 methacrylic acid The compounds of the acyl group are described below. From the viewpoints of the chemical resistance, adhesion, high resolution, or shape of the hem portion of the resist pattern, the photosensitive resin composition of the present embodiment preferably contains five or more ethylenically unsaturated bonds, and The (meth)acrylate compound having an alkylene oxide chain is (B) the compound having an ethylenically unsaturated bond. In this case, the ethylenically unsaturated bond is more preferably derived from a methacrylic acid group, and the alkylene oxide chain is more preferably an ethylene oxide chain. The (meth)acrylate compound having 5 or more ethylenically unsaturated bonds and having an alkylene oxide chain is described below as a (meth)acrylate compound having an ethylene oxide chain and a dipentaerythritol skeleton, for example Description. From the viewpoint of chemical resistance, adhesion, high resolution, or the shape of the hem portion of the resist pattern, the concentration of the methacrylic acid group in the compound having an ethylenically unsaturated bond (B) is preferably 0.20 mol/100 g or more, more preferably 0.30 mol/100 g or more, still more preferably 0.35 mol/100 g or more, and particularly preferably 0.40 mol/100 g or more. The upper limit of the concentration of the methacrylic acid group is not particularly limited as long as the polymerizability and alkaline developability are ensured. For example, it may be 0.90 mol/100 g or less or 0.80 mol/100 g or less. From the same point of view, the value of (B) the concentration of the methacrylic acid group in the compound having an ethylenically unsaturated bond/(the concentration of the methacrylic acid group + the concentration of the acrylic acid group) is preferably 0.50 or more , More preferably 0.60 or more, still more preferably 0.80 or more, particularly preferably 0.90 or more, most preferably 0.95 or more. From the viewpoint of chemical resistance, adhesion, high resolution, or shape of the hem portion of the resist pattern, the concentration of the ethylene oxide unit in the compound having an ethylenically unsaturated bond (B) is preferably 0.80 mol/100 g or more, more preferably 0.90 mol/100 g or more, still more preferably 1.00 mol/100 g or more, particularly preferably 1.10 mol/100 g or more. The upper limit of the concentration of the ethylene oxide unit is not particularly limited as long as the chemical resistance, adhesion, and resolution of the resist pattern are ensured. For example, it can be 1.60 mol/100 g or less, 1.50 mol/ 100 g or less, 1.45 mol/100 g or less, or 1.40 mol/100 g or less. In this embodiment, from the viewpoints of the chemical resistance, adhesion, high resolution of the resist pattern, or the shape of the hem portion, the photosensitive resin composition preferably contains an alkylene oxide chain and a dipentaerythritol skeleton. The (meth)acrylate compound is (B) a compound having an ethylenically unsaturated bond. As the alkylene oxide chain, for example, an ethylene oxide chain, a propylene oxide chain, a butylene oxide chain, a pentane oxide chain, an oxirane chain, etc. are mentioned. When the photosensitive resin composition contains a plurality of alkylene oxide chains, these may be the same or different from each other. From the above point of view, as the alkylene oxide chain, an ethylene oxide chain, a propylene oxide chain, or a butylene oxide chain is more preferable, and an ethylene oxide chain or a propylene oxide chain is more preferable. It is preferably an ethylene oxide chain. In the photosensitive resin composition, by using (A) an alkali-soluble polymer in combination with a (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton, it has chemical resistance and adhesiveness to maintain the resist pattern And the tendency of resolving balance. The so-called (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton refers to an ester of a dipentaerythritol compound and (meth)acrylic acid obtained by modifying at least one of a plurality of hydroxyl groups with an alkyleneoxy group . The 6 hydroxyl groups of the dipentaerythritol skeleton can also be modified with alkyleneoxy groups. The number of ester bonds in one ester molecule can be 1 to 6, preferably 6. As the (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton, for example, the addition of alkylene oxide to dipentaerythritol has an average of 4 to 30 mol, an average of 6 to 24 mol, or an average of 10 to 14 moles of hexa(meth)acrylate. Specifically, as a (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton, it is more effective in terms of chemical resistance, adhesiveness, high resolution of the resist pattern, or the shape of the hem It is preferably a compound represented by the following general formula (III), [formation 3]
Figure 02_image005
{In the formula, R each independently represents a hydrogen atom or a methyl group, n is an integer from 0 to 30, and the total value of all n is 1 or more}. In the general formula (III), it is preferable that the average value of all n is 4 or more, or each n is 1 or more. As R, methyl is preferred. From the viewpoint of the chemical resistance of the resist pattern, the content of the (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton in the photosensitive resin composition is preferably 1% by mass to 50% by mass , More preferably 5% by mass to 40% by mass, and still more preferably in the range of 7% by mass to 30% by mass. In this embodiment, in order to suppress the exudation of the constituent components of the dry film resist and improve the storage stability, the total solid content of (B) the compound having ethylenically unsaturated bonds is used as a reference, and (B) has ethylene 70% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 100% by mass of the compound having a sexually unsaturated bond is a compound having a weight average molecular weight of 500 or more. From the viewpoint of suppression of bleeding and chemical resistance of the resist pattern, the weight average molecular weight of the compound having an ethylenically unsaturated bond (B) is preferably 760 or more, more preferably 800 or more, and still more preferably 830 or more , Particularly preferably above 900. (B) The weight average molecular weight of the compound having an ethylenically unsaturated bond is measured by the method described in the examples. In order to improve the flexibility of the resist pattern and improve the adhesion, and to suppress the bleeding of the constituent components of the dry film resist, the photosensitive resin composition preferably contains (b1) a compound having at least 3 methacrylic groups as (B) A compound having an ethylenically unsaturated bond. From the standpoint of suppressing bleeding, (b1) the compound having at least 3 methacrylic groups has a weight average molecular weight of preferably 500 or more, more preferably 700 or more, and still more preferably 900 or more. Regarding (b1) the compound having at least 3 methacryloyl groups, the number of methacryloyl groups is preferably 4 or more, 5 or more, or 6 or more. The compound having at least 3 methacrylic groups may also have an alkylene oxide chain, such as an ethylene oxide chain, a propylene oxide chain, or a combination thereof. (B1) Compounds having at least 3 methacrylic acid groups include trimethacrylates, such as ethoxylated glycerol trimethacrylate, and ethoxylated isocyanuric acid trimethacrylate Ester, pentaerythritol trimethacrylate, trimethylolpropane trimethacrylate (for example, from the viewpoints of flexibility, adhesion, and exudation suppression, it is preferable to add trimethylolpropane An average of 21 mol of ethylene oxide trimethacrylate, or trimethylolpropane with an average of 30 mol of ethylene oxide trimethacrylate), etc.; tetramethacrylate , Such as di-trimethylolpropane tetramethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, etc.; pentamethacrylate, such as dipentaerythritol pentamethacrylate, etc.; hexamethyl Acrylate, for example, dipentaerythritol hexamethacrylate and the like. Among these, four, five, or hexamethacrylate is preferred. As the tetramethacrylate, pentaerythritol tetramethacrylate is preferred. The pentaerythritol tetramethacrylate may be tetramethacrylate in which a total of 1-40 mol of alkylene oxide is added to the 4 ends of pentaerythritol. The tetramethacrylate is more preferably a tetramethacrylate compound represented by the following general formula (I), [formation 4]
Figure 02_image007
{In the formula, R 3 to R 6 each independently represent an alkyl group having 1 to 4 carbon atoms, X represents an alkylene group having 2 to 6 carbon atoms, and m 1 , m 2 , m 3 and m 4 are each independently 0-40 The integer of m 1 + m 2 + m 3 + m 4 is 1-40. When m 1 + m 2 + m 3 + m 4 is 2 or more, a plurality of Xs may be the same or different from each other}. Although not wishing to be limited to theory, it is believed that the tetramethacrylate compound represented by the general formula (I) has the group R 3 to R 6 and the fourth part of the H 2 C=CH-CO-O- Compared with acrylate, it inhibits hydrolysis in alkaline solution. From the viewpoint of improving the resolution of the resist pattern, in detail, the shape of the line, more specifically, the shape of the underline, and the adhesiveness of the resist, it is preferable to use the formula (I) The photosensitive resin composition of the tetramethacrylate compound shown. In the general formula (I), it is preferable that at least one of the groups R 3 to R 6 is a methyl group, and it is more preferable that all of the groups R 3 to R 6 are a methyl group. Regarding the resist pattern, from the viewpoint of obtaining the required resolution, the shape of the hem portion, and the residual film rate, in the general formula (I), X is preferably -CH 2 -CH 2 -. Regarding the resist pattern, in terms of obtaining the required resolution, hem shape, and residual film rate, in the general formula (I), m 1 , m 2 , m 3 and m 4 are preferably independent of each other It is an integer of 1-20, more preferably an integer of 2-10. Furthermore, in the general formula (I), m 1 +m 2 +m 3 +m 4 is preferably 1 to 36 or 4 to 36. As a compound represented by general formula (I), pentaerythritol (poly)alkoxy tetramethacrylate etc. are mentioned, for example. In addition, in this specification, "pentaerythritol (poly) alkoxy tetramethacrylate" is included in the above general formula (I), m 1 + m 2 ＋ m 3 ＋ m 4 = 1 "pentaerythritol alkoxy tetramethyl Both of "acrylic ester" and "pentaerythritol polyalkoxy tetramethacrylate" with m 1 + m 2 + m 3 + m 4 = 2-40. As the compound represented by the general formula (I), the compounds listed in JP 2013-156369 A, for example, pentaerythritol (poly)alkoxy tetramethacrylate and the like can be cited. The hexamethacrylate compound is preferably hexamethacrylate in which a total of 1-24 mol of ethylene oxide is added to the 6 terminals of dipentaerythritol, and the total is added to the 6 terminals of dipentaerythritol. 1 to 10 moles of hexamethacrylate of ε-caprolactone. The content of the compound having at least 3 methacryl groups with respect to the total solid content of the photosensitive resin composition is preferably more than 0% by mass and 16% by mass or less. If the content exceeds 0% by mass, the resolution tends to increase, and if it is 16% by mass or less, the flexibility of the cured resist is improved and the peeling time tends to be shortened. The content is more preferably 2% by mass or more and 15% by mass or less, and still more preferably 4% by mass or more and 12% by mass or less. The photosensitive resin composition preferably contains (b2) a compound having a butylene oxide chain and one or two (meth)acrylic groups as (B) a compound having an ethylenically unsaturated bond. From the viewpoint of suppressing bleeding, (b2) the compound having a butylene oxide chain and one or two (meth)acrylic groups has preferably 500 or more, more preferably 700 or more, and more preferably 1000 The above molecular weight. (B2) Compounds having a butylene oxide chain and one or two (meth)acrylic groups include polytetramethylene glycol (meth)acrylate and polytetramethylene glycol Di(meth)acrylate etc. Specifically, (b2) the compound having a butylene oxide chain and one or two (meth)acrylic groups has preferably 1-20, more preferably 4-15, and more preferably 6-12 C 4 H 8 O (meth)acrylate or di(meth)acrylate. The content of (b2) the compound having a butylene oxide chain and one or two (meth)acrylic acid groups is preferably more than 0% by mass and 20% with respect to the total solid content of the photosensitive resin composition Less than mass%. The photosensitive resin composition may contain (b3) a compound having an aromatic ring and an ethylenically unsaturated bond as (B) a compound having an ethylenically unsaturated bond. (b3) The compound having an aromatic ring and an ethylenically unsaturated bond may further have an alkylene oxide chain. The aromatic ring is preferably incorporated into the compound as a bivalent skeleton derived from bisphenol A, a divalent skeleton derived from naphthalene, a divalent aromatic group such as phenylene and methylphenylene. The alkylene oxide chain can be an ethylene oxide chain, a propylene oxide chain, or a combination of these. The ethylenically unsaturated bond is preferably incorporated into the compound as a (meth)acryloyl group. Specifically, as (b3) a compound having an aromatic ring and an ethylenically unsaturated bond, a compound represented by the following general formula (II) can be used, [form 5]
Figure 02_image009
{In the formula, R 1 and R 2 each independently represent a hydrogen atom or a methyl group, A is C 2 H 4 , B is C 3 H 6 , n 1 and n 3 are each independently an integer of 1 to 39, and n 1 + n 3 is an integer from 2 to 40, n 2 and n 4 are each independently an integer from 0 to 29, and n 2 + n 4 is an integer from 0 to 30, arrangement of repeating units of -(AO)- and -(BO)- It may be random or block. In the case of block, either of -(AO)- and -(BO)- may be biphenyl side}. From the standpoint of resolution and adhesion, for example, it is preferable to add polyethylene glycol dimethacrylate with an average of 5 mol of ethylene oxide to both ends of bisphenol A, Dimethacrylate of polyethylene glycol with an average of 2 mol of ethylene oxide is added to both ends of bisphenol A, and an average of 1 mol is added to both ends of bisphenol A. Dimethacrylate of polyethylene glycol of ethylene oxide, etc. In addition, as the compound having an aromatic ring, an alkylene oxide chain, and an ethylenically unsaturated bond, a compound having a hetero atom and/or a substituent in the aromatic ring in the general formula (II) can also be used. Examples of heteroatoms include halogen atoms and the like. Examples of substituents include alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 18 carbon atoms, and benzyl groups. Methyl, amino, alkylamino with 1 to 10 carbons, dialkylamino with 2 to 20 carbons, nitro, cyano, carbonyl, mercapto, alkyl mercapto with 1 to 10 carbons, aromatic Group, hydroxyl group, hydroxyalkyl group with 1 to 20 carbons, carboxyl group, carboxyalkyl group with 1 to 10 carbon atoms, alkyl group with 1 to 10 carbon atoms, alkyl group with 1 to 20 carbon atoms Oxy group, alkoxycarbonyl group with 1 to 20 carbons, alkylcarbonyl group with 2 to 10 carbons, alkenyl group with 2 to 10 carbons, N-alkylamine methanoyl group with 2 to 10 carbons or containing hetero Ring groups, or aryl groups substituted with these substituents, etc. These substituents may also form a condensed ring, or the hydrogen atoms in these substituents may be substituted with heteroatoms such as halogen atoms. When the aromatic ring in the general formula (II) has plural substituents, the plural substituents may be the same or different. The content of (b3) the compound having an aromatic ring and an ethylenically unsaturated bond is preferably more than 0% by mass and 50% by mass or less relative to the total amount of solid components of the photosensitive resin composition. If the content exceeds 0% by mass, the resolution and adhesion tend to be improved. From the viewpoint of development time and edge melting, it is preferably 50% by mass or less. The (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton and the compounds (b1) to (b3) described above can be used independently or in combination. The photosensitive resin composition may contain not only (meth)acrylate compounds having an alkylene oxide chain and dipentaerythritol skeleton and (b1) to (b3) compounds as (B) compounds having ethylenically unsaturated bonds, but may also contain Other compounds are referred to as (B) compounds having ethylenic unsaturated bonds. Examples of other compounds include: acrylate compounds having at least one (meth)acrylic acid group, (meth)acrylates having a urethane bond, a combination of α,β-unsaturated carboxylic acid and polyol Compounds obtained by reaction, compounds obtained by reacting α,β-unsaturated carboxylic acids with glycidyl group-containing compounds, phthalic acid-based compounds, etc. Among them, from the viewpoint of resolution, adhesion, and peeling time, an acrylate compound having at least two (meth)acrylic groups is preferred. The acrylate compound having at least 2 (meth)acrylic acid groups may be di-, tri-, tetra-, penta-, hexa-(meth)acrylate and the like. From the viewpoints of flexibility, resolution, adhesion, etc., for example, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, having ethylene oxide and polyepoxy Two (meth)acrylates of propane (for example, "FA-023M, FA-024M, FA-027M, product name, manufactured by Hitachi Chemical Industry"). Also, from the viewpoint of peelability or cured film flexibility, it is preferable to include 4-n-nonylphenoxy octaethylene glycol acrylate, 4-n-nonylphenoxy tetraethylene glycol acrylate, and o- A compound with one ethylenically unsaturated bond such as phthalic acid γ-chloro-β-hydroxypropyl-β'-methacrylic acid ethyl ester, from the viewpoint of sensitivity, resolution, or adhesion In other words, it is also preferable to include phthalic acid γ-chloro-β-hydroxypropyl-β'-methacrylic acid ethyl ester. In this embodiment, from the viewpoint of improving the adhesion of the resist pattern, and suppressing poor curing of the resist pattern, delay of development time, cold flow or bleeding, or delay of peeling of the cured resist, the photosensitive resin combination The total content of all (B) compounds having ethylenic unsaturated bonds in the compound is preferably 1% by mass to 70% by mass, more preferably 2% by mass to 60% by mass, and still more preferably 4% by mass to 50% by mass Within the range of %. (C) Photopolymerization initiator (C) The photopolymerization initiator is a compound that polymerizes monomers by light. The photosensitive resin composition contains a compound generally known in the technical field as (C) a photopolymerization initiator. The total content of the (C) photopolymerization initiator in the photosensitive resin composition is preferably 0.01 to 20% by mass, more preferably 0.05% to 10% by mass, and still more preferably 0.1% to 7% by mass, More preferably, it is in the range of 0.1% by mass to 6% by mass. (C) The total content of the photopolymerization initiator is preferably 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity, so that light can be sufficiently transmitted to the bottom surface of the resist to obtain good high resolution From a standpoint, it is preferably 20% by mass or less. (C) Photopolymerization initiators include quinones, aromatic ketones, acetophenones, phosphine oxides, benzoin or benzoin ethers, dialkyl ketals, and 9-oxysulfur 𠮿
Figure 108122448-xxxx-3
Type, dialkylaminobenzoic acid esters, oxime esters, acridines (from the viewpoint of sensitivity, resolution, and adhesion, for example, 9-phenylacridine, bisacridinyl Heptane, 9-(p-methylphenyl) acridine, 9-(m-methylphenyl) acridine), and further examples include: hexaarylbiimidazole, pyrazoline compounds, anthracene compounds (in terms of sensitivity, solution From the viewpoint of image property and adhesion, for example, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 9,10-diphenylanthracene), coumarin compound ( From the viewpoint of sensitivity, resolution, and adhesion, for example, 7-diethylamino-4-methylcoumarin), N-arylamino acid or its ester compound (in terms of sensitivity In terms of resolution, resolution, and adhesion, for example, N-phenylglycine), halogen compounds (for example, tribromomethylphenyl sulfide), and the like are preferable. These can be used individually by 1 type or in combination of 2 or more types. In addition, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-(4-methylthienyl)-2-morpholine can also be used Propan-1-one, 2,4,6-trimethylbenzyl-diphenylphosphine oxide, triphenylphosphine oxide, etc. As aromatic ketones, for example, benzophenone, Michelone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamine) Group) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone. These can be used individually by 1 type or in combination of 2 or more types. Among them, 4,4'-bis(diethylamino)benzophenone is preferred from the viewpoint of adhesion. Furthermore, from the viewpoint of transmittance, the content of aromatic ketones in the photosensitive resin composition is preferably 0.01% by mass to 0.5% by mass, and more preferably in the range of 0.02% by mass to 0.3% by mass. Examples of hexaarylbiimidazole include: 2-(o-chlorophenyl)-4,5-diphenylbiimidazole, 2,2',5-tri-(o-chlorophenyl)-4-( 3,4-Dimethoxyphenyl)-4',5'-diphenylbiimidazole, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl) )-Diphenylbiimidazole, 2,4,5-tris-(o-chlorophenyl)-diphenylbiimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-di Methoxyphenyl)-biimidazole, 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-Bis-(2,3-Difluoromethylphenyl)-4,4',5,5'-Tetra-(3-methoxyphenyl)-biimidazole, 2,2'- Bis-(2,4-difluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5- Difluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,6-difluorophenyl)-4 ,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5 ,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetra -(3-Methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetra-(3-methyl (Oxyphenyl)-biimidazole, 2,2'-bis-(2,4,5-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl) -Biimidazole, 2,2'-bis-(2,4,6-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2 ,2'-bis-(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-Bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, and 2,2'-bis -(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, etc., these can be used alone Or use a combination of two or more. From the viewpoints of high sensitivity, resolution, and adhesion, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferred. In this embodiment, from the viewpoint of improving the peeling characteristics and/or sensitivity of the photosensitive resin layer, the content of the hexaarylbisimidazole compound in the photosensitive resin composition is preferably 0.05% by mass to 7% by mass. It is more preferably 0.1% by mass to 6% by mass, and still more preferably in the range of 1% by mass to 4% by mass. From the viewpoint of peeling characteristics, sensitivity, resolution, or adhesion of the photosensitive resin layer, the photosensitive resin composition preferably also contains a pyrazoline compound as a photosensitizer. As the pyrazoline compound, from the above viewpoint, for example, 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)- Pyrazoline, 1-(4-(benzo
Figure 108122448-A0304-12-0015-1
(Azol-2-yl)phenyl)-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3- (4-Biphenyl)-5-(4-tertiary butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tertiary octyl) -Phenyl)-pyrazoline, 1-phenyl-3-(4-isopropylstyryl)-5-(4-isopropylphenyl)-pyrazoline, 1-phenyl-3- (4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline, 1-phenyl-3-(3,5-dimethoxystyryl)-5- (3,5-Dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(3,4-dimethoxystyryl)-5-(3,4-dimethoxybenzene Yl)-pyrazoline, 1-phenyl-3-(2,6-dimethoxystyryl)-5-(2,6-dimethoxyphenyl)-pyrazoline, 1-benzene Group-3-(2,5-dimethoxystyryl)-5-(2,5-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,3-di Methoxystyryl)-5-(2,3-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,4-dimethoxystyryl)-5- (2,4-Dimethoxyphenyl)-pyrazoline, etc., more preferably 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)- Pyrazoline. The photosensitive resin composition may contain one or two or more pyrazoline compounds as a photosensitizer. In this embodiment, from the viewpoint of improving the peeling characteristics and/or sensitivity of the photosensitive resin layer, the content of the photosensitizer in the photosensitive resin composition is preferably 0.05% by mass to 5% by mass, more preferably 0.1 Within the range of mass% to 3 mass%. (D) Additives The photosensitive resin composition may contain additives such as dyes, plasticizers, antioxidants, and stabilizers as necessary. For example, the additives listed in JP 2013-156369 A can be used. From the viewpoints of colorability, hue stability and exposure contrast, the photosensitive resin composition preferably contains tris(4-dimethylaminophenyl) methane [leuco crystal violet] and/or diamond green (Hodogaya Aizen (registered trademark) DIAMOND GREEN GH manufactured by Chemical Co., Ltd. is used as a dye. In this embodiment, the content of the dye in the photosensitive resin composition is preferably 0.001% to 3% by mass, more preferably 0.01% to 2% by mass, and still more preferably 0.02% to 1% by mass Within range. The content of the dye is preferably 0.001% by mass or more in terms of obtaining good coloring properties, and preferably 3% by mass or less in terms of maintaining the sensitivity of the photosensitive resin layer. From the viewpoint of the thermal stability or storage stability of the photosensitive resin composition, the photosensitive resin composition preferably contains a radical polymerization inhibitor, such as nitrosophenylhydroxyamine aluminum salt, p-methoxy Phenol, 4-tertiary butylcatechol, 4-ethyl-6-tertiary butylphenol, etc.; benzotriazoles, such as 1-(2-di-n-butylaminomethyl) A 1:1 mixture of -5-carboxybenzotriazole and 1-(2-di-n-butylaminomethyl)-6-carboxybenzotriazole, etc.; carboxybenzotriazoles, such as 4-carboxy -1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, 6-carboxy-1,2,3-benzotriazole, etc.; and rings with glycidyl groups At least one of the oxane compound, for example, neopentyl glycol diglycidyl ether, etc. is used as a stabilizer. In addition, it can also contain 2-mercaptobenzimidazole, 1H-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, 2-amino-5-mercapto-1,3,4-thiadi Azole, 3-amino-5-mercapto-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 3-mercaptotriazole, 4,5-diphenyl-1,3 -Diazol-2-yl, 5-amino-1H-tetrazole, etc. In this embodiment, the total content of all stabilizers in the photosensitive resin composition is preferably 0.001% by mass to 3% by mass, more preferably 0.01% by mass to 1% by mass, and still more preferably 0.05% by mass to 0.7 Within the range of mass%. Regarding the total content of the stabilizer, from the viewpoint of imparting good storage stability to the photosensitive resin composition, it is preferably 0.001% by mass or more, and from the viewpoint of maintaining the sensitivity of the photosensitive resin layer, it is preferably 3 Less than mass%. The additives described above can be used alone or in combination of two or more. <Photosensitive resin composition preparation liquid> In this embodiment, by adding a solvent to the photosensitive resin composition, a photosensitive resin composition preparation liquid can be formed. As suitable solvents, ketones, such as methyl ethyl ketone (MEK), etc.; and alcohols, such as methanol, ethanol, isopropanol, etc., can be cited. It is preferable to add the solvent to the photosensitive resin composition so that the viscosity of the photosensitive resin composition preparation liquid becomes 500 mPa·sec to 4000 mPa·sec at 25°C. <Photosensitive resin laminate> In this embodiment, a photosensitive resin laminate can be provided which has a support and a photosensitive resin layer containing the above-mentioned photosensitive resin composition laminated on the support. The photosensitive resin laminate may have a protective layer on the side of the photosensitive resin layer opposite to the support side as needed. The support is not particularly limited, but it is preferably a transparent one that transmits light emitted from the exposure light source. Examples of such a support include: polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, and vinylidene chloride copolymer film , Polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, and cellulose derivative film. These films can also be extended as needed. The haze is preferably 0.01% to 5.0%, more preferably 0.01% to 2.5%, and still more preferably 0.01% to 1.0%. Regarding the thickness of the film, although the thinner the film is, the more advantageous it is in terms of image formation and economy, but it is preferably 10 μm to 30 μm due to the need to maintain strength. In addition, the important characteristics of the protective layer used in the photosensitive resin laminate are as follows: Regarding the adhesive force with the photosensitive resin layer, the protective layer is smaller than the support and can be easily peeled off. As the protective layer, for example, a polyethylene film, a polypropylene film, etc. are preferable. For example, a film with excellent peelability described in Japanese Patent Application Laid-Open No. 59-202457 can be used. The thickness of the protective layer is preferably 10 μm to 100 μm, more preferably 10 μm to 50 μm. In this embodiment, the thickness of the photosensitive resin layer in the photosensitive resin laminate is preferably 5 μm to 100 μm, more preferably 7 μm to 60 μm. The smaller the thickness of the photosensitive resin layer, the more improved the resolution of the resist pattern. On the other hand, the greater the thickness of the photosensitive resin layer, the stronger the strength of the cured film, so it can be selected according to the application. A known method can be used as a method of laminating a support, a photosensitive resin layer, and a protective layer as necessary to produce a photosensitive resin laminate in order. For example, the above-mentioned photosensitive resin composition preparation liquid is prepared, and then a bar coater or a roll coater is used to coat and dry it on the support, and a layer containing the photosensitive resin composition preparation liquid is laminated on the support Photosensitive resin layer. Furthermore, if necessary, a protective layer is laminated on the photosensitive resin layer, whereby a photosensitive resin laminate can be produced. <Method for forming resist pattern> Preferably, the method for forming a resist pattern includes the following steps in sequence: a laminating step of laminating a photosensitive resin layer containing the above-mentioned photosensitive resin composition on a support; and an exposure step of The photosensitive resin layer is exposed; and a developing step, which develops the exposed photosensitive resin layer. In this embodiment, one of the specific methods of forming the resist pattern is illustrated below. First, in the laminating step, a laminating machine is used to form a photosensitive resin layer on the substrate. Specifically, when the photosensitive resin laminate has a protective layer, after the protective layer is peeled off, the photosensitive resin layer is heated and pressure-bonded to the substrate surface with a laminator to laminate. Examples of the material of the substrate include copper, stainless steel (SUS), glass, indium tin oxide (ITO), and the like. In this embodiment, the photosensitive resin layer may be laminated on only one side of the substrate surface, or may be laminated on both sides as necessary. The heating temperature during lamination is usually 40°C to 160°C. In addition, by performing heat and pressure bonding during lamination twice or more, the adhesion of the obtained resist pattern to the substrate can be improved. In the heating and pressure bonding, a two-stage laminating machine equipped with two rollers is used, or the laminate of the substrate and the photosensitive resin layer may be repeatedly passed through the rollers for pressure bonding. Next, in the exposure step, an exposure machine is used to expose the photosensitive resin group layer to active light. The exposure can be carried out after peeling off the support if necessary. In the case of exposure using a photomask, the exposure amount is determined according to the light source illuminance and exposure time, and it can also be measured with a light meter. In the exposure step, direct imaging exposure can also be performed. In direct imaging exposure, a direct drawing device is used to perform exposure on the substrate without using a photomask. As a light source, a semiconductor laser with a wavelength of 350 nm to 410 nm or an ultra-high pressure mercury lamp can be used. When using a computer to control the drawing pattern, the amount of exposure is determined according to the illuminance of the exposure light source and the moving speed of the substrate. Exposure can also be performed by projecting the image of the mask through a lens. Next, in the developing step, a developing device is used to remove the unexposed part or exposed part of the photosensitive resin layer after exposure with a developing solution. After exposure, if there is a support on the photosensitive resin layer, it is removed. Then, a developer containing an alkaline aqueous solution is used to develop and remove the unexposed part or the exposed part to obtain a resist image. The alkaline aqueous solution is preferably an aqueous solution of Na 2 CO 3 , K 2 CO 3 or the like. The alkaline aqueous solution is selected according to the characteristics of the photosensitive resin layer, and a Na 2 CO 3 aqueous solution with a concentration of 0.2% to 2% by mass is usually used. In the alkaline aqueous solution, surfactants, defoamers, and a small amount of organic solvents to promote development can also be mixed. The temperature of the developer in the development step is preferably kept constant within the range of 20°C to 40°C. The resist pattern can be obtained through the above steps, and the heating step may be further performed at 100°C to 300°C if necessary. By implementing this heating step, the chemical resistance of the resist pattern can be improved. A heating furnace using hot air, infrared rays, or far infrared rays can be used in the heating step. The photosensitive resin composition of this embodiment can be suitably used for forming the circuit of a printed circuit board. Generally, as a circuit formation method of a printed circuit board, a subtractive method and a semi-additive method (SAP) are used. The subtractive method is a method of forming a circuit by removing only non-circuit parts from a conductor disposed on the entire surface of the substrate by etching. SAP is a method in which resist is formed on the non-circuit part of the conductor seed layer disposed on the entire surface of the substrate, and then only the circuit part is formed by plating. In this embodiment, the photosensitive resin composition is more preferably used for SAP. <The cured product of the photosensitive resin composition> In this embodiment, in order to improve the flexibility of the resist pattern, the elongation of the cured product of the photosensitive resin composition is preferably 1 mm or more, more preferably 2 mm or more. More preferably, it is 3 mm or more. The elongation of the cured product is measured by the following method: the photosensitive resin laminate made of the photosensitive resin composition is exposed through a 5 mm×40 mm rectangular photomask, and then the minimum development time Development is carried out in twice the time, and the obtained hardened resist is stretched using a tensile tester (RTM-500 manufactured by Orientec Co., Ltd.) at a speed of 100 mm/min. In this embodiment, from the viewpoint of the resolution and flexibility of the resist pattern, the Young's modulus of the cured product of the photosensitive resin composition is preferably 1.5 GPa or more and less than 8 GPa. In this manual, "Young's modulus" can be measured by the nanoindenter DCM manufactured by Toyo Technica Co., Ltd. Specifically, "Young's modulus" is to laminate the resin composition to be measured on a substrate, expose and develop, and use Toyo Technica Co., Ltd. on the surface of the photosensitive resin composition on the obtained substrate. DCM was used for the measurement. As the measurement method, use DCM Basic Hardness, Modulus, Tip Cal, Load Control. msm (MultiLoad Unload Method, MultiLoad Method), the parameters of the press-in test are set to Percent To Unload = 90%, the maximum load ( Maximum Load = 1 gf, Load Rate Multiple For Unload Rate = 1, Number Of Times to Load = 5, Peak Hold time = 10 s, Load time (Time To Load) = 15 s, Poisson's ratio = 0.25. Young’s modulus is set to the value of "Modulas At Max Load". <The manufacturing method of the conductor pattern> The manufacturing method of the conductor pattern preferably includes the following steps in sequence: a laminating step, laminating a photosensitive resin layer containing the above-mentioned photosensitive resin composition on a substrate such as a metal plate and a metal film insulating plate; The exposure step, which exposes the photosensitive resin layer; the development step, by using a developer to remove the unexposed or exposed portions of the exposed photosensitive resin layer to obtain a substrate with a resist pattern formed; and the formation of a conductor pattern The step of etching or plating the substrate on which the resist pattern is formed. In this embodiment, the manufacturing method of the conductor pattern is performed by using a metal plate or a metal film insulating plate as a substrate, after forming a resist pattern by the above-mentioned resist pattern forming method, and then going through a conductor pattern forming step. In the conductor pattern forming step, the conductor pattern is formed on the substrate surface (for example, the copper surface) exposed by development using a known etching method or plating method. Furthermore, the present invention is suitably applied to the following applications, for example. <The manufacturing method of the wiring board> After the conductor pattern is manufactured by the manufacturing method of the conductor pattern, a peeling step of peeling the resist pattern from the substrate using an aqueous solution with an alkaline stronger than the developer is performed to obtain Wiring boards with required wiring patterns (such as printed wiring boards). In the manufacture of a wiring board, a laminate of an insulating resin layer and a copper layer, or a flexible substrate is used as the substrate. In order to perform SAP, it is preferable to use a laminate of an insulating resin layer and a copper layer. Regarding SAP, the copper layer is preferably an electroless copper plating layer containing palladium as a catalyst. Regarding SAP, it is also preferable to perform the conductor pattern formation step by a known plating method. In order to perform the improved semi-additive method (MSAP), the substrate is preferably a laminate of an insulating resin layer and copper foil, and more preferably a copper foil laminate. The alkaline aqueous solution for peeling (hereinafter, also referred to as "peeling liquid") is not particularly limited, and an aqueous solution of NaOH or KOH with a concentration of 2% to 5% by weight or an organic amine-based peeling liquid is usually used. A small amount of water-soluble solvent can be added to the stripping liquid. As a water-soluble solvent, alcohol etc. are mentioned, for example. The temperature of the peeling liquid in the peeling step is preferably in the range of 40°C to 70°C. In order to perform SAP, the manufacturing method of the wiring board preferably further includes a step of removing palladium from the obtained wiring board. <Manufacturing of Lead Frame> A metal plate such as copper, copper alloy, or iron-based alloy is used as a substrate, and a resist pattern is formed by a resist pattern forming method, and then the lead frame can be manufactured through the following steps. First, a step of forming a conductor pattern by etching the substrate exposed by development is performed. Thereafter, a peeling step of peeling off the resist pattern by the same method as the manufacturing method of the wiring board is performed to obtain the desired lead frame. <Production of base material with uneven pattern> The resist pattern formed by the resist pattern forming method can be used as a protective mask member when the substrate is processed by the sandblasting method. In this case, as the substrate, for example, glass, silicon wafer, amorphous silicon, polycrystalline silicon, ceramics, sapphire, metal materials, etc. can be cited. On the substrates, a resist pattern is formed by the same method as the resist pattern forming method. After that, the sandblasting step of blowing sandblasting material from the formed resist pattern and cutting to the target depth can be carried out; and the peeling step of removing the resist pattern remaining on the substrate from the substrate by using an alkaline stripping liquid or the like , And manufacture the base material with fine uneven pattern on the substrate. In the sandblasting step, a well-known sandblasting material can be used, for example, particles containing SiC, SiO 2 , Al 2 O 3 , CaCO 3 , ZrO, glass, stainless steel, etc., with a particle size of 2 μm to 100 μm are usually used. <Manufacturing of semiconductor package> Use the wafer after the formation of the large-scale integrated circuit (LSI) as the substrate, and after the resist pattern is formed on the wafer by the resist pattern forming method, go through the following steps, thereby Can manufacture semiconductor packages. First, a step of forming a conductor pattern by applying columnar plating of copper, solder, or the like to the opening exposed by development is performed. After that, a step of peeling off the resist pattern by the same method as the manufacturing method of the wiring board is performed, and further, a step of removing the thinner metal layer other than the columnar plating layer by etching is performed to obtain The required semiconductor package. In this embodiment, the photosensitive resin composition can be used in the manufacture of printed wiring boards; IC (Integrated Circuit) chip mounting lead frame manufacturing; metal mask manufacturing and other metal foil precision processing; ball grid array (BGA) ), chip size package (CSP) and other packaging manufacturing; chip-on-film (COF), tape and tape automatic bonding (TAB) and other tape substrate manufacturing; semiconductor bump manufacturing; and ITO electrodes, address electrodes, electromagnetic wave shielding Manufacturing of partition walls for flat panel displays such as covers. Furthermore, as for the values of the above-mentioned parameters, unless otherwise specified, they are measured according to the measurement methods in the following examples. [Examples] The measurement of the physical properties of polymers, the calculation of the glass transition temperature of the polymers, and the preparation methods of the evaluation samples of the examples and comparative examples are explained, and then the evaluation methods and the evaluation methods for the obtained samples are shown Evaluation results. (1) Measurement or calculation of physical property values <Determination of the weight average molecular weight or number average molecular weight of polymers> The weight average molecular weight or number average molecular weight of polymers is measured by a gel permeation chromatograph manufactured by JASCO Corporation ( GPC) (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko Co., Ltd. (KF-807, KF-806M, KF-806M, KF-802.5) 4 series in series, fluid layer Solvent: Tetrahydrofuran, using a calibration curve of polystyrene standard sample (Shodex STANDARD SM-105 manufactured by Showa Denko Co., Ltd.), calculated in terms of polystyrene. Furthermore, the degree of dispersion of the polymer is calculated as the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight/number average molecular weight). <Acid Equivalent> In this specification, the so-called acid equivalent refers to the mass (gram) of a polymer having 1 equivalent of carboxyl group in the molecule. The Hiranuma automatic titration device (COM-555) manufactured by Hiranuma Sangyo Co., Ltd. was used to determine the acid equivalent by using a 0.1 mol/L sodium hydroxide aqueous solution and the potentiometric titration method. <Glass transition temperature> The glass transition temperature of alkali-soluble polymers is calculated according to the following formula (Fox formula), [Number 1]
Figure 02_image011
{Wherein, W i is the mass of each of the comonomers constituting the alkali-soluble polymer, Tg i is the glass transition temperature when each of the comonomers constituting the alkali-soluble polymer is a homopolymer, W total is The total mass of the alkali-soluble polymer, and n is the number of types of comonomers constituting the alkali-soluble polymer}. Here, when calculating the glass transition temperature Tg i , the glass transition temperature of the homopolymer including the comonomer forming the corresponding alkali-soluble polymer is set to use Brandrup, J. Immergut, EH edit "Polymer handbook, Third edition, John wiley & sons, 1989, p. 209 Chapter VI "Glass transition temperatures of polymers"". Furthermore, the Tg i of the homopolymer containing each comonomer used in the calculation in the examples is shown in Table 1. <(B) Weight average molecular weight of the compound having ethylenically unsaturated bond> In Examples I-1 to I-16 and Comparative Examples I-1 to I-3, according to (B) the weight average molecular weight of the compound having ethylenically unsaturated bond The molecular structure of the compound is calculated to obtain the molecular weight. When there are a plurality of (B) compounds having ethylenically unsaturated bonds, it is determined by weighting the molecular weight utilization content of each compound. In addition, in Examples II-1 to II-6 and Comparative Examples II-1 to II-5, the weight average molecular weight of the compound having an ethylenically unsaturated bond is a gel permeable layer manufactured by JASCO Corporation Analyzer (GPC) (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) (K-801, K-801, K-802, KF-802.5) manufactured by Showa Denko Co., Ltd. 4 pieces in series , Fluidized bed solvent: Tetrahydrofuran, using a polystyrene standard sample (TSK standard POLYSTYRENE manufactured by Tosoh Co., Ltd., calibration curve), calculated in terms of polystyrene conversion. <(B) The concentration of the methacrylic acid group in the compound having an ethylenically unsaturated bond> By calculating the molar number of the methacrylic acid group relative to 100 g of the compound having an ethylenic unsaturated bond in (B) Find out. <B) The concentration of ethylene oxide (EO) unit in the compound with ethylenically unsaturated bond> By calculating the ethylene oxide (EO) unit relative to (B) the compound with ethylenically unsaturated bond 100 g Calculated by the number of moles. (2) Preparation method of evaluation sample The evaluation sample was prepared as follows. <Production of photosensitive resin laminate> The components shown in the following Tables 2 to 5 (wherein, the number of each component indicates the blending amount (parts by mass) in terms of solid content) and the solvent are thoroughly stirred and mixed, And the photosensitive resin composition preparation liquid was obtained. The names of the ingredients indicated by the abbreviations in Tables 2 and 4 are shown in Tables 3 and 5 below, respectively. A 16 μm thick polyethylene terephthalate film (FB-40 manufactured by Toray Co., Ltd.) was used as a support film, and a bar coater was used to uniformly coat the mixed liquid on the surface. Drying was performed for 2.5 minutes in a dryer at °C to form a photosensitive resin composition layer. The dry thickness of the photosensitive resin composition layer was 25 μm. Then, on the surface of the photosensitive resin composition layer on the side where the polyethylene terephthalate film is not laminated, a 19 μm thick polyethylene film (GF-818 manufactured by Tamapoly Co., Ltd.) was attached as a protective layer The photosensitive resin laminate was obtained. <The entire surface of the substrate> In Examples I-1 to I-16 and Comparative Examples I-1 to I-3, a soft etchant was used as evaluation substrates for sensitivity, image quality, adhesion, and chemical resistance. CPE-900 manufactured by Ryoge Chemical Co., Ltd. treats a 0.4 mm thick copper laminate laminate with 35 μm rolled copper foil, and cleans the substrate surface with 10% by mass H 2 SO 4 . In addition, in Examples II-1 to II-6 and Comparative Examples II-1 to II-5, grinding materials (Sakurundum R (registered trademark #220) manufactured by Carlit Co., Ltd., Japan) were used, and the thickness of the laminate layer was 35 μm. The 0.4 mm thick copper foil laminated board of rolled copper foil was sandblasted, rinsed and polished at a spray pressure of 0.2 MPa to produce a substrate for evaluation. <Laminating> One side peels off the polyethylene film of the photosensitive resin laminate, and the other side cleans and trims the surface and places it on a copper foil laminate board preheated to 60°C using a heated roll laminator (manufactured by Asahi Kasei Co., Ltd.) AL-700), the photosensitive resin laminate was laminated at a roll temperature of 105°C to obtain a test piece. The air pressure is set to 0.35 MPa, and the lamination speed is set to 1.5 m/min. <Exposure> In Examples I-1 to I-16 and Comparative Examples I-1 to I-3, a direct plotting exposure machine (manufactured by Hitachi Via Mechanics Co., Ltd., DE-1DH, light source: GaN blue-violet diode) was used Body, the main wavelength is 405±5 nm), using a Stufer 41-segment step-type exposure meter or a specific photomask pattern for direct imaging (DI) exposure, and exposure under the conditions of illuminance 85 mW/cm 2 . The exposure was performed using the above-mentioned Stufer 41-segment step-type exposure meter as a photomask, and the maximum number of remaining film segments during development was the exposure amount of 15 segments. In addition, in Examples II-1 to II-6 and Comparative Examples II-1 to II-5, a chromium glass mask was used, and a parallel light exposure machine (HMW-801 manufactured by Oak Co., Ltd.) was used to Exposure was performed at the exposure level shown in Table 4. <Development> In Examples I-1 to I-16 and Comparative Examples I-1 to I-3, after peeling off the polyethylene terephthalate film of the exposed evaluation substrate, an alkaline developing machine (FUJI Dry film developing machine manufactured by KIKO), spray a 1% by mass Na 2 CO 3 aqueous solution at 30°C for a specific time to dissolve and remove the unexposed part of the photosensitive resin layer. At this time, development is performed for twice the minimum development time to produce a hardened resist pattern. Furthermore, the so-called minimum development time refers to the minimum time required for the unexposed portion of the photosensitive resin layer to completely dissolve. In addition, in Examples II-1 to II-6 and Comparative Examples II-1 to II-5, after peeling the polyethylene terephthalate film from the photosensitive resin laminate, manufactured by FUJI KIKO Co., Ltd. The developing device uses a full cone nozzle at a developing spray pressure of 0.15 MPa to spray a 1% by mass Na 2 CO 3 aqueous solution at 30°C for a specific period of time and develop it, and the photosensitive resin layer The exposed part is dissolved and removed. At this time, the minimum time required for the complete dissolution of the photosensitive resin layer in the unexposed part is set as the minimum development time for measurement, and development is performed at twice the minimum development time to prepare a resist pattern. At this time, the washing step uses a flat-plate nozzle, and the washing spray pressure is 0.15 MPa for the same time as the development step. (3) Evaluation method of the sample <Sensitivity evaluation> The substrate for sensitivity evaluation that has passed 15 minutes after lamination was exposed through the photomask of the Stuffey 41-segment stepped exposure meter. The development is carried out at twice the minimum development time, and the exposure level at which the maximum number of remaining film segments becomes 15 segments is classified according to the following criteria. ○ (Good): The maximum number of grids in the remaining film segment is 15 segments and the exposure is less than 70 mJ/cm 2 . × (bad): The maximum number of remaining film segments is 15 segments and the exposure is 70 mJ/cm 2 or more. <Resolvability> The substrate for resolution evaluation 15 minutes after lamination was exposed using drawing data having a line pattern with a ratio of the width of the exposed part and the unexposed part of 1:1. Develop with a development time twice the minimum development time to form a hardened resist line. In Examples I-1 to I-16 and Comparative Examples I-1 to I-3, the minimum line width of the normally formed hardened resist line was set as the value of the resolution and graded according to the following criteria. ○ (good): The value of the resolution is 12 μm or less. △ (allowable): The value of the resolution exceeds 12 μm and is 17 μm or less. × (bad): The value of the resolution exceeds 17 μm. In addition, in Examples II-1 to II-6 and Comparative Examples II-1 to II-5, the minimum line width of the normally formed hardened resist line was set as the value of the resolution, and the classification was performed based on the following criteria. ◎ (very good): The value of the resolution is 7.5 μm or less. ○ (good): The value of the resolution exceeds 7.5 μm and is 9 μm or less. △(allowable): The value of the resolution exceeds 9 μm. <FT-IR measurement> After peeling off the polyethylene film of the photosensitive resin laminate, FT-IR (NICOLET 380 manufactured by Thermo Scientific) measurement was performed. The peak height P at a wave number of 810 cm -1 was obtained by measuring the absorbance by FT-IR before exposure. When the wave crest overlaps with other wave crests, connect the rising points on both sides of the wave crest with a line, and measure the highest height from the line. The reaction rate Q of the ethylenic double bond is obtained by the following method. Direct drawing exposure machine (manufactured by Hitachi Via Mechanics Co., Ltd., DE-1DH, light source: GaN blue-violet diode (main wavelength) from the polyethylene terephthalate film (support layer) side of the photosensitive resin laminate 405±5 nm)), and expose. The illuminance during exposure is set to 85 mW/cm 2 . Regarding the exposure amount at this time, the exposure was carried out by the above-mentioned method using the Stufer 41-segment step-type exposure meter as a mask, and then the exposure amount was carried out with the maximum number of remaining film segments at the time of developing being 15-segment division. For the reaction rate Q of the ethylenic double bond of the hardened resist obtained by the above operation, calculate the disappearance rate (%) of the ethylenic double bond group based on the peak height before and after the exposure of the wave number 810 cm -1 , and Calculate the response rate Q (%). R is the film thickness (μm) of the photosensitive resin layer, and P×Q/R is calculated by calculation. <Adhesiveness> In Examples I-1 to I-16 and Comparative Examples I-1 to I-3, the substrate for resolving evaluation 15 minutes after lamination was used with an exposed part and an unexposed part Expose the drawing data of the line pattern with a width of 1:400. Develop with a development time twice the minimum development time, set the minimum line width of the normally formed hardened resist line as the value of adhesion, and classify it according to the following criteria. ○ (very good): The value of adhesion is 12 μm or less. ○△ (good): The value of adhesion exceeds 12 μm and is 13 μm or less. △ (allowable): The value of adhesion exceeds 13 μm and is 15 μm or less. × (bad): The value of adhesion exceeds 15 μm. In addition, in Examples II-1 to II-6 and Comparative Examples II-1 to II-5, the substrate for evaluation 15 minutes after the lamination was passed through a substrate having an exposed part and an unexposed part with a width of 1:100 The ratio of the line pattern chrome glass mask for exposure. The development is carried out at twice the minimum development time, the minimum line width of the normally formed hardened resist line is set as the value of adhesion, and the classification is carried out as follows. ◎ (very good): The value of the adhesion is 7.5 μm or less. ○ (good): The value of adhesion exceeds 7.5 μm and is 9 μm or less. △ (allowable): The value of adhesion exceeds 9 μm and does not reach 10 μm. × (bad): The value of adhesion is 10 μm or more. <Evaluation of drug resistance> 100 mL of CupraPro S2 manufactured by Atotech Japan Co., Ltd., 60 mL of 98% sulfuric acid, and 840 mL of pure water were mixed to prepare a drug solution. The substrate for resolvability evaluation 15 minutes after lamination was exposed using drawing data having a line pattern with a ratio of the width of the exposed part and the unexposed part of 1:400. Perform development with a development time twice the minimum development time, and immerse the beaker in a chemical solution heated to 40°C for 5 minutes. After immersion, it is washed with pure water, and the minimum line width of the normally formed hardened resist line is set to the value of the chemical resistance. In addition, in Table 2, only the case where the drug resistance value exceeds 17 μm is expressed as "× (bad)". <Bleeding property> Store the photosensitive resin laminate rolled into a roll at 23°C under light-shielding conditions. The time before the surface of the support film (except the outermost layer of the roll) is sticky due to the bleeding is as follows Carry out classification and evaluate exudation. ○ (Good): The time before the surface of the support film became sticky was more than 1 month × (Poor): The time before the surface of the support film became sticky was less than 1 month (4) Evaluation results Show the evaluation results in The following tables 2 to 5. The photosensitive resin composition designed in such a way that the chemical resistance evaluation is 17 μm or less has excellent adhesion, resolution, or balance of the shape of the hem. Moreover, by using such a photosensitive resin composition, when forming a wiring pattern by plating, a short circuit can be suppressed. After the chemical resistance evaluation, copper plating was performed. As a result, the composition of Comparative Example I-1 showed that a short circuit was observed in the 15 μm portion of the hardened resist. However, the composition of Example I-1 did not A short circuit is observed, and it is speculated that defects may be reduced. [Table 1]
Figure 108122448-A0304-0001
 [Table 2]
Figure 108122448-A0304-0002
 [table 3]
Figure 108122448-A0304-0003
 [Table 4]
Figure 108122448-A0304-0004
 [table 5]
Figure 108122448-A0304-0005

Claims (17)

一種感光性樹脂組合物，其包含：(A)鹼溶性高分子、(B)具有乙烯性不飽和鍵之化合物、及(C)光聚合起始劑；並且上述(A)鹼溶性高分子之玻璃轉移溫度Tg之重量平均值Tgtotal為105℃以下；且包含具有3個以上乙烯性不飽和鍵之(甲基)丙烯酸酯化合物作為上述(B)具有乙烯性不飽和鍵之化合物，於相對於上述感光性樹脂組合物之固形物成分總量超過0質量%且為16質量%以下之範圍內包含(b1)具有至少3個甲基丙烯醯基之化合物作為上述(B)具有乙烯性不飽和鍵之化合物，且上述(B)具有乙烯性不飽和鍵之化合物中之70質量%以上為具有500以上之重量平均分子量之化合物。 A photosensitive resin composition comprising: (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator; and the above-mentioned (A) alkali-soluble polymer The weight average Tg total of the glass transition temperature Tg is 105°C or less; and contains a (meth)acrylate compound having 3 or more ethylenic unsaturated bonds as the compound having ethylenic In the range of the total solid content of the photosensitive resin composition exceeding 0% by mass and 16% by mass or less, (b1) a compound having at least 3 methacrylic groups is included as the above (B) having an ethylenic property A compound with a saturated bond, and 70% by mass or more of the compound having an ethylenically unsaturated bond (B) above is a compound having a weight average molecular weight of 500 or more. 如請求項1之感光性樹脂組合物，其包含具有5個以上乙烯性不飽和鍵並具有環氧烷鏈之(甲基)丙烯酸酯化合物作為上述(B)具有乙烯性不飽和鍵之化合物。 The photosensitive resin composition according to claim 1, which contains a (meth)acrylate compound having 5 or more ethylenic unsaturated bonds and an alkylene oxide chain as the compound having an ethylenic unsaturated bond (B). 如請求項1之感光性樹脂組合物，其中上述(A)鹼溶性高分子具有100~600之酸當量及5,000~500,000之重量平均分子量，且於其側鏈具有芳香族基。 The photosensitive resin composition of claim 1, wherein the above-mentioned (A) alkali-soluble polymer has an acid equivalent of 100 to 600 and a weight average molecular weight of 5,000 to 500,000, and has an aromatic group in its side chain. 如請求項2之感光性樹脂組合物，其中上述(A)鹼溶性高分子具有 100~600之酸當量及5,000~500,000之重量平均分子量，且於其側鏈具有芳香族基。 The photosensitive resin composition of claim 2, wherein the above-mentioned (A) alkali-soluble polymer has The acid equivalent of 100~600 and the weight average molecular weight of 5,000~500,000, and the side chain has an aromatic group. 如請求項1至4中任一項之感光性樹脂組合物，其包含具有5個以上乙烯性不飽和鍵並具有環氧乙烷鏈之(甲基)丙烯酸酯化合物作為上述(B)具有乙烯性不飽和鍵之化合物。 The photosensitive resin composition according to any one of claims 1 to 4, which contains a (meth)acrylate compound having 5 or more ethylenic unsaturated bonds and an ethylene oxide chain as the above (B) having ethylene Compounds with unsaturated bonds. 如請求項1至4中任一項之感光性樹脂組合物，其包含具有環氧乙烷鏈與二季戊四醇骨架之(甲基)丙烯酸酯化合物作為上述(B)具有乙烯性不飽和鍵之化合物。 The photosensitive resin composition according to any one of claims 1 to 4, which comprises a (meth)acrylate compound having an ethylene oxide chain and a dipentaerythritol skeleton as the compound having an ethylenically unsaturated bond (B) . 如請求項1至4中任一項之感光性樹脂組合物，其進而包含下述通式(II)所表示之化合物作為上述(B)具有乙烯性不飽和鍵之化合物，
Figure 108122448-A0305-02-0052-1
 {式中，R1及R2分別獨立表示氫原子或甲基，A為C2H4，B為C3H6，n1及n3分別獨立為1~39之整數，且n1+n3為2~40之整 數，n2及n4分別獨立為0~29之整數，且n2+n4為0~30之整數，-(A-O)-及-(B-O)-之重複單元之排列可為無規亦可為嵌段，於嵌段之情形時，-(A-O)-與-(B-O)-之任一者亦可為聯苯基側}。 The photosensitive resin composition according to any one of claims 1 to 4, which further comprises a compound represented by the following general formula (II) as the compound having an ethylenically unsaturated bond (B),
Figure 108122448-A0305-02-0052-1
 {In the formula, R 1 and R 2 each independently represent a hydrogen atom or a methyl group, A is C 2 H 4 , B is C 3 H 6 , n 1 and n 3 are each independently an integer from 1 to 39, and n 1 + n 3 is an integer from 2 to 40, n 2 and n 4 are each independently an integer from 0 to 29, and n 2 +n 4 is an integer from 0 to 30, repeating units of -(AO)- and -(BO)- The arrangement can be random or block. In the case of block, either of -(AO)- and -(BO)- can also be biphenyl side}. 如請求項1至4中任一項之感光性樹脂組合物，其進而包含下述通式(I)所表示之化合物作為上述(B)具有乙烯性不飽和鍵之化合物，
Figure 108122448-A0305-02-0053-2
 {式中，R3~R6分別獨立表示碳數1~4之烷基，X表示碳數2~6之伸烷基，m1、m2、m3及m4分別獨立為0~40之整數，m1+m2+m3+m4為1~40，於m1+m2+m3+m4為2以上之情形時，複數個X可相互相同或不同}。 The photosensitive resin composition according to any one of claims 1 to 4, which further comprises a compound represented by the following general formula (I) as the compound having an ethylenically unsaturated bond (B),
Figure 108122448-A0305-02-0053-2
 {In the formula, R 3 ~ R 6 each independently represent an alkyl group with 1 to 4 carbon atoms, X represents an alkylene group with 2 to 6 carbon atoms, and m 1 , m 2 , m 3 and m 4 are each independently 0-40 The integer of m 1 +m 2 +m 3 +m 4 is 1-40. When m 1 +m 2 +m 3 +m 4 is 2 or more, a plurality of Xs may be the same or different from each other}. 如請求項1至4中任一項之感光性樹脂組合物，其包含六芳基雙咪唑化合物作為上述(C)光聚合起始劑。 The photosensitive resin composition according to any one of claims 1 to 4, which contains a hexaarylbisimidazole compound as the aforementioned (C) photopolymerization initiator. 如請求項1至4中任一項之感光性樹脂組合物，其包含吡唑啉化合物作為上述(C)光聚合起始劑。 The photosensitive resin composition according to any one of claims 1 to 4, which contains a pyrazoline compound as the aforementioned (C) photopolymerization initiator. 如請求項1至4中任一項之感光性樹脂組合物，其係直接成像曝光用。 The photosensitive resin composition according to any one of claims 1 to 4, which is used for direct imaging exposure. 如請求項1至4中任一項之感光性樹脂組合物，其中上述(b1)具有至少3個甲基丙烯醯基之化合物具有500以上之重量平均分子量。 The photosensitive resin composition according to any one of claims 1 to 4, wherein the compound (b1) having at least 3 methacryl groups has a weight average molecular weight of 500 or more. 如請求項1至4中任一項之感光性樹脂組合物，其包含(b2)具有環氧丁烷鏈與1個或2個(甲基)丙烯醯基之化合物作為上述(B)具有乙烯性不飽和鍵之化合物。 The photosensitive resin composition according to any one of claims 1 to 4, which comprises (b2) a compound having a butylene oxide chain and one or two (meth)acrylic groups as the above (B) having ethylene Compounds with unsaturated bonds. 如請求項13之感光性樹脂組合物，其中上述(b2)具有環氧丁烷鏈與1個或2個(甲基)丙烯醯基之化合物具有500以上之重量平均分子量。 The photosensitive resin composition of claim 13, wherein the compound (b2) having a butylene oxide chain and one or two (meth)acrylic groups has a weight average molecular weight of 500 or more. 如請求項1至4中任一項之感光性樹脂組合物，其係半加成法(SAP)用。 The photosensitive resin composition according to any one of claims 1 to 4, which is used for the semi-additive method (SAP). 一種抗蝕圖案之形成方法，其包括如下步驟：層壓步驟，其將包含如請求項1至15中任一項之感光性樹脂組合物之感光性樹脂層積層於支持體；曝光步驟，其對該感光性樹脂層進行曝光；及顯影步驟，其將該經曝光之感光性樹脂層進行顯影。 A method for forming a resist pattern, comprising the following steps: a laminating step of laminating a photosensitive resin comprising the photosensitive resin composition of any one of claims 1 to 15 on a support; an exposure step, which Exposing the photosensitive resin layer; and a developing step, which develops the exposed photosensitive resin layer. 一種配線板之製造方法，其包括如下步驟：層壓步驟，其將包含如請求項1至15中任一項之感光性樹脂組 合物之感光性樹脂層積層於基板；曝光步驟，其對該感光性樹脂層進行曝光；顯影步驟，其將該經曝光之感光性樹脂層進行顯影，而獲得形成有抗蝕圖案之基板；導體圖案形成步驟，其對該形成有抗蝕圖案之基板進行蝕刻或鍍敷；及剝離步驟，其剝離該抗蝕圖案。 A manufacturing method of a wiring board, comprising the following steps: a laminating step, which will include the photosensitive resin group as claimed in any one of claims 1 to 15 The photosensitive resin of the compound is laminated on the substrate; the exposure step is to expose the photosensitive resin layer; the development step is to develop the exposed photosensitive resin layer to obtain a substrate with a resist pattern formed; The conductor pattern formation step includes etching or plating the substrate on which the resist pattern is formed; and the peeling step includes peeling the resist pattern.
TW108122448A 2015-04-08 2016-04-08 Photosensitive resin composition TWI706222B (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2015-079381 2015-04-08
JP2015079381 2015-04-08
JP2015-166570 2015-08-26
JP2015166570 2015-08-26

Publications (2)

Publication Number Publication Date
TW201947323A TW201947323A (en) 2019-12-16
TWI706222B true TWI706222B (en) 2020-10-01

Family

ID=57073148

Family Applications (3)

Application Number Title Priority Date Filing Date
TW106146049A TWI667539B (en) 2015-04-08 2016-04-08 Photosensitive resin composition
TW105111187A TWI620017B (en) 2015-04-08 2016-04-08 Photosensitive resin composition
TW108122448A TWI706222B (en) 2015-04-08 2016-04-08 Photosensitive resin composition

Family Applications Before (2)

Application Number Title Priority Date Filing Date
TW106146049A TWI667539B (en) 2015-04-08 2016-04-08 Photosensitive resin composition
TW105111187A TWI620017B (en) 2015-04-08 2016-04-08 Photosensitive resin composition

Country Status (6)

Country Link
JP (3) JPWO2016163540A1 (en)
KR (2) KR102286107B1 (en)
CN (2) CN114437251B (en)
MY (1) MY187481A (en)
TW (3) TWI667539B (en)
WO (1) WO2016163540A1 (en)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI666518B (en) * 2016-12-30 2019-07-21 奇美實業股份有限公司 Photosensitive resin composition and uses thereof
JP6981864B2 (en) * 2017-01-30 2021-12-17 旭化成株式会社 A method for manufacturing a photosensitive resin composition, a photosensitive resin laminate, a substrate on which a resist pattern is formed, and a circuit board.
WO2018159629A1 (en) * 2017-03-01 2018-09-07 旭化成株式会社 Photosensitive resin composition
CN115524922A (en) * 2017-03-29 2022-12-27 旭化成株式会社 Photosensitive resin composition
CN109976092B (en) * 2017-12-27 2022-04-01 太阳油墨（苏州）有限公司 Curable resin composition, dry film, cured product, and printed wiring board
JP7170723B2 (en) * 2018-06-22 2022-11-14 旭化成株式会社 Photosensitive resin composition and method for forming resist pattern
CN112352197A (en) * 2018-06-22 2021-02-09 旭化成株式会社 Photosensitive resin composition and method for forming resist pattern
JPWO2020013111A1 (en) * 2018-07-11 2021-08-19 富士フイルム株式会社 Chemical solution, chemical solution container
CN112534351A (en) * 2018-08-09 2021-03-19 旭化成株式会社 Photosensitive resin composition and method for forming resist pattern
JP7300619B2 (en) * 2019-01-11 2023-06-30 太陽ホールディングス株式会社 Laminated structures, dry films, cured products thereof, and electronic components
US20220362110A1 (en) * 2019-09-19 2022-11-17 Kuraray Noritake Dental Inc. Dental curable composition
US20230041025A1 (en) * 2019-10-08 2023-02-09 Tokyo Ohka Kogyo Co., Ltd. Negative-working photosensitive resin composition, photosensitive resist film, pattern formation method, cured film, cured film production method, and rolled body
WO2021095784A1 (en) * 2019-11-11 2021-05-20 旭化成株式会社 Photosensitive resin composition and photosensitive resin multilayer body
WO2022030053A1 (en) * 2020-08-07 2022-02-10 昭和電工マテリアルズ株式会社 Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board
CN116847983A (en) * 2021-02-26 2023-10-03 太阳控股株式会社 Laminated structure and flexible printed circuit board
JPWO2022181485A1 (en) * 2021-02-26 2022-09-01
KR20240031514A (en) * 2022-08-30 2024-03-08 삼성에스디아이 주식회사 Photosensitive resin composition, photosensitive resin layer using the same and color filter

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006145844A (en) * 2004-11-19 2006-06-08 Asahi Kasei Electronics Co Ltd Photopolymerizable resin composition
US20070269738A1 (en) * 2004-07-30 2007-11-22 Hitachi Chemical Company, Ltd. Photosensitive Film, Photosensitive Film Laminate and Photosensitive Film Roll
JP2008094803A (en) * 2006-10-16 2008-04-24 Asahi Kasei Electronics Co Ltd Photosensitive resin composition and its laminate
TW200846824A (en) * 2007-01-23 2008-12-01 Fujifilm Corp Curing composition for photonano-imprinting lithography and pattern forming method by using the same
EP2096493A1 (en) * 2006-12-19 2009-09-02 Hitachi Chemical Company, Ltd. Photosensitive element
TW200947116A (en) * 2007-12-18 2009-11-16 Asahi Kasei Emd Corp Method for producing cured resist using negative photosensitive resin laminate, negative photosensitive resin laminate, and use of negative photosensitive resin laminate
CN101627339A (en) * 2007-06-18 2010-01-13 旭化成电子材料株式会社 Photosensitive resin composition, flexographic printing plate, and method for producing flexographic printing plate
TW201120572A (en) * 2009-09-25 2011-06-16 Asahi Kasei E Materials Corp Photosensitive resin composition for resist material, and photosensitive resin laminate
WO2015178462A1 (en) * 2014-05-21 2015-11-26 旭化成イーマテリアルズ株式会社 Photosensitive resin composition and method for forming circuit pattern

Family Cites Families (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3619852B2 (en) * 1999-06-08 2005-02-16 ニチゴー・モートン株式会社 Photosensitive resin composition and dry film resist using the same
WO2003042758A1 (en) * 2001-11-12 2003-05-22 Asahi Kasei Emd Corporation Photosensitive resin composition and applications thereof
JP4646759B2 (en) 2005-09-20 2011-03-09 旭化成イーマテリアルズ株式会社 Pattern forming material, pattern forming apparatus and pattern forming method
JP2007133349A (en) * 2005-10-14 2007-05-31 Hitachi Chem Co Ltd Photosensitive film roll
TWI536094B (en) * 2007-12-25 2016-06-01 Asahi Kasei Emd Corp Photosensitive resin laminate
JP5396833B2 (en) * 2008-11-28 2014-01-22 Ｊｓｒ株式会社 Radiation-sensitive resin composition, spacer and protective film for liquid crystal display element, and method for forming them
WO2011013664A1 (en) * 2009-07-29 2011-02-03 旭化成イーマテリアルズ株式会社 Photosensitive resin composition, photosensitive resin laminate, and method for forming resist pattern
JP5526868B2 (en) * 2010-03-03 2014-06-18 Ｊｓｒ株式会社 Radiation-sensitive resin composition, display element spacer and protective film, and method for forming them
JP5570275B2 (en) * 2010-03-31 2014-08-13 旭化成イーマテリアルズ株式会社 Dry film resist roll
KR20120002864A (en) * 2010-07-01 2012-01-09 동우 화인켐 주식회사 A black photosensitive resin composition, color filter and liquid crystal display device having the same
CN106918991A (en) * 2010-07-13 2017-07-04 日立化成工业株式会社 Photosensitive element, the forming method of corrosion-resisting pattern, the manufacture method of printed circuit board and printed circuit board
JP6022749B2 (en) 2010-07-30 2016-11-09 日立化成株式会社 Photosensitive resin composition, photosensitive element, method for producing resist pattern, method for producing lead frame, and method for producing printed wiring board
JP5771944B2 (en) * 2010-10-18 2015-09-02 Jsr株式会社 Manufacturing method of color filter
KR20150017384A (en) 2010-12-24 2015-02-16 아사히 가세이 이-매터리얼즈 가부시키가이샤 Photosensitive resin composition
JP5835014B2 (en) * 2011-03-31 2015-12-24 Jsr株式会社 Pixel pattern forming method and color filter manufacturing method
KR20130047656A (en) * 2011-10-31 2013-05-08 히타치가세이가부시끼가이샤 Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board
JP6229256B2 (en) 2011-10-31 2017-11-15 日立化成株式会社 Photosensitive element, resist pattern forming method, and printed wiring board manufacturing method
JP5948539B2 (en) * 2012-01-27 2016-07-06 旭化成株式会社 Photosensitive resin composition
JP2013195681A (en) * 2012-03-19 2013-09-30 Mitsubishi Chemicals Corp Photosensitive resin composition, color filter, liquid crystal display device, and organic el display
JP5853806B2 (en) * 2012-03-23 2016-02-09 Jsr株式会社 Radiation sensitive resin composition, cured film and method for forming cured film
JP6019791B2 (en) * 2012-06-19 2016-11-02 日立化成株式会社 Partition wall forming material, photosensitive element using the same, partition wall forming method, and image display device manufacturing method
JP5826135B2 (en) * 2012-08-23 2015-12-02 富士フイルム株式会社 Colored radiation-sensitive composition and color filter using the same
JP6063200B2 (en) 2012-10-15 2017-01-18 旭化成株式会社 Photosensitive resin composition
JP6120560B2 (en) * 2012-12-26 2017-04-26 第一工業製薬株式会社 Color filter, black matrix, or curable resin composition for circuit formation
JP6135314B2 (en) * 2012-12-26 2017-05-31 Jsr株式会社 Coloring composition, color filter and display element
JP6257164B2 (en) 2013-03-28 2018-01-10 旭化成株式会社 Method for forming resist pattern
KR20150143679A (en) * 2013-05-27 2015-12-23 후지필름 가부시키가이샤 Method for producing color filter, composition for forming base layer, and organic el display device
KR102162752B1 (en) 2013-07-23 2020-10-07 히타치가세이가부시끼가이샤 Photosensitive resin composition for projection exposure, photosensitive element, method for forming resist pattern, process for producing printed wiring board and process for producing lead frame

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070269738A1 (en) * 2004-07-30 2007-11-22 Hitachi Chemical Company, Ltd. Photosensitive Film, Photosensitive Film Laminate and Photosensitive Film Roll
JP2006145844A (en) * 2004-11-19 2006-06-08 Asahi Kasei Electronics Co Ltd Photopolymerizable resin composition
JP2008094803A (en) * 2006-10-16 2008-04-24 Asahi Kasei Electronics Co Ltd Photosensitive resin composition and its laminate
EP2096493A1 (en) * 2006-12-19 2009-09-02 Hitachi Chemical Company, Ltd. Photosensitive element
TW200846824A (en) * 2007-01-23 2008-12-01 Fujifilm Corp Curing composition for photonano-imprinting lithography and pattern forming method by using the same
CN101627339A (en) * 2007-06-18 2010-01-13 旭化成电子材料株式会社 Photosensitive resin composition, flexographic printing plate, and method for producing flexographic printing plate
TW200947116A (en) * 2007-12-18 2009-11-16 Asahi Kasei Emd Corp Method for producing cured resist using negative photosensitive resin laminate, negative photosensitive resin laminate, and use of negative photosensitive resin laminate
TW201120572A (en) * 2009-09-25 2011-06-16 Asahi Kasei E Materials Corp Photosensitive resin composition for resist material, and photosensitive resin laminate
WO2015178462A1 (en) * 2014-05-21 2015-11-26 旭化成イーマテリアルズ株式会社 Photosensitive resin composition and method for forming circuit pattern

Also Published As

Publication number Publication date
KR102286107B1 (en) 2021-08-04
MY187481A (en) 2021-09-23
JP2020126251A (en) 2020-08-20
TW201812454A (en) 2018-04-01
TW201947323A (en) 2019-12-16
JP2021131556A (en) 2021-09-09
CN114437251B (en) 2024-02-20
CN114437251A (en) 2022-05-06
KR101990230B1 (en) 2019-06-17
WO2016163540A1 (en) 2016-10-13
TW201701070A (en) 2017-01-01
TWI667539B (en) 2019-08-01
TWI620017B (en) 2018-04-01
CN107407880B (en) 2022-02-08
JPWO2016163540A1 (en) 2017-11-02
KR20170101263A (en) 2017-09-05
JP7242748B2 (en) 2023-03-20
CN107407880A (en) 2017-11-28
JP7162030B2 (en) 2022-10-27
KR20190047146A (en) 2019-05-07

Similar Documents

Publication Publication Date Title
TWI706222B (en) Photosensitive resin composition
TWI570513B (en) And a method for forming a photosensitive resin composition and a circuit pattern
JP6865811B2 (en) Photosensitive resin composition
JP7340643B2 (en) Photosensitive resin composition and photosensitive resin laminate
JP4749305B2 (en) Photosensitive resin composition and laminate
JP5205464B2 (en) Photosensitive resin composition, photosensitive resin laminate, resist pattern forming method, conductor pattern, printed wiring board, lead frame, substrate, and method for manufacturing semiconductor package
JP6630088B2 (en) Photosensitive resin composition
JP2014081440A (en) Photosensitive resin composition
JP2015148642A (en) Photosensitive resin composition, photosensitive resin laminate, and method for forming resist pattern
JP2011075706A (en) Photosensitive resin composition, photosensitive resin laminate, resist pattern-forming method, and method for producing conductor pattern, printed wiring board, lead frame, substrate with uneven pattern and semiconductor package