TW202124458A - Photosensitive resin composition - Google Patents

Photosensitive resin composition Download PDF

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TW202124458A
TW202124458A TW109129479A TW109129479A TW202124458A TW 202124458 A TW202124458 A TW 202124458A TW 109129479 A TW109129479 A TW 109129479A TW 109129479 A TW109129479 A TW 109129479A TW 202124458 A TW202124458 A TW 202124458A
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resin composition
photosensitive resin
meth
epoxy resin
photosensitive
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TW109129479A
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唐川成弘
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日商味之素股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/144—Polymers containing more than one epoxy group per molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/282—Applying non-metallic protective coatings for inhibiting the corrosion of the circuit, e.g. for preserving the solderability
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H05K3/3452—Solder masks

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Materials Engineering (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Polymerisation Methods In General (AREA)
  • Epoxy Resins (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

To provide a photosensitive resin composition or the like which can give a cured product excellent in undercut resistance and is excellent in resolution. The photosensitive resin composition contains (A) a resin containing an ethylenically unsaturated group and a carboxyl group, (B) a photopolymerization initiator, (C) an epoxy resin, and (D) a volatile component. When a weight reduction rate (%) after drying the photosensitive resin composition at 130 DEG C for 15 minutes is a and a weight reduction rate (%) after drying the photosensitive resin composition at 180 DEG C for 15 minutes is b, relationships of the following formulae (1) and (2) are satisfied: V=a2+b2 where V ≤ 30 (1); and a/b ≤ 0.6 (2).

Description

感光性樹脂組成物Photosensitive resin composition

本發明為關於一種感光性樹脂組成物。進而為關於使用該感光性樹脂組成物而得到的感光性薄膜、附支撐體的感光性薄膜、印刷配線板及半導體裝置。The present invention relates to a photosensitive resin composition. Furthermore, it is about the photosensitive film obtained using this photosensitive resin composition, the photosensitive film with a support body, a printed wiring board, and a semiconductor device.

在印刷配線板中有設置阻焊劑(solder resist)作為永久保護膜之情形，以用來抑制焊錫附著到不需要焊錫的部分之同時並抑制電路基板的腐蝕。作為阻焊劑，一般使用例如專利文獻1中所記載之類的感光性樹脂組成物。 [先前技術文獻] [專利文獻]In the printed wiring board, a solder resist is sometimes provided as a permanent protective film to prevent the solder from adhering to the parts that do not require the solder and to suppress the corrosion of the circuit board. As the solder resist, for example, a photosensitive resin composition described in Patent Document 1 is generally used. [Prior Technical Literature] [Patent Literature]

[專利文獻1]日本特開2014-115672號公報[Patent Document 1] JP 2014-115672 A

[發明所欲解決之課題][The problem to be solved by the invention]

阻焊劑用的感光性樹脂組成物，一般為要求解析性、絕緣性等。近年來，阻焊劑，為了使基板間以焊接來進行連接，而要求著具有微細的開口圖型以使具有配線圖型的導體層的一部分露出，就密著性之觀點而言，要求著該開口部的開口形狀不成為倒錐形狀。於此，所謂倒錐形狀的開口形狀，係意指開口越深越廣之形狀。本申請案中，有時將如此般的開口形狀不易成為倒錐形狀之性質，稱為「底切耐性(undercut resistance)」為優異。The photosensitive resin composition for solder resist generally requires resolution, insulation, etc. In recent years, solder resists are required to have a fine opening pattern to expose a part of the conductor layer with a wiring pattern in order to connect the substrates by soldering. From the viewpoint of adhesion, this is required The opening shape of the opening does not become an inverted tapered shape. Here, the so-called inverted cone-shaped opening shape means a shape in which the opening becomes deeper and wider. In the present application, the property that such an opening shape is not easy to become an inverted cone shape is sometimes referred to as "undercut resistance" as excellent.

本發明之課題係提供一種解析性為優異的感光性樹脂組成物，其可得到底切耐性為優異的硬化物；以及提供使用該感光性樹脂組成物而得到的感光性薄膜、附支撐體的感光性薄膜、印刷配線板及半導體裝置。 [解決課題之手段]The subject of the present invention is to provide a photosensitive resin composition with excellent resolution, which can obtain a cured product with excellent undercut resistance; and to provide a photosensitive film obtained by using the photosensitive resin composition and a support Photosensitive films, printed wiring boards and semiconductor devices. [Means to solve the problem]

本發明人經深入研究之結果發現，藉由使感光性薄膜的重量減少率滿足指定關係之方式來調整樹脂組成物的各成分，底切耐性及解析性會提升，因而完成本發明。As a result of intensive research, the inventors found that by adjusting the components of the resin composition so that the weight reduction rate of the photosensitive film satisfies a specified relationship, the undercut resistance and resolution are improved, and thus completed the present invention.

即，本發明包含以下的內容。 [1]. 一種感光性樹脂組成物，含有下述(A)~(D)成分： (A)含有乙烯性不飽和基與羧基的樹脂； (B)光聚合起始劑； (C)環氧樹脂； (D)揮發成分， 將感光性樹脂組成物以130℃進行乾燥15分鐘時的重量減少率(%)設為a，將感光性樹脂組成物以180℃進行乾燥15分鐘時的重量減少率(%)設為b時，滿足以下的式(1)及式(2)的關係，

Figure 02_image001
。 [2]. 如[1]之感光性樹脂組成物，其中，進而包含(F)無機填充材。 [3]. 如[1]或[2]之感光性樹脂組成物，其中，(A)成分包含酸改質不飽和環氧酯樹脂。 [4]. 如[1]~[3]中任一項之感光性樹脂組成物，其中，(A)成分包含酸改質環氧(甲基)丙烯酸酯。 [5]. 如[1]~[4]中任一項之感光性樹脂組成物，其中，(A)成分包含含酸改質萘骨架的環氧(甲基)丙烯酸酯及含酸改質雙酚骨架的環氧(甲基)丙烯酸酯中的任1種。 [6]. 如[1]~[5]中任一項之感光性樹脂組成物，其中，(B)成分包含醯基氧化膦(acylphosphine oxide)系光聚合起始劑及肟酯系光聚合起始劑中的任1種。 [7]. 如[1]~[6]中任一項之感光性樹脂組成物，其中，(D)成分具有酮類及二醇醚(glycol ether)類中的任1種。 [8]. 一種感光性薄膜，其含有如[1]~[7]中任一項之感光性樹脂組成物。 [9]. 一種附支撐體的感光性薄膜，其具有支撐體與設置於該支撐體上的感光性樹脂組成物層，該感光性樹脂組成物層包含如[1]~[7]中任一項之感光性樹脂組成物。 [10]. 一種印刷配線板，其包含藉由如[1]~[7]中任一項之感光性樹脂組成物的硬化物所形成的絕緣層。 [11]. 如[10]之印刷配線板，其中，絕緣層為阻焊劑。 [12]. 一種半導體裝置，其包含[10]或[11]之印刷配線板。 [發明的效果]That is, the present invention includes the following contents. [1]. A photosensitive resin composition containing the following components (A) to (D): (A) a resin containing an ethylenically unsaturated group and a carboxyl group; (B) a photopolymerization initiator; (C) ring Oxygen resin; (D) Volatile component, the weight reduction rate (%) when the photosensitive resin composition is dried at 130°C for 15 minutes is set to a, and the weight when the photosensitive resin composition is dried at 180°C for 15 minutes When the reduction rate (%) is set to b, the relationship of the following formula (1) and formula (2) is satisfied,
Figure 02_image001
. [2]. The photosensitive resin composition according to [1], which further contains (F) an inorganic filler. [3]. The photosensitive resin composition according to [1] or [2], wherein the component (A) contains an acid-modified unsaturated epoxy ester resin. [4]. The photosensitive resin composition according to any one of [1] to [3], wherein the component (A) contains an acid-modified epoxy (meth)acrylate. [5]. The photosensitive resin composition of any one of [1] to [4], wherein the component (A) includes epoxy (meth)acrylate containing acid-modified naphthalene skeleton and acid-containing modification Any one of epoxy (meth)acrylates of bisphenol skeleton. [6]. The photosensitive resin composition of any one of [1] to [5], wherein the component (B) contains an acylphosphine oxide-based photopolymerization initiator and an oxime ester-based photopolymerization Any one of the initiators. [7]. The photosensitive resin composition according to any one of [1] to [6], wherein the component (D) has any one of ketones and glycol ethers. [8]. A photosensitive film containing the photosensitive resin composition of any one of [1] to [7]. [9]. A photosensitive film with a support, which has a support and a photosensitive resin composition layer provided on the support, the photosensitive resin composition layer including any of [1] to [7] A photosensitive resin composition. [10]. A printed wiring board comprising an insulating layer formed by a cured product of the photosensitive resin composition as described in any one of [1] to [7]. [11]. As in [10], the printed wiring board, where the insulating layer is solder resist. [12]. A semiconductor device comprising the printed wiring board of [10] or [11]. [Effects of the invention]

依據本發明，能夠提供一種解析性為優異的感光性樹脂組成物，其可得到底切耐性為優異的硬化物；以及提供使用該感光性樹脂組成物而得到的感光性薄膜、附支撐體的感光性薄膜、印刷配線板及半導體裝置。According to the present invention, it is possible to provide a photosensitive resin composition with excellent resolution, which can obtain a cured product with excellent undercut resistance; and a photosensitive film obtained by using the photosensitive resin composition, and a supporting body Photosensitive films, printed wiring boards and semiconductor devices.

[實施發明之最佳形態][Best form to implement the invention]

以下，對於本發明的感光性樹脂組成物、感光性薄膜、附支撐體的感光性薄膜、印刷配線板及半導體裝置進行詳細說明。Hereinafter, the photosensitive resin composition, photosensitive film, photosensitive film with a support, printed wiring board, and semiconductor device of the present invention will be described in detail.

[感光性樹脂組成物] 本發明的感光性樹脂組成物，含有下述(A)~(D)成分：(A)含有乙烯性不飽和基與羧基的樹脂；(B)光聚合起始劑；(C)環氧樹脂；(D)揮發成分，將感光性樹脂組成物以130℃進行乾燥15分鐘時的重量減少率(%)設為a，將感光性樹脂組成物以180℃進行乾燥15分鐘時的重量減少率(%)設為b時，滿足以下的式(1)及式(2)的關係，

Figure 02_image003
。[Photosensitive resin composition] The photosensitive resin composition of the present invention contains the following (A) to (D) components: (A) a resin containing an ethylenically unsaturated group and a carboxyl group; (B) a photopolymerization initiator (C) Epoxy resin; (D) Volatile components, the weight loss rate (%) when the photosensitive resin composition is dried at 130°C for 15 minutes is set to a, and the photosensitive resin composition is dried at 180°C When the weight loss rate (%) at 15 minutes is set to b, the relationship of the following formula (1) and formula (2) is satisfied,
Figure 02_image003
.

本發明係藉由使重量減少率滿足指定關係之方式來調整感光性樹脂組成物的各成分，而能夠提供一種解析性為優異的感光性樹脂組成物，其可得到底切耐性為優異的硬化物。又，通常而言，亦能夠得到埋置性亦為優異的硬化物。本發明人為著眼於加熱之際的感光性樹脂組成物中所包含的揮發成分的揮發量。其結果發現，當加熱溫度為130℃時的揮發量與為180℃時的揮發量滿足上述式(1)及式(2)時，將能夠得到底切耐性為優異的硬化物。著眼於揮發成分的揮發量，並調整揮發成分以使揮發量滿足指定關係之技術思想，據本發明人所得知之範圍，可以說是以往未有過的提案。The present invention is to adjust the components of the photosensitive resin composition in such a way that the weight reduction rate meets the specified relationship, and can provide a photosensitive resin composition with excellent resolution, which can be cured with excellent undercut resistance Things. In addition, generally, a cured product with excellent embedding properties can also be obtained. The present inventors focused on the amount of volatile components contained in the photosensitive resin composition during heating. As a result, it was found that when the amount of volatilization at a heating temperature of 130°C and the amount of volatilization at 180°C satisfy the above-mentioned formulas (1) and (2), a cured product having excellent undercut resistance can be obtained. The technical idea of focusing on the volatilization amount of volatile components and adjusting the volatile components so that the volatilization amount satisfies the specified relationship can be said to be an unprecedented proposal based on the range known to the inventors.

感光性樹脂組成物可進而包含任意成分，來與(A)~(D)成分組合。作為任意成分，可舉例如(E)反應性稀釋劑、(F)無機填充材及(G)其他的添加劑等。以下，對於感光性樹脂組成物中所包含的各成分來進行詳細說明。The photosensitive resin composition may further contain arbitrary components and be combined with (A) to (D) components. Examples of optional components include (E) a reactive diluent, (F) an inorganic filler, and (G) other additives. Hereinafter, each component contained in the photosensitive resin composition is demonstrated in detail.

＜(A)含有乙烯性不飽和基與羧基的樹脂＞ 感光性樹脂組成物含有作為(A)成分的含有乙烯性不飽和基與羧基的樹脂。藉由在感光性樹脂組成物中含有(A)成分，可更加提升顯影性。<(A) Resin containing ethylenically unsaturated group and carboxyl group> The photosensitive resin composition contains the resin containing an ethylenic unsaturated group and a carboxyl group as (A) component. By including the component (A) in the photosensitive resin composition, the developability can be further improved.

作為乙烯性不飽和基，可舉例如乙烯基、烯丙基、丙炔基(propargyl group)、丁烯基、乙炔基、苯乙炔基(phenylethynyl group)、馬來醯亞胺基、納迪克醯亞胺基(nadimide group)、(甲基)丙烯醯基，就光自由基聚合的反應性之觀點而言，較佳為(甲基)丙烯醯基。所謂「(甲基)丙烯醯基」係指甲基丙烯醯基及丙烯醯基。Examples of ethylenically unsaturated groups include vinyl groups, allyl groups, propargyl groups, butenyl groups, ethynyl groups, phenylethynyl groups, maleimino groups, and nadic acid groups. From the viewpoint of the reactivity of photoradical polymerization, the nadimide group and (meth)acryloyl group are preferably (meth)acryloyl group. The so-called "(meth)acryloyl" refers to methacryloyl and acryloyl.

(A)成分可使用具有乙烯性不飽和基及羧基，且能夠進行光自由基聚合之同時，能夠進行鹼液顯影的任意的化合物，較佳為例如1分子中同時具有羧基與2個以上的乙烯性不飽和基的樹脂。(A) Any compound that has an ethylenically unsaturated group and a carboxyl group can be used as the component, and is capable of undergoing photoradical polymerization and alkali solution development. For example, it is preferably a compound having both a carboxyl group and two or more in one molecule. Ethylene unsaturated resin.

作為含有乙烯性不飽和基及羧基的樹脂之一樣態，可舉出使環氧化合物與不飽和羧酸反應，進而與酸酐反應而得到的酸改質不飽和環氧酯樹脂等。詳細為使環氧化合物與不飽和羧酸反應而得到不飽和環氧酯樹脂，再藉由使不飽和環氧酯樹脂與酸酐反應而得到的酸改質不飽和環氧酯樹脂。Examples of the same state of the resin containing an ethylenically unsaturated group and a carboxyl group include an acid-modified unsaturated epoxy ester resin obtained by reacting an epoxy compound with an unsaturated carboxylic acid and further reacting with an acid anhydride. In detail, an unsaturated epoxy ester resin is obtained by reacting an epoxy compound with an unsaturated carboxylic acid, and the unsaturated epoxy ester resin is modified by an acid obtained by reacting the unsaturated epoxy ester resin with an acid anhydride.

作為環氧化合物，只要是分子內具有環氧基的化合物即可使用，可舉例如：含環氧基的共聚物、雙酚A型環氧樹脂、氫化雙酚A型環氧樹脂、雙酚F型環氧樹脂、氫化雙酚F型環氧樹脂、雙酚S型環氧樹脂、使雙酚F型環氧樹脂與表氯醇反應並改質為3官能以上的改質雙酚F型環氧樹脂等的雙酚型環氧樹脂；聯苯型環氧樹脂、四甲基聯苯型等的聯苯型環氧樹脂；苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、雙酚A型酚醛清漆型環氧樹脂、烷基苯酚酚醛清漆型環氧樹脂等的酚醛清漆型環氧樹脂；雙酚AF型環氧樹脂及全氟烷基型環氧樹脂等的含氟的環氧樹脂；萘型環氧樹脂、二羥基萘型環氧樹脂、聚羥基聯萘型環氧樹脂、萘酚型環氧樹脂、聯萘酚型環氧樹脂、伸萘基醚型環氧樹脂萘酚酚醛清漆型環氧樹脂、藉由聚羥基萘與醛類的縮合反應而得到的萘型環氧樹脂等的具有萘骨架的環氧樹脂(含萘骨架的環氧樹脂)；聯二甲酚型環氧樹脂；二環戊二烯型環氧樹脂；三酚型環氧樹脂；tert-丁基-兒茶酚型環氧樹脂；蒽型環氧樹脂等的含有縮合環骨架的環氧樹脂；縮水甘油胺型環氧樹脂；縮水甘油酯型環氧樹脂；聯苯型環氧樹脂；線狀脂肪族環氧樹脂；具有丁二烯構造的環氧樹脂；脂環式環氧樹脂；雜環式環氧樹脂；含螺環的環氧樹脂；環己烷二甲醇型環氧樹脂；三羥甲基型環氧樹脂；四苯乙烷型環氧樹脂；聚縮水甘油(甲基)丙烯酸酯、縮水甘油甲基丙烯酸酯與丙烯酸酯的共聚物等的含縮水甘油基的丙烯酸樹脂；芴型環氧樹脂；鹵化環氧樹脂等。The epoxy compound can be used as long as it has an epoxy group in the molecule, and examples include epoxy group-containing copolymers, bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, and bisphenols. F-type epoxy resin, hydrogenated bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, bisphenol F-type epoxy resin reacts with epichlorohydrin and modified into modified bisphenol F-type with more than trifunctional Bisphenol type epoxy resin such as epoxy resin; Biphenyl type epoxy resin such as biphenyl type epoxy resin and tetramethyl biphenyl type; Phenol novolak type epoxy resin and cresol novolak type epoxy resin , Bisphenol A type novolac type epoxy resin, alkylphenol novolac type epoxy resin, etc. Novolac type epoxy resin; Bisphenol AF type epoxy resin and perfluoroalkyl type epoxy resin, etc. containing fluorine Epoxy resin; naphthalene epoxy resin, dihydroxy naphthalene epoxy resin, polyhydroxy binaphthyl epoxy resin, naphthol epoxy resin, binaphthol epoxy resin, naphthyl ether epoxy Resin naphthol novolac type epoxy resin, naphthalene type epoxy resin obtained by the condensation reaction of polyhydroxynaphthalene and aldehydes, and other naphthalene skeleton epoxy resins (naphthalene skeleton-containing epoxy resins); Cresol type epoxy resin; dicyclopentadiene type epoxy resin; triphenol type epoxy resin; tert-butyl-catechol type epoxy resin; anthracene type epoxy resin and other ring containing condensed ring skeleton Oxygen resin; glycidylamine type epoxy resin; glycidyl ester type epoxy resin; biphenyl type epoxy resin; linear aliphatic epoxy resin; epoxy resin with butadiene structure; alicyclic epoxy resin ; Heterocyclic epoxy resin; epoxy resin containing spiro ring; cyclohexane dimethanol type epoxy resin; trimethylol type epoxy resin; tetraphenylethane type epoxy resin; polyglycidyl (methyl) ) Glycidyl group-containing acrylic resins such as acrylates, copolymers of glycidyl methacrylate and acrylates; fluorene type epoxy resins; halogenated epoxy resins, etc.

就降低平均線熱膨脹率之觀點而言，環氧化合物係以含環氧基的共聚物、含芳香族骨架的環氧樹脂為較佳。於此，所謂芳香族骨架係亦包含多環芳香族及芳香族雜環之概念。環氧化合物較佳為：含萘骨架的環氧樹脂；含有縮合環骨架的環氧樹脂；聯苯型環氧樹脂；雙酚F型環氧樹脂、雙酚A型環氧樹脂等的雙酚型環氧樹脂；甲酚酚醛清漆型環氧樹脂；縮水甘油酯型環氧樹脂。From the viewpoint of reducing the average linear thermal expansion coefficient, the epoxy compound is preferably an epoxy group-containing copolymer or an aromatic skeleton-containing epoxy resin. Here, the so-called aromatic skeleton system also includes the concepts of polycyclic aromatics and aromatic heterocycles. The epoxy compound is preferably: epoxy resin containing naphthalene skeleton; epoxy resin containing condensed ring skeleton; biphenyl type epoxy resin; bisphenol F type epoxy resin, bisphenol A type epoxy resin, etc. Type epoxy resin; cresol novolac type epoxy resin; glycidyl ester type epoxy resin.

可藉由使含環氧基的單體及因應所需的任意的單體進行聚合，而得到含環氧基的共聚物。作為含環氧基的單體，可舉例如縮水甘油(甲基)丙烯酸酯、3,4-環氧丁基(甲基)丙烯酸酯、2-甲基-3,4-環氧環己基(甲基)丙烯酸酯、烯丙基縮水甘油醚等的含環氧基的(甲基)丙烯酸酯單體，較佳為縮水甘油(甲基)丙烯酸酯。含環氧基的單體係可單獨使用、亦可混合2種以上來使用。The epoxy group-containing copolymer can be obtained by polymerizing the epoxy group-containing monomer and any monomer as needed. As the epoxy group-containing monomer, for example, glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 2-methyl-3,4-epoxycyclohexyl ( An epoxy group-containing (meth)acrylate monomer such as meth)acrylate and allyl glycidyl ether is preferably glycidyl (meth)acrylate. The epoxy group-containing single system may be used alone or in combination of two or more kinds.

作為任意的單體，可舉例如苯乙烯、(甲基)丙烯酸、(甲基)丙烯酸甲酯、甲基丙烯酸乙酯、(甲基)丙烯酸n-丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸n-丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸t-丁酯、(甲基)丙烯酸n-戊酯、(甲基)丙烯酸n-己酯、(甲基)丙烯酸n-庚酯、(甲基)丙烯酸n-辛酯、甲基丙烯酸2-乙基己酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸硬脂基酯、(甲基)丙烯酸二十二烷基酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸4-tert-丁基環己酯、(甲基)丙烯酸異莰基酯、(甲基)丙烯酸二環戊二烯酯、(甲基)丙烯酸苄基酯、丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、(甲基)丙烯腈、3-(甲基)丙烯醯基丙基三甲氧基矽烷、(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸縮水甘油酯、苯乙烯、α-甲基苯乙烯、p-甲基苯乙烯、p-甲氧基苯乙烯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸4-羥基-n-丁酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基-n-丁酯、(甲基)丙烯酸3-羥基-n-丁酯、1,4-環己烷二甲醇單(甲基)丙烯酸酯、甘油單(甲基)丙烯酸酯、聚乙二醇單(甲基)丙烯酸酯、聚丙二醇單(甲基)丙烯酸酯、2-羥基-3-苯氧基丙基(甲基)丙烯酸酯、鄰苯二甲酸2-(甲基)丙烯醯氧基乙基-2-羥基乙酯、末端具有羥基的內酯改質(甲基)丙烯酸酯、1-金剛烷基(甲基)丙烯酸酯等，較佳為(甲基)丙烯酸n-丁酯。任意的單體係可單獨使用、亦可混合2種以上來使用。所謂「(甲基)丙烯酸」係指丙烯酸及甲基丙烯酸。所謂「(甲基)丙烯酸酯」係指丙烯酸酯及甲基丙烯酸酯。As arbitrary monomers, for example, styrene, (meth)acrylic acid, methyl (meth)acrylate, ethyl methacrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate , N-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, N-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl methacrylate, nonyl (meth)acrylate, decyl (meth)acrylate, (meth) Lauryl acrylate, tridecyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate , Cyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentadiene (meth)acrylate, (meth) ) Benzyl acrylate, acrylamide, N,N-dimethyl(meth)acrylamide, (meth)acrylonitrile, 3-(meth)acrylonitrile propyltrimethoxysilane, (form Base) N,N-dimethylaminoethyl acrylate, glycidyl (meth)acrylate, styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene, ( 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxy-n-butyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth) 2-hydroxy-n-butyl acrylate, 3-hydroxy-n-butyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, glycerol mono(meth)acrylate, Polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl(meth)acrylate, 2-(methyl)phthalate Acrylic oxyethyl-2-hydroxyethyl, lactone-modified (meth)acrylate having a hydroxyl group at the end, 1-adamantyl (meth)acrylate, etc., preferably (meth)acrylic acid n -Butyl ester. Any single system may be used alone, or two or more of them may be mixed and used. The so-called "(meth)acrylic acid" refers to acrylic acid and methacrylic acid. The so-called "(meth)acrylate" refers to acrylate and methacrylate.

作為含萘骨架的環氧樹脂，較佳為二羥基萘型環氧樹脂、聚羥基聯萘型環氧樹脂、藉由聚羥基萘與醛類的縮合反應而得到的萘型環氧樹脂。作為二羥基萘型環氧樹脂，可舉例如1,3-二縮水甘油氧基萘、1,4-二縮水甘油氧基萘、1,5-二縮水甘油氧基萘、1,6-二縮水甘油氧基萘、2,3-二縮水甘油氧基萘、2,6-二縮水甘油氧基萘、2,7-二縮水甘油氧基萘等。作為聚羥基聯萘型環氧樹脂，可舉例如1,1’-聯-(2-縮水甘油氧基)萘基、1-(2,7-二縮水甘油氧基)-1’-(2’-縮水甘油氧基)聯萘基、1,1’-聯-(2,7-二縮水甘油氧基)萘基等。作為藉由聚羥基萘與醛類的縮合反應而得到的萘型環氧樹脂，可舉例如1,1’-雙(2,7-二縮水甘油氧基萘基)甲烷、1-(2,7-二縮水甘油氧基萘基)-1’-(2’-縮水甘油氧基萘基)甲烷、1,1’-雙(2-縮水甘油氧基萘基)甲烷。The naphthalene skeleton-containing epoxy resin is preferably a dihydroxynaphthalene type epoxy resin, a polyhydroxybinaphthyl type epoxy resin, and a naphthalene type epoxy resin obtained by the condensation reaction of polyhydroxynaphthalene and aldehydes. Examples of dihydroxynaphthalene-type epoxy resins include 1,3-diglycidoxynaphthalene, 1,4-diglycidoxynaphthalene, 1,5-diglycidoxynaphthalene, 1,6-diglycidoxynaphthalene, Glycidyloxynaphthalene, 2,3-diglycidyloxynaphthalene, 2,6-diglycidyloxynaphthalene, 2,7-diglycidyloxynaphthalene, etc. Examples of polyhydroxy binaphthyl epoxy resins include 1,1'-bi-(2-glycidyloxy)naphthyl, 1-(2,7-diglycidyloxy)-1'-(2 '-Glycidyloxy)binaphthyl, 1,1'-bi-(2,7-diglycidyloxy)naphthyl and the like. Examples of naphthalene-type epoxy resins obtained by the condensation reaction of polyhydroxynaphthalene and aldehydes include 1,1'-bis(2,7-diglycidoxynaphthyl)methane, 1-(2, 7-Diglycidoxynaphthyl)-1'-(2'-glycidoxynaphthyl)methane, 1,1'-bis(2-glycidoxynaphthyl)methane.

作為不飽和羧酸，可舉例如丙烯酸、甲基丙烯酸、桂皮酸、巴豆酸等，該等係可使用單獨1種，亦可併用2種以上。其中，就提升感光性樹脂組成物的光硬化性之觀點而言，較佳為丙烯酸、甲基丙烯酸。尚，於本說明書中，有時將作為上述的環氧化合物與(甲基)丙烯酸之反應物的環氧酯樹脂記載為「環氧(甲基)丙烯酸酯」，於此，在藉由與(甲基)丙烯酸的反應中，環氧化合物的環氧基實質上為消滅。As an unsaturated carboxylic acid, acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, etc. are mentioned, for example, These systems may be used individually by 1 type, and may use 2 or more types together. Among them, from the viewpoint of improving the photocurability of the photosensitive resin composition, acrylic acid and methacrylic acid are preferred. In addition, in this specification, the epoxy ester resin that is the reaction product of the above-mentioned epoxy compound and (meth)acrylic acid is sometimes described as "epoxy (meth)acrylate". In the reaction of (meth)acrylic acid, the epoxy group of the epoxy compound is substantially eliminated.

作為酸酐，可舉例如馬來酸酐、琥珀酸酐、伊康酸酐、鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、偏苯三甲酸酐、均苯四甲酸酐、二苯基酮四羧酸二酐等，該等係可單獨使用任1種，亦可併用2種以上。其中，就硬化物的解析性及絕緣可靠性提升之方面而言，較佳為琥珀酸酐、四氫鄰苯二甲酸酐。Examples of acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, For benzophenone tetracarboxylic dianhydride, etc., any one of these systems may be used alone, or two or more of them may be used in combination. Among them, succinic anhydride and tetrahydrophthalic anhydride are preferred in terms of improving the resolution and insulation reliability of the cured product.

於得到酸改質不飽和環氧酯樹脂時，因應所需亦可使用觸媒、溶劑及聚合抑制劑等。When obtaining an acid-modified unsaturated epoxy ester resin, catalysts, solvents, polymerization inhibitors, etc. can also be used as needed.

作為酸改質不飽和環氧酯樹脂，較佳為酸改質環氧(甲基)丙烯酸酯，又較佳為包含含酸改質萘骨架的環氧(甲基)丙烯酸酯、及含酸改質雙酚骨架的環氧(甲基)丙烯酸酯之任一者。所謂酸改質不飽和環氧酯樹脂中的「環氧基」，係表示源自上述的環氧化合物的構造。例如所謂「酸改質雙酚型環氧(甲基)丙烯酸酯」係指使用雙酚型環氧樹脂作為環氧化合物，並使用(甲基)丙烯酸作為不飽和羧酸而得到的酸改質不飽和環氧酯樹脂。As the acid-modified unsaturated epoxy ester resin, an acid-modified epoxy (meth)acrylate is preferable, and an epoxy (meth)acrylate containing an acid-modified naphthalene skeleton and an acid-containing Any one of the epoxy (meth)acrylates of the modified bisphenol skeleton. The "epoxy group" in the acid-modified unsaturated epoxy ester resin means a structure derived from the above-mentioned epoxy compound. For example, the so-called "acid-modified bisphenol epoxy (meth)acrylate" refers to the acid modification obtained by using bisphenol-type epoxy resin as the epoxy compound and (meth)acrylic acid as the unsaturated carboxylic acid Unsaturated epoxy ester resin.

酸改質不飽和環氧酯樹脂係以玻璃轉移溫度為-20℃以下的(甲基)丙烯酸聚合物為較佳。所謂(甲基)丙烯酸聚合物係指包含具有將(甲基)丙烯酸單體聚合後所形成的構造的構造單位的聚合物。作為如此般的(甲基)丙烯酸聚合物，可舉出將(甲基)丙烯酸單體聚合而成的聚合物、或將(甲基)丙烯酸單體及能夠與該(甲基)丙烯酸單體共聚合的單體共聚合而成的聚合物。The acid-modified unsaturated epoxy ester resin is preferably a (meth)acrylic polymer having a glass transition temperature of -20°C or less. The (meth)acrylic polymer refers to a polymer containing a structural unit having a structure formed by polymerizing a (meth)acrylic monomer. As such a (meth)acrylic polymer, a polymer obtained by polymerizing a (meth)acrylic monomer, or a (meth)acrylic monomer and a (meth)acrylic monomer that can be combined with the (meth)acrylic monomer can be mentioned. A polymer formed by copolymerization of copolymerized monomers.

作為玻璃轉移溫度為-20℃以下的(甲基)丙烯酸聚合物，可舉出使含環氧基的共聚物與(甲基)丙烯酸反應，進而與酸酐反應而得到的酸改質不飽和環氧(甲基)丙烯酸共聚物等。詳細為使含環氧基的共聚物與(甲基)丙烯酸反應而得到不飽和環氧(甲基)丙烯酸共聚物，再使不飽和環氧(甲基)丙烯酸共聚物與酸酐反應，藉此能夠得到酸改質不飽和環氧(甲基)丙烯酸共聚物。Examples of the (meth)acrylic polymer having a glass transition temperature of -20°C or less include an acid-modified unsaturated ring obtained by reacting an epoxy group-containing copolymer with (meth)acrylic acid and then reacting with an acid anhydride. Oxygen (meth)acrylic acid copolymer, etc. In detail, the unsaturated epoxy (meth)acrylic copolymer is obtained by reacting the epoxy-containing copolymer with (meth)acrylic acid, and then the unsaturated epoxy (meth)acrylic copolymer is reacted with acid anhydride, thereby An acid-modified unsaturated epoxy (meth)acrylic copolymer can be obtained.

作為玻璃轉移溫度為-20℃以下的(甲基)丙烯酸聚合物之較佳樣態，如下述的化合物：使藉由含環氧基的單體及任意的單體聚合而得到的含環氧基的共聚物、與(甲基)丙烯酸以及酸酐反應而得到的化合物，且含環氧基的單體為縮水甘油甲基丙烯酸酯、任意的單體為甲基丙烯酸丁酯、酸酐為四氫鄰苯二甲酸酐。As a preferable aspect of the (meth)acrylic polymer having a glass transition temperature of -20°C or less, such as the following compound: an epoxy-containing monomer obtained by polymerizing an epoxy-containing monomer and an arbitrary monomer Base copolymer, a compound obtained by reacting with (meth)acrylic acid and acid anhydride, and the epoxy-containing monomer is glycidyl methacrylate, the optional monomer is butyl methacrylate, and the acid anhydride is tetrahydro Phthalic anhydride.

如此般的酸改質不飽和環氧酯樹脂可使用市售品，作為具體例，可舉出日本化藥公司製的「ZAR-2000」(雙酚A型環氧樹脂、丙烯酸及琥珀酸酐的反應物)、「ZFR-1491H」、「ZFR-1533H」(雙酚F型環氧樹脂、丙烯酸及四氫鄰苯二甲酸酐的反應物(含雙酚F型骨架的酸改質環氧丙烯酸酯))、昭和電工公司製的「PR-300CP」(甲酚酚醛清漆型環氧樹脂、丙烯酸及酸酐的反應物)等。該等係可單獨使用1種、亦可組合2種以上來使用。Commercial products can be used for such acid-modified unsaturated epoxy ester resins. As a specific example, "ZAR-2000" manufactured by Nippon Kayaku Co., Ltd. (bisphenol A type epoxy resin, acrylic acid, and succinic anhydride) can be used. Reactant), "ZFR-1491H", "ZFR-1533H" (reactant of bisphenol F epoxy resin, acrylic acid, and tetrahydrophthalic anhydride (acid-modified epoxy acrylic acid containing bisphenol F type skeleton) Ester)), Showa Denko Corporation "PR-300CP" (reactant of cresol novolac epoxy resin, acrylic acid and acid anhydride), etc. These systems may be used individually by 1 type, and may be used in combination of 2 or more types.

作為含有乙烯性不飽和基及羧基的樹脂之其他的樣態，可舉出使具有(甲基)丙烯酸聚合而得到的構造單位的(甲基)丙烯酸樹脂與含乙烯性不飽和基的環氧化合物反應，而導入乙烯性不飽和基的不飽和改質(甲基)丙烯酸樹脂。含乙烯性不飽和基的環氧化合物，可舉例如縮水甘油甲基丙烯酸酯、(甲基)丙烯酸4-羥基丁酯縮水甘油醚、3,4-環氧環己基(甲基)丙烯酸甲酯等。進而亦可使導入不飽和基之際所產生的羥基與酸酐反應。作為酸酐係可使用與上述的酸酐為相同者，較佳範圍亦為相同。As other aspects of resins containing ethylenically unsaturated groups and carboxyl groups, (meth)acrylic resins having structural units obtained by polymerizing (meth)acrylic acid and epoxy resins containing ethylenically unsaturated groups can be mentioned. The compound reacts to introduce the unsaturated modified (meth)acrylic resin into which the ethylenic unsaturated group is introduced. The epoxy compound containing an ethylenically unsaturated group includes, for example, glycidyl methacrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and 3,4-epoxycyclohexyl methyl (meth)acrylate Wait. Furthermore, the hydroxyl group produced when introducing an unsaturated group can be made to react with acid anhydride. As an acid anhydride system, the same thing as the above-mentioned acid anhydride can be used, and a preferable range is also the same.

如此般的不飽和改質(甲基)丙烯酸樹脂可使用市售品，作為具體例，可舉出昭和電工公司製的「SPC-1000」、「SPC-3000」、Daicel-Allnex公司製「Cyclomer P(ACA)Z-250」、「Cyclomer P(ACA)Z-251」、「Cyclomer P(ACA)Z-254」、「Cyclomer P(ACA)Z-300」、「Cyclomer P(ACA)Z-320」等。Commercial products can be used for such unsaturated modified (meth)acrylic resins. Specific examples include "SPC-1000" and "SPC-3000" manufactured by Showa Denko Corporation and "Cyclomer" manufactured by Daicel-Allnex. P(ACA)Z-250", "Cyclomer P(ACA)Z-251", "Cyclomer P(ACA)Z-254", "Cyclomer P(ACA)Z-300", "Cyclomer P(ACA)Z- 320" and so on.

就製膜性之觀點而言，作為(A)成分的重量平均分子量係以1000以上為較佳，以1500以上為又較佳，以2000以上為更佳。就顯影性之觀點而言，作為上限係以10000以下為較佳，以8000以下為又較佳，以7500以下為更佳。重量平均分子量係藉由凝膠滲透層析(GPC)法所測量的聚苯乙烯換算的重量平均分子量。From the viewpoint of film forming properties, the weight average molecular weight as the component (A) is preferably 1,000 or more, more preferably 1,500 or more, and more preferably 2,000 or more. From the viewpoint of developability, the upper limit is preferably 10,000 or less, more preferably 8,000 or less, and more preferably 7,500 or less. The weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by the gel permeation chromatography (GPC) method.

就提升感光性樹脂組成物的鹼液顯影性之觀點而言，作為(A)成分的酸價係以酸價為0.1mgKOH/g以上為較佳，以0.5mgKOH/g以上為又較佳，以1mgKOH/g以上為更佳。另一方面，就抑制硬化物的微細圖型因顯影而溶出之情形、提升絕緣可靠性之觀點而言，以酸價為150mgKOH/g以下為較佳，以120mgKOH/g以下為又較佳，以100mgKOH/g以下為更佳。於此，所謂酸價係指(A)成分中存在的羧基的殘留酸價，酸價可藉由以下的方法來測量。首先，精密秤量所測量的樹脂溶液約1g後，於該樹脂溶液中添加丙酮30g，並將樹脂溶液均勻地溶解。接下來，於該溶液中適量添加作為指示劑的酚酞，並使用0.1N的KOH水溶液來進行滴定。又，依據下述式來算出酸價。

Figure 02_image005
From the viewpoint of improving the developability of the photosensitive resin composition in an alkaline solution, the acid value of the component (A) is preferably 0.1 mgKOH/g or more, and more preferably 0.5 mgKOH/g or more. More preferably, 1 mgKOH/g or more. On the other hand, from the viewpoint of suppressing the elution of fine patterns of the cured product due to development and improving insulation reliability, the acid value is preferably 150 mgKOH/g or less, and 120 mgKOH/g or less is more preferable. It is more preferably 100mgKOH/g or less. Here, the acid value refers to the residual acid value of the carboxyl group present in the component (A), and the acid value can be measured by the following method. First, after accurately weighing about 1 g of the measured resin solution, 30 g of acetone is added to the resin solution, and the resin solution is uniformly dissolved. Next, an appropriate amount of phenolphthalein as an indicator was added to this solution, and a 0.1N KOH aqueous solution was used for titration. In addition, the acid value was calculated according to the following formula.
Figure 02_image005

尚，上述式中，A(b)表示酸價(mgKOH/g)，Vf表示KOH的滴定量(mL)，Wp表示測量樹脂溶液的質量(g)，I表示測量樹脂溶液的不揮發分的比例(質量%)。Still, in the above formula, A(b) represents the acid value (mgKOH/g), Vf represents the titer of KOH (mL), Wp represents the mass (g) of the measured resin solution, and I represents the non-volatile content of the measured resin solution Proportion (mass%).

於(A)成分的製造時，就保存穩定性的提升之類的觀點而言，環氧樹脂的環氧基的莫耳數，及不飽和羧酸與酸酐的合計的羧基的莫耳數的比，較佳為1：0.8~1.3的範圍，又較佳為1：0.9~1.2的範圍。In the production of (A) component, from the viewpoint of improvement of storage stability, the number of moles of epoxy groups of epoxy resin and the number of moles of carboxyl groups of the total of unsaturated carboxylic acid and acid anhydride The ratio is preferably in the range of 1:0.8 to 1.3, and more preferably in the range of 1:0.9 to 1.2.

就提升柔軟性之觀點而言，(A)成分的玻璃轉移溫度(Tg)係較佳為-300℃以上，又較佳為-200℃以上，更佳為-80℃以上，較佳為-20℃以下，又較佳為-23℃以下，更佳為-25℃以下。於此，所謂(A)成分的玻璃轉移溫度係指(A)成分的主鏈的理論玻璃轉移溫度，該理論玻璃轉移溫度可藉由以下所示的FOX之式來算出。藉由FOX之式所求出的玻璃轉移溫度係與藉由示差掃描熱量測量(TMA、DSC、DTA)所測量的玻璃轉移溫度幾乎一樣，因此藉由示差掃描熱量測量，亦可測量(A)成分的主鏈的玻璃轉移溫度。

Figure 02_image007
Wm表示構成(A)成分的各單體的含有量(質量%)，Tgm表示構成(A)成分的各單體的玻璃轉移溫度(K)。From the viewpoint of improving flexibility, the glass transition temperature (Tg) of the component (A) is preferably -300°C or higher, more preferably -200°C or higher, more preferably -80°C or higher, and preferably- 20°C or less, more preferably -23°C or less, more preferably -25°C or less. Here, the glass transition temperature of (A) component means the theoretical glass transition temperature of the main chain of (A) component, and this theoretical glass transition temperature can be calculated by the formula of FOX shown below. The glass transition temperature calculated by the FOX formula is almost the same as the glass transition temperature measured by differential scanning calorimetry (TMA, DSC, DTA), so it can also be measured by differential scanning calorimetry (A) The glass transition temperature of the main chain of the ingredient.
Figure 02_image007
Wm represents the content (mass %) of each monomer constituting the (A) component, and Tgm represents the glass transition temperature (K) of each monomer constituting the (A) component.

就鹼液顯影性的提升之類的觀點而言，將感光性樹脂組成物中的不揮發成分設為100質量%時，(A)成分係較佳為5質量%以上，又較佳為10質量%以上，更佳為15質量%以上。就耐熱性或平均線膨脹率的提升之類的觀點而言，上限係較佳為40質量%以下，又較佳為35質量%以下，更佳為35質量%以下、30質量%以下、或25質量%以下。尚，於本發明中，若無特別說明，感光性樹脂組成物中的各成分的含有量，係指將感光性樹脂組成物中的不揮發成分設為100質量%時的值。From the viewpoint of improving the developability of the alkali solution, when the non-volatile content in the photosensitive resin composition is 100% by mass, the component (A) is preferably 5% by mass or more, and more preferably 10 Mass% or more, more preferably 15 mass% or more. From the viewpoint of heat resistance or improvement of the average linear expansion rate, the upper limit is preferably 40% by mass or less, more preferably 35% by mass or less, more preferably 35% by mass or less, 30% by mass or less, or 25% by mass or less. In the present invention, unless otherwise specified, the content of each component in the photosensitive resin composition refers to a value when the non-volatile content in the photosensitive resin composition is 100% by mass.

＜(B)光聚合起始劑＞ 感光性樹脂組成物含有作為(B)成分的光聚合起始劑。藉由在感光性樹脂組成物中含有(B)光聚合起始劑，可使感光性樹脂組成物有效地光硬化。＜(B) Photopolymerization initiator＞ The photosensitive resin composition contains a photopolymerization initiator as the component (B). By containing the (B) photopolymerization initiator in the photosensitive resin composition, the photosensitive resin composition can be effectively photocured.

(B)光聚合起始劑係可使用任意的化合物，可舉例如雙(2,4,6-三甲基苯甲醯)-苯基氧化膦)、2,4,6-三甲基苯甲醯-二苯基-氧化膦等的醯基氧化膦(acylphosphine oxide)系光聚合起始劑；1,2-辛二酮、1-4-(苯硫基)-2-(O-苯甲醯肟)、乙酮,1-[9-乙基-6-(2-甲基苯甲醯)-9H-咔唑-3-基]-,1-(O-乙醯肟)等的肟酯系光聚合起始劑；2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-1-丁酮、2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-[4-(4-嗎咻基)苯基]-1-丁酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基丙烷-1-酮等的α-胺基烷基苯酮系光聚合起始劑；烷基苯酮、甲基烷基苯酮、o-苯甲醯苯甲酸、苯甲醯乙基醚、2,2-二乙氧基苯乙酮、2,4-二乙基噻吨酮、二苯基-(2,4,6-三甲基苯甲醯)氧化膦、乙基-(2,4,6-三甲基苯甲醯)苯基次膦酸酯、4,4’-雙(二乙基胺基)烷基苯酮、1-羥基-環己基-苯基酮、2,2-二甲氧基-1,2-二苯乙烷-1-酮、1-[4-(2-羥基乙氧基)-苯基]-2-羥基-2-甲基-1-丙烷-1-酮、雙(2,4,6-三甲基苯甲醯)-苯基氧化膦；鋶鹽系光聚合起始劑等。該等係可使用單獨1種、亦可併用2種以上。該等之中，就可更有效地使感光性樹脂組成物光硬化之觀點而言，較佳為醯基氧化膦系光聚合起始劑及肟酯系光聚合起始劑中任一者，又較佳為肟酯系光聚合起始劑。該等係可單獨使用1種、亦可組合2種以上來使用。(B) Any compound can be used as the photopolymerization initiator system, for example, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide), 2,4,6-trimethylbenzene Acylphosphine oxide (acylphosphine oxide)-based photopolymerization initiators such as formaldehyde-diphenyl-phosphine oxide; 1,2-octanedione, 1-4-(phenylthio)-2-(O-benzene) Methyl oxime), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-, 1-(O-acetoxime), etc. Oxime ester-based photopolymerization initiator; 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-1-butanone, 2-(dimethylamino)-2 -[(4-Methylphenyl)methyl]-[4-(4-morphoyl)phenyl]-1-butanone, 2-methyl-1-[4-(methylthio)phenyl ]-2-morpholinopropan-1-one and other α-aminoalkylphenone photopolymerization initiators; alkylphenone, methylalkylphenone, o-benzoic acid, benzene Methyl ethyl ether, 2,2-diethoxy acetophenone, 2,4-diethyl thioxanthone, diphenyl-(2,4,6-trimethylbenzyl) phosphine oxide, Ethyl-(2,4,6-trimethylbenzyl)phenylphosphinate, 4,4'-bis(diethylamino)alkylphenone, 1-hydroxy-cyclohexyl-benzene Ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl 1-propan-1-one, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide; sulfonate-based photopolymerization initiator, etc. These systems may be used individually by 1 type, and may use 2 or more types together. Among these, from the viewpoint that the photosensitive resin composition can be photocured more effectively, any one of an acetoxy phosphine oxide-based photopolymerization initiator and an oxime ester-based photopolymerization initiator is preferred. It is also preferably an oxime ester-based photopolymerization initiator. These systems may be used individually by 1 type, and may be used in combination of 2 or more types.

作為(B)光聚合起始劑之具體例，可舉出IGM公司製的「Omnirad 907」、「Omnirad 369」、「Omnirad 379」、「Omnirad 819」、「Omnirad TPO」、BASF公司製的「Irgacure OXE-01」、「Irgacure OXE-02」、「Irgacure TPO」、「Irgacure 819」、ADEKA公司製的「N-1919」等。(B) Specific examples of the photopolymerization initiator include "Omnirad 907", "Omnirad 369", "Omnirad 379", "Omnirad 819", "Omnirad TPO", and "Omnirad TPO" manufactured by IGM Corporation. "Irgacure OXE-01", "Irgacure OXE-02", "Irgacure TPO", "Irgacure 819", "N-1919" manufactured by ADEKA, etc.

進而，感光性樹脂組成物可包含作為光聚合起始助劑的N,N-二甲基胺基苯甲酸乙酯、N,N-二甲基胺基苯甲酸異戊酯、戊基-4-二甲基胺基苯甲酸酯、三乙基胺、三乙醇胺等的第三級胺類，亦可包含吡唑啉類、蒽類、香豆素類、呫噸酮類、噻吨酮類等之類的光增感劑，來與(B)光聚合起始劑組合。該等係可使用任何的單獨1種、亦可併用2種以上。Furthermore, the photosensitive resin composition may contain ethyl N,N-dimethylaminobenzoate, isoamyl N,N-dimethylaminobenzoate, and pentyl-4 as a photopolymerization initiation assistant. -Tertiary amines such as dimethylamino benzoate, triethylamine, triethanolamine, etc., and may also include pyrazolines, anthracenes, coumarins, xanthones, and thioxanthones A photosensitizer, such as the A, etc., is used in combination with the (B) photopolymerization initiator. Any of these systems may be used alone, or two or more of them may be used in combination.

就使感光性樹脂組成物充分地光硬化、提升絕緣可靠性之類的觀點而言，將感光性樹脂組成物的不揮發成分設為100質量%時，作為(B)光聚合起始劑的含有量係較佳為0.001質量%以上，又較佳為0.005質量%以上，更佳為0.01質量%以上。另一方面，就抑制因感度過高而導致解析性的降低之類的觀點而言，上限係較佳為3質量%以下，又較佳為1質量%以下，更佳為0.5質量%以下。尚，若感光性樹脂組成物包含光聚合起始助劑時，以(B)光聚合起始劑與光聚合起始助劑的合計含有量為上述範圍內為較佳。From the viewpoint of sufficient photocuring of the photosensitive resin composition and improvement of insulation reliability, when the non-volatile content of the photosensitive resin composition is 100% by mass, it is used as the (B) photopolymerization initiator The content is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and more preferably 0.01% by mass or more. On the other hand, from the viewpoint of suppressing a decrease in resolution due to excessively high sensitivity, the upper limit is preferably 3% by mass or less, more preferably 1% by mass or less, and more preferably 0.5% by mass or less. In addition, when the photosensitive resin composition contains a photopolymerization start assistant, it is preferable that the total content of the (B) photopolymerization initiator and the photopolymerization start assistant is within the above-mentioned range.

＜(C)環氧樹脂＞ 感光性樹脂組成物含有作為(C)成分的環氧樹脂。藉由含有(C)成分，可使絕緣可靠性提升。但，於此所謂(C)成分係不包含含有乙烯性不飽和基及羧基的環氧樹脂。＜(C)Epoxy resin＞ The photosensitive resin composition contains epoxy resin as the (C) component. By containing the component (C), the insulation reliability can be improved. However, the (C) component system here does not include an epoxy resin containing an ethylenically unsaturated group and a carboxyl group.

作為(C)成分，可舉例如聯二甲酚型環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、雙酚AF型環氧樹脂、二環戊二烯型環氧樹脂、三酚型環氧樹脂、萘酚酚醛清漆型環氧樹脂、苯酚酚醛清漆型環氧樹脂、tert-丁基-兒茶酚型環氧樹脂、萘型環氧樹脂、萘酚型環氧樹脂、蒽型環氧樹脂、縮水甘油胺型環氧樹脂、縮水甘油酯型環氧樹脂、甲酚酚醛清漆型環氧樹脂、聯苯型環氧樹脂、線狀脂肪族環氧樹脂、具有丁二烯構造的環氧樹脂、脂環式環氧樹脂、雜環式環氧樹脂、含螺環的環氧樹脂、環己烷型環氧樹脂、環己烷二甲醇型環氧樹脂、伸萘基醚型環氧樹脂、三羥甲基型環氧樹脂、四苯乙烷型環氧樹脂等。(C)環氧樹脂係可使用單獨1種類、亦可組合2種類以上來使用。As the (C) component, for example, bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, Dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type ring Oxygen resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear Aliphatic epoxy resins, epoxy resins with butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexane type epoxy resins, cyclohexane two Methanol type epoxy resin, naphthyl ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, etc. (C) An epoxy resin system can be used individually by 1 type, and can also be used in combination of 2 or more types.

感光性樹脂組成物較佳包含1分子中具有2個以上的環氧基的環氧樹脂來作為(C)成分。就明顯得到本發明所期望之效果之觀點而言，相對於(C)成分的不揮發成分100質量%，1分子中具有2個以上的環氧基的環氧樹脂的比例係較佳為50質量%以上，又較佳為60質量%以上，特佳為70質量%以上。The photosensitive resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as the (C) component. From the viewpoint of clearly obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups per molecule relative to 100% by mass of the non-volatile content of the component (C) is preferably 50 Mass% or more, more preferably 60% by mass or more, particularly preferably 70% by mass or more.

(C)成分係有在溫度20℃為液狀的環氧樹脂(以下有時稱為「液狀環氧樹脂」)，與在溫度20℃為固體狀的環氧樹脂(以下有時稱為「固體狀環氧樹脂」)。樹脂組成物，作為(C)成分，可僅包含液狀環氧樹脂，或可僅包含固體狀環氧樹脂，亦可組合液狀環氧樹脂與固體狀環氧樹脂。The component (C) includes an epoxy resin that is liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resin"), and an epoxy resin that is solid at a temperature of 20°C (hereinafter sometimes referred to as "Solid epoxy resin"). The resin composition may contain only a liquid epoxy resin as the (C) component, or may contain only a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin.

作為固體狀環氧樹脂係以1分子中具有3個以上的環氧基的固體狀環氧樹脂為較佳，以1分子中具有3個以上的環氧基的芳香族系的固體狀環氧樹脂為又較佳。As a solid epoxy resin, a solid epoxy resin having 3 or more epoxy groups in a molecule is preferred, and an aromatic solid epoxy resin having 3 or more epoxy groups in a molecule is preferred. The resin is more preferable.

作為固體狀環氧樹脂係以聯二甲酚型環氧樹脂、萘型環氧樹脂、萘型4官能環氧樹脂、甲酚酚醛清漆型環氧樹脂、二環戊二烯型環氧樹脂、三酚型環氧樹脂、萘酚型環氧樹脂、聯苯型環氧樹脂、伸萘基醚型環氧樹脂、蒽型環氧樹脂、雙酚A型環氧樹脂、雙酚AF型環氧樹脂、四苯乙烷型環氧樹脂為較佳，以萘型環氧樹脂為又較佳。As a solid epoxy resin, dixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, Triphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthyl ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin Resin and tetraphenylethane type epoxy resin are preferable, and naphthalene type epoxy resin is more preferable.

作為固體狀環氧樹脂之具體例，可舉出DIC公司製的「HP4032H」(萘型環氧樹脂)；DIC公司製的「HP-4700」、「HP-4710」(萘型4官能環氧樹脂)；DIC公司製的「N-690」(甲酚酚醛清漆型環氧樹脂)；DIC公司製的「N-695」(甲酚酚醛清漆型環氧樹脂)；DIC公司製的「HP-7200」、「HP-7200HH」、「HP-7200H」(二環戊二烯型環氧樹脂)；DIC公司製的「EXA-7311」、「EXA-7311-G3」、「EXA-7311-G4」、「EXA-7311-G4S」、「HP6000」(伸萘基醚型環氧樹脂)；日本化藥公司製的「EPPN-502H」(三酚型環氧樹脂)；日本化藥公司製的「NC7000L」(萘酚酚醛清漆型環氧樹脂)；日本化藥公司製的「NC3000H」、「NC3000」、「NC3000L」、「NC3100」(聯苯型環氧樹脂)；新日鐵住金化學公司製的「ESN475V」(萘酚型環氧樹脂)；新日鐵住金化學公司製的「ESN485」(萘酚酚醛清漆型環氧樹脂)；Mitsubishi Chemical公司製的「YX4000H」、「YX4000」、「YL6121」(聯苯型環氧樹脂)；Mitsubishi Chemical公司製的「YX4000HK」(聯二甲酚型環氧樹脂)；Mitsubishi Chemical公司製的「YX8800」(蒽型環氧樹脂)；Osaka Gas Chemical公司製的「PG-100」、「CG-500」；Mitsubishi Chemical公司製的「YL7760」(雙酚AF型環氧樹脂)；Mitsubishi Chemical公司製的「YL7800」(芴型環氧樹脂)；Mitsubishi Chemical公司製的「jER1010」(固體狀雙酚A型環氧樹脂)；Mitsubishi Chemical公司製的「jER1031S」(肆羥基苯乙烷型環氧樹脂)等。該等係可使用單獨1種類、亦可組合2種類以上來使用。Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC Resin); "N-690" (cresol novolac type epoxy resin) manufactured by DIC; "N-695" (cresol novolak type epoxy resin) manufactured by DIC; "HP- 7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4" manufactured by DIC Corporation ", "EXA-7311-G4S", "HP6000" (naphthyl ether type epoxy resin); "EPPN-502H" (triphenol type epoxy resin) manufactured by Nippon Kayaku Corporation; manufactured by Nippon Kayaku Corporation "NC7000L" (naphthol novolak type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; Nippon Steel & Sumikin Chemical Co., Ltd. "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "ESN485" (naphthol novolak type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Corporation; "YL6121" (biphenyl type epoxy resin); "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical; Osaka Gas Chemical Company "PG-100" and "CG-500" manufactured by Mitsubishi Chemical; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical; Mitsubishi Chemical "JER1010" (solid bisphenol A type epoxy resin) manufactured by the company; "jER1031S" (4 hydroxystyrene type epoxy resin) manufactured by Mitsubishi Chemical. These systems can be used in one type alone or in combination of two or more types.

作為液狀環氧樹脂係以1分子中具有2個以上的環氧基的液狀環氧樹脂為較佳。As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable.

作為液狀環氧樹脂係以雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚AF型環氧樹脂、萘型環氧樹脂、縮水甘油酯型環氧樹脂、縮水甘油胺型環氧樹脂、苯酚酚醛清漆型環氧樹脂、具有酯骨架的脂環式環氧樹脂、環己烷型環氧樹脂、環己烷二甲醇型環氧樹脂、縮水甘油胺型環氧樹脂及具有丁二烯構造的環氧樹脂為較佳，以雙酚A型環氧樹脂、雙酚F型環氧樹脂為又較佳。As liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, and glycidyl amine type epoxy resin are used. Epoxy resin, phenol novolak type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, glycidylamine type epoxy resin and The epoxy resin with a butadiene structure is preferable, and the bisphenol A type epoxy resin and the bisphenol F type epoxy resin are more preferable.

作為液狀環氧樹脂之具體例，可舉出DIC公司製的「HP4032」、「HP4032D」、「HP4032SS」(萘型環氧樹脂)；Mitsubishi Chemical公司製的「828US」、「jER828EL」、「825」、「Epikote 828EL」(雙酚A型環氧樹脂)；Mitsubishi Chemical公司製的「jER807」、「1750」(雙酚F型環氧樹脂)；Mitsubishi Chemical公司製的「jER152」(苯酚酚醛清漆型環氧樹脂)；Mitsubishi Chemical公司製的「630」、「630LSD」(縮水甘油胺型環氧樹脂)；新日鐵住金化學公司製的「ZX1059」(雙酚A型環氧樹脂與雙酚F型環氧樹脂的混合品)；Nagasechemtex公司製的「EX-721」(縮水甘油酯型環氧樹脂)；Daicel公司製的「Celloxide 2021P」(具有酯骨架的脂環式環氧樹脂)；Daicel公司製的「PB-3600」(具有丁二烯構造的環氧樹脂)；新日鐵住金化學公司製的「ZX1658」、「ZX1658GS」(液狀1,4-縮水甘油環己烷型環氧樹脂)等。該等係可使用單獨1種類、亦可組合2種類以上來使用。Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "828US", "jER828EL" and " 825", "Epikote 828EL" (bisphenol A type epoxy resin); "jER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical; "jER152" (phenol phenolic resin) manufactured by Mitsubishi Chemical Varnish type epoxy resin); "630" and "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical; "ZX1059" (bisphenol A type epoxy resin and double Mixture of phenol F type epoxy resin); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagasechemtex; "Celloxide 2021P" (alicyclic epoxy resin with ester skeleton) manufactured by Daicel ; "PB-3600" manufactured by Daicel (epoxy resin with a butadiene structure); "ZX1658" and "ZX1658GS" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. (liquid 1,4-glycidylcyclohexane type Epoxy resin) and so on. These systems can be used in one type alone or in combination of two or more types.

若組合液狀環氧樹脂與固體狀環氧樹脂來作為(C)成分使用時，此等的量比(液狀環氧樹脂：固體狀環氧樹脂)以質量比計，較佳為1：1~1：20，又較佳為1：1.5~1：15，特佳為1：2~1：10。藉由液狀環氧樹脂與固體狀環氧樹脂的量比為上述的範圍，可明顯得到本發明所期望之效果。When a combination of liquid epoxy resin and solid epoxy resin is used as component (C), the ratio of these amounts (liquid epoxy resin: solid epoxy resin) by mass ratio is preferably 1: 1~1:20, more preferably 1:1.5~1:15, particularly preferably 1:2~1:10. When the ratio of the liquid epoxy resin to the solid epoxy resin is in the above range, the desired effect of the present invention can be clearly obtained.

(C)成分的環氧當量係較佳為50g/eq.~ 5000g/eq.，又較佳為50g/eq.~3000g/eq.，更佳為80g/eq.~ 2000g/eq.，又更佳為110g/eq.~1000g/eq.。藉由成為該範圍，樹脂組成物層的硬化物的交聯密度將變得充分，故可得到表面粗糙度為小的絕緣層。環氧當量係包含1當量的環氧基的環氧樹脂的質量。該環氧當量係可根據JIS K7236來進行測量。(C) The epoxy equivalent of the component is preferably 50g/eq.~5000g/eq., more preferably 50g/eq.~3000g/eq., more preferably 80g/eq.~2000g/eq., and More preferably, it is 110g/eq.~1000g/eq. By setting it in this range, the crosslink density of the cured product of the resin composition layer becomes sufficient, so an insulating layer with a small surface roughness can be obtained. The epoxy equivalent is the mass of an epoxy resin containing 1 equivalent of an epoxy group. The epoxy equivalent can be measured in accordance with JIS K7236.

就明顯得到本發明所期望之效果之觀點而言，(C)成分的重量平均分子量(Mw)係較佳為100~5000，又較佳為250~3000，更佳為400~1500。 樹脂的重量平均分子量係可藉由凝膠滲透層析(GPC)法，並以聚苯乙烯換算值來進行測量。From the viewpoint of clearly obtaining the desired effect of the present invention, the weight average molecular weight (Mw) of the component (C) is preferably 100 to 5000, more preferably 250 to 3000, and more preferably 400 to 1500. The weight average molecular weight of the resin can be measured by the gel permeation chromatography (GPC) method, in terms of polystyrene.

就得到展現出良好的拉伸機械強度及絕緣可靠性的絕緣層之觀點而言，將樹脂組成物中的不揮發成分設為100質量%時，(C)成分的含有量係較佳為1質量%以上，又較佳為2質量%以上，更佳為3質量%以上。就明顯得到本發明所期望之效果之觀點而言，(C)成分的含有量的上限係較佳為20質量%以下，又較佳為15質量%以下，特佳為12質量%以下。From the viewpoint of obtaining an insulating layer exhibiting good tensile mechanical strength and insulation reliability, when the non-volatile content in the resin composition is 100% by mass, the content of component (C) is preferably 1 Mass% or more, more preferably 2 mass% or more, more preferably 3 mass% or more. From the viewpoint of clearly obtaining the desired effect of the present invention, the upper limit of the content of the component (C) is preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 12% by mass or less.

＜(D)揮發成分＞ 感光性樹脂組成物含有作為(D)成分的揮發成分。藉由以滿足式(1)及式(2)之方式在感光性樹脂組成物中含有(D)成分，可得到底切耐性為優異的硬化物。又，藉由在感光性樹脂組成物中含有(D)成分，而能夠調整感光性樹脂組成物的清漆黏度。＜(D) Volatile components＞ The photosensitive resin composition contains a volatile component as the (D) component. By including the component (D) in the photosensitive resin composition so as to satisfy the formulas (1) and (2), a cured product having excellent undercut resistance can be obtained. In addition, by including the component (D) in the photosensitive resin composition, the varnish viscosity of the photosensitive resin composition can be adjusted.

作為(D)揮發成分，可舉出有機溶劑等的溶劑。作為有機溶劑，亦包含於感光性樹脂組成物的製作時，(A)~(C)成分、(E)成分或(G)成分所包含的有機溶劑溶液中的有機溶劑。(D) The volatile component includes solvents such as organic solvents. As an organic solvent, the organic solvent contained in the organic solvent solution contained in (A)-(C) component, (E) component, or (G) component also at the time of preparation of a photosensitive resin composition.

作為如此般的溶劑，可舉例如乙基甲基酮、環己酮等的酮類；甲苯、二甲苯、四甲基苯等的芳香族烴基類；甲基溶纖劑、丁基溶纖劑、甲基卡必醇、丁基卡必醇、丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇二乙基醚、三乙二醇單乙基醚等的二醇醚類；乙酸乙酯、乙酸丁酯、丁基溶纖劑乙酸酯、卡必醇乙酸酯、乙基二甘醇乙酸酯(ethyl diglycol acetate)等的酯類；辛烷、癸烷等的脂肪族烴基類；石油醚、石油腦、氫化石油腦、溶劑油等的石油系溶劑等。該等係可包含單獨1種類、亦可包含2種類以上之組合。其中，就得到底切耐性為優異的硬化物之觀點而言，作為溶劑較佳具有酮類及二醇醚(glycol ether)類中之任一者。Examples of such solvents include ketones such as ethyl methyl ketone and cyclohexanone; aromatic hydrocarbon groups such as toluene, xylene, and tetramethylbenzene; methyl cellosolve, butyl cellosolve, methyl Glycol ethers such as base carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, etc.; ethyl acetate, Esters such as butyl acetate, butyl cellosolve acetate, carbitol acetate, and ethyl diglycol acetate; aliphatic hydrocarbon groups such as octane and decane; petroleum ether , Naphtha, hydrogenated naphtha, mineral spirits and other petroleum-based solvents. These systems may include one type alone, or a combination of two or more types. Among them, from the viewpoint of obtaining a cured product having excellent undercut resistance, it is preferable to have any one of ketones and glycol ethers as the solvent.

就得到底切耐性為優異的硬化物之觀點而言，(D)揮發成分係以混合高沸點的有機溶劑與低沸點的有機溶劑來使用為較佳。作為高沸點的有機溶劑，沸點較佳為100℃以上，又較佳為120℃以上，更佳為150℃以上，上限無特別限定而能夠設為300℃以下等。作為低沸點的有機溶劑，沸點較佳為未滿100℃，又較佳為90℃以下，更佳為85℃以下，下限並無特別限定而能夠設為30℃以上等。From the viewpoint of obtaining a cured product having excellent undercut resistance, (D) the volatile component is preferably used by mixing a high-boiling organic solvent and a low-boiling organic solvent. As the high boiling point organic solvent, the boiling point is preferably 100°C or higher, more preferably 120°C or higher, more preferably 150°C or higher, and the upper limit is not particularly limited and can be 300°C or lower. As the low boiling point organic solvent, the boiling point is preferably less than 100°C, more preferably 90°C or less, more preferably 85°C or less, and the lower limit is not particularly limited and can be 30°C or more.

作為(D)揮發成分的含有量，能以滿足式(1)及式(2)之方式來進行調整。The content of (D) volatile components can be adjusted so as to satisfy formula (1) and formula (2).

＜(E)反應性稀釋劑＞ 除了上述的成分以外，作為任意成分，感光性樹脂組成物亦可進而含有作為(E)成分的反應性稀釋劑。但，(E)成分不包含(A)成分。藉由在感光性樹脂組成物中含有(E)反應性稀釋劑，可使光反應性提升。作為(E)成分，可使用例如1分子中具有1個以上的(甲基)丙烯醯基之在室溫下為液體、固體或半固形的感光性(甲基)丙烯酸酯化合物。所謂室溫係表示25℃左右。＜(E) Reactive diluent＞ In addition to the above-mentioned components, the photosensitive resin composition may further contain a reactive diluent as the (E) component as an optional component. However, (E) component does not contain (A) component. By containing (E) a reactive diluent in the photosensitive resin composition, the photoreactivity can be improved. As the (E) component, for example, a photosensitive (meth)acrylate compound having one or more (meth)acrylic groups in one molecule, which is liquid, solid, or semi-solid at room temperature, can be used. The term "room temperature" means about 25°C.

作為感光性(甲基)丙烯酸酯化合物，可舉例如丙烯酸2-羥基乙酯、丙烯酸2-羥基丁酯等的丙烯酸羥基烷基類、乙二醇、甲氧基四乙二醇、聚乙二醇、丙二醇等的二醇的單或二丙烯酸酯類、N,N-二甲基丙烯醯胺、N-羥甲基丙烯醯胺等的丙烯醯胺類、丙烯酸N,N-二甲基胺基乙酯等的丙烯酸胺基烷基酯類、三羥甲基丙烷、季戊四醇、二季戊四醇等的多元醇或該等的環氧乙烷、環氧丙烷或者ε-己內酯的加成物的多元丙烯酸酯類、丙烯酸苯氧基酯、丙烯酸苯氧基乙酯等酚類、或其環氧乙烷或者環氧丙烷加成物等的丙烯酸酯類、由三羥甲基丙烷三縮水甘油醚等的縮水甘油醚所衍生的環氧丙烯酸酯類、改質環氧丙烯酸酯類、三聚氰胺丙烯酸酯類、及/或對應於上述的丙烯酸酯的甲基丙烯酸酯類等。該等之中，較佳為多元丙烯酸酯類或多元甲基丙烯酸酯類，例如作為3價的丙烯酸酯類或甲基丙烯酸酯類，可舉出三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、三羥甲基丙烷EO加成三(甲基)丙烯酸酯、甘油PO加成三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、四糠醇寡(甲基)丙烯酸酯、乙基卡必醇寡(甲基)丙烯酸酯、1,4-丁二醇寡(甲基)丙烯酸酯、1,6-己二醇寡(甲基)丙烯酸酯、三羥甲基丙烷寡(甲基)丙烯酸酯、季戊四醇寡(甲基)丙烯酸酯、四羥甲基乙烷四(甲基)丙烯酯、二季戊四醇六(甲基)丙烯酸酯、N,N,N’，N’-肆(β-羥基乙基)乙二胺的(甲基)丙烯酸酯等，作為3價以上的丙烯酸酯類或甲基丙烯酸酯類，可舉出三(2-(甲基)丙烯醯氧基乙基)磷酸酯、三(2-(甲基)丙烯醯氧基丙基)磷酸酯、三(3-(甲基)丙烯醯氧基丙基)磷酸酯、三(3-(甲基)丙烯醯基-2-羥基氧基丙基)磷酸酯、二(3-(甲基)丙烯醯基-2-羥基氧基丙基)(2-(甲基)丙烯醯氧基乙基)磷酸酯、(3-(甲基)丙烯醯基-2-羥基氧基丙基)二(2-(甲基)丙烯醯氧基乙基)磷酸酯等的磷酸三酯(甲基)丙烯酸酯。該等感光性(甲基)丙烯酸酯化合物係可使用任何的單獨1種、亦可併用2種以上。所謂「EO」係指環氧乙烷。As the photosensitive (meth)acrylate compound, for example, acrylic hydroxyalkyls such as 2-hydroxyethyl acrylate, 2-hydroxybutyl acrylate, etc., ethylene glycol, methoxytetraethylene glycol, and polyethylene glycol Mono- or diacrylates of glycols such as alcohol and propylene glycol, acrylamides such as N,N-dimethylacrylamide, N-methylolacrylamide, N,N-dimethylamine acrylate Amino alkyl acrylates such as ethyl ester, polyols such as trimethylolpropane, pentaerythritol, and dipentaerythritol, or adducts of these ethylene oxide, propylene oxide, or ε-caprolactone Polyacrylates, phenols such as phenoxy acrylate and phenoxy ethyl acrylate, or acrylates such as ethylene oxide or propylene oxide adducts, trimethylolpropane triglycidyl ether Epoxy acrylates derived from glycidyl ethers, modified epoxy acrylates, melamine acrylates, and/or methacrylates corresponding to the above-mentioned acrylates. Among these, polyacrylates or polymethacrylates are preferred. For example, trivalent acrylates or methacrylates include trimethylolpropane tri(meth)acrylate , Pentaerythritol tri(meth)acrylate, trimethylolpropane EO addition tri(meth)acrylate, glycerol PO addition tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, tetrafurfuryl alcohol oligomer (Meth)acrylate, ethyl carbitol oligo(meth)acrylate, 1,4-butanediol oligo(meth)acrylate, 1,6-hexanediol oligo(meth)acrylate, Trimethylolpropane oligo(meth)acrylate, pentaerythritol oligo(meth)acrylate, tetramethylolethane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, N,N, N',N'-(β-hydroxyethyl)ethylenediamine (meth)acrylate, etc., as trivalent or higher acrylates or methacrylates, tris(2-(former) Yl) acryloxyethyl) phosphate, tris(2-(meth)acryloxypropyl) phosphate, tris(3-(meth)acryloxypropyl) phosphate, tris(2-(meth)acryloxypropyl) phosphate, tris( 3-(meth)acryloyl-2-hydroxyoxypropyl)phosphate, bis(3-(meth)acryloyl-2-hydroxyoxypropyl)(2-(meth)acryloyl) Oxyethyl) phosphate, (3-(meth)acryloyl-2-hydroxyoxypropyl)bis(2-(meth)acryloyloxyethyl) phosphate and other phosphate triesters ( Meth)acrylate. Any of these photosensitive (meth)acrylate compounds may be used alone, or two or more of them may be used in combination. The so-called "EO" refers to ethylene oxide.

(E)反應稀釋劑可使用市售品。作為市售品，可舉例如日本化藥公司製的「DPHA」、Daicel-Allnex公司製的「EBECRYL3708」等。(E) A commercially available product can be used as a reactive diluent. Examples of commercially available products include "DPHA" manufactured by Nippon Kayaku Co., Ltd., "EBECRYL3708" manufactured by Daicel-Allnex, and the like.

就促進光硬化之觀點而言，將感光性樹脂組成物的固形分全體設為100質量%時，作為(E)反應稀釋劑的含有量係較佳為1質量%以上，又較佳為2質量%以上，更佳為3質量%以上，較佳為25質量%以下，又較佳為20質量%以下，更較佳為15質量%以下。From the viewpoint of promoting light curing, when the total solid content of the photosensitive resin composition is 100% by mass, the content of (E) reaction diluent is preferably 1% by mass or more, and more preferably 2 Mass% or more, more preferably 3 mass% or more, preferably 25 mass% or less, still more preferably 20 mass% or less, more preferably 15 mass% or less.

＜(F)無機填充材＞ 除了上述的成分以外，作為任意成分，感光性樹脂組成物亦可進而含有作為(F)成分的無機填充材。＜(F) Inorganic fillers＞ In addition to the above-mentioned components, the photosensitive resin composition may further contain an inorganic filler as the (F) component as an optional component.

作為(F)無機填充材的材料係使用無機化合物。作為無機填充材的材料之例子，可舉出二氧化矽、氧化鋁、玻璃、堇青石、矽氧化物、硫酸鋇、碳酸鋇、滑石、黏土、雲母粉、氧化鋅、水滑石、水鋁礦、氫氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、氧化鎂、氮化硼、氮化鋁、氮化錳、硼酸鋁、碳酸鍶、鈦酸鍶、鈦酸鈣、鈦酸鎂、鈦酸鉍、氧化鈦、氧化鋯、鈦酸鋇、鈦酸鋯酸鋇、鋯酸鋇、鋯酸鈣、磷酸鋯及鎢磷酸鋯等。該等之中，以二氧化矽、氫氧化鎂為適合，以二氧化矽為特別適合。作為二氧化矽，可舉例如無定形二氧化矽、熔融二氧化矽、結晶二氧化矽、合成二氧化矽、中空二氧化矽等。又，作為二氧化矽，以球狀二氧化矽為較佳。(F)無機填充材係可使用單獨1種類、亦可組合2種類以上來使用。(F) An inorganic compound is used as the material system of the inorganic filler. Examples of materials for inorganic fillers include silica, alumina, glass, cordierite, silica, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, and gibbsite , Aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, titanic acid Bismuth, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate and zirconium tungstate, etc. Among them, silicon dioxide and magnesium hydroxide are suitable, and silicon dioxide is particularly suitable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. In addition, as the silica, spherical silica is preferred. (F) The inorganic filler system may be used alone or in combination of two or more types.

作為(F)成分的市售品，可舉例如Denca公司製的「UFP-20」、「UFP-30」；Nippon Steel & Sumikin Materials公司製的「SP60-05」、「SP507-05」；Admatechs公司製的「SC2050」、「YC100C」、「YA050C」、「YA050C-MJE」、「YA010C」、「SC2500SQ」、「SO-C4」、「SO-C2」、「SO-C1」；Tokuyama公司製的「Shirufiru NSS-3N」、「Shirufiru NSS-4N」、「Shirufiru NSS-5N」；神島化學公司製的「EP4-A」等。Examples of commercially available products of the component (F) include "UFP-20" and "UFP-30" manufactured by Denca; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Materials; Admatechs "SC2050", "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" manufactured by the company; manufactured by Tokuyama Corporation "Shirufiru NSS-3N", "Shirufiru NSS-4N", "Shirufiru NSS-5N"; "EP4-A" manufactured by Kamijima Chemical Co., Ltd., etc.

作為(F)成分的比表面積係較佳為1m2 /g以上，又較佳為2m2 /g以上，特佳為3m2 /g以上。雖上限沒有特別的限制，較佳為60m2 /g以下、50m2 /g以下或40m2 /g以下。比表面積係根據BET法，藉由使用比表面積測量裝置(Mountech公司製Macsorb HM-1210)使樣品表面吸附氮氣，並使用BET多點法來算出，而得到比表面積。The specific surface area as the component (F) is preferably 1 m 2 /g or more, more preferably 2 m 2 /g or more, and particularly preferably 3 m 2 /g or more. Although the upper limit is not particularly limited, it is preferably 60 m 2 /g or less, 50 m 2 /g or less, or 40 m 2 /g or less. The specific surface area was calculated by using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) to adsorb nitrogen on the surface of the sample according to the BET method, and calculated using the BET multipoint method, to obtain the specific surface area.

就明顯得到本發明所期望之效果之觀點而言，(F)成分的平均粒徑係較佳為0.01μm以上，又較佳為0.05μm以上，特佳為0.1μm以上，較佳為5μm以下，又較佳為2μm以下，更佳為1μm以下。From the viewpoint of clearly obtaining the desired effect of the present invention, the average particle size of the component (F) is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, and preferably 5 μm or less , It is more preferably 2 μm or less, more preferably 1 μm or less.

(F)成分的平均粒徑係可藉由基於米氏(Mie)散射理論之雷射繞射・散射法來進行測量。具體而言，可藉由雷射繞射散射式粒徑分布測量裝置，依體積基準來製作無機填充材的粒徑分布，並以該中值粒徑作為平均粒徑來進行測量。測量樣品係可使用在管形瓶中秤取無機填充材100mg、甲基乙基酮10g，並藉以超音波來使其分散10分鐘者。使用雷射繞射式粒徑分布測量裝置來測量樣品，將使用光源波長設為藍色及紅色，並以流動槽方式來測量(F)成分的體積基準的粒徑分布，可由所得到的粒徑分布來算出平均粒徑並作為中值粒徑。作為雷射繞射式粒徑分布測量裝置，可舉例如堀場製作所公司製「LA-960」等。The average particle size of the component (F) can be measured by the laser diffraction and scattering method based on the Mie scattering theory. Specifically, a laser diffraction scattering type particle size distribution measuring device can be used to produce the particle size distribution of the inorganic filler on a volume basis, and the median particle size can be used as the average particle size for measurement. The measurement sample can be used to weigh 100 mg of inorganic filler and 10 g of methyl ethyl ketone in a vial, and disperse it for 10 minutes by ultrasonic waves. Use a laser diffraction particle size distribution measuring device to measure the sample, set the wavelength of the light source to blue and red, and measure the volume-based particle size distribution of the (F) component by the flow cell method. The diameter distribution is used to calculate the average particle diameter and set it as the median particle diameter. As a laser diffraction type particle size distribution measuring device, for example, "LA-960" manufactured by Horiba Manufacturing Co., Ltd. can be cited.

就提高耐濕性及分散性之觀點而言，(F)成分係以經表面處理劑來進行處理為較佳。作為表面處理劑，可舉例如乙烯基矽烷系偶合劑、(甲基)丙烯酸系偶合劑、含氟的矽烷偶合劑、胺基矽烷系偶合劑、環氧基矽烷系偶合劑、巰基矽烷系偶合劑、矽烷系偶合劑、烷氧基矽烷、有機矽氮烷化合物、鈦酸酯系偶合劑等。其中，就明顯得到本發明的效果之觀點而言，以乙烯基矽烷系偶合劑、(甲基)丙烯酸系偶合劑、胺基矽烷系偶合劑為較佳。又，表面處理劑係可使用單獨1種類、亦可任意地組合2種類以上來使用。From the viewpoint of improving moisture resistance and dispersibility, the component (F) is preferably treated with a surface treatment agent. Examples of surface treatment agents include vinyl silane coupling agents, (meth)acrylic coupling agents, fluorine-containing silane coupling agents, aminosilane coupling agents, epoxy silane coupling agents, mercaptosilane coupling agents Mixtures, silane coupling agents, alkoxysilanes, organosilazane compounds, titanate coupling agents, etc. Among them, from the viewpoint of clearly obtaining the effects of the present invention, vinylsilane-based coupling agents, (meth)acrylic-based coupling agents, and aminosilane-based coupling agents are preferred. In addition, the surface treatment agent system may be used alone or in combination of two or more types arbitrarily.

作為表面處理劑的市售品，可舉例如信越化學工業公司製「KBM1003」(乙烯基三乙氧基矽烷)、信越化學工業公司製「KBM503」(3-甲基丙烯醯氧基丙基三乙氧基矽烷)、信越化學工業公司製「KBM403」(3-縮水甘油氧基丙基三甲氧基矽烷)、信越化學工業公司製「KBM803」(3-巰基丙基三甲氧基矽烷)、信越化學工業公司製「KBE903」(3-胺基丙基三乙氧基矽烷)、信越化學工業公司製「KBM573」(N-苯基-3-胺基丙基三甲氧基矽烷)、信越化學工業公司製「SZ-31」(六甲基二矽氮烷)、信越化學工業公司製「KBM103」(苯基三甲氧基矽烷)、信越化學工業公司製「KBM-4803」(長鎖環氧基型矽烷偶合劑)、信越化學工業公司製「KBM-7103」(3,3,3-三氟丙基三甲氧基矽烷)等。Commercial products of surface treatment agents include, for example, "KBM1003" (vinyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM503" (3-methacryloyloxypropyl triacetate) manufactured by Shin-Etsu Chemical Co., Ltd. Ethoxysilane), "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu "KBE903" (3-aminopropyltriethoxysilane) manufactured by Chemical Industry Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane) manufactured by the company, "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM-4803" manufactured by Shin-Etsu Chemical Co., Ltd. (long-lock epoxy Type silane coupling agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

就無機填充材的分散性提升之觀點而言，藉由表面處理劑之表面處理的程度係以在指定的範圍內為較佳。具體而言，相對於無機填充材100質量份，以0.2質量份~5質量份的表面處理劑來進行表面處理為較佳，以0.2質量份~3質量份來進行表面處理為較佳，以0.3質量份~2質量份來進行表面處理為較佳。From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment by the surface treatment agent is preferably within a specified range. Specifically, with respect to 100 parts by mass of the inorganic filler, 0.2 parts by mass to 5 parts by mass of the surface treatment agent is preferably used for surface treatment, and 0.2 parts by mass to 3 parts by mass for the surface treatment is preferably performed. It is preferable to perform surface treatment from 0.3 parts by mass to 2 parts by mass.

可藉由無機填充材的每單位表面積的碳量，來評估藉由表面處理劑之表面處理的程度。就無機填充材的分散性提升之觀點而言，無機填充材的每單位表面積的碳量係以0.02mg/m2 以上為較佳，以0.1mg/m2 以上為又較佳，以0.2mg/m2 以上為更佳。另一方面，就抑制樹脂清漆的熔融黏度及薄片形態下的熔融黏度的上昇之觀點而言，以1mg/m2 以下為較佳，以0.8mg/m2 以下為又較佳，以0.5mg/m2 以下為更佳。The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of inorganic fillers, the amount of carbon per unit surface area of the inorganic fillers is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 or more, and 0.2 mg /m 2 or more is more preferable. On the other hand, from the viewpoint of suppressing the increase in the melt viscosity of the resin varnish and the melt viscosity in the form of a sheet, 1 mg/m 2 or less is preferable, 0.8 mg/m 2 or less is more preferable, and 0.5 mg /m 2 or less is more preferable.

無機填充材的每單位表面積的碳量係可藉由溶劑(例如、甲基乙基酮(MEK))來洗淨處理表面處理後的無機填充材後來進行測量。具體而言，將作為溶劑為充分量的MEK加入於以表面處理劑來進行表面處理後的無機填充材中，並以25℃進行超音波洗淨5分鐘。去除上清液並乾燥固形分後，可使用碳分析計來測量無機填充材的每單位表面積的碳量。作為碳分析計係可使用堀場製作所公司製「EMIA-320V」等。The amount of carbon per unit surface area of the inorganic filler can be measured after washing the surface-treated inorganic filler with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid content, a carbon analyzer can be used to measure the amount of carbon per unit surface area of the inorganic filler. As the carbon analyzer system, "EMIA-320V" manufactured by Horiba Manufacturing Co., Ltd. can be used.

就明顯得到本發明的效果之觀點而言，將感光性樹脂組成物中的不揮發成分設為100質量%時，(F)成分的含有量係較佳為10質量%以上，又較佳為20質量%以上，更佳為25質量%以上、30質量%以上、40質量%以上、50質量%以上，較佳為90質量%以下，又較佳為80質量%以下，更佳為70質量%以下、60質量%以下、50質量%以下、40質量%以下。From the viewpoint of clearly obtaining the effect of the present invention, when the non-volatile component in the photosensitive resin composition is 100% by mass, the content of the component (F) is preferably 10% by mass or more, and more preferably 20 mass% or more, more preferably 25 mass% or more, 30 mass% or more, 40 mass% or more, 50 mass% or more, preferably 90 mass% or less, more preferably 80 mass% or less, more preferably 70 mass% % Or less, 60% by mass or less, 50% by mass or less, and 40% by mass or less.

＜(G)其他的添加劑＞ 在不損及本發明目的之程度內，感光性樹脂組成物亦可進而含有(G)其他的添加劑。作為(G)其他的添加劑，可添加例如熱可塑性樹脂、有機填充材、三聚氰胺、有機膨潤土等的微粒子、酞青藍、酞青綠、碘綠、重氮黃、結晶紫、氧化鈦、碳黑、萘黑等的著色劑、氫醌、吩噻嗪、甲基氫醌、氫醌單甲基醚、兒茶酚、鄰苯三酚等的聚合抑制劑、皂土、蒙特石等的增稠劑、聚矽氧系、氟系、乙烯樹脂系的消泡劑、溴化環氧化合物、酸改質溴化環氧化合物、銻化合物、磷系化合物、芳香族縮合磷酸酯、含鹵素縮合磷酸酯等的阻燃劑、酚系硬化劑、氰酸酯系硬化劑等的熱硬化樹脂、等的各種添加劑。＜(G) Other additives＞ The photosensitive resin composition may further contain (G) other additives to the extent that it does not impair the purpose of the present invention. As (G) other additives, fine particles such as thermoplastic resin, organic filler, melamine, organic bentonite, phthalocyanine blue, phthalocyanine green, iodo green, diazo yellow, crystal violet, titanium oxide, carbon black, etc. can be added. Coloring agents such as naphthalene black, polymerization inhibitors such as hydroquinone, phenothiazine, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, etc., thickeners such as bentonite, Montelite , Polysiloxane-based, fluorine-based, vinyl resin-based defoamers, brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphorus compounds, aromatic condensed phosphates, halogen-containing condensed phosphates Various additives such as flame retardants such as flame retardants, phenolic hardeners, cyanate ester hardeners, and other thermosetting resins.

感光性樹脂組成物係藉由如下述般來進行製造：將作為必須成分之上述(A)~(D)成分混合，並適當混合作為任意成分之上述(E)~(G)成分，又，因應所需依據三輥、球磨機、珠磨機、混砂機等的混練方法、或者超强混合機、行星式混合機等的攪拌方法予以混練或攪拌。The photosensitive resin composition is produced by mixing the above-mentioned (A) to (D) components as essential components, and appropriately mixing the above-mentioned (E) to (G) components as optional components, and, According to the needs, it can be mixed or stirred according to the mixing method of three-roller, ball mill, bead mill, sand mixer, etc., or the mixing method of super mixer, planetary mixer, etc.

＜感光性樹脂組成物的物理性質、用途＞ 將感光性樹脂組成物以130℃乾燥15分鐘時的重量減少率(%)設為a。又，將該感光性樹脂組成物以180℃乾燥15分鐘時的重量減少率(%)設為b。此時，藉由滿足式(1)及式(2)的關係，將能夠得到底切耐性為優異的硬化物，而使得解析性提升。感光性樹脂組成物，作為層狀態的感光性樹脂組成物層，只要是於曝光步驟之際為滿足式(1)及式(2)的關係即可。可舉例如：形成於支撐體上的感光性樹脂組成物層，又，將感光性樹脂組成物在電路基板上直接塗佈並乾燥後所形成的感光性樹脂組成物層等。

Figure 02_image009
<Physical properties and use of the photosensitive resin composition> The weight loss rate (%) when the photosensitive resin composition is dried at 130°C for 15 minutes is referred to as a. Moreover, the weight loss rate (%) when this photosensitive resin composition was dried at 180 degreeC for 15 minutes was set as b. At this time, by satisfying the relationship between the formula (1) and the formula (2), a cured product having excellent undercut resistance can be obtained, and the resolution can be improved. The photosensitive resin composition, as a photosensitive resin composition layer in a layer state, should just satisfy the relationship of formula (1) and formula (2) at the time of the exposure step. For example, a photosensitive resin composition layer formed on a support, and a photosensitive resin composition layer formed by directly coating and drying the photosensitive resin composition on a circuit board, and the like.
Figure 02_image009

於此，所謂重量減少率a(%)，係指將樹脂清漆塗佈於支撐體上並乾燥後得到附支撐體的感光性薄膜，將該附支撐體的感光性薄膜裁切成為10cm×10cm，在乾燥器中放置30分鐘後，將該附支撐體的感光性薄膜的質量(g)設為(a1)，之後，將附支撐體的感光性薄膜在130℃的烘箱中加熱15分鐘後，將該附支撐體的感光性薄膜的質量(g)設為(a2)，由下述式(A)所算出的值。又，於此所謂重量減少率b(%)，係指將樹脂清漆塗佈於支撐體上並乾燥後得到附支撐體的感光性薄膜，將該附支撐體的感光性薄膜裁切成為10cm×10cm，在乾燥器中放置30分鐘後，將該附支撐體的感光性薄膜的質量(g)設為(b1)，之後，將附支撐體的感光性薄膜在180℃的烘箱中加熱15分鐘後，將該附支撐體的感光性薄膜的質量(g)設為(b2)，由下述式(B)所算出的值。尚，所謂式(A)及式(B)中的「支撐體的質量(g)」係表示將支撐體裁切成為10cm×10cm，在乾燥器中放置30分鐘後的支撐體的質量(g)。

Figure 02_image011
Here, the weight reduction rate a (%) means that a photosensitive film with a support is obtained after the resin varnish is coated on a support and dried, and the photosensitive film with a support is cut into 10cm×10cm After being left in a desiccator for 30 minutes, the mass (g) of the photosensitive film with a support is set to (a1), and then the photosensitive film with a support is heated in an oven at 130°C for 15 minutes The mass (g) of the photosensitive film with a support is defined as (a2), and is a value calculated by the following formula (A). Here, the weight reduction rate b (%) means that a photosensitive film with a support is obtained after the resin varnish is coated on a support and dried, and the photosensitive film with a support is cut into 10 cm× 10cm, placed in a desiccator for 30 minutes, set the mass (g) of the photosensitive film with support as (b1), and then heat the photosensitive film with support in an oven at 180°C for 15 minutes After that, the mass (g) of the photosensitive film with a support is defined as (b2), and the value is calculated by the following formula (B). Still, the "mass of the support (g)" in the formulas (A) and (B) means the mass (g) of the support after the support is cut into 10cm×10cm and placed in a desiccator for 30 minutes .
Figure 02_image011

就得到底切耐性為優異的硬化物之同時使解析性提升之觀點而言，式(1)中的V為30以下，較佳為28以下，又較佳為27以下，更佳為26以下。就明顯得到本發明的效果之觀點而言，式(1)中的V的下限係較佳為1以上，又較佳為3以上，更佳為5以上。From the viewpoint of obtaining a cured product with excellent undercut resistance and improving resolution, V in formula (1) is 30 or less, preferably 28 or less, more preferably 27 or less, and more preferably 26 or less . From the viewpoint of clearly obtaining the effect of the present invention, the lower limit of V in the formula (1) is preferably 1 or more, more preferably 3 or more, and more preferably 5 or more.

就得到底切耐性為優異的硬化物之同時使解析性提升之觀點而言，式(2)中的a/b為0.6以下，較佳為0.55以下，又較佳為0.5以下，更佳為0.48以下。就明顯得到本發明的效果之觀點而言，式(2)中的a/b的下限係較佳為0.01以上，又較佳為0.05以上，更佳為0.1以上。From the viewpoint of obtaining a cured product with excellent undercut resistance and improving resolution, a/b in formula (2) is 0.6 or less, preferably 0.55 or less, more preferably 0.5 or less, more preferably Below 0.48. From the viewpoint of clearly obtaining the effect of the present invention, the lower limit of a/b in the formula (2) is preferably 0.01 or more, more preferably 0.05 or more, and more preferably 0.1 or more.

本發明的感光性樹脂組成物，藉由使本發明的感光性樹脂組成物光硬化而得的硬化物係展現出解析性為優異之類的特性。因此，在開口徑為100μm的圓孔(通孔(via))的底部沒有殘渣。通孔底殘渣的評估係可根據後述的＜通孔底的殘渣、底切耐性的評估＞中記載的方法來進行評估。In the photosensitive resin composition of the present invention, a cured product obtained by photocuring the photosensitive resin composition of the present invention exhibits characteristics such as excellent resolution. Therefore, there is no residue at the bottom of a circular hole (via) with an opening diameter of 100 μm. The evaluation of the residue at the bottom of the via can be performed according to the method described in <Evaluation of the residue at the bottom of the via and undercut resistance> described later.

使本發明的感光性樹脂組成物光硬化而得的硬化物係展現出底切耐性為優異之類的特性。意即，可獲得底切耐性為優異的絕緣層及阻焊劑。底切係較佳為5μm以下，又較佳為4μm以下，更佳為3μm以下。下限並無特別限定，能夠設為0.1μm以上等。底切係可根據後述的＜通孔底的殘渣、底切耐性的評估＞中記載的方法來進行測量。The cured product obtained by photocuring the photosensitive resin composition of the present invention exhibits the characteristic of being excellent in undercut resistance. This means that an insulating layer and solder resist with excellent undercut resistance can be obtained. The undercut is preferably 5 μm or less, more preferably 4 μm or less, and more preferably 3 μm or less. The lower limit is not particularly limited, and can be set to 0.1 μm or more. The undercut system can be measured according to the method described in <Residue at the bottom of a through hole and evaluation of undercut resistance> described later.

本發明的感光性樹脂組成物係展現出埋置性為優異之類的特性。埋置性的測量之具體例係將感光性薄膜層合在內層電路基板(導體厚18μm、0.8mm厚)。將層合感光性薄膜的內層電路基板的外觀，藉由目視來觀察空孔(void)的有無。此時空孔的數量通常為0個。埋置性的評估詳細內容係可根據後述的實施例中記載的方法來進行測量。The photosensitive resin composition of the present invention exhibits characteristics such as excellent embedding properties. A specific example of the measurement of the embedding property is to laminate a photosensitive film on an inner layer circuit board (conductor thickness 18 μm, 0.8 mm thickness). The appearance of the inner layer circuit board on which the photosensitive film was laminated was visually observed for the presence or absence of voids. At this time, the number of holes is usually zero. The details of the embedding evaluation can be measured according to the method described in the examples described later.

本發明的感光性樹脂組成物係展現出熔融黏度低之類的特性。作為熔融黏度係較佳為100poise以上，又較佳為500poise以上，更佳為1000poise以上，較佳為20000poise以下，又較佳為15000poise以下，更佳為10000 poise以下。熔融黏度的測量係可根據後述的實施例中記載的方法來進行測量。The photosensitive resin composition of the present invention exhibits characteristics such as low melt viscosity. The melt viscosity is preferably 100 poise or higher, more preferably 500 poise or higher, more preferably 1000 poise or higher, preferably 20000 poise or lower, more preferably 15000 poise or lower, and more preferably 10000 poise or lower. The melt viscosity can be measured according to the method described in Examples described later.

本發明的感光性樹脂組成物的用途並無特別限定，可使用於感光性薄膜、附支撐體的感光性薄膜、預浸體等的絕緣樹脂薄片、電路基板(層合板用途、多層印刷配線板用途等)、阻焊劑、底部填充材(underfill)、晶粒結著材、半導體密封材、填孔樹脂、零件埋置樹脂等的需要感光性樹脂組成物的用途的廣泛範圍。其中，可適合作為印刷配線板的絕緣層用感光性樹脂組成物(將感光性樹脂組成物的硬化物作為絕緣層的印刷配線板)、層間絕緣層用感光性樹脂組成物(將感光性樹脂組成物的硬化物作為層間絕緣層的印刷配線板)、鍍敷形成用感光性樹脂組成物(在感光性樹脂組成物的硬化物上形成有鍍敷的印刷配線板)、及阻焊劑用感光性樹脂組成物(將感光性樹脂組成物的硬化物作為阻焊劑的印刷配線板)。The use of the photosensitive resin composition of the present invention is not particularly limited, and it can be used for photosensitive films, photosensitive films with a support, insulating resin sheets such as prepregs, and circuit boards (for laminates, multilayer printed wiring boards). Applications, etc.), solder resists, underfills, die bonding materials, semiconductor sealing materials, filling resins, parts embedding resins, etc., which require a wide range of applications requiring photosensitive resin compositions. Among them, it can be suitably used as a photosensitive resin composition for an insulating layer of a printed wiring board (a printed wiring board in which a cured product of a photosensitive resin composition is used as an insulating layer), a photosensitive resin composition for an interlayer insulating layer (a photosensitive resin The cured product of the composition is used as a printed wiring board with an interlayer insulating layer), a photosensitive resin composition for plating formation (a printed wiring board with plating formed on the cured product of the photosensitive resin composition), and a photosensitive resin composition for solder resist A resin composition (a printed wiring board using a cured product of the photosensitive resin composition as a solder resist).

[感光性薄膜] 本發明的感光性樹脂組成物係藉由將包含該感光性樹脂組成物的樹脂清漆在支撐基板上塗佈並乾燥來形成感光性樹脂組成物層，而可製成感光性薄膜。又，亦可藉由將該樹脂清漆塗佈於支撐體上並乾燥來製成感光性薄膜。意即，本發明的感光性薄膜含有本發明的感光性樹脂組成物。作為支撐基板，主要可舉出玻璃環氧基板、金屬基板、聚酯基板、聚醯亞胺基板、BT樹脂基板、熱硬化型聚苯醚基板等的基板。[Photosensitive film] The photosensitive resin composition of the present invention can be made into a photosensitive film by coating and drying a resin varnish containing the photosensitive resin composition on a support substrate to form a photosensitive resin composition layer. Moreover, it can also be set as a photosensitive film by coating this resin varnish on a support body, and drying. That is, the photosensitive film of this invention contains the photosensitive resin composition of this invention. The supporting substrate mainly includes substrates such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate.

作為樹脂清漆的塗佈方式，可舉例如凹版塗佈方式、微凹版塗佈方式、逆塗佈法方式、逆向吻塗佈法法方式、模具式塗佈方式、狹縫式塗佈方式、唇式塗佈方式、柯馬(comma)塗佈方式、刮刀塗佈方式、輥塗方式、刀片塗佈方式、簾幕塗佈方式、腔室凹版塗佈方式、縫孔塗佈方式、噴霧塗佈方式、浸漬塗佈方式等。The coating method of the resin varnish includes, for example, a gravure coating method, a micro-gravure coating method, a reverse coating method, a reverse kiss coating method, a die coating method, a slit coating method, and a lip coating method. Coating method, comma coating method, knife coating method, roll coating method, blade coating method, curtain coating method, chamber gravure coating method, slot coating method, spray coating Method, dip coating method, etc.

樹脂清漆係可以分多次來塗佈，亦可以1次來塗佈，又，可組合多種不同的方式來塗佈。其中，以均勻塗佈性為優異的模具式塗佈(die coating)方式為較佳。又，為了避免異物混入等，以在無塵室等的異物產生較少的環境中來實施塗佈步驟為較佳。The resin varnish system can be applied multiple times, or applied once, and can be applied in a combination of many different methods. Among them, a die coating method that is excellent in uniform coating properties is preferred. In addition, in order to avoid mixing of foreign matter, etc., it is preferable to perform the coating step in an environment where the generation of foreign matter in a clean room or the like is small.

感光性薄膜可根據該所屬技術領域中具有通常知識者周知的方法來製造，例如，藉由將感光性樹脂組成物塗佈在支撐基板上或支撐體上，以加熱或熱風吹附等來使(D)成分乾燥。亦可使用例如包含感光性樹脂組成物的不揮發成分與過量的(D)成分的樹脂清漆，來製造感光性樹脂組成物。具體而言，首先以真空脫泡法等來完全去除樹脂清漆中的氣泡後，將樹脂清漆塗佈在支撐基板上，藉由在熱風爐或者遠紅外線爐內的乾燥來調整(D)成分的量，而可製造包含以感光性樹脂組成物所形成的感光性樹脂組成物層的感光性薄膜。作為感光性薄膜的製造方法的一實施形態，藉由將樹脂清漆以最高溫度設為105℃以上135℃以下，乾燥時間設為6分鐘以上20分以下來使其乾燥而可得到。The photosensitive film can be manufactured according to a method well known to those having ordinary knowledge in the technical field, for example, by coating a photosensitive resin composition on a support substrate or a support body, heating or hot air blowing, etc. (D) The ingredients are dry. For example, it is also possible to manufacture the photosensitive resin composition using the resin varnish containing the non-volatile component of a photosensitive resin composition and excess (D) component. Specifically, first, after the bubbles in the resin varnish are completely removed by a vacuum degassing method, etc., the resin varnish is coated on a supporting substrate, and the composition (D) is adjusted by drying in a hot air oven or a far-infrared oven. It is possible to manufacture a photosensitive film including a photosensitive resin composition layer formed with a photosensitive resin composition. As one embodiment of the manufacturing method of the photosensitive film, it can be obtained by drying the resin varnish at a maximum temperature of 105°C or more and 135°C or less, and a drying time of 6 minutes or more and 20 minutes or less.

乾燥溫度會依據感光性樹脂組成物的硬化性或樹脂清漆中的(D)成分的量而有所不同，但可以80℃~120℃來進行。但，就得到底切耐性為優異的硬化物之觀點而言，乾燥的最高溫度係較佳為105℃以上，又較佳為110℃以上。最高溫度的下限並無特別限定，較佳為135℃以下，又較佳為130℃以下。The drying temperature varies depending on the curability of the photosensitive resin composition or the amount of the (D) component in the resin varnish, but it can be performed at 80°C to 120°C. However, from the viewpoint of obtaining a cured product having excellent undercut resistance, the maximum drying temperature is preferably 105°C or higher, and more preferably 110°C or higher. The lower limit of the maximum temperature is not particularly limited, but is preferably 135°C or lower, and more preferably 130°C or lower.

乾燥時間會依據感光性樹脂組成物的硬化性或樹脂清漆中的(D)成分的量而有所不同，較佳為6分鐘以上，較佳為30分鐘以下，又較佳為20分鐘以下。於此，所謂乾燥時間係指從乾燥溫度到達80℃以後的時間。The drying time varies depending on the curability of the photosensitive resin composition or the amount of component (D) in the resin varnish, and is preferably 6 minutes or more, preferably 30 minutes or less, and more preferably 20 minutes or less. Here, the so-called drying time refers to the time after the drying temperature reaches 80°C.

相對於感光性樹脂組成物層的總量，感光性樹脂組成物層中的(D)成分的殘留量係以設為5質量%以下為較佳，以設為2質量%以下為又較佳。該所屬技術領域中具有通常知識者可藉由簡單的實驗來設定適當、適合的乾燥條件。Relative to the total amount of the photosensitive resin composition layer, the residual amount of the component (D) in the photosensitive resin composition layer is preferably set to 5 mass% or less, and more preferably 2 mass% or less . Those with ordinary knowledge in this technical field can set appropriate and suitable drying conditions through simple experiments.

本發明中，作為感光性樹脂組成物層，只要是於曝光步驟時為滿足式(1)及式(2)即可，而能夠得到底切耐性為優異的硬化物之同時並提升解析性，故感光性樹脂組成物層的厚度並無特別限定，就使操作性提升、且抑制感光性樹脂組成物層內部的感度及解析度降低之類的觀點而言，較佳為5μm以上，又較佳為10μm以上，更佳為15μm以上，較佳為50μm以下，又較佳為40μm以下，更佳為30μm以下。In the present invention, as the photosensitive resin composition layer, it is sufficient if it satisfies formula (1) and formula (2) in the exposure step, and it is possible to obtain a cured product with excellent undercut resistance and improve resolution. Therefore, the thickness of the photosensitive resin composition layer is not particularly limited. From the viewpoints of improving operability and suppressing the decrease in sensitivity and resolution inside the photosensitive resin composition layer, it is preferably 5 μm or more, and more It is preferably 10 μm or more, more preferably 15 μm or more, preferably 50 μm or less, still more preferably 40 μm or less, and more preferably 30 μm or less.

[附支撐體的感光性薄膜] 本發明的感光性樹脂組成物，可適合以在支撐體上層形成有感光性樹脂組成物層的附支撐體的感光性薄膜的形態來使用。意即，附支撐體的感光性薄膜包含：支撐體與設置於該支撐體上的以本發明的感光性樹脂組成物所形成的感光性樹脂組成物層。[Photosensitive film with support] The photosensitive resin composition of the present invention can be suitably used in the form of a photosensitive film with a support in which a photosensitive resin composition layer is formed on a support. That is, the photosensitive film with a support includes a support and a photosensitive resin composition layer formed of the photosensitive resin composition of the present invention provided on the support.

作為支撐體，可舉例如聚對苯二甲酸乙二酯薄膜、聚萘二甲酸乙二酯薄膜、聚丙烯薄膜、聚乙烯薄膜、聚乙烯醇薄膜、三乙醯乙酸酯薄膜等，特別是以聚對苯二甲酸乙二酯薄膜為較佳。As the support, for example, a polyethylene terephthalate film, a polyethylene naphthalate film, a polypropylene film, a polyethylene film, a polyvinyl alcohol film, a triacetate film, etc. can be mentioned, especially A polyethylene terephthalate film is preferred.

作為市售的支撐體，可舉例如王子製紙公司製的製品名「Arufun MA-410」、「E-200C」、Shinetsu film公司製等的聚丙烯薄膜、帝人公司製的製品名「PS-25」等的PS系列等的聚對苯二甲酸乙二酯薄膜等，但並非限定於該等。為了容易去除該等的支撐體，宜於表面上塗佈聚矽氧塗佈劑之類的剝離劑。支撐體的厚度係以5μm~50μm的範圍為較佳，以10μm~25μm的範圍為又較佳。藉由將厚度設為5μm以上，可抑制於顯影前進行剝離支撐體時支撐體破裂，藉由將厚度設為50μm以下，可使從支撐體上進行曝光時的解析度提升。又，以低魚眼(fish eye)的支撐體為較佳。於此，所謂的魚眼係指將材料進行熱熔融，並藉由混練、擠壓、雙軸延伸、澆鑄法等來製造薄膜時，材料的異物、未溶解物、氧化劣化物等進入至薄膜中者。As a commercially available support, for example, the product names "Arufun MA-410" and "E-200C" manufactured by Oji Paper Co., Ltd., polypropylene films manufactured by Shinetsu Film Co., Ltd., and the product name "PS-25" manufactured by Teijin Co., Ltd. PS series and other polyethylene terephthalate films, etc., but are not limited to these. In order to easily remove these supports, it is advisable to coat the surface with a release agent such as a silicone coating agent. The thickness of the support is preferably in the range of 5 μm to 50 μm, and more preferably in the range of 10 μm to 25 μm. By setting the thickness to 5 μm or more, the support can be prevented from breaking when the support is peeled off before development, and by setting the thickness to be 50 μm or less, the resolution during exposure from the support can be improved. Moreover, a support body with low fish eyes is preferable. Here, the so-called fisheye means that when the material is hot-melted, and the film is made by kneading, extrusion, biaxial stretching, casting, etc., foreign matter, undissolved matter, and oxidation deterioration of the material enter the film. In the middle.

又，為了減低藉由紫外線等的活性能量線之曝光時的光散射，支撐體係以透明性優異者為較佳。具體而言，支撐體係以成為透明性指標的濁度(以JIS K6714規格化的濁度)為0.1~5者為較佳。進而，可以保護薄膜來保護感光性樹脂組成物層。In addition, in order to reduce light scattering during exposure by active energy rays such as ultraviolet rays, the support system preferably has excellent transparency. Specifically, the support system preferably has a haze (haze standardized in JIS K6714) of 0.1 to 5, which is an index of transparency. Furthermore, the protective film can protect the photosensitive resin composition layer.

藉由以保護薄膜來保護附支撐體的感光性薄膜的感光性樹脂組成物層側，可防止對感光性樹脂組成物層表面的髒汙等的附著或傷痕。作為保護薄膜，可使用藉由與上述的支撐體相同的材料所構成的薄膜。保護薄膜的厚度並無特別限定，以1μm~40μm的範圍為較佳，以5μm~30μm的範圍為又較佳，以10μm~30μm的範圍為更佳。藉由將厚度設為1μm以上，可使保護薄膜的操作性提升，藉由設為40μm以下，廉價性將有改善之傾向。尚，保護薄膜較佳如下：相對於感光性樹脂組成物層與支撐體的接著力，感光性樹脂組成物層與保護薄膜的接著力為較小。By protecting the photosensitive resin composition layer side of the photosensitive film with a support by the protective film, adhesion or scratches such as dirt on the surface of the photosensitive resin composition layer can be prevented. As the protective film, a film made of the same material as the above-mentioned support can be used. The thickness of the protective film is not particularly limited, but is preferably in the range of 1 μm to 40 μm, more preferably in the range of 5 μm to 30 μm, and more preferably in the range of 10 μm to 30 μm. By setting the thickness to 1 μm or more, the handleability of the protective film can be improved, and by setting it to 40 μm or less, the low cost will tend to be improved. Furthermore, the protective film is preferably as follows: the adhesive force between the photosensitive resin composition layer and the protective film is smaller than the adhesive force between the photosensitive resin composition layer and the support.

就使操作性提升、且抑制感光性樹脂組成物層內部的感度及解析度降低之類的觀點而言，感光性樹脂組成物層的厚度係較佳為10μm以上，又較佳為15μm以上，更佳為20μm以上，較佳為30μm以下，又較佳為28μm以下，更佳為25μm以下。From the viewpoints of improving operability and suppressing the decrease in sensitivity and resolution inside the photosensitive resin composition layer, the thickness of the photosensitive resin composition layer is preferably 10 μm or more, and more preferably 15 μm or more. It is more preferably 20 μm or more, preferably 30 μm or less, still more preferably 28 μm or less, and more preferably 25 μm or less.

[印刷配線板] 本發明的印刷配線板，其包含藉由本發明的感光性樹脂組成物的硬化物所形成的絕緣層。該絕緣層係較佳為使用作為阻焊劑。[Printed Wiring Board] The printed wiring board of the present invention includes an insulating layer formed of a cured product of the photosensitive resin composition of the present invention. The insulating layer is preferably used as a solder resist.

詳細而言，本發明的印刷配線板係可使用上述的感光性薄膜、或附支撐體的感光性薄膜來進行製造。以下，對於絕緣層為阻焊劑之情況時之一例子來進行說明。Specifically, the printed wiring board of the present invention can be manufactured using the above-mentioned photosensitive film or a photosensitive film with a support. Hereinafter, an example of the case where the insulating layer is a solder resist will be described.

＜塗佈及乾燥步驟＞ 將包含感光性樹脂組成物的樹脂清漆直接塗佈在電路基板上時，藉由使(D)成分乾燥、揮發，而在電路基板上形成感光性薄膜。＜Coating and drying steps＞ When the resin varnish containing the photosensitive resin composition is directly coated on the circuit board, the (D) component is dried and volatilized to form a photosensitive film on the circuit board.

作為電路基板，可舉例如玻璃環氧基板、金屬基板、聚酯基板、聚醯亞胺基板、BT樹脂基板、熱硬化型聚苯醚基板等。尚，於此所謂電路基板係指在如上述般的支撐基板的單面或雙面形成有經圖型加工的導體層(電路)的基板。又，於交替層合導體層與絕緣層而成的多層印刷配線板中，該多層印刷配線板的最外層的單面或雙面成為經圖型加工的導體層(電路)的基板，亦包含在於此所謂的電路基板中。尚，導體層表面亦可藉由黑化處理、銅蝕刻等來預先施予粗化處理。As the circuit board, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, etc. may be mentioned. Here, the term "circuit board" refers to a board on which a pattern-processed conductor layer (circuit) is formed on one side or both sides of the support substrate as described above. Furthermore, in a multilayer printed wiring board formed by alternately laminating conductor layers and insulating layers, the outermost layer of the multilayer printed wiring board has one or both sides as a pattern-processed conductor layer (circuit) substrate, including In this so-called circuit board. Furthermore, the surface of the conductor layer can also be roughened in advance by blackening, copper etching, or the like.

作為塗佈方式，一般大多使用藉由網板印刷法之整面印刷，除此之外，若為可均勻塗佈的塗佈方式則可使用任何的方法。例如，噴霧塗佈方式、熱熔塗佈方式、桿塗方式、塗敷器方式、刮刀塗佈方式、刀片塗佈方式、氣刀塗佈方式、簾式淋塗方式、輥塗方式、凹版塗佈方式、平版印刷方式、浸漬塗佈方式、刷毛塗佈、其他通常的塗佈方式係全部皆可使用。塗佈後因應所需以熱風爐或者遠紅外線爐等來進行乾燥。乾燥條件係以80℃~120℃設為3分鐘~13分鐘為較佳。以如此般之方式，在電路基板上形成感光性薄膜。As a coating method, full-surface printing by a screen printing method is generally used. In addition, any method can be used as long as it is a coating method capable of uniform coating. For example, spray coating method, hot melt coating method, rod coating method, applicator method, knife coating method, blade coating method, air knife coating method, curtain coating method, roll coating method, gravure coating All of the cloth method, lithographic method, dip coating method, brush coating method, and other usual coating methods can be used. After coating, it can be dried in a hot air oven or a far-infrared oven as required. The drying conditions are preferably set at 80°C to 120°C for 3 minutes to 13 minutes. In this way, a photosensitive film is formed on the circuit board.

＜層合步驟＞ 另一方面，使用附支撐體的感光性薄膜時，則使用真空貼合機來將感光性樹脂組成物層側層合於電路基板的單面或雙面。於層合步驟中，附支撐體的感光性薄膜具有保護薄膜時，於去除該保護薄膜後，因應所需將附支撐體的感光性薄膜及電路基板預加熱，一邊加壓及加熱感光性樹脂組成物層來壓黏於電路基板。附支撐體的感光性薄膜之中，以利用藉由真空層合法在減壓下來層合於電路基板的方法為適合。＜Laminating step＞ On the other hand, when a photosensitive film with a support is used, a vacuum laminator is used to laminate the photosensitive resin composition layer side on one side or both sides of the circuit board. In the laminating step, when the photosensitive film with a support has a protective film, after removing the protective film, the photosensitive film with the support and the circuit board are preheated as needed, while pressing and heating the photosensitive resin The composition layer is pressure-bonded to the circuit substrate. Among the photosensitive film with a support, a method of laminating on a circuit board under reduced pressure by a vacuum lamination method is suitable.

層合步驟的條件並無特別限定，以例如將壓黏溫度(層合溫度)較佳設為70℃~140℃，將壓黏壓力較佳設為1kgf/cm2 ~11kgf/cm2 (9.8×104 N/m2 ~107.9×104 N/m2 )，將壓黏時間較佳設為5秒鐘~300秒鐘，將空氣壓設為20mmHg(26.7hPa)以下的減壓下來進行層合為較佳。又，層合步驟可使用分批式，亦可以是使用輥的連續式。真空層合法可使用市售的真空貼合機來進行。作為市售的真空貼合機，可舉例如Nikko・Materials公司製真空貼合機、名機製作所公司製真空加壓式貼合機、Hitachi industries公司製輥式乾式塗佈機、Hitachi AIC公司製真空貼合機等。The conditions of the lamination step are not particularly limited. For example, the pressing temperature (laminating temperature) is preferably set to 70°C to 140°C, and the pressing pressure is preferably set to 1kgf/cm 2 to 11kgf/cm 2 (9.8 ×10 4 N/m 2 ~107.9×10 4 N/m 2 ), the pressure bonding time is preferably set to 5 seconds to 300 seconds, and the air pressure is set to 20mmHg (26.7hPa) or less to reduce pressure. Laminating is better. In addition, a batch type may be used for the lamination step, or a continuous type using a roll may be used. The vacuum lamination method can be performed using a commercially available vacuum laminating machine. Examples of commercially available vacuum laminators include vacuum laminators manufactured by Nikko Materials Co., vacuum press laminators manufactured by Meike Manufacturing Co., Ltd., roll dry coaters manufactured by Hitachi Industries, and Hitachi AIC Co., Ltd. Vacuum laminating machine, etc.

＜曝光步驟＞ 藉由塗佈及乾燥步驟、或者層合步驟，在電路基板上設置感光性樹脂組成物層後，接下來，進行通過遮罩圖型，對感光性樹脂組成物層的指定部分來照射活性光線，使照射部的感光性樹脂組成物層光硬化之曝光步驟。作為活性光線，可舉例如紫外線、可見光線、電子線、X線等，特別是以紫外線為較佳。紫外線的照射量大約為10mJ/cm2 ~1000mJ/cm2 。曝光方法係有將遮罩圖型密著於印刷配線板來進行之接觸曝光法，與不密著而是使用平行光線來進行曝光之非接觸曝光法，可使用任一種。又，在感光性樹脂組成物層上存在支撐體時，可從支撐體上來進行曝光，亦可於將支撐體剝離後來進行曝光。<Exposure step> After the photosensitive resin composition layer is placed on the circuit board through the coating and drying step, or the lamination step, then the mask pattern is used to specify the portion of the photosensitive resin composition layer To irradiate active light to lightly harden the photosensitive resin composition layer of the irradiated part. Examples of active rays include ultraviolet rays, visible rays, electron rays, X-rays, etc., and ultraviolet rays are particularly preferred. The amount of ultraviolet radiation is about 10mJ/cm 2 ~1000mJ/cm 2 . The exposure method includes a contact exposure method in which a mask pattern is adhered to a printed wiring board, and a non-contact exposure method in which exposure is performed using parallel light instead of adhesion. Either one can be used. In addition, when a support is present on the photosensitive resin composition layer, exposure may be performed from the support, or exposure may be performed after the support is peeled off.

由於使用本發明的感光性樹脂組成物，故阻焊劑的解析性為優異。因此，作為遮罩圖型中的曝光圖型，能夠使用例如電路寬(線；L)與電路間的寬(間距；S)的比(L/S)為100μm/100μm以下(即，配線間距200μm以下)、L/S=80μm/80μm以下(配線間距160μm以下)、L/S= 70μm/70μm以下(配線間距140μm以下)、L/S=60μm/60μm以下(配線間距120μm以下)的圖型。尚，電路基板的整體間距並不需要相同。Since the photosensitive resin composition of the present invention is used, the resolution of the solder resist is excellent. Therefore, as the exposure pattern in the mask pattern, for example, the ratio (L/S) of the circuit width (line; L) to the width (pitch; S) between the circuits is 100μm/100μm or less (that is, the wiring pitch 200μm or less), L/S=80μm/80μm or less (wiring pitch 160μm or less), L/S= 70μm/70μm or less (wiring pitch 140μm or less), L/S=60μm/60μm or less (wiring pitch 120μm or less) type. Still, the overall pitch of the circuit board does not need to be the same.

由於使用本發明的感光性樹脂組成物，故阻焊劑的底切耐性為優異。因此，作為通孔徑，能以較佳設為200μm以下，又較佳設為150μm以下，更佳設為100μm以下。下限並無特別限定，能夠設為1μm以上、10μm以上等。Since the photosensitive resin composition of the present invention is used, the undercut resistance of the solder resist is excellent. Therefore, the through-hole diameter can be preferably set to 200 μm or less, more preferably to 150 μm or less, and more preferably to 100 μm or less. The lower limit is not particularly limited, and can be 1 μm or more, 10 μm or more, or the like.

＜顯影步驟＞ 曝光步驟後，在感光性樹脂組成物層上存在支撐體時，於去除該支撐體後，藉由以濕式顯影或乾式顯影來去除未光硬化的部分(未曝光部)並進行顯影，而可形成圖型。<Development step> After the exposure step, when there is a support on the photosensitive resin composition layer, after removing the support, the uncured part (unexposed part) is removed by wet development or dry development and developed, and Can form a pattern.

於上述濕式顯影時，作為顯影液可使用鹼性水溶液、水系顯影液、有機溶劑等的安全且穩定之操作性為良好的顯影液，其中，以藉由鹼性水溶液之顯影步驟為較佳。又，作為顯影方法，可適當採用噴霧、搖動浸漬、刷塗、拍擊等的周知方法。In the above wet development, alkaline aqueous solution, water-based developer, organic solvent, etc. can be used as the developer. The safe and stable operability is a good developer. Among them, the development step by alkaline aqueous solution is preferred. . Moreover, as a development method, well-known methods, such as spraying, shaking dipping, brushing, and slap, can be suitably used.

作為顯影液來使用的鹼性水溶液，可舉例如氫氧化鋰、氫氧化鈉、氫氧化鉀等的金屬氫氧化物、碳酸鈉、重碳酸鈉等的碳酸鹽或重碳酸鹽、磷酸鈉、磷酸鉀等的鹼金屬磷酸鹽、焦磷酸鈉、焦磷酸鉀等的鹼金屬焦磷酸鹽的水溶液、或氫氧化四烷基銨等的不含有金屬離子的有機鹼的水溶液，就不含有金屬離子，且不會對半導體晶片帶來影響之方面而言，較佳為氫氧化四甲基銨(TMAH)的水溶液。The alkaline aqueous solution used as the developer includes, for example, metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, carbonates or bicarbonates such as sodium carbonate, sodium bicarbonate, sodium phosphate, and phosphoric acid. An aqueous solution of alkali metal phosphate such as potassium, alkali metal pyrophosphate such as sodium pyrophosphate, potassium pyrophosphate, or an aqueous solution of an organic base that does not contain metal ions, such as tetraalkylammonium hydroxide, does not contain metal ions. In terms of not affecting the semiconductor wafer, an aqueous solution of tetramethylammonium hydroxide (TMAH) is preferred.

該等的鹼性水溶液中，為了顯影效果的提升，可在顯影液中添加界面活性劑、消泡劑等。上述鹼性水溶液的pH係以例如8~12的範圍為較佳，以9~11的範圍為又較佳。又，上述鹼性水溶液的鹼濃度係以設為0.1質量%~10質量%為較佳。上述鹼性水溶液的溫度係可配合感光性樹脂組成物層的顯影性來進行適當選擇，以設為20℃~50℃為較佳。In these alkaline aqueous solutions, in order to improve the development effect, a surfactant, a defoamer, etc. may be added to the developer. The pH of the alkaline aqueous solution is preferably in the range of, for example, 8-12, and more preferably in the range of 9-11. In addition, the alkali concentration of the alkaline aqueous solution is preferably set to 0.1% by mass to 10% by mass. The temperature of the alkaline aqueous solution can be appropriately selected according to the developability of the photosensitive resin composition layer, and is preferably set to 20°C to 50°C.

作為顯影液來使用的有機溶劑，有例如丙酮、乙酸乙酯、具有碳原子數1~4的烷氧基的烷氧基乙醇、乙醇、異丙醇、丁醇、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單丁基醚。The organic solvent used as the developer includes, for example, acetone, ethyl acetate, alkoxy ethanol having an alkoxy group having 1 to 4 carbon atoms, ethanol, isopropanol, butanol, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether.

相對於顯影液全量，如此般的有機溶劑的濃度係以2質量%~90質量%為較佳。又，如此般的有機溶劑的溫度係可配合顯影性來進行調節。進而，如此般的有機溶劑係可單獨或組合2種類以上來使用。作為單獨來使用的有機溶劑系顯影液，可舉例如1,1,1-三氯乙烷、N-甲基吡咯啶酮、N,N-二甲基甲醯胺、環己酮、甲基異丁基酮、γ-丁內酯。The concentration of such an organic solvent is preferably 2% by mass to 90% by mass relative to the total amount of the developer. In addition, the temperature of such an organic solvent can be adjusted according to the developability. Furthermore, such an organic solvent system can be used individually or in combination of 2 or more types. As an organic solvent-based developer used alone, for example, 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl Isobutyl ketone, γ-butyrolactone.

於圖型形成時，因應所需亦可併用上述的2種類以上的顯影方法來使用。顯影的方式有浸漬方式、攪拌方式、噴霧方式、高壓噴霧方式、刷塗、拍塗等，就用於提升解析度而言以高壓噴霧方式為適合。作為採用噴霧方式時的噴霧壓係以0.05MPa~0.3MPa為較佳。At the time of pattern formation, two or more of the above-mentioned developing methods can also be used in combination as required. There are immersion method, stirring method, spray method, high-pressure spray method, brush coating, pat coating, etc. for the development method, and the high-pressure spray method is suitable for improving the resolution. The spray pressure when the spray method is adopted is preferably 0.05 MPa to 0.3 MPa.

＜熱硬化(後烘烤)步驟＞ 上述顯影步驟結束後，進行熱硬化(後烘烤(post-bake))步驟來形成阻焊劑。作為後烘烤步驟，可舉出藉由高壓水銀燈之紫外線照射步驟或使用潔淨烘箱之加熱步驟等。照射紫外線時，可因應所需來調整其照射量，例如可以0.05J/cm2 ~10J/cm2 左右的照射量來進行照射。又，可因應感光性樹脂組成物中的樹脂成分的種類、含有量等，來適當選擇加熱的條件，較佳以150℃~220℃進行20分鐘~180分鐘的範圍，又較佳以160℃~200℃進行30分鐘~120分鐘的範圍來予以選擇。<Thermal hardening (post-bake) step> After the above-mentioned development step is completed, a thermal hardening (post-bake) step is performed to form a solder resist. As the post-baking step, there may be an ultraviolet irradiation step by a high-pressure mercury lamp or a heating step using a clean oven. When irradiating ultraviolet rays, the irradiation amount can be adjusted according to the needs, for example, the irradiation amount can be about 0.05J/cm 2 ~10J/cm 2 . In addition, the heating conditions can be appropriately selected according to the type and content of the resin component in the photosensitive resin composition, and the heating conditions are preferably 150°C to 220°C for 20 minutes to 180 minutes, and 160°C is more preferred. Choose from the range of ~200℃ for 30 minutes to 120 minutes.

＜其他的步驟＞ 於形成阻焊劑後，印刷配線板係可進而包含開孔步驟、除膠渣步驟。可根據使用於印刷配線板的製造中該所屬技術領域中具有通常知識者周知的各種方法，來實施該等的步驟。＜Other steps＞ After the solder resist is formed, the printed wiring board may further include a hole opening step and a desmear step. These steps can be implemented in accordance with various methods known to those having ordinary knowledge in the technical field used in the manufacture of printed wiring boards.

形成阻焊劑後，依據期望對於在電路基板上所形成的阻焊劑進行開孔步驟，來形成通孔洞(via hole)、貫穿孔(through hole)。開孔步驟有例如鑽孔、雷射、電漿等的周知方法，又，依據所需可組合該等的方法來進行開孔步驟，但較佳為藉由二氧化碳雷射、YAG雷射等的雷射之開孔步驟。After the solder resist is formed, the solder resist formed on the circuit board is subjected to a hole-opening step as desired to form a via hole and a through hole. The hole-opening step includes well-known methods such as drilling, laser, plasma, etc. Moreover, these methods can be combined to perform the hole-opening step as required, but it is preferably by carbon dioxide laser, YAG laser, etc. The opening step of the laser.

除膠渣(desmear)步驟係進行除膠渣處理之步驟。於開孔步驟中所形成的開口部內部一般會附著有樹脂殘渣(膠渣)。由於上述膠渣會成為電氣連接不良的原因，故於該步驟中實施去除膠渣的處理(除膠渣處理)。The desmear step is a step of performing desmear treatment. Resin residue (smear) generally adheres to the inside of the opening formed in the hole-opening step. Since the above-mentioned scum may cause poor electrical connection, a process of removing scum (desmear treatment) is implemented in this step.

可藉由乾式除膠渣處理、濕式除膠渣處理或該等的組合，來實施除膠渣處理。The desmear treatment can be implemented by dry desmear treatment, wet desmear treatment or a combination of these.

作為乾式除膠渣處理，可舉例如使用電漿的除膠渣處理等。使用電漿的除膠渣處理係可使用市售的電漿除膠渣處理裝置來進行實施。市售的電漿除膠渣處理裝置之中，作為印刷配線板的製造用途為適合的例子，可舉出Nissin公司製的微波電漿裝置、積水化學工業公司製的常壓電漿蝕刻裝置等。Examples of the dry desmear treatment include desmear treatment using plasma. The desmear treatment system using plasma can be carried out using a commercially available plasma desmear treatment device. Among commercially available plasma desmear processing devices, suitable examples for the production use of printed wiring boards include a microwave plasma device manufactured by Nissin Co., Ltd., an atmospheric plasma etching device manufactured by Sekisui Chemical Industry Co., Ltd., etc. .

作為濕式除膠渣處理，可舉例如使用氧化劑溶液的除膠渣處理等。使用氧化劑溶液來進行除膠渣處理時，較佳為依序進行藉由膨潤液之膨潤處理、藉由氧化劑溶液之氧化處理、藉由中和液之中和處理。作為膨潤液，可舉例如Atotech Japan公司製的「Swelling Dip Securiganth P」、「Swelling Dip Securiganth SBU」等。膨潤處理較佳如下述般來進行：藉由將形成有通孔洞等的的基板浸漬在加熱至60℃~80℃的膨潤液中5分鐘~10分鐘。作為氧化劑溶液較佳為鹼性過錳酸水溶液，可舉例如在氫氧化鈉的水溶液中溶解過錳酸鉀或過錳酸鈉而成的溶液。藉由氧化劑溶液之氧化處理較佳如下述般來進行：藉由將膨潤處理後的基板浸漬在加熱至60℃~80℃的氧化劑溶液中10分鐘~30分鐘。作為鹼性過錳酸水溶液的市售品，可舉例如Atotech Japan公司製的「Concentrate Compact CP」、「Dosing solution Securiganth P」等。藉由中和液之中和處理較佳如下述般來進行：藉由將氧化處理後的基板浸漬在30℃~50℃的中和液中3分鐘~10分鐘。作為中和液較佳為酸性的水溶液，作為市售品可舉例如Atotech Japan公司製的「Reduction solution Securiganth P」。Examples of the wet desmear treatment include desmear treatment using an oxidizing agent solution. When the oxidizing agent solution is used for the scum removal treatment, it is preferable to sequentially perform the swelling treatment by the swelling solution, the oxidation treatment by the oxidizing agent solution, and the neutralization treatment by the neutralization solution. Examples of the swelling liquid include "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan. The swelling treatment is preferably performed as follows: by immersing a substrate on which a through hole or the like is formed in a swelling solution heated to 60° C. to 80° C. for 5 minutes to 10 minutes. The oxidizing agent solution is preferably an alkaline permanganic acid aqueous solution, and for example, a solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous sodium hydroxide solution. The oxidation treatment by the oxidant solution is preferably performed as follows: the substrate after the swelling treatment is immersed in the oxidant solution heated to 60°C to 80°C for 10 minutes to 30 minutes. Examples of commercially available products of the alkaline permanganic acid aqueous solution include "Concentrate Compact CP" manufactured by Atotech Japan, "Dosing solution Securiganth P", and the like. The neutralization treatment by the neutralization solution is preferably performed as follows: The substrate after the oxidation treatment is immersed in a neutralization solution at 30° C. to 50° C. for 3 minutes to 10 minutes. The neutralizing liquid is preferably an acidic aqueous solution, and as a commercially available product, for example, "Reduction solution Securiganth P" manufactured by Atotech Japan can be mentioned.

組合乾式除膠渣處理與濕式除膠渣處理來進行實施時，可先實施乾式除膠渣處理，亦可先實施濕式除膠渣處理。When a combination of dry desmear treatment and wet desmear treatment is implemented, the dry desmear treatment can be implemented first, or the wet desmear treatment can be implemented first.

將絕緣層作為層間絕緣層來使用時，可與阻焊劑之情形相同地進行，亦可於熱硬化步驟後進行開孔步驟、除膠渣步驟及鍍敷步驟。When the insulating layer is used as an interlayer insulating layer, it can be carried out in the same manner as in the case of a solder resist, and it is also possible to carry out a hole opening step, a desmearing step, and a plating step after the thermal hardening step.

鍍敷(plating)步驟係在絕緣層上形成導體層之步驟。可組合無電解鍍敷與電解鍍敷來形成導體層，又，亦可形成與導體層為相反圖型的鍍敷阻劑(plating resist)，而僅以無電解鍍敷來形成導體層。作為之後的圖型形成方法，可使用例如該所屬技術領域中具有通常知識者周知的減成法(subtractive method)、半加成法(semi-additive method)等。The plating step is a step of forming a conductor layer on the insulating layer. Electroless plating and electrolytic plating can be combined to form a conductor layer, and a plating resist having a pattern opposite to that of the conductor layer can also be formed, and only electroless plating can be used to form the conductor layer. As a subsequent pattern forming method, for example, a subtractive method, a semi-additive method, etc., which are well-known to those having ordinary knowledge in the relevant technical field, can be used.

[半導體裝置] 本發明的半導體裝置包含印刷配線板。可使用本發明的印刷配線板來製造本發明的半導體裝置。[Semiconductor device] The semiconductor device of the present invention includes a printed wiring board. The printed wiring board of the present invention can be used to manufacture the semiconductor device of the present invention.

作為半導體裝置，可舉出供給於電氣製品(例如：電腦、行動電話、數位相機及電視等)及交通工具(例如：機車、汽車、電車、船舶及飛機等)等的各種半導體裝置。Examples of semiconductor devices include various semiconductor devices supplied to electrical products (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, locomotives, automobiles, trams, ships, and airplanes, etc.).

可藉由在印刷配線板的導通部位安裝零件(半導體晶片)，來製造本發明的半導體裝置。所謂「導通部位」，係指「印刷配線板中傳遞電訊號的部位」，該場所可以是表面，亦可以是埋入的部位均可。又，半導體晶片方面，只要是將半導體作為材料的電氣電路元件即可，並無特別限定。The semiconductor device of the present invention can be manufactured by mounting parts (semiconductor chips) on the conductive parts of the printed wiring board. The so-called "conducting part" refers to "the part of the printed wiring board that transmits electrical signals." This place can be the surface or the buried part. In addition, regarding the semiconductor wafer, it is not particularly limited as long as it is an electrical circuit element using a semiconductor as a material.

於製造本發明的半導體裝置之際的半導體晶片的安裝方法，只要是能有效地發揮半導體晶片機能即可，並無特別限定，具體而言可舉出導線接合安裝方法、倒裝晶片安裝方法、藉由無凸塊增層(BBUL)之安裝方法、藉由異向性導電薄膜(ACF)之安裝方法、藉由非導電性薄膜(NCF)之安裝方法等。於此，所謂「藉由無凸塊增層(BBUL)之安裝方法」，係指「將半導體晶片直接埋置於印刷配線板的凹部，並將半導體晶片與印刷配線板上的配線連接的安裝方法」。 [實施例]The mounting method of the semiconductor chip when manufacturing the semiconductor device of the present invention is not particularly limited as long as it can effectively exert the function of the semiconductor chip. Specifically, a wire bonding mounting method, a flip chip mounting method, Mounting method by bumpless build-up layer (BBUL), mounting method by anisotropic conductive film (ACF), mounting method by non-conductive film (NCF), etc. Here, the so-called "mounting method by bumpless build-up (BBUL)" refers to "mounting in which the semiconductor chip is directly buried in the recess of the printed wiring board, and the semiconductor chip is connected to the wiring on the printed wiring board. method". [Example]

以下，藉由實施例更具體地說明本發明，但本發明並非被限定於該等的實施例。尚，於以下的記載中，表示量的「份」及「%」，若無特別說明係分別意指「質量份」及「質量%」。Hereinafter, the present invention will be explained in more detail through examples, but the present invention is not limited to these examples. However, in the following description, the "parts" and "%" that indicate the amount, unless otherwise specified, mean "parts by mass" and "% by mass", respectively.

(合成例1：樹脂(A-1)的合成) 將環氧當量為162g/eq.的1,1’-雙(2,7-二縮水甘油氧基萘基)甲烷(「EXA-4700」，大日本油墨化學工業公司製)162份放入具備有氣體導入管、攪拌裝置、冷卻管及溫度計的燒瓶中，加入EDGAc(乙基二甘醇乙酸酯，Daicel公司製)340份，進行加熱溶解後再加入氫醌0.46份與三苯基膦1份。將該混合物加熱至95~105℃，緩慢地滴下72份的丙烯酸，並使其反應16小時。將該反應生成物冷卻至80~90℃，加入80份的四氫酞酐來使其反應8小時，並使其冷卻。以如此般之方式得到固形物的酸價為90mgKOH/g的樹脂溶液(不揮發分70%，以下簡稱為(A-1))。(Synthesis example 1: Synthesis of resin (A-1)) Put 162 parts of 1,1'-bis(2,7-diglycidoxynaphthyl)methane ("EXA-4700", manufactured by Dai Nippon Ink Chemical Industry Co., Ltd.) with an epoxy equivalent of 162 g/eq. Add 340 parts of EDGAc (Ethyl Diethylene Glycol Acetate, manufactured by Daicel) to a flask with a gas introduction tube, stirring device, cooling tube, and thermometer. After heating and dissolving, add 0.46 parts of hydroquinone and triphenylphosphine 1 serving. This mixture was heated to 95-105 degreeC, 72 parts of acrylic acid was dripped slowly, and it was made to react for 16 hours. This reaction product was cooled to 80-90 degreeC, 80 parts of tetrahydrophthalic anhydride was added, it was made to react for 8 hours, and it was made to cool. In this way, a resin solution with a solid acid value of 90 mgKOH/g (non-volatile content 70%, hereinafter referred to as (A-1)) was obtained.

＜製造例1、2＞ 如下述的調配表所表示般來調配樹脂材料，並使用高速旋轉混煉機得到樹脂清漆1及2。

Figure 02_image013
<Production Examples 1, 2> The resin materials were prepared as shown in the following preparation table, and resin varnishes 1 and 2 were obtained using a high-speed rotary kneader.
Figure 02_image013

表中的縮寫等係如同下述。 ・(A-1)成分：合成例1所製作的樹脂(A-1)、固形分70%的乙基二甘醇乙酸酯溶液 ・ZFR-1491H：含bis-F骨架的酸改質環氧丙烯酸酯、日本化藥公司製、EDGAc稀釋、固形分70% ・Irgacure TPO：雙(2,4,6-三甲基苯甲醯)-苯基氧化膦、BASF公司製 ・Irgacure OXE-02：乙酮,1-[9-乙基-6-(2-甲基苯甲醯)-9H-咔唑-3-基]-,1-(O-乙醯肟)、BASF公司製 ・NC3000H：聯苯型環氧樹脂、日本化藥公司製、環氧當量約272g/eq. ・ZX1059：雙酚A型環氧樹脂與雙酚F型環氧樹脂的混合環氧樹脂、新日鐵住金化學公司製、環氧當量約165 g/eq. ・1031S：肆羥基苯乙烷型環氧樹脂、Mitsubishi Chemical公司製、環氧當量約200g/eq. ・EDGAc：乙基二甘醇乙酸酯(卡必醇乙酸酯)、Daicel公司製、沸點217.4℃ ・MEK：甲基乙基酮、純正化學公司製、沸點79.6℃ ・DPHA：二季戊四醇六丙烯酸酯、日本化藥公司製 ・EBECRYL3708：改質環氧丙烯酸酯、Daicel-Allnex公司製 ・SC2050：對於熔融二氧化矽(Admatechs公司製、平均粒徑0.5μm)100質量份，以0.5質量份的胺基矽烷(信越化學公司製、KBM573)進行表面處理者 ・EP4-A：對於平均粒徑0.8μm的氫氧化鎂，以1質量份的胺基矽烷(信越化學公司製、KBM573)進行表面處理者，神島化學公司製The abbreviations in the table are as follows. ・(A-1) Ingredients: Resin (A-1) made in Synthesis Example 1, and 70% solid content of ethyl diethylene glycol acetate solution ・ZFR-1491H: Acid-modified epoxy acrylate containing bis-F skeleton, manufactured by Nippon Kayaku Co., Ltd., diluted with EDGAc, solid content 70% ・Irgacure TPO: Bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide, manufactured by BASF ・Irgacure OXE-02: ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1-(O-acetoxime), BASF company system ・NC3000H: Biphenyl type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent approximately 272g/eq. ・ZX1059: Mixed epoxy resin of bisphenol A type epoxy resin and bisphenol F type epoxy resin, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent approximately 165 g/eq. ・1031S: 4-hydroxystyrene type epoxy resin, manufactured by Mitsubishi Chemical Company, epoxy equivalent about 200g/eq. ・EDGAc: Ethyl diethylene glycol acetate (carbitol acetate), manufactured by Daicel, boiling point 217.4°C ・MEK: Methyl ethyl ketone, manufactured by Junsei Chemical Co., Ltd., boiling point 79.6°C ・DPHA: Dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd. ・EBECRYL3708: modified epoxy acrylate, manufactured by Daicel-Allnex ・SC2050: For 100 parts by mass of fused silica (manufactured by Admatechs, average particle size 0.5μm), 0.5 parts by mass of aminosilane (manufactured by Shin-Etsu Chemical Co., KBM573) is surface-treated ・EP4-A: For magnesium hydroxide with an average particle size of 0.8μm, surface treated with 1 part by mass of aminosilane (manufactured by Shin-Etsu Chemical Co., KBM573), manufactured by Kamishima Chemical Co., Ltd.

＜實施例1＞ 作為支撐體，準備以醇酸樹脂系脫模劑(Lintec公司製「AL-5」)進行脫模處理後的PET薄膜(Toray公司製「LumirrorT6AM」、厚度38μm、軟化點130℃、「脫模PET」)。藉由模具塗佈機，將調製的樹脂清漆以乾燥後的感光性樹脂組成物層的厚度成為25μm之方式，均勻地塗佈於上述脫模PET上，並以80℃至110℃(最高溫度110℃)進行乾燥6分鐘。接下來，藉由將覆蓋薄膜(雙軸延伸聚丙烯薄膜、MA-411、Oji F-tex公司製)與感光性樹脂組成物層表面對齊並以80℃來進行層合，得到有脫模PET、感光性樹脂組成物層、覆蓋薄膜的三層構成的附支撐體的感光性薄膜。層合係藉由使用Nikko Materials公司製的真空加壓式貼合機MVLP-500，藉以溫度80℃進行真空吸引30秒鐘後，以溫度80℃、壓力7.0kg/cm2 之條件，隔著耐熱橡膠，從脫模PET上方進行壓製(pressing)60秒鐘來進行層合。接下來，在大氣壓下使用SUS鏡面板，以溫度80℃、壓力5.5kg/cm2 之條件進行壓製90秒鐘。<Example 1> As a support, a PET film (“LumirrorT6AM” manufactured by Toray Company”, thickness 38μm, softening point 130 ℃, "release PET"). Using a die coater, the prepared resin varnish is uniformly coated on the mold release PET so that the thickness of the dried photosensitive resin composition layer becomes 25μm, and the temperature is 80°C to 110°C (maximum temperature). 110°C) Drying is performed for 6 minutes. Next, the cover film (biaxially stretched polypropylene film, MA-411, manufactured by Oji F-tex) was aligned with the surface of the photosensitive resin composition layer and laminated at 80°C to obtain a mold-releasing PET , A photosensitive film with a support composed of three layers of a photosensitive resin composition layer and a cover film. The lamination was performed by using a vacuum pressure laminator MVLP-500 manufactured by Nikko Materials. After vacuum suction was performed at a temperature of 80°C for 30 seconds, the temperature was 80°C and a pressure of 7.0 kg/cm 2 The heat-resistant rubber was laminated by pressing from above the demolded PET for 60 seconds. Next, using a SUS mirror panel under atmospheric pressure, press for 90 seconds under the conditions of a temperature of 80°C and a pressure of 5.5 kg/cm 2.

＜實施例2~5、比較例1~3＞ 於實施例1中，將得到附支撐體的感光性薄膜時的乾燥時間及乾燥時的最高溫度改變成下述表所示的值。除了上述事項以外，其餘係與實施例1以相同之方式來得到附支撐體的感光性薄膜。<Examples 2 to 5, Comparative Examples 1 to 3> In Example 1, the drying time and the maximum temperature during drying when the photosensitive film with a support was obtained were changed to the values shown in the following table. Except for the above-mentioned matters, in the same manner as in Example 1, a photosensitive film with a support was obtained.

＜實施例6、比較例4＞ 於實施例1中，將感光性樹脂組成物1改變成感光性樹脂組成物2，並將得到附支撐體的感光性薄膜時的乾燥時間及乾燥時的最高溫度改變成下述表所示的值。除了上述事項以外，其餘係與實施例1以相同之方式來得到附支撐體的感光性薄膜。<Example 6, Comparative Example 4> In Example 1, the photosensitive resin composition 1 was changed to the photosensitive resin composition 2, and the drying time and the maximum temperature during drying when a photosensitive film with a support was obtained were changed as shown in the following table value. Except for the above-mentioned matters, in the same manner as in Example 1, a photosensitive film with a support was obtained.

＜重量減少率的測量＞ 將藉由實施例、比較例所得到的附支撐體的感光性薄膜裁切成10cm×10cm。將該等與充分乾燥的二氧化矽凝膠放入乾燥器中並放置30分鐘。之後，在將覆蓋薄膜剝離的狀態下測量附支撐體的感光性薄膜的質量，並將該值設為(a1)(單位為g)。接下來，將附支撐體的感光性薄膜在130℃的烘箱中加熱15分鐘，再次測量附支撐體的感光性薄膜的質量，並將該值設為(a2)(單位為g)。由上述式(A)算出a(將附支撐體的感光性薄膜以130℃乾燥15分鐘時的重量減少率)的值。又，關於b(將附支撐體的感光性薄膜以180℃乾燥15分鐘時的重量減少率)，除了將烘箱的溫度設為180℃以外，其餘係與a以相同之方式由上述式(B)來算出。算出a及b後，算出V及a/b。＜Measurement of weight loss rate＞ The photosensitive film with a support obtained by the Example and the comparative example was cut into 10 cm x 10 cm. Put the fully dried silica gel into a desiccator and let it stand for 30 minutes. After that, the mass of the photosensitive film with a support was measured in a state where the cover film was peeled off, and the value was set to (a1) (unit: g). Next, the photosensitive film with a support was heated in an oven at 130° C. for 15 minutes, and the quality of the photosensitive film with a support was measured again, and the value was set to (a2) (unit: g). The value of a (the weight loss rate when the photosensitive film with a support was dried at 130°C for 15 minutes) was calculated from the above-mentioned formula (A). Also, regarding b (the weight loss rate when the photosensitive film with a support is dried at 180°C for 15 minutes), except that the temperature of the oven is set to 180°C, the rest is derived from the above formula (B) in the same manner as a ) To calculate. After calculating a and b, calculate V and a/b.

＜熔融黏度的測量＞ 從附支撐體的感光性薄膜的脫模PET上僅剝離感光性樹脂組成物層，並用金屬模具進行壓縮來製作測量用顆粒(直徑18mm、1.2~1.3g)。使用測量用顆粒，並利用動態黏彈性測量裝置(UBM公司製「Rheosoｌ-G3000」)，對於樣品的感光性樹脂組成物層1g，使用直徑18mm的平行板，藉以昇溫速度5℃/分鐘，從開始溫度60℃至200℃為止來進行昇溫，並藉以測量溫度間隔2.5℃、振動數1Hz、變形1deg之測量條件來測量動態黏彈性率，而算出最低熔融黏度(poise)。＜Melting viscosity measurement＞ Only the photosensitive resin composition layer was peeled from the release PET of the photosensitive film with a support, and compressed with a metal mold to produce measurement pellets (diameter 18 mm, 1.2 to 1.3 g). Using measurement particles and using a dynamic viscoelasticity measuring device ("Rheosol-G3000" manufactured by UBM), for 1g of the photosensitive resin composition layer of the sample, a parallel plate with a diameter of 18mm is used, and the temperature rise rate is 5°C/min. The temperature is raised from 60°C to 200°C, and the dynamic viscoelasticity is measured under the measurement conditions of 2.5°C temperature interval, vibration number 1Hz, and deformation 1deg, and the lowest melt viscosity (poise) is calculated.

＜埋置性的評估＞ 準備內層電路基板(IPC MULTI-PURPOSE TESTBOARD No.IPC-B-25、導體厚18μm、0.8mm厚)。將附支撐體的感光性薄膜的覆蓋薄膜剝離後，於上述基板上，使用分批式真空加壓貼合機(Nikko・Materials公司製、VP160)，以感光性樹脂組成物層與內層電路基板接合之方式，來將附支撐體的感光性薄膜層合處理在內層電路基板的雙面。層合處理為藉由進行減壓30秒鐘並將氣壓設為13hPa以下後，藉以90℃、壓力0.7MPa下進行壓黏30秒鐘而來實施。接下來，藉以90℃、壓力0.5MPa下進行熱壓(hot pressing)60秒鐘。＜Evaluation of embedding ability＞ Prepare the inner circuit board (IPC MULTI-PURPOSE TESTBOARD No. IPC-B-25, conductor thickness 18μm, 0.8mm thickness). After peeling off the cover film of the photosensitive film with support, on the above-mentioned substrate, using a batch-type vacuum pressure laminator (manufactured by Nikko·Materials, VP160), the photosensitive resin composition layer and the inner layer circuit The substrate bonding method is to laminate the photosensitive film with a support on both sides of the inner layer circuit board. The lamination process was performed by performing pressure reduction for 30 seconds and setting the air pressure to 13 hPa or less, and then performing pressure bonding at 90° C. and a pressure of 0.7 MPa for 30 seconds. Next, hot pressing is performed at 90° C. and a pressure of 0.5 MPa for 60 seconds.

藉由目視來觀察層合後的內層電路基板的外觀，並依據以下的基準來進行評估。 ○：於銅配線之間沒有空孔，且樹脂從支撐體的外邊緣到外部的滲出為1cm以下。 △：些微發現空孔。 × ：樹脂的滲出為1cm以上。The appearance of the inner layer circuit board after the lamination was observed visually, and the evaluation was made based on the following criteria. ○: There are no voids between the copper wirings, and the resin exudation from the outer edge of the support to the outside is 1 cm or less. △: Holes are slightly found. ×: The bleed-out of resin is 1 cm or more.

＜通孔底的殘渣、底切耐性的評估＞ (評估用層合體的製作) 藉由包含有機酸的表面處理劑(CZ8100、MEC公司製)之處理，對於厚度18μm的已形成圖形化銅層的電路之玻璃環氧基板(覆銅層合板)的銅層來施予粗化。接下來，以藉由實施例、比較例所得到的附支撐體的感光性薄膜的感光性樹脂組成物層與銅電路表面接觸之方式來進行配置，並使用真空貼合機(Nikko・Materials公司製、VP160)，而形成依序層合前述覆銅層合板、前述感光性樹脂組成物層與前述支撐體的層合體。壓黏條件係設為抽真空的時間30秒鐘、壓黏溫度90℃、壓黏壓力0.7MPa、加壓時間30秒鐘。將該層合體靜置於室溫30分鐘以上，使用圓孔圖型並利用圖型形成裝置，從該層合體的支撐體上以紫外線來進行曝光。曝光圖型係使用描繪開口：100μm的圓孔(通孔)的石英玻璃遮罩。藉以室溫靜置30分鐘後，從前述層合體上將支撐體剝去。藉以0.2MPa的噴霧壓下，將作為顯影液30℃的1質量%碳酸鈉水溶液，對於該層合板上的感光性樹脂組成物層的整面，進行2分鐘的噴霧顯影。噴霧顯影後，進行1J/cm2 的紫外線照射，進而以180℃進行30分鐘的加熱處理，而在該層合體上形成具有開口部的絕緣層。將此作為評估用層合體。<Evaluation of residue and undercut resistance at the bottom of a through hole> (Production of evaluation laminate) A surface treatment agent (CZ8100, manufactured by MEC) containing an organic acid is used to form a patterned copper layer with a thickness of 18μm The copper layer of the glass epoxy substrate (copper clad laminate) of the circuit is roughened. Next, the photosensitive resin composition layer of the photosensitive film with a support obtained by the Examples and Comparative Examples was placed in contact with the surface of the copper circuit, and a vacuum laminator (Nikko·Materials) was used. VP160), to form a laminate in which the copper clad laminate, the photosensitive resin composition layer, and the support are sequentially laminated. The pressure-bonding conditions were set to vacuum time for 30 seconds, pressure-bonding temperature 90°C, pressure-bonding pressure 0.7 MPa, and press-bonding time 30 seconds. The laminate was allowed to stand at room temperature for more than 30 minutes, and a circular hole pattern was used and a pattern forming device was used to expose the laminate with ultraviolet rays from the support. The exposure pattern uses a quartz glass mask that depicts an opening: 100 μm round holes (through holes). After standing at room temperature for 30 minutes, the support was peeled off from the aforementioned laminate. Under a spray pressure of 0.2 MPa, a 1% by mass sodium carbonate aqueous solution at 30°C as a developer was spray-developed for 2 minutes on the entire surface of the photosensitive resin composition layer on the laminate. After spray development, 1 J/cm 2 of ultraviolet rays was irradiated, and further heat treatment was performed at 180° C. for 30 minutes to form an insulating layer having openings on the laminate. This was used as a laminate for evaluation.

(通孔底殘渣的評估) 對於在評估用層合體所形成的100μm的圓孔，依據以下的基準來進行評估。 ○：沒有殘渣。 × ：觀察到殘渣。(Evaluation of the residue on the bottom of the via) The round holes of 100 μm formed in the evaluation laminate were evaluated based on the following criteria. ○: No residue. ×: Residues are observed.

(底切耐性的評估) 對於在評估用層合體所形成的100μm的圓孔，進行藉由SEM之截面觀察，測量截面的最上部的半徑(μm)與底部的半徑(μm)並求出其差(最上部的半徑-底部的半徑)。(Evaluation of undercut resistance) For the 100 μm circular hole formed in the evaluation laminate, cross-sectional observation by SEM was performed, and the uppermost radius (μm) and the bottom radius (μm) of the cross-section were measured and the difference (the uppermost radius- The radius of the bottom).

Figure 02_image015
Figure 02_image015

於各實施例中，即使是不含有(E)成分及(F)成分，儘管程度上存在有差異，但仍可確認結論為與上述實施例相同之結果。In each example, even if the (E) component and (F) component are not included, although there is a difference in degree, it can be confirmed that the result is the same as the above-mentioned embodiment.

Claims (12)

一種感光性樹脂組成物，含有下述(A)~(D)成分： (A)含有乙烯性不飽和基與羧基的樹脂； (B)光聚合起始劑； (C)環氧樹脂； (D)揮發成分， 將感光性樹脂組成物以130℃進行乾燥15分鐘時的重量減少率(%)設為a，將感光性樹脂組成物以180℃進行乾燥15分鐘時的重量減少率(%)設為b時，滿足以下的式(1)及式(2)的關係，
Figure 03_image001
。A photosensitive resin composition containing the following components (A) to (D): (A) a resin containing an ethylenically unsaturated group and a carboxyl group; (B) a photopolymerization initiator; (C) an epoxy resin; D) Volatile components, the weight loss rate (%) when the photosensitive resin composition is dried at 130°C for 15 minutes is set to a, and the weight loss rate when the photosensitive resin composition is dried at 180°C for 15 minutes (% When) is set to b, it satisfies the relationship of the following formula (1) and formula (2),
Figure 03_image001
. 如請求項1之感光性樹脂組成物，其中，進而包含(F)無機填充材。The photosensitive resin composition of claim 1, which further contains (F) an inorganic filler. 如請求項1之感光性樹脂組成物，其中，(A)成分包含酸改質不飽和環氧酯樹脂。The photosensitive resin composition according to claim 1, wherein the component (A) contains an acid-modified unsaturated epoxy ester resin. 如請求項1之感光性樹脂組成物，其中，(A)成分包含酸改質環氧(甲基)丙烯酸酯。The photosensitive resin composition according to claim 1, wherein the component (A) contains acid-modified epoxy (meth)acrylate. 如請求項1之感光性樹脂組成物，其中，(A)成分包含含酸改質萘骨架的環氧(甲基)丙烯酸酯及含酸改質雙酚骨架的環氧(甲基)丙烯酸酯中的任1種。The photosensitive resin composition according to claim 1, wherein the component (A) contains epoxy (meth)acrylate containing an acid-modified naphthalene skeleton and epoxy (meth)acrylate containing an acid-modified bisphenol skeleton Any one of them. 如請求項1之感光性樹脂組成物，其中，(B)成分包含醯基氧化膦系光聚合起始劑及肟酯系光聚合起始劑中的任1種。The photosensitive resin composition according to claim 1, wherein the component (B) contains any one of an phosphine oxide-based photopolymerization initiator and an oxime ester-based photopolymerization initiator. 如請求項1之感光性樹脂組成物，其中，(D)成分具有酮類及二醇醚類中的任1種。The photosensitive resin composition according to claim 1, wherein the component (D) has any one of ketones and glycol ethers. 一種感光性薄膜，其含有如請求項1~7中任一項之感光性樹脂組成物。A photosensitive film containing the photosensitive resin composition according to any one of claims 1 to 7. 一種附支撐體的感光性薄膜，其具有支撐體與設置於該支撐體上的感光性樹脂組成物層，該感光性樹脂組成物層包含如請求項1~7中任一項之感光性樹脂組成物。A photosensitive film with a support, which has a support and a photosensitive resin composition layer provided on the support, the photosensitive resin composition layer comprising the photosensitive resin according to any one of claims 1 to 7 Composition. 一種印刷配線板，其包含藉由如請求項1~7中任一項之感光性樹脂組成物的硬化物所形成的絕緣層。A printed wiring board comprising an insulating layer formed by a cured product of the photosensitive resin composition according to any one of claims 1 to 7. 如請求項10之印刷配線板，其中，絕緣層為阻焊劑。Such as the printed wiring board of claim 10, wherein the insulating layer is a solder resist. 一種半導體裝置，其包含請求項10之印刷配線板。A semiconductor device including the printed wiring board of claim 10.
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