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TWI774740B - Photosensitive resin composition - Google Patents

Photosensitive resin composition Download PDF

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TWI774740B
TWI774740B TW107108397A TW107108397A TWI774740B TW I774740 B TWI774740 B TW I774740B TW 107108397 A TW107108397 A TW 107108397A TW 107108397 A TW107108397 A TW 107108397A TW I774740 B TWI774740 B TW I774740B
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resin composition
photosensitive resin
mass
component
photosensitive
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TW107108397A
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Chinese (zh)
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TW201841931A (en
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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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    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus
    • 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
    • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
    • G03F7/0043—Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof
    • 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
    • G03F7/032—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
    • 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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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Laminated Bodies (AREA)
  • Epoxy Resins (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

本發明的課題為提供一種可得到平均線熱膨脹率低，玻璃轉移溫度高，阻燃性及抗裂性優異之硬化物，解析性優異之感光性樹脂組成物等。 　　本發明的解決手段為一種感光性樹脂組成物，其係含有：(A)含有乙烯性不飽和基及羧基之樹脂、(B)平均粒徑為0.5μm以上2.5μm以下之無機填充材、(C)平均粒徑為0.7μm以上2.0μm以下之粒子，且含有下述一般式(1)或下述一般式(2)表示之磷化合物之粒子、(D)光聚合起始劑及(E)環氧樹脂之感光性樹脂組成物，其特徵為(B)成分的含量將感光性樹脂組成物的固形分全體定為100質量%時，為60質量%以上85質量%以下(一般式(1)及一般式(2)中，n表示1或2)。

Figure 107108397-A0101-11-0001-1
An object of the present invention is to provide a cured product having a low average linear thermal expansion coefficient, a high glass transition temperature, excellent flame retardancy and crack resistance, a photosensitive resin composition having excellent analytical properties, and the like. The solution of the present invention is a photosensitive resin composition comprising: (A) a resin containing an ethylenically unsaturated group and a carboxyl group, (B) an inorganic filler having an average particle diameter of 0.5 μm or more and 2.5 μm or less, ( C) Particles having an average particle diameter of 0.7 μm or more and 2.0 μm or less, and containing particles of a phosphorus compound represented by the following general formula (1) or the following general formula (2), (D) a photopolymerization initiator, and (E) ) The photosensitive resin composition of epoxy resin is characterized in that the content of (B) component is 60 mass % or more and 85 mass % or less when the total solid content of the photosensitive resin composition is 100 mass % (general formula ( In 1) and general formula (2), n represents 1 or 2).
Figure 107108397-A0101-11-0001-1

Description

感光性樹脂組成物Photosensitive resin composition

本發明係關於感光性樹脂組成物。進而，係關於使用該感光性樹脂組成物所得之感光性薄膜、附支持體之感光性薄膜、印刷電路板及半導體裝置。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, a printed wiring board, and a semiconductor device.

於印刷電路板，作為對不需要焊接的部分抑制附著焊接，並且用以抑制腐蝕電路基板之永久保護膜，而設置阻焊劑。作為阻焊劑，例如一般係使用如專利文獻1所記載之感光性樹脂組成物。 [先前技術文獻] [專利文獻]On the printed circuit board, a solder resist is provided as a permanent protective film to inhibit adhesion soldering to parts that do not require soldering and to inhibit corrosion of the circuit substrate. As a soldering resist, the photosensitive resin composition as described in patent document 1 is generally used, for example. [Prior Art Literature] [Patent Literature]

[專利文獻1]國際公開第2012/090532號[Patent Document 1] International Publication No. 2012/090532

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

阻焊劑用之感光性樹脂組成物，一般而言要求解析性、絕緣性、焊接耐熱性、鍍金耐性、耐濕熱特性、抗裂性(TCT耐性)及對於在微細配線間之超加速高溫高濕壽命試驗(HAST)之HAST耐性。近年來，對應印刷電路板之高密度化，阻焊劑亦要求作業性或進一步高性能化。尤其是關於抗裂性之要求亦年年提昇，具有更強耐久性變為重要。Photosensitive resin compositions for solder resists generally require analytical properties, insulating properties, soldering heat resistance, gold plating resistance, wet heat resistance, crack resistance (TCT resistance), and ultra-accelerated high temperature and high humidity between fine wirings. HAST resistance of life test (HAST). In recent years, in response to the increase in density of printed wiring boards, workability and further performance enhancement of solder resists are also required. In particular, the requirements for crack resistance are increasing year by year, and it is important to have stronger durability.

為了提昇抗裂性，例如雖考量將無機填充材高填充在感光性樹脂組成物之方法，但由於與被著體之密著性降低，或光之透過並未足夠，貫孔底之感度惡化，而產生底切(Undercut)，或因光之光暈(halation)等導致有無法充分開口的可能性。In order to improve the crack resistance, for example, a method of filling the photosensitive resin composition with an inorganic filler is considered, but the sensitivity of the bottom of the through hole is deteriorated because the adhesion to the substrate is reduced, or the light transmission is not enough. , resulting in an undercut, or there is a possibility that the opening cannot be fully opened due to the halo of light.

又，印刷電路板由於搭載在電子機器，已被要求阻燃性，印刷電路板之一部分即阻焊劑亦被要求阻燃性。In addition, since the printed circuit board is mounted in electronic equipment, flame retardancy is required, and the solder resist, which is a part of the printed circuit board, is also required to have flame retardancy.

為了提昇阻焊劑等之阻燃性，例如雖考量使10-(2,5-二羥基苯基)-9,10-二氫9-氧雜-10-磷雜菲(Phosphaphenanthrene)-10-氧化物等之含有磷之阻燃劑含有在感光性樹脂組成物之方法，但含有此含有磷之阻燃劑時，由於缺乏溶劑溶解性且粗粒大，有貫孔形狀惡化的可能性。又，亦有阻聚效果，有得不到充分之感度的可能性。In order to improve the flame retardancy of solder resists, for example, 10-(2,5-dihydroxyphenyl)-9,10-dihydro9-oxa-10-phosphaphenanthrene (Phosphaphenanthrene)-10-oxidation is considered. However, when the phosphorus-containing flame retardant is contained in the photosensitive resin composition, there is a possibility that the shape of the through-hole may be deteriorated due to lack of solvent solubility and large coarse particles. In addition, there is also a polymerization inhibitory effect, and there is a possibility that a sufficient sensitivity cannot be obtained.

本發明之課題為提供一種可得到平均線熱膨脹率低，玻璃轉移溫度高，阻燃性及抗裂性優異之硬化物，解析性優異之感光性樹脂組成物；使用該感光性樹脂組成物所得之感光性薄膜、附支持體之感光性薄膜、印刷電路板及半導體裝置。 [用以解決課題之手段]The subject of the present invention is to provide a photosensitive resin composition that can obtain a cured product with a low average linear thermal expansion coefficient, a high glass transition temperature, excellent flame retardancy and crack resistance, and excellent analytical properties; the photosensitive resin composition obtained by using the photosensitive resin composition Photosensitive films, photosensitive films with supports, printed circuit boards and semiconductor devices. [means to solve the problem]

本發明者們，瞭解到上述之含有磷之阻燃劑由於缺乏溶劑溶解性且粗粒大，有藉由酚性羥基等之阻聚效果，有貫孔形狀惡化，且得不到充分之感度的可能性。本發明者們為了解決上述課題經努力研究的結果，發現藉由使具有指定平均粒徑之指定一般式表示之含有磷之化合物含有在感光性樹脂組成物，保持阻聚效果與阻燃效果的平衡，可解決上述課題，而終至完成本發明。The inventors of the present invention have found that the above-mentioned phosphorus-containing flame retardant lacks solvent solubility and has large coarse particles, has a polymerization inhibitory effect due to phenolic hydroxyl groups, etc., deteriorates the shape of the through-hole, and cannot obtain sufficient sensitivity possibility. As a result of diligent studies to solve the above-mentioned problems, the present inventors found that by including a phosphorus-containing compound represented by a specified general formula having a specified average particle diameter in a photosensitive resin composition, the polymerization inhibitory effect and the flame retardant effect can be maintained. In balance, the above-mentioned problems can be solved, and the present invention is finally completed.

亦即，本發明包含以下之內容。 　　[1] 一種感光性樹脂組成物，其係含有： 　　(A)含有乙烯性不飽和基及羧基之樹脂、 　　(B)平均粒徑為0.5μm以上2.5μm以下之無機填充材、 　　(C)平均粒徑為0.7μm以上2.0μm以下之粒子，且含有下述一般式(1)或下述一般式(2)表示之磷化合物之粒子、 　　(D)光聚合起始劑及 　　(E)環氧樹脂之感光性樹脂組成物，其特徵為 　　將感光性樹脂組成物的固形分全體定為100質量%時，(B)成分的含量為60質量%以上85質量%以下，

Figure 02_image003
(一般式(1)及一般式(2)中，n表示1或2)。 　　[2] 如[1]所記載之感光性樹脂組成物，其中，(E)成分係含有聯苯型環氧樹脂及四苯基乙烷型環氧樹脂之至少任一種。 　　[3] 如[1]或[2]所記載之感光性樹脂組成物，其中，(A)成分係具有萘骨架。 　　[4] 如[1]～[3]中任一項記載之感光性樹脂組成物，其中，(A)成分係含有含酸改質萘骨架之環氧(甲基)丙烯酸酯。 　　[5] 如[1]～[4]中任一項記載之感光性樹脂組成物，其中，將感光性樹脂組成物之樹脂成分定為100質量%時，磷原子的含量為0.1質量%以上1.2質量%以下。 　　[6] 如[1]～[5]中任一項記載之感光性樹脂組成物，其中，將感光性樹脂組成物的固形分全體定為100質量%時，(C)成分的含量為0.1質量%以上10質量%以下。 　　[7] 如[1]～[6]中任一項記載之感光性樹脂組成物，其係光硬化感光性樹脂組成物後，以190℃熱硬化90分鐘時在25℃～150℃之平均線熱膨脹率為50ppm以下。 　　[8] 如[1]～[7]中任一項記載之感光性樹脂組成物，其中，(B)成分係包含二氧化矽。 　　[9] 一種感光性薄膜，其係含有如[1]～[8]中任一項之感光性樹脂組成物。 　　[10] 一種附支持體之感光性薄膜，其係具有支持體、與設置在該支持體上之包含如[1]～[8]中任一項之感光性樹脂組成物之感光性樹脂組成物層。 　　[11] 一種印刷電路板，其係包含藉由如[1]～[8]中任一項之感光性樹脂組成物的硬化物所形成之絕緣層。 　　[12] 如[11]所記載之印刷電路板，其中，絕緣層為阻焊劑。 　　[13] 一種半導體裝置，其係包含如[11]或[12]所記載之印刷電路板。 [發明的效果]That is, the present invention includes the following contents. [1] A photosensitive resin composition comprising: (A) a resin containing an ethylenically unsaturated group and a carboxyl group, (B) an inorganic filler having an average particle size of 0.5 μm or more and 2.5 μm or less, (C) an average particle size Particles with a particle size of 0.7 μm or more and 2.0 μm or less, and particles containing a phosphorus compound represented by the following general formula (1) or the following general formula (2), (D) photopolymerization initiator and (E) epoxy The photosensitive resin composition of resin is characterized in that the content of component (B) is 60 mass % or more and 85 mass % or less when the total solid content of the photosensitive resin composition is 100 mass %,
Figure 02_image003
(In general formula (1) and general formula (2), n represents 1 or 2). [2] The photosensitive resin composition according to [1], wherein the component (E) contains at least any one of a biphenyl-type epoxy resin and a tetraphenylethane-type epoxy resin. [3] The photosensitive resin composition according to [1] or [2], wherein the component (A) has a naphthalene skeleton. [4] The photosensitive resin composition according to any one of [1] to [3], wherein the component (A) contains an acid-modified naphthalene skeleton-containing epoxy (meth)acrylate. [5] The photosensitive resin composition according to any one of [1] to [4], wherein the content of phosphorus atoms is 0.1 mass % or more when the resin component of the photosensitive resin composition is 100 mass % 1.2 mass % or less. [6] The photosensitive resin composition according to any one of [1] to [5], wherein the content of the component (C) is 0.1 when the total solid content of the photosensitive resin composition is 100% by mass. mass % or more and 10 mass % or less. [7] The photosensitive resin composition according to any one of [1] to [6], wherein after photocuring the photosensitive resin composition, the average temperature at 25°C to 150°C when thermally cured at 190°C for 90 minutes The coefficient of linear thermal expansion is 50 ppm or less. [8] The photosensitive resin composition according to any one of [1] to [7], wherein the component (B) contains silica. [9] A photosensitive film containing the photosensitive resin composition according to any one of [1] to [8]. [10] A photosensitive film with a support, comprising a support and a photosensitive resin comprising the photosensitive resin composition of any one of [1] to [8] arranged on the support material layer. [11] A printed wiring board including an insulating layer formed of a cured product of the photosensitive resin composition according to any one of [1] to [8]. [12] The printed wiring board according to [11], wherein the insulating layer is a solder resist. [13] A semiconductor device comprising the printed circuit board as described in [11] or [12]. [Effect of invention]

根據本發明，可提供可得到平均線熱膨脹率低，玻璃轉移溫度高，阻燃性及抗裂性優異之硬化物，解析性優異之感光性樹脂組成物；使用該感光性樹脂組成物所得之感光性薄膜、附支持體之感光性薄膜、印刷電路板及半導體裝置。According to the present invention, it is possible to provide a cured product with a low average linear thermal expansion coefficient, a high glass transition temperature, excellent flame retardancy and crack resistance, and a photosensitive resin composition with excellent resolution; the photosensitive resin composition obtained by using the photosensitive resin composition Photosensitive films, photosensitive films with supports, printed circuit boards and semiconductor devices.

以下，針對本發明之感光性樹脂組成物、感光性薄膜、附支持體之感光性薄膜、印刷電路板及半導體裝置進行詳細說明。Hereinafter, the photosensitive resin composition, the photosensitive film, the photosensitive film with a support, the printed wiring board, and the semiconductor device of the present invention will be described in detail.

[感光性樹脂組成物] 　　本發明之感光性樹脂組成物係含有：(A)含有乙烯性不飽和基及羧基之樹脂、(B)平均粒徑為0.5μm以上2.5μm以下之無機填充材、(C)平均粒徑為0.7μm以上2.0μm以下之粒子，且含有下述一般式(1)或下述一般式(2)表示之磷化合物之粒子、(D)光聚合起始劑及(E)環氧樹脂之感光性樹脂組成物，其特徵為將感光性樹脂組成物的固形分全體定為100質量%時，(B)成分的含量為60質量%以上85質量%以下。

Figure 02_image005
(一般式(1)及一般式(2)中，n表示1或2)。[Photosensitive resin composition] The photosensitive resin composition of the present invention contains: (A) a resin containing an ethylenically unsaturated group and a carboxyl group, (B) an inorganic filler with an average particle diameter of 0.5 μm or more and 2.5 μm or less, (C) Particles having an average particle diameter of 0.7 μm or more and 2.0 μm or less, and containing particles of a phosphorus compound represented by the following general formula (1) or the following general formula (2), (D) a photopolymerization initiator, and ( E) The photosensitive resin composition of epoxy resin is characterized in that content of (B) component is 60 mass % or more and 85 mass % or less when the total solid content of the photosensitive resin composition is 100 mass %.
Figure 02_image005
(In general formula (1) and general formula (2), n represents 1 or 2).

藉由含有(A)成分～(E)成分，可得到平均線熱膨脹率低，玻璃轉移溫度高，阻燃性及抗裂性優異之硬化物，又，解析性亦優異。又，如有必要可進一步包含(F)反應性稀釋劑、(G)有機溶劑。以下，針對感光性樹脂組成物所包含之各成分進行詳細說明。By containing (A) component - (E) component, the average linear thermal expansion coefficient is low, the glass transition temperature is high, and the hardened|cured material which is excellent in flame retardance and crack resistance can be obtained, and also it is excellent in analytical property. Moreover, if necessary, (F) a reactive diluent and (G) an organic solvent may be further contained. Hereinafter, each component contained in the photosensitive resin composition will be described in detail.

＜(A)含有乙烯性不飽和基及羧基之樹脂＞ 　　感光性樹脂組成物係含有(A)含有乙烯性不飽和基及羧基之樹脂。<(A) Resin containing ethylenically unsaturated group and carboxyl group> The photosensitive resin composition contains (A) resin containing ethylenically unsaturated group and carboxyl group.

作為乙烯性不飽和基，例如可列舉乙烯基、烯丙基、丙炔基、丁烯基、乙炔基、苯基乙炔基、馬来醯亞胺基、納迪克醯亞胺基(nadiimide)、(甲基)丙烯醯基，從光自由基聚合之反應性的觀點來看，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, allyl, propynyl, butenyl, ethynyl, phenylethynyl, maleimide, nadiimide, The (meth)acryloyl group is preferably a (meth)acryloyl group from the viewpoint of the reactivity of photoradical polymerization. The "(meth)acryloyl group" refers to a methacryloyl group and an acryl group.

(A)成分雖若為具有乙烯性不飽和基及羧基，可進行光自由基聚合而且可以鹼顯影之化合物，則並未特別限制，但較佳為於1分子中一併具有羧基與2個以上乙烯性不飽和基之樹脂。The component (A) is not particularly limited as long as it has an ethylenically unsaturated group and a carboxyl group, which can undergo photo-radical polymerization and can be developed with alkali, but preferably has a carboxyl group and two carboxyl groups in one molecule. Resins of the above ethylenically unsaturated groups.

作為含有乙烯性不飽和基及羧基之樹脂之一態樣，可列舉於環氧基化合物使不飽和羧酸反應，進而使酸酐反應之酸改質不飽和環氧基酯樹脂等。詳細而言，藉由於環氧基化合物使不飽和羧酸反應而得到不飽和環氧基酯樹脂，使不飽和環氧基酯樹脂與酸酐進行反應可得到酸改質不飽和環氧基酯樹脂。As one aspect of the resin containing an ethylenically unsaturated group and a carboxyl group, an acid-modified unsaturated epoxy ester resin obtained by reacting an unsaturated carboxylic acid with an epoxy compound and further reacting an acid anhydride can be mentioned. Specifically, an unsaturated epoxy ester resin can be obtained by reacting an unsaturated carboxylic acid with an epoxy compound, and an acid-modified unsaturated epoxy ester resin can be obtained by reacting an unsaturated epoxy ester resin with an acid anhydride. .

作為環氧基化合物，若為於分子內具有環氧基之化合物，則可使用，例如可列舉雙酚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、於雙酚F型環氧樹脂使環氧氯丙烷進行反應改質成3官能以上之改質雙酚F型環氧樹脂等之雙酚型環氧樹脂；聯酚型環氧樹脂、四甲基聯酚型等之聯酚型環氧樹脂；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、烷基酚酚醛清漆型環氧樹脂等之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之含有氟之環氧樹脂；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之縮合反應所得之萘型環氧樹脂等之具有萘骨架之環氧樹脂(含有萘骨架之環氧樹脂)；聯二甲酚型環氧樹脂；雙環戊二烯型環氧樹脂；參酚型環氧樹脂；tert-丁基-鄰苯二酚型環氧樹脂；蔥型環氧樹脂等之含有縮合環骨架之環氧樹脂；縮水甘油基胺型環氧樹脂；縮水甘油基酯型環氧樹脂；聯苯型環氧樹脂；線狀脂肪族環氧樹脂；具有丁二烯構造之環氧樹脂；脂環式環氧樹脂；雜環式環氧樹脂；螺環含有環氧樹脂；環己烷二甲醇型環氧樹脂；三羥甲基型環氧樹脂；四苯基乙烷型環氧樹脂；聚縮水甘油基(甲基)丙烯酸酯、縮水甘油基甲基丙烯酸酯與丙烯酸酯之共聚物等之含有縮水甘油基之丙烯酸樹脂；茀型環氧樹脂；鹵素化環氧樹脂等。As an epoxy compound, if it is a compound which has an epoxy group in a molecule|numerator, it can be used, for example, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, Hydrogenated bisphenol F type epoxy resin, bisphenol S type epoxy resin, modified bisphenol F type epoxy resin by reacting epichlorohydrin in bisphenol F type epoxy resin to three or more functionalities, etc. Bisphenol type epoxy resin; biphenol type epoxy resin, tetramethyl biphenol type epoxy resin, etc.; novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type Novolak epoxy resins, such as novolak epoxy resins, alkylphenol novolak epoxy resins, etc.; fluorine-containing epoxy resins such as bisphenol AF epoxy resins and perfluoroalkyl epoxy resins; Naphthalene type epoxy resin, dihydroxynaphthalene type epoxy resin, polyhydroxy binaphthyl type epoxy resin, naphthol type epoxy resin, binaphthol type epoxy resin, naphthyl ether type epoxy resin, naphthol novolac type epoxy resin, naphthalene type epoxy resin obtained by condensation reaction of polyhydroxynaphthalene and aldehydes, etc. epoxy resin with naphthalene skeleton (epoxy resin containing naphthalene skeleton); bixylenol type epoxy resin ; Dicyclopentadiene type epoxy resin; Samphenol type epoxy resin; Tert-butyl-catechol type epoxy resin; Onion type epoxy resin and other epoxy resin containing condensed ring skeleton; Glycidyl group Amine 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 type Epoxy resin; Spiro-containing epoxy resin; Cyclohexanedimethanol type epoxy resin; Trimethylol type epoxy resin; Tetraphenylethane type epoxy resin; Polyglycidyl (meth)acrylate , glycidyl methacrylate and acrylate copolymer, etc. acrylic resin containing glycidyl group; Phenyl epoxy resin; halogenated epoxy resin, etc.

從降低平均線熱膨脹率的觀點來看，較佳為含有芳香族骨架之環氧樹脂。於此，所謂芳香族骨架係亦包含多環芳香族及芳香族雜環的概念。其中，較佳為含有萘骨架之環氧樹脂、含有縮合環骨架之環氧樹脂、聯苯型環氧樹脂、雙酚F型環氧樹脂、雙酚A型環氧樹脂、甲酚酚醛清漆型環氧樹脂、縮水甘油基酯型環氧樹脂。其中，由於分子之剛性提高抑制分子之動作，其結果，從更加提高樹脂組成物之硬化物的玻璃轉移溫度，更加降低硬化物之平均線熱膨脹率的觀點來看，更佳為含有萘骨架之環氧樹脂、含有縮合環骨架之環氧樹脂、聯苯型環氧樹脂，再更佳為含有萘骨架之環氧樹脂。作為含有萘骨架之環氧樹脂，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之縮合反應所得之萘型環氧樹脂。From the viewpoint of reducing the average linear thermal expansion coefficient, an epoxy resin containing an aromatic skeleton is preferred. Here, the term "aromatic skeleton system" also includes the concept of polycyclic aromatics and aromatic heterocycles. Among them, 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, cresol novolac type are preferred. Epoxy resin, glycidyl ester type epoxy resin. Among them, the improvement of the rigidity of the molecules suppresses the movement of the molecules, and as a result, the glass transition temperature of the cured product of the resin composition is further increased, and the average linear thermal expansion coefficient of the cured product is further reduced. Epoxy resin, epoxy resin containing condensed ring skeleton, biphenyl type epoxy resin, and more preferably epoxy resin containing naphthalene skeleton. As the epoxy resin containing a naphthalene skeleton, a dihydroxynaphthalene type epoxy resin, a polyhydroxybinaphthalene type epoxy resin, and a naphthalene type epoxy resin obtained by a condensation reaction of polyhydroxynaphthalene and an aldehyde are preferable.

作為二羥基萘型環氧樹脂，例如可列舉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。As the dihydroxynaphthalene type epoxy resin, for example, 1,3-diglycidoxynaphthalene, 1,4-diglycidoxynaphthalene, 1,5-diglycidoxynaphthalene, 1,6-diglycidoxynaphthalene can be mentioned. Glycidoxynaphthalene, 2,3-diglycidoxynaphthalene, 2,6-diglycidoxynaphthalene, 2,7-diglycidoxynaphthalene, and the like.

作為聚羥基聯萘型環氧樹脂，例如可列舉1,1’-雙(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’-雙(2,7-二縮水甘油氧基)萘基等。Examples of polyhydroxybinaphthyl-type epoxy resins include 1,1'-bis(2-glycidyloxy)naphthyl, 1-(2,7-diglycidyloxy)-1'-(2' -Glycidyloxy)binaphthyl, 1,1'-bis(2,7-diglycidyloxy)naphthyl, and the like.

作為藉由聚羥基萘與醛類的縮合反應所得之萘型環氧樹脂，例如可列舉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。Examples of naphthalene-type epoxy resins obtained by condensation reaction of polyhydroxynaphthalene and aldehydes include 1,1'-bis(2,7-diglycidoxynaphthyl)methane, 1-(2,7 -Diglycidyloxynaphthyl)-1'-(2'-glycidoxynaphthyl)methane, 1,1'-bis(2-glycidoxynaphthyl)methane.

此等當中，較佳為於1分子中具有2個以上萘骨架之聚羥基聯萘型環氧樹脂、藉由聚羥基萘與醛類之縮合反應所得之萘型環氧樹脂，尤其是於1分子中具有3個以上環氧基之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-(2,7-二縮水甘油氧基)-1’-(2’-縮水甘油氧基)聯萘基、1,1’-雙(2,7-二縮水甘油氧基)萘基，以除了平均線熱膨脹率而且耐熱性優異的點來看較佳。Among these, preferred are polyhydroxybinaphthyl-type epoxy resins having two or more naphthalene skeletons in one molecule, and naphthalene-type epoxy resins obtained by condensation reaction of polyhydroxynaphthalene and aldehydes, especially in 1 1,1'-bis(2,7-diglycidyloxynaphthyl)methane, 1-(2,7-diglycidyloxynaphthyl)-1'- having three or more epoxy groups in the molecule (2'-glycidyloxynaphthyl)methane, 1-(2,7-diglycidyloxy)-1'-(2'-glycidyloxy)binaphthyl, 1,1'-bis( 2,7-diglycidyloxy) naphthyl is preferable in that it is excellent in heat resistance in addition to the average linear thermal expansion coefficient.

作為不飽和羧酸，例如可列舉丙烯酸、甲基丙烯酸、桂皮酸、巴豆酸等，此等可1種單獨使用，亦可併用2種以上。其中，丙烯酸、甲基丙烯酸從提昇感光性樹脂組成物之光硬化性的觀點來看較佳。尚，在本說明書，有將上述之環氧基化合物與(甲基)丙烯酸的反應物即環氧基酯樹脂記載為「環氧基(甲基)丙烯酸酯」的情況，於此，環氧基化合物之環氧基係藉由與(甲基)丙烯酸之反應實質上消滅。所謂「(甲基)丙烯酸酯」，係指甲基丙烯酸酯及丙烯酸酯。有時集合丙烯酸與甲基丙烯酸稱為「(甲基)丙烯酸」。Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, cinnamic acid, and crotonic acid, and these may be used alone or in combination of two or more. Among them, acrylic acid and methacrylic acid are preferable from the viewpoint of improving the photocurability of the photosensitive resin composition. Furthermore, in this specification, the epoxy ester resin, which is the reaction product of the above-mentioned epoxy compound and (meth)acrylic acid, may be described as "epoxy (meth)acrylate". Here, epoxy The epoxy group of the base compound is substantially eliminated by the reaction with (meth)acrylic acid. The "(meth)acrylate" refers to methacrylate and acrylate. Sometimes the combination of acrylic and methacrylic acid is called "(meth)acrylic acid".

作為酸酐，例如可列舉馬來酸酐、琥珀酸酐、衣康酸酐、苯二甲酸酐、四氫苯二甲酸酐、六氫苯二甲酸酐、偏苯三酸酐、均苯四甲酸酐、二苯甲酮四羧酸二酐等，此等可任1種單獨使用亦可併用2種以上。其中，琥珀酸酐、四氫苯二甲酸酐從提昇硬化物之解析性及絕緣信賴性的點來看較佳。Examples of acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxyl Acid dianhydrides and the like may be used alone or in combination of two or more. Among them, succinic anhydride and tetrahydrophthalic anhydride are preferable from the viewpoint of improving the analytical properties and insulation reliability of the cured product.

在得到酸改質不飽和環氧基酯樹脂，於觸媒存在下使不飽和羧酸與環氧樹脂進行反應，而得到不飽和環氧基酯樹脂後，可使不飽和環氧基酯樹脂與酸酐進行反應。又，如有必要可使用溶劑、阻聚劑。After obtaining acid-modified unsaturated epoxy ester resin, reacting unsaturated carboxylic acid with epoxy resin in the presence of a catalyst to obtain unsaturated epoxy ester resin, unsaturated epoxy ester resin can be React with acid anhydrides. Moreover, if necessary, a solvent and a polymerization inhibitor can be used.

作為酸改質不飽和環氧基酯樹脂，較佳為酸改質環氧基(甲基)丙烯酸酯。所謂在酸改質不飽和環氧基酯樹脂之「環氧基」，係表示源自上述之環氧基化合物的構造。例如所謂「酸改質雙酚型環氧基(甲基)丙烯酸酯」，係指使用雙酚型環氧樹脂作為環氧基化合物，使用(甲基)丙烯酸作為不飽和羧酸所得之酸改質不飽和環氧基酯樹脂。酸改質環氧基(甲基)丙烯酸酯之較佳的範圍，係源自環氧基化合物之較佳的範圍。即，酸改質不飽和環氧基酯樹脂從提高樹脂組成物之硬化物的玻璃轉移溫度，且降低平均線熱膨脹率的觀點來看，較佳為含酸改質萘骨架之環氧基(甲基)丙烯酸酯。所謂含酸改質萘骨架之環氧基(甲基)丙烯酸酯，係於萘型環氧樹脂與(甲基)丙烯酸酯的反應物，使琥珀酸酐或四氫苯二甲酸酐等之酸酐進行反應所得之化合物。The acid-modified unsaturated epoxy ester resin is preferably an acid-modified epoxy (meth)acrylate. 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-type epoxy (meth)acrylate" refers to an acid-modified compound obtained by using a bisphenol-type epoxy resin as an epoxy compound and (meth)acrylic acid as an unsaturated carboxylic acid. Quality unsaturated epoxy ester resin. The preferable range of an acid-modified epoxy (meth)acrylate is derived from the preferable range of an epoxy compound. That is, the acid-modified unsaturated epoxy ester resin is preferably an epoxy group containing an acid-modified naphthalene skeleton ( meth)acrylate. The so-called acid-modified naphthalene skeleton-containing epoxy (meth)acrylate is a reaction product of a naphthalene-type epoxy resin and a (meth)acrylate, and an acid anhydride such as succinic anhydride or tetrahydrophthalic anhydride is reacted. The compound obtained by the reaction.

如此之酸改質不飽和環氧基酯樹脂可使用市售品，作為具體例，可列舉日本化藥公司製之「ZAR-2000」(雙酚A型環氧樹脂、丙烯酸及琥珀酸酐之反應物)、「ZFR-1491H」、「ZFR-1533H」(雙酚F型環氧樹脂、丙烯酸及四氫苯二甲酸酐之反應物)、昭和電工公司製之「PR-300CP」(甲酚酚醛清漆型環氧樹脂、丙烯酸及酸酐之反應物)等。此等可1種單獨使用，亦可組合2種以上使用。Such an acid-modified unsaturated epoxy ester resin can be a commercially available product, and as a specific example, "ZAR-2000" (reaction of bisphenol A type epoxy resin, acrylic acid and succinic anhydride) manufactured by Nippon Kayaku Co., Ltd. product), "ZFR-1491H", "ZFR-1533H" (the reaction product of bisphenol F epoxy resin, acrylic acid and tetrahydrophthalic anhydride), "PR-300CP" (cresol novolac) manufactured by Showa Denko Corporation Varnish type epoxy resin, acrylic acid and acid anhydride reactant), etc. These 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之樹脂之其他態樣，可列舉於聚合(甲基)丙烯酸所得之構造單元所具有之(甲基)丙烯酸樹脂，使含有乙烯性不飽和基之環氧基化合物進行反應，而導入乙烯性不飽和基之不飽和改質(甲基)丙烯酸樹脂。含有乙烯性不飽和基之環氧基化合物，例如可列舉縮水甘油基甲基丙烯酸酯、4-羥基丁基(甲基)丙烯酸酯縮水甘油基醚、3,4-環氧基環己基甲基(甲基)丙烯酸酯等。進而，亦可於不飽和基導入時所產生之羥基使酸酐進行反應。作為酸酐，可使用與上述之酸酐相同者，較佳的範圍亦相同。As another aspect of the resin containing an ethylenically unsaturated group and a carboxyl group, the (meth)acrylic resin contained in the structural unit obtained by polymerizing (meth)acrylic acid can be mentioned, and an epoxy group containing an ethylenically unsaturated group can be used. The compound reacts to introduce an unsaturated modified (meth)acrylic resin into which an ethylenically unsaturated group is introduced. Examples of epoxy compounds containing ethylenically unsaturated groups include glycidyl methacrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and 3,4-epoxycyclohexylmethyl. (Meth)acrylate, etc. Furthermore, an acid anhydride can also be made to react with the hydroxyl group which generate|occur|produced at the time of introduction of an unsaturated group. As the acid anhydride, the same as the above-mentioned acid anhydride can be used, and the preferable range is also the same.

如此之不飽和改質(甲基)丙烯酸樹脂可使用市售品，作為具體例，可列舉昭和電工公司製之「SPC-1000」、「SPC-3000」、Daicel･Ornex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。As such unsaturated modified (meth)acrylic resins, commercially available products can be used, and specific examples include "SPC-1000" and "SPC-3000" manufactured by Showa Denko Co., Ltd., and "Cyclomer P (Cyclomer P) manufactured by Daicel Ornex Corporation. "ACA)Z-250", "Cyclomer P(ACA)Z-251", "Cyclomer P(ACA)Z-254", "Cyclomer P(ACA)Z-300", "Cyclomer P(ACA)Z-320" Wait.

作為(A)成分之重量平均分子量，從製膜性的觀點來看，較佳為1000以上，更佳為1500以上，再更佳為2000以上。作為上限，從解析性的觀點來看，較佳為10000以下，更佳為8000以下，再更佳為7500以下。重量平均分子量係藉由凝膠滲透層析(GPC)法所測定之聚苯乙烯換算的重量平均分子量。The weight average molecular weight of the component (A) is preferably 1,000 or more, more preferably 1,500 or more, and even more preferably 2,000 or more, from the viewpoint of film-forming properties. The upper limit is preferably 10,000 or less, more preferably 8,000 or less, and even more preferably 7,500 or less, from the viewpoint of analytical performance. The weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

作為(A)成分之酸價，從提昇感光性樹脂組成物之鹼顯影性的觀點來看，較佳為酸價為0.1mgKOH/g以上，更佳為0.5mgKOH/g以上，再更佳為1mgKOH/g以上。另外，從抑制硬化物之微細圖型因顯影而熔化，提昇絕緣信賴性的觀點來看，較佳為酸價為150mgKOH/g以下，更佳為120mgKOH/g以下，再更佳為100mgKOH/g以下。於此，所謂酸價，係存在於(A)成分之羧基的殘存酸價，酸價可藉由以下之方法測定。首先，秤取測定樹脂溶液約1g後，於該樹脂溶液添加30g丙酮，均勻溶解樹脂溶液。接著，將指示藥之酚酞適量添加在該溶液，使用0.1N之KOH水溶液進行滴定。而且藉由下述式算出酸價。 　　式：A=10×Vf×56.1/(Wp×I)As the acid value of the component (A), from the viewpoint of improving the alkali developability of the photosensitive resin composition, the acid value is preferably 0.1 mgKOH/g or more, more preferably 0.5 mgKOH/g or more, and even more preferably 1mgKOH/g or more. In addition, from the viewpoint of suppressing the melting of the fine pattern of the cured product by development and improving the insulation reliability, the acid value is preferably 150 mgKOH/g or less, more preferably 120 mgKOH/g or less, still more preferably 100 mgKOH/g the following. Here, the acid value refers to the residual acid value present in the carboxyl group of the component (A), and the acid value can be measured by the following method. First, after weighing about 1 g of the resin solution for measurement, 30 g of acetone was added to the resin solution to dissolve the resin solution uniformly. Next, an appropriate amount of phenolphthalein, an indicator drug, was added to the solution, and titration was performed using a 0.1 N aqueous KOH solution. And the acid value was calculated by the following formula. Formula: A=10×Vf×56.1/(Wp×I)

尚，上述式中，A表示酸價(mgKOH/g)，Vf表示KOH之滴定量(mL)，Wp表示測定樹脂溶液質量(g)，I表示測定樹脂溶液之不揮發分的比例(質量%)。Still, in the above formula, A represents the acid value (mgKOH/g), Vf represents the titration of KOH (mL), Wp represents the measured resin solution mass (g), and I represents the non-volatile matter ratio (mass %) of the measured resin solution. ).

於(A)成分之製造，從提昇保存安定性的觀點來看，環氧樹脂之環氧基的莫耳數、與不飽和羧酸與酸酐的合計之羧基之莫耳數的比，較佳為1：0.8～1.3的範圍，更佳為1：0.9～1.2的範圍。In the production of the component (A), from the viewpoint of improving storage stability, the ratio of the molar number of epoxy groups of the epoxy resin to the molar number of carboxyl groups in the sum of the unsaturated carboxylic acid and the acid anhydride is preferable. It is the range of 1:0.8-1.3, More preferably, it is the range of 1:0.9-1.2.

(A)成分從提昇鹼顯影性的觀點來看，將感光性樹脂組成物之固形分全體定為100質量%時，較佳為將其含量定為5質量%以上，更佳為定為10質量%以上，再更佳為定為15質量%以上。上限從提昇耐熱性或平均線膨脹率的觀點來看，較佳為定為35質量%以下，更佳為定為30質量%以下，再更佳為定為25質量%以下。Component (A) From the viewpoint of improving alkali developability, when the total solid content of the photosensitive resin composition is 100% by mass, the content is preferably 5% by mass or more, more preferably 10% by mass % by mass or more, more preferably 15% by mass or more. The upper limit is preferably set to 35 mass % or less, more preferably 30 mass % or less, and even more preferably 25 mass % or less, from the viewpoint of improving heat resistance or average linear expansion coefficient.

＜(B)平均粒徑為0.5μm以上2.5μm以下之無機填充材＞ 　　感光性樹脂組成物含有(B)平均粒徑為0.5μm以上2.5μm以下之無機填充材。藉由含有(B)成分，變成可提供可得到平均線熱膨脹率低之硬化物的感光性樹脂組成物。<(B) Inorganic filler having an average particle diameter of 0.5 μm or more and 2.5 μm or less> The photosensitive resin composition contains (B) an inorganic filler having an average particle diameter of 0.5 μm or more and 2.5 μm or less. By containing (B) component, it becomes the photosensitive resin composition which can provide the hardened|cured material with a low average linear thermal expansion coefficient.

無機填充材的材料雖並未特別限定，但例如可列舉二氧化矽、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、水鋁石、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、磷酸鋯及磷酸鎢酸鋯等。此等當中，特別適合二氧化矽。又，作為二氧化矽，較佳為球形二氧化矽。無機填充材可1種單獨使用，亦可組合2種以上使用。Although the material of the inorganic filler is not particularly limited, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, Diabsite, 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 , bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate and zirconium tungstate phosphate, etc. Among these, silica is particularly suitable. Moreover, as silica, spherical silica is preferable. The inorganic filler may be used alone or in combination of two or more.

無機填充材之平均粒徑為了得到平均線熱膨脹率低之硬化物，需要大量包含無機填充材，從其填充性的觀點來看，為0.5μm以上，較佳為0.8μm以上，更佳為1μm以上。該平均粒徑的上限從得到優異之解析性的觀點來看，為2.5μm以下，較佳為2μm以下，更佳為1.5μm以下，再更佳為1.3μm以下。作為具有如此平均粒徑之無機填充材的市售品，例如可列舉Admatex公司製「SC4050」、「Adma fine」、電氣化學工業公司製「SFP系列」、新日鐵住金材料公司製「SP(H)系列」、堺化學工業公司製「Sciqas系列」、日本觸媒公司製「Sea Hoster系列」、新日鐵住金材料公司製之「AZ系列」、「AX系列」、堺化學工業公司製之「B系列」、「BF系列」等。The average particle size of the inorganic fillers needs to contain a large amount of inorganic fillers in order to obtain a cured product with a low average coefficient of linear thermal expansion, and from the viewpoint of its fillability, it is 0.5 μm or more, preferably 0.8 μm or more, more preferably 1 μm above. The upper limit of the average particle diameter is 2.5 μm or less, preferably 2 μm or less, more preferably 1.5 μm or less, and even more preferably 1.3 μm or less, from the viewpoint of obtaining excellent analytical properties. Examples of commercially available inorganic fillers having such an average particle size include "SC4050" and "Adma fine" manufactured by Admatex, "SFP series" manufactured by Denki Chemical Industries, and "SP (SP)" manufactured by Nippon Steel & Sumitomo Metal Corporation. H) Series", "Sciqas Series" manufactured by Sakai Chemical Industry Co., Ltd., "Sea Hoster Series" manufactured by Nippon Shokubai Co., Ltd., "AZ Series", "AX Series" manufactured by Nippon Steel & Sumitomo Metal Materials Co., Ltd., and "AX Series" manufactured by Sakai Chemical Industry Co., Ltd. "B series", "BF series", etc.

無機填充材之平均粒徑可根據米氏(Mie)散射理論藉由雷射繞射･散射法測定。具體而言，可藉由由雷射繞射散射式粒度分布測定裝置，將無機填充材之粒度分布以體積基準作成，將其中位徑定為平均粒徑進行測定。測定樣品可優選使用將無機填充材藉由超音波而分散在甲基乙基酮中者。作為雷射繞射散射式粒度分布測定裝置，可使用堀場製作所公司製「LA-500」、島津製作所公司製「SALD-2200」等。The average particle size of the inorganic filler can be measured by the laser diffraction/scattering method according to the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction scattering particle size distribution measuring apparatus, and its locus diameter can be determined as an average particle size for measurement. As a measurement sample, what disperse|distributed the inorganic filler in methyl ethyl ketone by ultrasound can be preferably used. As a laser diffraction scattering particle size distribution measuring apparatus, "LA-500" manufactured by Horiba Corporation, "SALD-2200" manufactured by Shimadzu Corporation, and the like can be used.

無機填充材從提高耐濕性及分散性的觀點來看，較佳為以胺基矽烷系偶合劑、環氧基矽烷系偶合劑、巰基矽烷系偶合劑、矽烷系偶合劑、烷氧基矽烷化合物、有機矽氮烷化合物、鈦酸酯系偶合劑等之1種以上的表面處理劑處理。作為表面處理劑之市售品，例如可列舉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」(長鏈環氧基型矽烷偶合劑)等。From the viewpoint of improving moisture resistance and dispersibility, the inorganic filler is preferably an aminosilane-based coupling agent, an epoxy-based silane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, or an alkoxysilane-based coupling agent. Compounds, organosilazanes, titanate-based coupling agents, etc. are treated with one or more surface treatment agents. Examples of commercially available surface treatment agents include "KBM403" (3-glycidyloxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. oxysilane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. Silane), "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" manufactured by Shin-Etsu Chemical Co., Ltd. (Long-chain epoxy type silane coupling agent), etc.

無機填充材的含量，從得到平均線熱膨脹率低之硬化物的觀點來看，將感光性樹脂組成物中之不揮發成分定為100質量%時，為60質量%以上，較佳為61質量%以上，更佳為62質量%以上。上限從抑制光反射的觀點來看，為85質量%以下，較佳為80質量%以下，更佳為75質量%以下。The content of the inorganic filler is 60 mass % or more, preferably 61 mass %, when the non-volatile content in the photosensitive resin composition is 100 mass %, from the viewpoint of obtaining a cured product with a low average linear thermal expansion coefficient. % or more, more preferably 62 mass % or more. From the viewpoint of suppressing light reflection, the upper limit is 85% by mass or less, preferably 80% by mass or less, and more preferably 75% by mass or less.

＜(C)平均粒徑為0.7μm以上2.0μm以下之粒子，且含有一般式(1)或一般式(2)表示之磷化合物之粒子＞ 　　感光性樹脂組成物係含有(C)平均粒徑為0.7μm以上2.0μm以下之粒子，且含有一般式(1)或一般式(2)表示之磷化合物的粒子。

Figure 02_image007
(一般式(1)及一般式(2)中，n表示1或2)。<(C) Particles having an average particle diameter of 0.7 μm or more and 2.0 μm or less, and particles containing a phosphorus compound represented by general formula (1) or general formula (2)> The photosensitive resin composition contains (C) an average particle diameter The particles are particles of 0.7 μm or more and 2.0 μm or less, and contain the phosphorus compound represented by the general formula (1) or the general formula (2).
Figure 02_image007
(In general formula (1) and general formula (2), n represents 1 or 2).

一般式(1)及一般式(2)中，n表示1或2，較佳為2。為一般式(1)時，羥基較佳為與2位及5位鍵結。為一般式(2)時，羥基較佳為與2位及7位鍵結。In the general formula (1) and the general formula (2), n represents 1 or 2, preferably 2. In the case of the general formula (1), the hydroxyl group is preferably bonded to the 2-position and the 5-position. In the case of the general formula (2), the hydroxyl group is preferably bonded to the 2-position and the 7-position.

作為(C)成分，較佳為含有平均粒徑為0.7μm以上2.0μm以下之一般式(1)表示之磷化合物的粒子。As the component (C), particles containing a phosphorus compound represented by the general formula (1) having an average particle diameter of 0.7 μm or more and 2.0 μm or less are preferred.

如先述，由於含有磷之阻燃劑有溶劑溶解性貧乏，粗粒大，藉由酚性羥基等之阻聚效果，雖有貫孔形狀惡化，且得不到充分之感度的可能性，但本發明者們之努力研究的結果，藉由將含有磷化合物之粒子的平均粒徑定為0.7μm以上2.0μm以下，可保持阻聚效果與阻燃效果的平衡，其結果，變成可提供一種可得到阻燃性、解析性及抗裂性優異之硬化物的感光性樹脂組成物。又，於感光性樹脂組成物含有60質量%以上如(B)成分般平均粒徑較大之無機填充材時，雖有導致光反射解析性劣化的可能性，但藉由含有(C)成分，即使大量含有如(B)成分般平均粒徑較大之無機填充材，亦可抑制光反射，可提昇解析性。As mentioned above, the flame retardants containing phosphorus have poor solvent solubility and large coarse particles, and the through-hole shape may be deteriorated due to the polymerization inhibitory effect of phenolic hydroxyl groups, and a sufficient sensitivity may not be obtained. As a result of the diligent study of the present inventors, by setting the average particle diameter of the phosphorus compound-containing particles to be 0.7 μm or more and 2.0 μm or less, it is possible to maintain a balance between the polymerization inhibitory effect and the flame retardant effect, and as a result, it is possible to provide a A photosensitive resin composition that can obtain a cured product excellent in flame retardancy, resolution, and crack resistance. In addition, when the photosensitive resin composition contains 60% by mass or more of an inorganic filler having a large average particle size like the component (B), there is a possibility that the light reflection analysis performance is deteriorated. However, by containing the component (C) , Even if a large amount of inorganic fillers with a large average particle size such as the component (B) is contained, light reflection can be suppressed and resolution can be improved.

(C)成分之平均粒徑，從縮小比表面積，且抑制阻聚效果的觀點來看，為0.7μm以上，較佳為0.75μm以上，更佳為0.8μm以上。上限從提昇解析度的觀點來看，為2.0μm以下，較佳為1.7μm以下，更佳為1.6μm以下。(C)成分之平均粒徑可依後述之((C)成分之調製)的記載進行測定。The average particle diameter of the component (C) is 0.7 μm or more, preferably 0.75 μm or more, and more preferably 0.8 μm or more, from the viewpoint of reducing the specific surface area and suppressing the polymerization inhibitory effect. From the viewpoint of improving the resolution, the upper limit is 2.0 μm or less, preferably 1.7 μm or less, and more preferably 1.6 μm or less. The average particle diameter of the component (C) can be measured according to the description of (Preparation of the component (C)) described later.

(C)成分可使用市售品，例如可使用三光公司製之「HCA-HQ」、「HCA-HQ-HS」、「HCA=NQ」。(C) A commercially available product can be used, for example, "HCA-HQ", "HCA-HQ-HS", and "HCA=NQ" manufactured by Sanko Corporation can be used.

磷原子的含量從提昇阻燃性的觀點來看，將感光性樹脂組成物中之樹脂成分定為100質量%時，較佳為0.1質量%以上，更佳為0.13質量%以上，再更佳為0.15質量%以上。上限較佳為1質量%以下，更佳為0.8質量%以下，再更佳為0.5質量%以下。所謂「樹脂成分」，係指構成樹脂組成物之不揮發成分當中，去除(B)成分的成分。於此，所謂「磷原子的含量」，係於(C)成分中所包含之磷原子以外，亦包含去除(C)成分之(A)成分～(H)成分中所包含之磷原子的含量之概念。The content of phosphorus atoms is preferably 0.1 mass % or more, more preferably 0.13 mass % or more, even more preferably 100 mass % of the resin component in the photosensitive resin composition from the viewpoint of improving flame retardancy It is 0.15 mass % or more. The upper limit is preferably 1 mass % or less, more preferably 0.8 mass % or less, and still more preferably 0.5 mass % or less. The "resin component" refers to a component from which the (B) component is removed among the nonvolatile components constituting the resin composition. Here, the "content of phosphorus atoms" refers to the content of phosphorus atoms contained in components (A) to (H) excluding (C) components in addition to phosphorus atoms contained in component (C). concept.

(C)成分的含量從提昇解析性的觀點來看，將感光性樹脂組成物中之不揮發成分定為100質量%時，較佳為0.1質量%以上，更佳為0.5質量%以上，再更佳為1質量%以上。上限較佳為10質量%以下，更佳為5質量%以下，再更佳為3質量%以下。The content of the component (C) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, when the nonvolatile content in the photosensitive resin composition is 100% by mass, from the viewpoint of improving the analytical performance, and more preferably 0.5% by mass or more. More preferably, it is 1 mass % or more. The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less.

＜(D)光聚合起始劑＞ 　　感光性樹脂組成物係含有(D)光聚合起始劑。藉由含有(D)成分，可有效率地光硬化感光性樹脂組成物。<(D) Photopolymerization Initiator> The photosensitive resin composition contains (D) a photopolymerization initiator. By containing (D)component, the photosensitive resin composition can be photohardened efficiently.

(D)成分雖並未特別限制，但例如可列舉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-酮等之α-胺基烷基苯酮系光聚合起始劑；乙酮，1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-，1-(O-乙醯肟)等之肟酯系光聚合起始劑；二苯甲酮、甲基二苯甲酮、o-苯甲醯基苯甲酸、苯甲醯基乙基醚、2,2-二乙氧基苯乙酮、2,4-二乙基噻噸酮、二苯基-(2,4,6-三甲基苯甲醯基)氧化膦、乙基-(2,4,6-三甲基苯甲醯基)苯基亞膦酸酯(Phosphinate)、4,4’-雙(二乙基胺基)二苯甲酮、1-羥基-環己基-苯基酮、2,2-二甲氧基-1,2-二苯基乙烷-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基)-苯基膦氧化物等，又，亦可使用鋶鹽系光聚合起始劑等。此等可任1種單獨使用亦可併用2種以上。Although the component (D) is not particularly limited, for example, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino) Amino)-2-[(4-methylphenyl)methyl]-[4-(4-morphoyl)phenyl]-1-butanone, 2-methyl-1-[4-(methyl) Sulfanyl)phenyl]-2-morpholinopropan-1-one and other α-aminoalkylphenone series photopolymerization initiators; ethyl ketone, 1-[9-ethyl-6-(2- Oxime ester photopolymerization initiators such as methylbenzyl)-9H-carbazol-3-yl]-, 1-(O-acetoxime); Benzophenone, Methylbenzophenone , o-benzyl benzoic acid, benzyl ethyl ether, 2,2-diethoxyacetophenone, 2,4-diethylthioxanthone, diphenyl-(2,4, 6-Trimethylbenzyl)phosphine oxide, ethyl-(2,4,6-trimethylbenzyl)phenylphosphonite (Phosphinate), 4,4'-bis(diethyl) amino) benzophenone, 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-[4-(2 -Hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide etc., and a perylene salt-based photopolymerization initiator or the like can also be used. Any of these may be used alone or in combination of two or more.

進而，感光性樹脂組成物係與(D)成分組合，作為光聚合起始輔助劑，可包含N,N-二甲基胺基苯甲酸乙基酯、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、三乙醇胺等之第三級胺類，亦可包含如吡唑啉(Pyrazoline)類、蔥類、香豆素類、呫噸類、噻噸酮類等之光增感劑。此等可任1種單獨使用亦可併用2種以上。Furthermore, the photosensitive resin composition may contain N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzene as a photopolymerization initiation adjuvant in combination with the component (D). Tertiary amines such as isoamyl formate, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine, etc. can also include pyrazoline, onion, Photosensitizers of coumarin, xanthene, thioxanthone, etc. Any of these may be used alone or in combination of two or more.

作為(D)成分之具體例，可列舉IGM公司製之「Omnirad907」、「Omnirad369」、「Omnirad379」、「Omnirad819」、「OmniradTPO」、BASF公司製之「IrgacureOXE-01」、「IrgacureOXE-02」、ADEKA公司製之「N-1919」等。Specific examples of the component (D) include "Omnirad907", "Omnirad369", "Omnirad379", "Omnirad819", "OmniradTPO" manufactured by IGM Corporation, "IrgacureOXE-01" and "IrgacureOXE-02" manufactured by BASF Corporation , "N-1919" manufactured by ADEKA Corporation, etc.

(D)成分的含量從充分光硬化感光性樹脂組成物，提昇絕緣信賴性的觀點來看，將感光性樹脂組成物之固形分全體定為100質量%時，較佳為0.01質量%以上，更佳為0.03質量%以上，再更佳為0.05質量%以上。另一方面，從抑制因感度過多導致解析性降低的觀點來看，上限較佳為1質量%以下，更佳為0.5質量%以下，再更佳為0.1質量%以下。The content of the component (D) is preferably 0.01 mass % or more when the total solid content of the photosensitive resin composition is 100 mass % from the viewpoint of sufficiently photocuring the photosensitive resin composition and improving the insulation reliability, More preferably, it is 0.03 mass % or more, and still more preferably 0.05 mass % or more. On the other hand, the upper limit is preferably 1 mass % or less, more preferably 0.5 mass % or less, and even more preferably 0.1 mass % or less, from the viewpoint of suppressing a decrease in resolution due to excessive sensitivity.

＜(E)環氧樹脂＞ 　　感光性樹脂組成物係含有(E)環氧樹脂。藉由含有(E)成分，可提昇絕緣信賴性。惟，於此所謂(E)成分係未包含含有乙烯性不飽和基及羧基之環氧樹脂。<(E) Epoxy resin> The photosensitive resin composition contains (E) epoxy resin. Insulation reliability can be improved by containing (E) component. However, the said (E) component here does not contain the epoxy resin containing an ethylenically unsaturated group and a carboxyl group.

作為(E)成分，例如可列舉雙酚AF型環氧樹脂及全氟烷基型環氧樹脂等之含有氟之環氧樹脂；雙酚A型環氧樹脂；雙酚F型環氧樹脂；雙酚S型環氧樹脂；聯二甲酚型環氧樹脂；雙環戊二烯型環氧樹脂；參酚型環氧樹脂；萘酚酚醛清漆型環氧樹脂；酚酚醛清漆型環氧樹脂；tert-丁基-鄰苯二酚型環氧樹脂；萘型環氧樹脂；萘酚型環氧樹脂；蔥型環氧樹脂；縮水甘油基胺型環氧樹脂；縮水甘油基酯型環氧樹脂；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；具有丁二烯構造之環氧樹脂；脂環式環氧樹脂、具有酯骨架之脂環式環氧樹脂；雜環式環氧樹脂；含有螺環之環氧樹脂；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；四苯基乙烷型環氧樹脂、鹵素化環氧樹脂等，從提昇密著性的觀點來看，較佳為雙酚F型環氧樹脂、聯苯型環氧樹脂，更佳為聯苯型環氧樹脂。又，從提昇耐熱性的觀點來看，較佳為萘型環氧樹脂、萘酚型環氧樹脂、蔥型環氧樹脂、伸萘基醚型環氧樹脂、四苯基乙烷型環氧樹脂，更佳為四苯基乙烷型環氧樹脂。環氧樹脂可1種單獨使用，亦可組合2種以上使用。(E)成分從提昇密著性及耐熱性的觀點來看，較佳為含有聯苯型環氧樹脂及四苯基乙烷型環氧樹脂之至少任一種。As the component (E), for example, fluorine-containing epoxy resins such as bisphenol AF type epoxy resins and perfluoroalkyl type epoxy resins; bisphenol A type epoxy resins; bisphenol F type epoxy resins; Bisphenol S type epoxy resin; Bixylenol type epoxy resin; Dicyclopentadiene type epoxy resin; Samphenol type epoxy resin; Naphthol novolac type epoxy resin; Phenol novolak type epoxy resin; tert-butyl-catechol type epoxy resin; naphthalene type epoxy resin; naphthol type epoxy resin; onion type epoxy resin; glycidyl amine type epoxy resin; glycidyl ester type epoxy resin ;Cresol novolac type epoxy resin; Biphenyl type epoxy resin; Linear aliphatic epoxy resin; Epoxy resin with butadiene structure; Alicyclic epoxy resin, alicyclic ring with ester skeleton Oxygen resin; heterocyclic epoxy resin; epoxy resin containing spiro ring; cyclohexane dimethanol type epoxy resin; naphthylene ether type epoxy resin; trimethylol type epoxy resin; tetraphenylethyl ether Alkyl-type epoxy resins, halogenated epoxy resins, and the like are preferably bisphenol F-type epoxy resins, biphenyl-type epoxy resins, and more preferably biphenyl-type epoxy resins from the viewpoint of improving adhesion . Also, from the viewpoint of improving heat resistance, naphthalene-type epoxy resins, naphthol-type epoxy resins, onion-type epoxy resins, naphthylene ether-type epoxy resins, and tetraphenylethane-type epoxy resins are preferred. The resin, more preferably a tetraphenylethane type epoxy resin. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types. (E) It is preferable that a component contains at least any one of a biphenyl type epoxy resin and a tetraphenylethane type epoxy resin from a viewpoint of improving adhesiveness and heat resistance.

環氧樹脂較佳為包含於1分子中具有2個以上環氧基之環氧樹脂。將環氧樹脂之不揮發成分定為100質量%時，較佳為至少50質量%以上為於1分子中具有2個以上環氧基之環氧樹脂。作為(E)成分，可併用2個以上環氧樹脂。The epoxy resin is preferably contained in an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile content of the epoxy resin is defined as 100% by mass, it is preferably at least 50% by mass or more of an epoxy resin having two or more epoxy groups in one molecule. As the component (E), two or more epoxy resins can be used in combination.

作為環氧樹脂之具體例，可列舉DIC公司製之「HP4032」、「HP4032D」、「HP4032SS」、「HP4032H」(萘型環氧樹脂)、三菱化學公司製之「828US」、「jER828EL」(雙酚A型環氧樹脂)、「jER807」(雙酚F型環氧樹脂)、「jER152」(酚酚醛清漆型環氧樹脂)、「630」、「630LSD」(縮水甘油基胺型環氧樹脂)、新日鐵住金化學公司製之「ZX1059」(雙酚A型環氧樹脂與雙酚F型環氧樹脂之混合品)、新日鐵住金化學公司製之「YD-8125G」(雙酚A型環氧樹脂)、Nagase ChemteX公司製之「EX-721」(縮水甘油基酯型環氧樹脂)、Daicel公司製之「Celloxide 2021P」(具有酯骨架之脂環式環氧樹脂)、「PB-3600」(具有丁二烯構造之環氧樹脂)、新日鐵住金化學公司製之「ZX1658」、「ZX1658GS」(液狀1,4-縮水甘油基環己烷)、三菱化學公司製之「630LSD」(縮水甘油基胺型環氧樹脂)、大金工業公司製之「E-7432」、「E-7632」(全氟烷基型環氧樹脂)、DIC公司製之「HP-4700」、「HP-4710」(萘型4官能環氧樹脂)、「N-690」(甲酚酚醛清漆型環氧樹脂)、「N-695」(甲酚酚醛清漆型環氧樹脂)、「HP-7200」、「HP-7200HH」、「HP-7200H」(雙環戊二烯型環氧樹脂)、「EXA-7311」、「EXA-7311-G3」、「EXA-7311-G4」、「EXA-7311-G4S」、「HP6000」(伸萘基醚型環氧樹脂)、日本化藥公司製之「EPPN-502H」(參酚型環氧樹脂)、「NC7000L」(萘酚酚醛清漆型環氧樹脂)、「NC3000H」、「NC3000」、「NC3000L」、「NC3100」(聯苯型環氧樹脂)、新日鐵住金化學公司製之「ESN475V」(萘型環氧樹脂)、「ESN485」(萘酚酚醛清漆型環氧樹脂)、「YSLV-80XY」(四甲基雙酚F型環氧樹脂)、三菱化學公司製之「YX4000H」、「YL6121」(聯苯型環氧樹脂)、「YX4000HK」(聯二甲酚型環氧樹脂)、「YX8800」(蔥型環氧樹脂)、大阪Gas Chemicals公司製之「PG-100」、「CG-500」、三菱化學公司製之「YL7800」(茀型環氧樹脂)、三菱化學公司製之「1010」(固體狀雙酚A型環氧樹脂)、「1031S」(四苯基乙烷型環氧樹脂)、「YL7760」(雙酚AF型環氧樹脂)等。Specific examples of epoxy resins include "HP4032", "HP4032D", "HP4032SS", "HP4032H" (naphthalene-type epoxy resins) manufactured by DIC Corporation, "828US" and "jER828EL" manufactured by Mitsubishi Chemical Corporation ( Bisphenol A epoxy resin), "jER807" (bisphenol F epoxy resin), "jER152" (phenol novolac epoxy resin), "630", "630LSD" (glycidyl amine epoxy resin) resin), "ZX1059" (a mixture of bisphenol A epoxy resin and bisphenol F epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., "YD-8125G" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. (double Phenol A epoxy resin), "EX-721" (glycidyl ester epoxy resin) manufactured by Nagase ChemteX, "Celloxide 2021P" (alicyclic epoxy resin with ester skeleton) manufactured by Daicel, "PB-3600" (epoxy resin with butadiene structure), "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., Mitsubishi Chemical Corporation "630LSD" (glycidyl amine type epoxy resin) manufactured by Daikin Industries, "E-7432", "E-7632" (perfluoroalkyl type epoxy resin) manufactured by DIC Corporation, "HP" manufactured by DIC Corporation -4700", "HP-4710" (naphthalene type 4-functional epoxy resin), "N-690" (cresol novolac type epoxy resin), "N-695" (cresol novolak type epoxy resin) , "HP-7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene epoxy resin), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4" , "EXA-7311-G4S", "HP6000" (naphthyl ether type epoxy resin), "EPPN-502H" (Shenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., "NC7000L" (naphthol novolac) Varnish type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475V" (naphthalene type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., "ESN485" (naphthol novolac type epoxy resin), "YSLV-80XY" (tetramethylbisphenol F type epoxy resin), "YX4000H", "YL6121" (biphenyl type epoxy resin manufactured by Mitsubishi Chemical Corporation) resin), "YX4000HK" (bixylenol-type epoxy resin), "YX8800" (onion-type epoxy resin), "PG-100", "CG-500" manufactured by Osaka Gas Chemicals Co., Ltd., manufactured by Mitsubishi Chemical Corporation "YL7800" (Fu-type epoxy resin), "1010" (solid two-phase resin) manufactured by Mitsubishi Chemical Corporation Phenol A type epoxy resin), "1031S" (tetraphenylethane type epoxy resin), "YL7760" (bisphenol AF type epoxy resin), etc.

(E)成分的含量從得到顯示良好之拉伸破壞強度、絕緣信賴性之絕緣層的觀點來看，將感光性樹脂組成物之固形分全體定為100質量%時，較佳為1質量%以上，更佳為5質量%以上，再更佳為10質量%以上。環氧樹脂的含量之上限，雖只要能發揮本發明的效果則並未特別限定，但較佳為25質量%以下，更佳為20質量%以下，再更佳為15質量%以下。The content of the component (E) is preferably 1 mass % when the total solid content of the photosensitive resin composition is 100 mass % from the viewpoint of obtaining an insulating layer exhibiting good tensile rupture strength and insulation reliability. Above, more preferably 5 mass % or more, still more preferably 10 mass % or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effects of the present invention can be exhibited, but is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.

環氧樹脂之環氧基當量較佳為50～5000，更佳為50～3000，再更佳為80～2000，又再更佳為110～1000。藉由成為此範圍，感光性樹脂組成物之硬化物的交聯密度變充分可帶來表面粗糙度小之絕緣層。尚，環氧基當量可依JIS K7236測定，係包含1當量之環氧基的樹脂的質量。The epoxy group equivalent of the epoxy resin is preferably 50-5000, more preferably 50-3000, still more preferably 80-2000, still more preferably 110-1000. By making it into this range, the crosslinking density of the hardened|cured material of the photosensitive resin composition becomes sufficient, and an insulating layer with small surface roughness can be provided. Furthermore, the epoxy group equivalent can be measured according to JIS K7236, and is the mass of the resin containing 1 equivalent of epoxy groups.

環氧樹脂之重量平均分子量較佳為100～5000，更佳為250～3000，再更佳為400～1500。於此，環氧樹脂之重量平均分子量係藉由凝膠滲透層析(GPC)法所測定之聚苯乙烯換算的重量平均分子量。The weight-average molecular weight of the epoxy resin is preferably 100-5000, more preferably 250-3000, still more preferably 400-1500. Here, the weight average molecular weight of the epoxy resin is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

＜(F)反應性稀釋劑＞ 　　感光性樹脂組成物可進一步含有(F)反應性稀釋劑。藉由含有(F)成分，可提昇光反應性。作為(F)成分，例如可使用於1分子中具有1個以上(甲基)丙烯醯基之於室溫為液體、固體或半固形之感光性(甲基)丙烯酸酯化合物。所謂室溫係表示25℃左右。所謂「(甲基)丙烯醯基」，係指丙烯醯基及甲基丙烯醯基。<(F) Reactive diluent> The photosensitive resin composition may further contain (F) reactive diluent. By containing (F) component, photoreactivity can be improved. As the component (F), for example, it can be used for a photosensitive (meth)acrylate compound having one or more (meth)acryloyl groups in one molecule and being liquid, solid, or semi-solid at room temperature. The so-called room temperature means about 25°C. The "(meth)acryloyl group" refers to an acryl group and a methacryloyl group.

作為代表性之感光性(甲基)丙烯酸酯化合物，例如可列舉2-羥基乙基丙烯酸酯、2-羥基丁基丙烯酸酯等之羥基烷基丙烯酸酯類、乙二醇、甲氧基四乙二醇、聚乙二醇、丙二醇等之甘醇之單或二丙烯酸酯類、N,N-二甲基丙烯醯胺、N-羥甲基丙烯醯胺等之丙烯醯胺類、N,N-二甲基胺基乙基丙烯酸酯等之胺基烷基丙烯酸酯類、三羥甲基丙烷、季戊四醇、二季戊四醇等之多價醇或此等之氧化乙烯、氧化丙烯或ε-己內酯之加成物之多價丙烯酸酯類、苯氧基丙烯酸酯、苯氧基乙基丙烯酸酯等酚類或其氧化乙烯或氧化丙烯加成物等之丙烯酸酯類、三羥甲基丙烷三縮水甘油基醚等之由縮水甘油基醚所衍生之環氧基丙烯酸酯類、三聚氰胺丙烯酸酯類及/或對應上述之丙烯酸酯之甲基丙烯酸酯類等。此等當中，較佳為多價丙烯酸酯類或多價甲基丙烯酸酯類，例如作為3價之丙烯酸酯類或甲基丙烯酸酯類，可列舉三羥甲基丙烷三(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、四糠基醇寡(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、四羥甲基甲烷四(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、N,N,N',N'-肆(β-羥基乙基)乙基二胺之(甲基)丙烯酸酯等，作為3價以上之丙烯酸酯類或甲基丙烯酸酯類，可列舉三(2-(甲基)丙烯醯氧基乙基)磷酸鹽、三(2-(甲基)丙烯醯氧基丙基)磷酸鹽、三(3-(甲基)丙烯醯氧基丙基)磷酸鹽、三(3-(甲基)丙烯醯基-2-羥基氧基丙基)磷酸鹽、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)磷酸鹽、(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)磷酸鹽等之磷酸三酯(甲基)丙烯酸酯。此等感光性(甲基)丙烯酸酯化合物可任1種單獨使用亦可併用2種以上。Examples of typical photosensitive (meth)acrylate compounds include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate, ethylene glycol, and methoxytetraethyl acrylate. Mono- or diacrylates of glycols such as glycol, polyethylene glycol, propylene glycol, etc., acrylamides such as N,N-dimethylacrylamide, N-methylol acrylamide, N,N - Amino alkyl acrylates such as dimethylaminoethyl acrylate, polyvalent alcohols such as trimethylolpropane, pentaerythritol, dipentaerythritol, or such ethylene oxide, propylene oxide or ε-caprolactone Polyvalent acrylates of adducts, phenols such as phenoxyacrylates, phenoxyethylacrylates, or acrylates such as ethylene oxide or propylene oxide adducts, trimethylolpropane triglycerides Epoxy acrylates derived from glycidyl ethers such as glyceryl ethers, melamine acrylates and/or methacrylates corresponding to the above acrylates, and the like. Among these, polyvalent acrylates or polyvalent methacrylates are preferred, and examples of 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 Oligo(meth)acrylate, ethylcarbitol oligo(meth)acrylate, 1,4-butanediol oligo(meth)acrylate, 1,6-hexanediol oligo(meth)acrylate ester, trimethylolpropane oligo(meth)acrylate, pentaerythritol oligo(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, N,N ,N',N'-(β-hydroxyethyl)ethyldiamine (meth)acrylate, etc. Tris(2-( Meth)acryloyloxyethyl)phosphate, tris(2-(meth)acryloyloxypropyl)phosphate, tris(3-(meth)acryloyloxypropyl)phosphate, tris(2-(meth)acryloyloxypropyl)phosphate (3-(meth)acryloyl-2-hydroxyoxypropyl)phosphate, bis(3-(meth)acryloyl-2-hydroxyoxypropyl)(2-(meth)propene) Phosphate triesters such as acyloxyethyl)phosphate, (3-(meth)acryloyl-2-hydroxyoxypropyl)bis(2-(meth)acryloyloxyethyl)phosphate, etc. (Meth)acrylate. These photosensitive (meth)acrylate compounds may be used alone or in combination of two or more.

摻合(F)成分時的含量，從促進光硬化，且抑制成為硬化物時之沾黏的觀點來看，將感光性樹脂組成物之固形分全體定為100質量%時，較佳為0.5質量%～10質量%，更佳為2質量%～8質量%。The content at the time of blending the component (F) is preferably 0.5 when the total solid content of the photosensitive resin composition is 100% by mass from the viewpoint of promoting photocuring and suppressing sticking when the cured product is formed. % by mass to 10% by mass, more preferably 2% by mass to 8% by mass.

＜(G)有機溶劑＞ 　　感光性樹脂組成物可進一步含有(G)有機溶劑。藉由含有(G)成分，可調整清漆黏度。作為(G)有機溶劑，例如可列舉乙基甲基酮、環己酮等之酮類、甲苯、二甲苯、四甲基苯等之芳香族烴類、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之甘醇醚類、乙酸乙酯、乙酸丁酯、丁基溶纖劑乙酸酯、卡必醇乙酸酯、乙基二甘醇乙酸酯等之酯類、辛烷、癸烷等之脂肪族烴類、石油醚、石腦油、氫化石腦油、溶劑石腦油等之石油系溶劑等。此等可1種單獨或組合2種以上使用。使用有機溶劑時的含量，可從感光性樹脂組成物之塗佈性的觀點來適當調整。<(G) Organic solvent> The photosensitive resin composition may further contain (G) an organic solvent. The viscosity of the varnish can be adjusted by containing the component (G). Examples of the organic solvent (G) include ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethyl benzene, methyl cellosolve, butyl cellosolve, Glycol ethers such as methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, etc., ethyl acetate , butyl acetate, butyl cellosolve acetate, carbitol acetate, ethyl diethylene glycol acetate and other esters, octane, decane and other aliphatic hydrocarbons, petroleum ether, naphtha , Hydrogenated naphtha, solvent naphtha and other petroleum-based solvents. These can be used alone or in combination of two or more. The content in the case of using an organic solvent can be appropriately adjusted from the viewpoint of coatability of the photosensitive resin composition.

＜(H)其他添加劑＞ 　　感光性樹脂組成物於不阻礙本發明之目的的程度，可進一步含有(H)其他添加劑。作為(H)其他添加劑，例如可添加熱塑性樹脂、有機填充材、三聚氰胺、有機膨潤土等之微粒子、酞菁藍、酞菁綠、碘綠、重氮黃、結晶紫、氧化鈦、碳黑、萘黑等之著色劑、氫醌、吩噻嗪、甲基氫醌、氫醌單甲基醚、鄰苯二酚、鄰苯三酚等之阻聚劑、本頓、蒙脫石等之增黏劑、聚矽氧系、氟系、乙烯樹脂系之消泡劑、溴化環氧基化合物、酸改質溴化環氧基化合物、銻化合物、(C)成分以外之磷系化合物、芳香族縮合磷酸酯、含鹵素縮合磷酸酯等之阻燃劑、酚系硬化劑、氰酸酯系硬化劑等之熱硬化樹脂、等之各種添加劑。<(H) Other additives> The photosensitive resin composition may further contain (H) other additives to such an extent that the object of the present invention is not inhibited. As other additives (H), for example, thermoplastic resins, organic fillers, melamine, fine particles of organobentonite, phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, naphthalene can be added. Colorants such as black, hydroquinone, phenothiazine, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, etc. polymerization inhibitor, Benton, montmorillonite, etc. Agents, polysiloxane-based, fluorine-based, and vinyl-based defoaming agents, brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphorus-based compounds other than (C), and aromatic compounds Flame retardants such as condensed phosphate esters, halogen-containing condensed phosphate esters, etc., phenol-based hardeners, thermosetting resins such as cyanate-based hardeners, and various additives.

感光性樹脂組成物可藉由混合上述(A)～(E)成分作為必須成分，適當混合上述(F)～(H)成分作為任意成分，又，如有必要藉由三輥，球磨機，珠磨機，砂磨機等之混練手段或超級混合機、行星型混合機等之攪拌手段進行混練或攪拌，作為樹脂清漆製造。The photosensitive resin composition can be prepared by mixing the above-mentioned components (A) to (E) as essential components, and appropriately mixing the above-mentioned components (F) to (H) as optional components. Kneading or stirring with kneading means such as mills, sand mills, etc., or stirring means such as super mixers and planetary mixers, is produced as a resin varnish.

＜感光性樹脂組成物之物性、用途＞ 　　將本發明之感光性樹脂組成物於190℃熱硬化90分鐘之硬化物，顯示阻燃性優異之特性。即，帶來阻燃性優異之絕緣層及阻焊劑。阻燃性在UL-94V試驗，較佳為「V0」或較其更優異。阻燃性之評估可依照後述之＜阻燃性之評估＞所記載之方法進行測定。<Physical Properties and Uses of Photosensitive Resin Composition> The cured product obtained by thermally curing the photosensitive resin composition of the present invention at 190° C. for 90 minutes exhibits excellent flame retardancy. That is, an insulating layer and a solder resist excellent in flame retardancy are provided. In the UL-94V test, the flame retardancy is preferably "V0" or more excellent. The evaluation of flame retardancy can be measured according to the method described in <Evaluation of flame retardancy> mentioned later.

將本發明之感光性樹脂組成物以190℃熱硬化90分鐘之硬化物，顯示平均線熱膨脹率低之特性。即，帶來平均線熱膨脹率低之絕緣層及阻焊劑。平均線熱膨脹率較佳為50ppm以下，更佳為49ppm以下，再更佳為48ppm以下、40ppm以下。下限雖並未特別限定但可成為0.1ppm以上等。平均線熱膨脹率的測定可依照後述之＜平均線膨脹率及玻璃轉移溫度的測定＞所記載之方法測定。The cured product obtained by thermally curing the photosensitive resin composition of the present invention at 190° C. for 90 minutes exhibits a low average linear thermal expansion coefficient. That is, an insulating layer and a solder resist having a low average linear thermal expansion coefficient are provided. The average linear thermal expansion coefficient is preferably 50 ppm or less, more preferably 49 ppm or less, still more preferably 48 ppm or less, and 40 ppm or less. Although the lower limit is not particularly limited, it may be 0.1 ppm or more. The measurement of the average coefficient of linear thermal expansion can be carried out according to the method described in the below-mentioned <Measurement of the average coefficient of linear expansion and glass transition temperature>.

將本發明之感光性樹脂組成物以190℃熱硬化90分鐘之硬化物，顯示玻璃轉移溫度高之特性。即，由於玻璃轉移溫度高帶來耐熱性優異之絕緣層及阻焊劑。玻璃轉移溫度較佳為140℃以上，更佳為145℃以上，再更佳為150℃以上、170℃以上。上限雖並未特別限定，但可成為300℃以下等。玻璃轉移溫度的測定可依照後述之＜平均線膨脹率及玻璃轉移溫度的測定＞所記載之方法測定。The cured product of the photosensitive resin composition of the present invention was thermally cured at 190° C. for 90 minutes, showing the characteristic of high glass transition temperature. That is, since the glass transition temperature is high, the insulating layer and solder resist excellent in heat resistance are obtained. The glass transition temperature is preferably 140°C or higher, more preferably 145°C or higher, still more preferably 150°C or higher, and 170°C or higher. The upper limit is not particularly limited, but may be 300° C. or lower. The glass transition temperature can be measured in accordance with the method described in <Measuring of Average Linear Expansion and Glass Transition Temperature> described later.

本發明之感光性樹脂組成物由於含有(C)成分，即使(B)成分的含量多，亦顯示解析性優異之特性。因此，無殘渣之最小貫孔徑較佳為100μm以下，更佳為90μm以下，再更佳為80μm以下、70μm以下。下限雖並未特別限定，但可成為0.1μm以上等。又，由於解析性優異，於L/S(線/空間)之間不存在樹脂裝填或剝離。最小之L/S較佳為80μm/80μm以下，更佳為70μm/70μm以下，再更佳為60μm/60μm以下。下限雖並未特別限定，但可成為1μm/1μm以上等。解析性的評估可依照後述之＜解析性及抗裂性的評估＞所記載之方法評估。Since the photosensitive resin composition of this invention contains (C)component, even if content of (B)component is large, it shows the characteristic which is excellent in analytical property. Therefore, the minimum through hole diameter without residue is preferably 100 μm or less, more preferably 90 μm or less, still more preferably 80 μm or less, and 70 μm or less. The lower limit is not particularly limited, but may be 0.1 μm or more. In addition, since it is excellent in resolution, there is no resin filling or peeling between L/S (line/space). The minimum L/S is preferably 80 μm/80 μm or less, more preferably 70 μm/70 μm or less, and still more preferably 60 μm/60 μm or less. The lower limit is not particularly limited, but may be 1 μm/1 μm or more. Analytical evaluation can be performed according to the method described in the below-mentioned <Evaluation of Analytical Properties and Crack Resistance>.

將本發明之感光性樹脂組成物以190℃熱硬化90分鐘之硬化物，顯示抗裂性優異之特性。即，帶來抗裂性優異之絕緣層及阻焊劑。即使重複500次-65℃與150℃之間的昇溫試驗，亦未觀察到裂紋及剝離。抗裂性的評估可依照後述之＜解析性及抗裂性的評估＞所記載之方法評估。The cured product obtained by thermally curing the photosensitive resin composition of the present invention at 190° C. for 90 minutes exhibits excellent crack resistance. That is, an insulating layer and a solder resist excellent in crack resistance are provided. Even if the temperature rise test between -65°C and 150°C was repeated 500 times, cracks and peeling were not observed. The evaluation of crack resistance can be performed according to the method described in the later-mentioned <Evaluation of Analytical Properties and Crack Resistance>.

本發明之感光性樹脂組成物的用途雖並未特別限定，但可使用在感光性薄膜、附支持體之感光性薄膜、預浸料等之絕緣樹脂薄片、電路基板(層合板用途、多層印刷電路板用途等)、阻焊劑、底層填充材料，芯片黏結材料、半導體密封材、填充樹脂、零件嵌入樹脂等、感光性樹脂組成物成為必要之用途的廣泛範圍。其中，可適合作為印刷電路板之絕緣層用感光性樹脂組成物(將感光性樹脂組成物之硬化物作為絕緣層之印刷電路板)、層間絕緣層用感光性樹脂組成物(將感光性樹脂組成物之硬化物作為層間絕緣層之印刷電路板)、鍍敷形成用感光性樹脂組成物(鍍敷在感光性樹脂組成物之硬化物上所形成之印刷電路板)及阻焊劑用感光性樹脂組成物(將感光性樹脂組成物之硬化物作為阻焊劑之印刷電路板)使用。Although the application of the photosensitive resin composition of the present invention is not particularly limited, it can be used in photosensitive films, photosensitive films with supports, insulating resin sheets such as prepregs, circuit boards (for laminates, multilayer printing) Circuit board applications, etc.), solder resists, underfill materials, die attach materials, semiconductor sealing materials, filling resins, parts embedding resins, etc., photosensitive resin compositions are required in a wide range of applications. Among them, photosensitive resin compositions for insulating layers of printed wiring boards (printed wiring boards using a cured product of the photosensitive resin composition as insulating layers), photosensitive resin compositions for interlayer insulating layers (photosensitive resin compositions for insulating layers) The cured product of the composition is used as a printed circuit board for an interlayer insulating layer), a photosensitive resin composition for plating formation (a printed circuit board formed by plating on the cured product of the photosensitive resin composition), and a photosensitive resin for solder resist. Resin composition (printed wiring board using the cured product of the photosensitive resin composition as a solder resist) is used.

[感光性薄膜] 　　本發明之感光性樹脂組成物可藉由以樹脂清漆狀態塗佈在支持基板上，使有機溶劑乾燥，形成感光性樹脂組成物層，而成為感光性薄膜。又，亦可預先將形成在支持體上之感光性薄膜層合在支持基板使用。感光性薄膜可層合在各式各樣的支持基板。作為支持基板，主要可列舉玻璃環氧基板、金屬基板、聚酯基板、聚醯亞胺基板、BT樹脂基板、熱硬化型聚伸苯基醚基板等之基板。[Photosensitive film] The photosensitive resin composition of the present invention can be formed into a photosensitive film by coating it on a support substrate in a resin varnish state, drying the organic solvent, and forming a photosensitive resin composition layer. In addition, the photosensitive thin film formed on the support may be laminated on the support substrate in advance and used. The photosensitive film can be laminated on various support substrates. As the support substrate, substrates such as glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates are mainly used.

[附支持體之感光性薄膜] 　　本發明之感光性樹脂組成物，可適合以感光性樹脂組成物層層形成在支持體上之附支持體之感光性薄膜的形態使用。亦即，附支持體之感光性薄膜，包含支持體、與設置在該支持體上之以本發明之感光性樹脂組成物所形成之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 the photosensitive resin composition is formed layer by layer on the 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.

作為支持體，例如可列舉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，尤其是以聚對苯二甲酸乙二酯薄膜較佳。Examples of the support include a polyethylene terephthalate film, a polyethylene naphthalate film, a polypropylene film, a polyethylene film, a polyvinyl alcohol film, a triacetate film, and the like, especially A polyethylene terephthalate film is preferred.

作為市售之支持體，例如雖可列舉王子製紙公司製之製品名「Alfan MA-410」、「E-200C」、信越薄膜公司製等之聚丙烯薄膜、帝人公司製之製品名「PS-25」等之PS系列等之聚對苯二甲酸乙二酯薄膜等，但並非被限定於此等。此等之支持體由於感光性樹脂組成物層的去除變容易，將如聚矽氧塗佈劑之剝離劑塗佈在表面即可。支持體的厚度較佳為5μm～50μm的範圍，更佳為10μm～25μm的範圍。藉由將厚度定為5μm以上，可抑制進行顯影前於支持體剝離時破壞支持體，藉由將厚度定為50μm以下，可提昇從支持體上進行曝光時之解析度。又，較佳為低魚眼(Fish eye)之支持體。於此所謂魚眼，係熱熔融材料，且藉由混練、擠出、2軸拉延、澆鑄法等製造薄膜時，材料之異物、未溶解物、氧化劣化物等被帶入薄膜中者。Examples of commercially available supports include "Alfan MA-410" and "E-200C" manufactured by Oji Paper Co., Ltd., polypropylene films manufactured by Shin-Etsu Film Co., Ltd., and "PS-200C" manufactured by Teijin Corporation. Polyethylene terephthalate films such as PS series such as 25", etc., etc., are not limited to these. Since the removal of the photosensitive resin composition layer becomes easy for these supports, a release agent such as a polysiloxane coating agent may be applied on the surface. 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, breakage of the support when the support is peeled off before development can be suppressed, and by setting the thickness to 50 μm or less, the resolution at the time of exposure from the support can be improved. Moreover, it is preferable that it is a low fish-eye support. The so-called fisheye here refers to a material that is hot-melted, and foreign matter, undissolved matter, oxidatively degraded matter, etc. of the material are brought into the film when the film is produced by kneading, extrusion, biaxial drawing, casting, or the like.

又，由於減低因紫外線等之活性能量線導致曝光時之光的散射，故支持體較佳為透明性優異者。支持體具體而言，較佳為成為透明性指標之濁度(以JIS K6714規格化而成之霧值)為0.1～5者。進而，感光性樹脂組成物層可以保護薄膜保護。Moreover, in order to reduce the scattering of light at the time of exposure by active energy rays, such as an ultraviolet-ray, it is preferable that a support is excellent in transparency. Specifically, it is preferable that the turbidity (a haze value standardized according to JIS K6714), which is an index of transparency, is 0.1 to 5 for the support. Furthermore, the photosensitive resin composition layer can protect the protective film.

藉由將附支持體之感光性薄膜之感光性樹脂組成物層側以保護薄膜進行保護，可防止對感光性樹脂組成物層表面之髒污等之附著或傷痕。作為保護薄膜，可使用藉由死與上述之支持體相同之材料所構成之薄膜。保護薄膜的厚度雖並未特別限定，但較佳為1μm～40μm的範圍，更佳為5μm～30μm的範圍，再更佳為10μm～30μm的範圍。藉由將厚度定為1μm以上，可提昇保護薄膜之操作性，藉由成為40μm以下，有廉價性變好的傾向。尚，保護薄膜相對於感光性樹脂組成物層與支持體的接著力，較佳為感光性樹脂組成物層與保護薄膜之接著力較小者。By protecting the photosensitive resin composition layer side of the support-attached photosensitive film with a protective film, it is possible to prevent adhesion or scratches such as dirt on the surface of the photosensitive resin composition layer. 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 even more preferably in the range of 10 μm to 30 μm. By setting the thickness to be 1 μm or more, the handleability of the protective film can be improved, and by setting the thickness to 40 μm or less, the low cost tends to be improved. Furthermore, the adhesive force of the protective film with respect to the photosensitive resin composition layer and the support is preferably the one with the smaller adhesive force between the photosensitive resin composition layer and the protective film.

本發明之附支持體之感光性薄膜，對本發明領域具有通常知識者而言，依照周知之方法，例如可藉由調製將本發明之感光性樹脂組成物溶解在有機溶劑之樹脂清漆，於支持體上塗佈此樹脂清漆，藉由加熱或熱風吹附等使有機溶劑乾燥，形成感光性樹脂組成物層來製造。具體而言，首先，可藉由以真空脱泡法等完全去除感光性樹脂組成物中之泡後，將感光性樹脂組成物塗佈在支持體上，藉由熱風爐或遠紅外線爐去除溶劑，讓其乾燥，接著，如有必要於所得之感光性樹脂組成物層上層合保護薄膜，製造附支持體之感光性薄膜。具體之乾燥條件雖因感光性樹脂組成物之硬化性或樹脂清漆中之有機溶劑量而異，但在包含30質量%～60質量%之有機溶劑的樹脂清漆，可於80℃～120℃乾燥3分鐘～13分鐘。感光性樹脂組成物層中之殘存有機溶劑量，從防止於後述步驟之有機溶劑的擴散的點來看，較佳為相對於感光性樹脂組成物層的總量成為5質量%以下，更佳為成為2質量%以下。本發明領域具有通常知識者可藉由簡單之實驗設定適當、適合之乾燥條件。感光性樹脂組成物層的厚度，從提昇操作性，且抑制感光性樹脂組成物層內部之感度及解析度降低的觀點來看，較佳為成為5μm～500μm的範圍，更佳為成為10μm～200μm的範圍，再更佳為成為15μm～150μm的範圍，又再更佳為成為20μm～100μm的範圍，最佳為成為20μm～60μm的範圍。The photosensitive film with a support of the present invention is known to those skilled in the field of the present invention, according to a well-known method, for example, by preparing a resin varnish in which the photosensitive resin composition of the present invention is dissolved in an organic solvent, on the support This resin varnish is applied on the body, and the organic solvent is dried by heating, hot air blowing, or the like to form a photosensitive resin composition layer to manufacture. Specifically, first, the photosensitive resin composition can be completely removed by a vacuum defoaming method, etc., and then the photosensitive resin composition can be coated on the support, and the solvent can be removed by a hot air furnace or a far-infrared furnace. Then, if necessary, a protective film is laminated on the obtained photosensitive resin composition layer to produce a photosensitive film with a support. The specific drying conditions vary depending on the curability of the photosensitive resin composition and the amount of the organic solvent in the resin varnish, but the resin varnish containing 30 to 60 mass % of the organic solvent can be dried at 80°C to 120°C 3 minutes to 13 minutes. The amount of the residual organic solvent in the photosensitive resin composition layer is preferably 5 mass % or less with respect to the total amount of the photosensitive resin composition layer, more preferably from the viewpoint of preventing the diffusion of the organic solvent in the steps described later. In order to be 2 mass % or less. Those with ordinary knowledge in the field of the present invention can set appropriate and suitable drying conditions through simple experiments. The thickness of the photosensitive resin composition layer is preferably in the range of 5 μm to 500 μm, and more preferably in the range of 10 μm to The range of 200 μm is more preferably the range of 15 μm to 150 μm, still more preferably the range of 20 μm to 100 μm, and the most preferable range is the range of 20 μm to 60 μm.

作為感光性樹脂組成物之塗佈方式，例如可列舉凹印塗佈方式、微凹版塗佈方式、逆向塗佈方式、吻反向塗佈方式、模塗方式、槽模法方式、唇塗方式、逗號塗佈方式、刮刀塗佈方式、輥塗方式、刀塗佈方式、簾式塗佈方式、腔凹版塗佈方式、狹孔塗佈方式、噴塗方式、浸塗方式等。 　　感光性樹脂組成物可分成數次塗佈，亦可以1次塗佈，又，亦可複數組合不同方式塗佈。其中，較佳為均勻塗佈性優異之模塗方式。又，為了防止異物混入等，較佳為於潔淨室等之異物發生較少之環境實施塗佈步驟。Examples of the coating method of the photosensitive resin composition include gravure coating, microgravure coating, reverse coating, kiss reverse coating, die coating, slot die coating, and lip coating. , comma coating method, blade coating method, roll coating method, knife coating method, curtain coating method, cavity gravure coating method, narrow hole coating method, spray coating method, dip coating method, etc. The photosensitive resin composition can be divided into several coats, one coat, or multiple combinations of different coats. Among them, a die coating method excellent in uniform coating properties is preferred. In addition, in order to prevent the contamination of foreign matter, etc., it is preferable to perform the coating step in an environment such as a clean room where the occurrence of foreign matter is small.

[印刷電路板] 　　本發明之印刷電路板係包含藉由本發明之感光性樹脂組成物的硬化物所形成之絕緣層。該絕緣層較佳為作為阻焊劑使用。[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，本發明之印刷電路板可使用上述之感光性薄膜或附支持體之感光性薄膜製造。以下，針對絕緣層為阻焊劑的情況進行說明。Specifically, the printed circuit board of the present invention can be produced using the above-mentioned photosensitive film or the photosensitive film with a support. Hereinafter, the case where the insulating layer is a solder resist will be described.

＜塗佈及乾燥步驟＞ 　　藉由將感光性樹脂組成物以樹脂清漆狀態直接塗佈在電路基板上，使有機溶劑乾燥，而於電路基板上形成感光性薄膜。<Coating and drying step> A photosensitive film is formed on the circuit board by directly coating the photosensitive resin composition on the circuit board in a resin varnish state and drying the organic solvent.

作為電路基板，例如可列舉玻璃環氧基板、金屬基板、聚酯基板、聚醯亞胺基板、BT樹脂基板、熱硬化型聚伸苯基醚基板等。尚，於此所謂電路基板，係指形成圖型加工在如上述之基板的單面或兩面之導體層(電路)的基板。且，在交互層合導體層與絕緣層而成之多層印刷電路板，成為圖型加工該多層印刷電路板之最外層的單面或兩面之導體層(電路)的基板，亦包含在於此所謂電路基板。尚，導體層表面中可藉由黑化處理、銅蝕刻等預先實施粗糙化處理。As a circuit board, a glass epoxy board, a metal board, a polyester board, a polyimide board, a BT resin board, a thermosetting polyphenylene ether board etc. are mentioned, for example. Also, the so-called circuit substrate herein refers to a substrate on which a conductor layer (circuit) is formed and patterned on one or both sides of the above-mentioned substrate. In addition, a multilayer printed circuit board obtained by alternately laminating conductor layers and insulating layers becomes a substrate for patterning the conductor layers (circuits) on one or both sides of the outermost layer of the multilayer printed circuit board. circuit board. Furthermore, the surface of the conductor layer may be roughened in advance by blackening treatment, copper etching, or the like.

作為塗佈方式，雖一般多數使用藉由絲網印刷法之全面印刷，但其他若為可均勻塗佈之塗佈方式可使用任何手段。例如噴塗方式、熱熔塗佈方式、棒塗方式、敷抹方式、刮刀塗佈方式、刀塗佈方式、氣刀塗佈方式、幕流塗佈方式、輥塗方式、凹印塗佈方式、膠印印刷方式、浸塗方式、刷毛塗佈、其他通常之塗佈方式全部可使用。塗佈後，如有必要以熱風爐或遠紅外線爐等進行乾燥。乾燥條件較佳為於80℃～120℃定為3分鐘～13分鐘。如此進行，於電路基板上形成感光性薄膜。As a coating method, although the full-surface printing by the screen printing method is generally used, any method can be used for other coating methods that can be uniformly coated. For example, spray coating, hot melt coating, bar coating, application, blade coating, knife coating, air knife coating, curtain flow coating, roll coating, gravure coating, Offset printing, dip coating, brush coating, and other common coating methods can all be used. After coating, if necessary, it is dried with a hot-air oven, a far-infrared oven, or the like. The drying conditions are preferably set at 80°C to 120°C for 3 minutes to 13 minutes. In this way, a photosensitive thin film is formed on the circuit board.

＜層合步驟＞ 　　又，使用附支持體之感光性薄膜時，將感光性樹脂組成物層側使用真空層壓機層合在電路基板之單面或兩面。在層合步驟，附支持體之感光性薄膜具有保護薄膜時，去除該保護薄膜後，如有必要預熱附支持體之感光性薄膜及電路基板，邊加壓及加熱感光性樹脂組成物層邊壓接在電路基板。在附支持體之感光性薄膜，適合使用藉由真空層合法於減壓下層合在電路基板之方法。<Lamination step> Furthermore, when using a photosensitive film with a support, the photosensitive resin composition layer side is laminated on one side or both sides of the circuit board using a vacuum laminator. In the lamination step, when the photosensitive film with the support has a protective film, after removing the protective film, if necessary, preheat the photosensitive film with the support and the circuit board, while pressing and heating the photosensitive resin composition layer side crimp to the circuit board. For the photosensitive film with a support, a method of laminating on a circuit board under reduced pressure by a vacuum lamination method is suitably used.

層合步驟之條件雖並非被特別限定者，但例如以將壓接溫度(層合溫度)較佳為定為70℃～140℃，將壓接壓力較佳為定為1kgf/cm2 ～11kgf/cm2 (9.8×104 N/m2 ～107.9×104 N/m2 )，將壓接時間較佳為定為5秒～300秒，空氣壓定為20mmHg(26.7hPa)以下之減壓下進行層合較佳。又，層合步驟可為批量式，亦可為使用輥之連續式。真空層合法可使用市售之真空層壓機進行。作為市售之真空層壓機，例如可列舉日光材料公司製真空施加器、名機製作所公司製真空加壓式層壓機、日立工業公司製輥式幹塗佈機、日立AIC公司製真空層壓機等。如此進行，於電路基板上形成感光性樹脂組成物層。Although the conditions of the lamination step are not particularly limited, for example, the crimping temperature (lamination temperature) is preferably 70°C to 140°C, and the crimping pressure is preferably 1kgf/cm 2 to 11kgf /cm 2 (9.8×10 4 N/m 2 to 107.9×10 4 N/m 2 ), the crimping time is preferably set to 5 seconds to 300 seconds, and the air pressure is set to 20mmHg (26.7hPa) or less Depression is preferred for lamination. In addition, the lamination step may be a batch type or a continuous type using a roll. The vacuum lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum applicator manufactured by Nikko Materials Co., Ltd., a vacuum pressurized laminator manufactured by Meiki Seisakusho Co., Ltd., a dry roll coater manufactured by Hitachi Kogyo Co., Ltd., and a vacuum layer manufactured by Hitachi AIC Co., Ltd. Press, etc. In this way, the photosensitive resin composition layer is formed on the circuit board.

＜曝光步驟＞ 　　藉由塗佈及乾燥步驟或層合步驟，於電路基板上設置感光性薄膜(感光性樹脂組成物層)後，接著，進行通過遮罩圖型，於感光性樹脂組成物層之指定部分照射活性光線，光硬化照射部之感光性樹脂組成物層之曝光步驟。作為活性光線，例如可列舉紫外線、可見光線、電子束、X光等，尤其是以紫外線較佳。紫外線之照射量大約為10mJ/cm2 ～1000mJ/cm2 。曝光方法中有使遮罩圖型密著在印刷電路板進行之接觸曝光法、與未密著使用平行光線進行曝光之非接觸曝光法，任一者皆可使用無妨。又，於感光性樹脂組成物層上存在支持體時，可從支持體上曝光，亦可於剝離支持體後曝光。<Exposure step> After the photosensitive film (photosensitive resin composition layer) is provided on the circuit board by the coating and drying step or the lamination step, a mask pattern is then performed on the photosensitive resin composition layer. The designated part is irradiated with actinic rays, and the exposure step of the photosensitive resin composition layer of the photo-hardening irradiation part. Examples of actinic rays include ultraviolet rays, visible rays, electron beams, X-rays, and the like, and ultraviolet rays are particularly preferred. The irradiation dose of ultraviolet rays is about 10mJ/cm 2 to 1000mJ/cm 2 . As the exposure method, there are contact exposure method in which the mask pattern is adhered to the printed circuit board, and non-contact exposure method in which the mask pattern is not adhered and exposed using parallel light, and any of them can be used. Moreover, when a support exists in the photosensitive resin composition layer, it may expose from a support, and may expose after peeling a support.

阻焊劑由於使用本發明之感光性樹脂組成物，解析性優異。因此，作為在遮罩圖型之曝光圖型，例如，可使用電路寬(線；L)與電路間之寬(空間；S)的比(L/S)為100μm/100μm以下(亦即、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，間距通過電路基板整體不需要相同。The solder resist is excellent in resolution by using the photosensitive resin composition of the present invention. Therefore, as the exposure pattern in the mask pattern, for example, the ratio (L/S) of the circuit width (line; L) to the width (space; S) between the circuits is 100 μm/100 μm or less (ie, 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) pattern. Also, the pitch need not be the same throughout the circuit substrate.

＜顯影步驟＞ 　　曝光步驟後，可藉由於感光性樹脂組成物層上存在支持體時，去除該支持體後，以濕式顯影或乾式顯影，去除未光硬化之部分(未曝光部)進行顯影，來形成圖型。<Development step> After the exposure step, when there is a support on the photosensitive resin composition layer, after removing the support, wet development or dry development can be used to remove the unphotocured part (unexposed part) for development. , to form a pattern.

為上述濕式顯影時，作為顯影液，使用鹼性水溶液、水系顯影液、有機溶劑等之安全且安定，操作性良好之顯影液，其中，較佳為藉由鹼水溶液之顯影步驟。又，作為顯影方法，可適當採用噴灑、搖動浸漬、塗刷、刮削(Scraping)等之周知方法。In the above wet development, as the developing solution, an alkaline aqueous solution, an aqueous developing solution, an organic solvent, etc., which are safe, stable, and have good workability are used. Among them, the developing step by an alkaline aqueous solution is preferred. Moreover, as a developing method, well-known methods, such as spraying, shaking and dipping, brushing, scraping, etc. can be used suitably.

作為作為顯影液使用之鹼性水溶液，例如可列舉氫氧化鋰、氫氧化鈉、氫氧化鉀等之鹼金屬氫氧化物、碳酸鈉、重碳酸鈉等之碳酸鹽或重碳酸鹽、磷酸鈉、磷酸鉀等之鹼金屬磷酸鹽、焦磷酸鈉、焦磷酸鉀等之鹼金屬焦磷酸鹽之水溶液，或氫氧化四烷基銨等之未含有金屬離子之有機鹼的水溶液，以未含有金屬離子，未對半導體晶片帶來影響的點來看，較佳為氫氧化四甲基銨(TMAH)之水溶液。 　　此等之鹼性水溶液為了提昇顯影效果，可將界面活性劑、消泡劑等添加在顯影液。上述鹼性水溶液之pH，例如較佳為8～12的範圍，更佳為9～11的範圍。又，上述鹼性水溶液之鹼濃度較佳為成為0.1質量%～10質量%。上述鹼性水溶液之溫度雖可配合感光性樹脂組成物層之解析性適當選擇，但較佳為成為20℃～50℃。Examples of the alkaline aqueous solution used as the developer include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, carbonates such as sodium carbonate and sodium bicarbonate or bicarbonate, sodium phosphate, Aqueous solutions of alkali metal phosphates such as potassium phosphate, alkali metal pyrophosphates such as sodium pyrophosphate, potassium pyrophosphate, etc., or aqueous solutions of organic bases such as tetraalkylammonium hydroxide that do not contain metal ions, so that they do not contain metal ions , An aqueous solution of tetramethylammonium hydroxide (TMAH) is preferable in terms of not affecting the semiconductor wafer. In order to improve the development effect of these alkaline aqueous solutions, surfactants, antifoaming agents, etc. can be added to the developer solution. The pH of the above-mentioned alkaline aqueous solution is, for example, preferably in the range of 8 to 12, more preferably in the range of 9 to 11. Moreover, it is preferable that the alkali concentration of the said alkaline aqueous solution shall be 0.1 mass % - 10 mass %. The temperature of the above-mentioned alkaline aqueous solution can be appropriately selected according to the resolution of the photosensitive resin composition layer, but it is preferably 20°C to 50°C.

作為顯影液使用之有機溶劑，例如有丙酮、乙酸乙酯、具有碳原子數1～4之烷氧基之烷氧基乙醇、乙基醇、異丙基醇、丁基醇、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, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, and diethylene glycol. Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether.

如此之有機溶劑的濃度相對於顯影液全量，較佳為2質量%～90質量%。又，如此之有機溶劑的溫度可配合解析性調節。進而，如此之有機溶劑可單獨或組合2種類以上使用。作為單使用之有機溶劑系顯影液，例如可列舉1,1,1-三氯乙烷、N-甲基吡咯烷酮、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 analytical performance. Furthermore, such an organic solvent can be used individually or in combination of 2 or more types. Examples of organic solvent-based developing solutions to be used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, and methyl isobutyl ketone, gamma-butyrolactone.

在圖型形成，如有必要可併用上述之2種類以上之顯影方法使用。顯影之方式中，有漬方式、戰鬥(Battle)方式、噴灑方式、高壓噴灑方式、塗刷、拍擊(Slapping)等，高壓噴灑方式由於提昇解析度故適合。作為採用噴灑方式時之噴灑壓，較佳為0.05MPa～0.3MPa。For pattern formation, if necessary, two or more of the above-mentioned developing methods can be used in combination. Among the developing methods, there are stain method, battle method, spray method, high-pressure spray method, brushing, slapping, etc. The high-pressure spray method is suitable because the resolution is improved. As the spray pressure when the spray method is adopted, it is preferably 0.05 MPa to 0.3 MPa.

＜熱硬化(後烘焙)步驟＞ 　　上述顯影步驟結束後，進行熱硬化(後烘焙)步驟，形成阻焊劑。作為後烘焙步驟，可列舉藉由高壓水銀燈之紫外線照射步驟或使用清潔烤箱之加熱步驟等。照射紫外線時，如有必要可調整其照射量，例如可用0.05J/cm2 ～10J/cm2 程度之照射量進行照射。又，加熱之條件雖可因應感光性樹脂組成物中之樹脂成分的種類、含量等適當選擇，但較佳為於150℃～220℃於20分鐘～180分鐘的範圍選擇，更佳為於160℃～200℃於30分鐘～120分鐘的範圍選擇。<The thermosetting (post-baking) process> After the said image development process is complete|finished, the thermosetting (post-baking) process is performed, and a soldering resist is formed. As a post-baking process, the ultraviolet irradiation process by a high pressure mercury lamp, the heating process using a clean oven, etc. are mentioned. When irradiating ultraviolet rays, the irradiation amount can be adjusted if necessary. For example, it can be irradiated with an irradiation amount of about 0.05 J/cm 2 to 10 J/cm 2 . In addition, although the heating conditions can be appropriately selected according to the type and content of the resin component in the photosensitive resin composition, it is preferably selected in the range of 150°C to 220°C for 20 minutes to 180 minutes, more preferably 160°C. °C to 200°C are selected in the range of 30 minutes to 120 minutes.

＜其他步驟＞ 　　印刷電路板形成阻焊劑後，可進一步包含鑽孔步驟、除膠渣步驟。此等之步驟對使用在印刷電路板的製造之本發明領域具有通常知識者而言，可依照周知之各種方法實施。<Other steps> After the solder resist is formed on the printed circuit board, it may further include a drilling step and a desmearing step. These steps can be carried out according to various methods known to those skilled in the field of the present invention used in the manufacture of printed circuit boards.

形成阻焊劑後，依期望於電路基板上所形成之阻焊劑進行鑽孔步驟，形成通孔、貫通孔。鑽孔步驟例如雖可藉由鑽孔機、雷射、電漿等之周知之方法，且視必要組合此等之方法進行，但較佳為藉由碳酸氣體雷射、YAG雷射等之雷射之鑽孔步驟。After the solder resist is formed, a drilling step is performed on the solder resist formed on the circuit substrate as desired to form through holes and through holes. For example, the drilling step can be performed by known methods such as drilling machine, laser, plasma, etc., and these methods can be combined as necessary, but preferably by carbon dioxide gas laser, YAG laser, etc. Shooting drilling steps.

除膠渣步驟係進行除膠渣處理之步驟。在鑽孔步驟所形成之開口部內部中，一般附著有樹脂殘渣(污跡)。該污跡由於成為電氣連接不佳的原因，在此步驟實施去除污跡之處理(除膠渣處理)。The step of removing glue residue is a step of performing the treatment of removing glue residue. Resin residues (smudges) generally adhere to the inside of the opening formed in the drilling step. Since this stain may cause poor electrical connection, a stain removal process (smear removal process) is performed in this step.

除膠渣處理可藉由乾式除膠渣處理、濕式除膠渣處理或此等之組合實施。The desmear treatment can be performed by dry desmear treatment, wet desmear treatment, or a combination of these.

作為乾式除膠渣處理，例如可列舉使用電漿之除膠渣處理等。使用電漿之除膠渣處理可使用市售之電漿除膠渣處理裝置實施。市售之電漿除膠渣處理裝置當中，作為適合在印刷電路板之製造用途之例，可列舉Nissin公司製之微波電漿裝置、積水化學工業公司製之常壓電漿蝕刻裝置等。As a dry desmear process, the desmear process using a plasma etc. are mentioned, for example. The desmear treatment using plasma can be performed using a commercially available plasma desmear treatment device. Among the commercially available plasma desmear treatment apparatuses, examples suitable for the production of printed circuit boards include microwave plasma apparatuses manufactured by Nissin Corporation, atmospheric pressure plasma etching apparatuses manufactured by Sekisui Chemical Industry Co., Ltd., and the like.

作為濕式除膠渣處理，例如可列舉使用氧化劑溶液之除膠渣處理等。使用氧化劑溶液進行除膠渣處理時，較佳為依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順序進行。作為膨潤液，例如可列舉Atotech Japan公司製之「Swelling Dip Securiganth P」、「Swelling Dip Securiganth SBU」等。膨潤處理較佳為藉由將形成通孔等之基板於加熱至60℃～80℃之膨潤液浸漬5分鐘～10分鐘來進行。作為氧化劑溶液，較佳為鹼性過錳酸水溶液，例如可列舉於氫氧化鈉之水溶液溶解過錳酸鉀或過錳酸鈉之溶液。藉由氧化劑溶液之氧化處理，較佳為將膨潤處理後之基板於加熱至60℃～80℃之氧化劑溶液浸漬10分鐘～30分鐘來進行。作為鹼性過錳酸水溶液之市售品，例如可列舉Atotech Japan公司製之「Concentrate･Compact CP」、「Dosing solution･Securiganth P」等。藉由中和液之處理可藉由將氧化處理後之基板於30℃～50℃之中和液浸漬3分鐘～10分鐘來進行。作為中和液，較佳為酸性之水溶液，作為市售品，例如可列舉Atotech Japan公司製之「Reduction solution･Securigant P」。As the wet desmear treatment, for example, desmear treatment using an oxidizing agent solution, etc. can be mentioned. When using the oxidizing agent solution to carry out the desmear treatment, it is preferably performed in the order of swelling treatment with a swelling liquid, oxidation treatment with an oxidizing agent solution, and neutralization treatment with a neutralizing liquid. 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 by immersing the substrate on which the through holes and the like are formed in a swelling liquid heated at 60° C. to 80° C. for 5 minutes to 10 minutes. As an oxidizing agent solution, an alkaline permanganic acid aqueous solution is preferable, for example, the solution which melt|dissolved potassium permanganate or sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. The oxidation treatment by the oxidizing agent solution is preferably performed by immersing the substrate after the swelling treatment in the oxidizing agent solution heated to 60° C. to 80° C. for 10 minutes to 30 minutes. As a commercial item of the alkaline permanganic acid aqueous solution, "Concentrate・Compact CP", "Dosing solution・Securiganth P" manufactured by Atotech Japan, etc. are mentioned, for example. The treatment with the neutralizing solution can be performed by immersing the substrate after the oxidation treatment in the neutralizing solution at 30° C. to 50° C. for 3 minutes to 10 minutes. As a neutralization liquid, an acidic aqueous solution is preferable, and "Reduction solution Securigant P" by Atotech Japan is mentioned as a commercial item, for example.

組合乾式除膠渣處理與濕式除膠渣處理實施時，可先實施乾式除膠渣處理，亦可先實施濕式除膠渣處理。When combined dry desmear treatment and wet desmear treatment are implemented, dry desmear treatment can be performed first, or wet desmear treatment can be performed first.

將絕緣層作為層間絕緣層使用時，亦可與阻焊劑的情況同樣進行，於熱硬化步驟後進行鑽孔步驟、除膠渣步驟及鍍敷步驟。When the insulating layer is used as an interlayer insulating layer, it is also possible to perform the drilling step, the desmear step, and the plating step after the thermal hardening step in the same manner as in the case of the solder resist.

鍍敷步驟係於絕緣層上形成導體層之步驟。導體層可組合無電解鍍敷與電解鍍敷形成，又，形成與導體層相反圖型之鍍敷抗蝕劑，可僅以無電解鍍敷形成導體層。作為之後之圖型形成的方法，例如對本發明領域具有通常知識者而言，可使用周知之減成法(Subtractive)法、半添加法等。The plating step is a step of forming a conductor layer on the insulating layer. The conductor layer can be formed by combining electroless plating and electrolytic plating, and the conductor layer can be formed only by electroless plating by forming a plating resist of a pattern opposite to that of the conductor layer. As a method for the subsequent pattern formation, for example, a known subtractive method, a semi-additive method, etc. can be used for those skilled in the field of the present invention.

[半導體裝置] 　　本發明之半導體裝置係包含印刷電路板。本發明之半導體裝置可使用本發明之印刷電路板製造。[Semiconductor Device] The semiconductor device of the present invention includes a printed circuit board. The semiconductor device of the present invention can be manufactured using the printed circuit board of the present invention.

作為半導體裝置，可列舉供於電氣製品(例如電腦、手機、數位相機及電視等)及交通工具(例如摩托車、汽車，火車、船舶及航空機等)等之各種半導體裝置。Examples of semiconductor devices include various semiconductor devices used in electrical products (eg, computers, cell phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, trains, ships, aircraft, etc.).

本發明之半導體裝置可藉由於印刷電路板之導通處實裝零件(半導體晶片)製造。所謂「導通處」，係「傳達在印刷電路板之電信號之處」，該場所可為表面，亦可為嵌入之處皆無妨。又，半導體晶片若為將半導體作為材料之電氣電路元件，則並未特別限定。The semiconductor device of the present invention can be manufactured by mounting a part (semiconductor chip) at the conductive portion of the printed circuit board. The so-called "conduction place" refers to "the place where the electrical signal is transmitted on the printed circuit board", and the place can be the surface or the embedded place. In addition, if a semiconductor wafer is an electric circuit element which uses a semiconductor as a material, it will not specifically limit.

製造本發明之半導體裝置時之半導體晶片的實裝方法，半導體晶片只要有效進行機能，雖並未特別限定，但具體而言，可列舉引線鍵合實裝方法、倒裝晶片實裝方法、藉由無凹凸堆積層(BBUL)之實裝方法、藉由各向異性導電薄膜(ACF)之實裝方法、藉由非導電性薄膜(NCF)之實裝方法、等。於此，所謂「藉由無凹凸堆積層(BBUL)之實裝方法」，係「將半導體晶片直接嵌入印刷電路板之凹部，連接半導體晶片與印刷電路板上之配線的實裝方法」。 [實施例]The method for mounting a semiconductor chip when manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively. Mounting method by uneven 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 means of a bumpless build-up layer (BBUL)" refers to "mounting method in which a semiconductor chip is directly embedded in a concave portion of a printed circuit board to connect the semiconductor chip and wiring on the printed circuit board". [Example]

以下，雖藉由實施例具體說明本發明，但本發明並非被限定於此等之實施例者。尚，在以下，表示量之「份」及「%」除非另有明確說明，係分別意指「質量份」及「質量%」。Hereinafter, although the present invention will be specifically described by way of examples, the present invention is not limited to these examples. Also, in the following, "parts" and "%" indicating amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

((C)成分之調製) 　　作為(C)成分，係進行10-(2,5-二羥基苯基)-9,10-二氫9-氧雜-10-磷雜菲(Phosphaphenanthrene)-10-氧化物(HCA-HQ、三光公司製)之粉碎與分級，調製4種類之(C)成分(HCA-HQ(1)～HCA-HQ(4))。 　　又，作為(C)成分，係進行10-[2-(二羥基萘基)]-9,10-二氫-9-氧雜-10-磷雜菲(Phosphaphenanthrene)-10-氧化物(HCA=NQ、三光公司製)之粉碎與分級，調製HCA=NQ。 　　HCA-HQ(1)～HCA-HQ(4)及HCA=NQ之平均粒徑藉由以下之方法測定。(Preparation of component (C)) As component (C), 10-(2,5-dihydroxyphenyl)-9,10-dihydro9-oxa-10-phosphaphenanthrene-10 - Pulverization and classification of oxides (HCA-HQ, manufactured by Sanko Co., Ltd.) to prepare four types of (C) components (HCA-HQ(1) to HCA-HQ(4)). Furthermore, as the component (C), 10-[2-(dihydroxynaphthyl)]-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (HCA =NQ, manufactured by Sanguang Co., Ltd.), pulverizing and classifying, and modulating HCA=NQ. The average particle size of HCA-HQ(1) to HCA-HQ(4) and HCA=NQ is measured by the following method.

在小玻璃瓶稱重HCA-HQ(1)之粉體50mg、非離子系分散劑(日本油脂公司製「T208.5」)2g、純水40g，在超音波分散20分鐘。使用雷射繞射式粒度分布測定裝置(堀場製作所公司製、LA-950)，以間歇式小槽(Batch cell)方式測定粒度分布，算出平均粒徑。針對HCA-HQ(2)～HCA-HQ(4)及HCA=NQ亦同樣進行，算出平均粒徑。結果係如以下。 　　HCA-HQ(1)之平均粒徑：2.19μm 　　HCA-HQ(2)之平均粒徑：1.50μm 　　HCA-HQ(3)之平均粒徑：0.80μm 　　HCA-HQ(4)之平均粒徑：0.65μm 　　HCA=NQ之平均粒徑：1.65μm50 mg of HCA-HQ (1) powder, 2 g of a nonionic dispersant (“T208.5” manufactured by NOF Corporation), and 40 g of pure water were weighed in a small glass bottle, and dispersed by ultrasonic for 20 minutes. The particle size distribution was measured by a batch cell method using a laser diffraction particle size distribution analyzer (manufactured by Horiba, Ltd., LA-950), and the average particle size was calculated. The average particle diameter was calculated similarly for HCA-HQ(2) to HCA-HQ(4) and HCA=NQ. The results are as follows. Average particle size of HCA-HQ(1): 2.19μm Average particle size of HCA-HQ(2): 1.50μm Average particle size of HCA-HQ(3): 0.80μm Average particle size of HCA-HQ(4): 0.65μm Average particle size of HCA=NQ: 1.65μm

(合成例1：A-1成分之合成) 　　將環氧基當量為162之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，放入具備氣體導入管、攪拌裝置、冷卻管及溫度計之燒瓶，加入卡必醇乙酸酯340份進行加熱溶解，加入氫醌0.46份、與三苯基膦1份。將此混合物加熱至95～105℃，緩緩滴下丙烯酸72份，進行16小時反應。將此反應生成物冷卻至80～90℃，加入四氫苯二甲酸酐80份進行8小時反應，使其冷卻。如此進行，而得到固形物之酸價為90mgKOH/g之樹脂溶液(不揮發分70%、以下簡稱為「A-1」)。(Synthesis Example 1: Synthesis of A-1 Component) 1,1'-bis(2,7-diglycidyloxynaphthyl)methane ("EXA-4700" with an epoxy group equivalent of 162, Dainippon Ink Chemical Industry Co., Ltd.) 162 parts, put it into a flask equipped with a gas introduction tube, a stirring device, a cooling tube and a thermometer, add 340 parts of carbitol acetate to heat and dissolve, add 0.46 parts of hydroquinone, and 1 triphenylphosphine share. This mixture was heated to 95-105 degreeC, 72 parts of acrylic acid were dripped slowly, and reaction was performed for 16 hours. This reaction product was cooled to 80-90 degreeC, 80 parts of tetrahydrophthalic anhydrides were added, it was made to react for 8 hours, and it was cooled. In this way, a resin solution (nonvolatile content 70%, hereinafter abbreviated as "A-1") having an acid value of solid content of 90 mgKOH/g was obtained.

＜實施例1～6、比較例1～5＞ 　　以下述表所示之摻合比例摻合各成分，使用高速回轉混合機調製樹脂清漆。其次，準備以醇酸樹脂系脫模劑(琳得科公司製「AL-5」)脫模處理之PET薄膜(東麗公司製「Lumirror T6AM」、厚度38μm、軟化點130℃、「脫模PET」)作為支持體。藉由將經調製之樹脂清漆於該PET薄膜以乾燥後之感光性樹脂組成物層的厚度成為40μm的方式，在模塗機均勻塗佈，於80℃至110℃乾燥6分鐘，而得到於脫模PET上具有感光性樹脂組成物層之附支持體之感光性薄膜。<Examples 1 to 6, Comparative Examples 1 to 5> Each component was blended at the blending ratio shown in the following table, and a high-speed rotary mixer was used to prepare a resin varnish. Next, a PET film (“Lumirror T6AM” manufactured by Toray Corporation, thickness 38 μm, softening point 130° C., PET”) as a support. By applying the prepared resin varnish to the PET film so that the thickness of the photosensitive resin composition layer after drying becomes 40 μm, it is uniformly coated on a die coater, and dried at 80° C. to 110° C. for 6 minutes to obtain in A photosensitive film with a photosensitive resin composition layer attached to a support on the mold release PET.

針對在物性評估之測定方法及評估方法進行說明。The measurement method and evaluation method of the physical property evaluation will be explained.

＜阻燃性之評估＞ 　　重疊2枚於實施例及比較例製作之附支持體之感光性薄膜，使用批量式真空加壓層壓機(MVLP-500、名機公司製)進行層合，製作厚度80μm之薄膜。層合係藉由進行30秒減壓將氣壓成為13hPa以下，然後在30秒、100℃、壓力0.74MPa壓接來進行。將經重疊之附支持體之感光性薄膜使用批量式真空加壓層壓機(MVLP-500、名機公司製)，層合在層合板(無銅箔、基板厚度0.2mm、日立化成公司製、679FG)的兩面。層合係藉由進行30秒減壓將氣壓成為13hPa以下，然後在30秒、100℃、壓力0.74MPa壓接來進行。接著，剝離附支持體之感光性薄膜之脫模PET，以190℃、90分鐘之硬化條件硬化感光性樹脂組成物層，形成層合體。將所得之層合體(厚度約360μm)以12.7mm×127mm之大小、邊緣成為1.27mm的方式切斷，於70±1℃烤箱中處理168小時後，於乾燥器放冷4小時以上，而得到試驗片。依阻燃試驗UL-94V，將燃燒器移動至試驗片正下方，將火焰於試驗片之下端中央點燃火焰10秒，計測之後之燃燒時間。再次點燃火焰10秒，計測之後之燃燒時間。將此重複5次，根據以下之基準評估。 　　V0：無燃燒物之落下、試驗片之全燒，試驗片之燃燒時間未滿50秒。 　　V1：無燃燒物之落下、試驗片之全燒，試驗片之燃燒時間為50秒以上250秒以下。 　　×：燃燒物之落下、試驗片之全燒，或試驗片之燃燒時間超過250秒。<Evaluation of flame retardancy> Two photosensitive films with supports produced in Examples and Comparative Examples were stacked and laminated using a batch vacuum pressure laminator (MVLP-500, manufactured by Meiki Co., Ltd.) to produce Film with a thickness of 80 μm. The lamination system was performed by reducing the pressure for 30 seconds to reduce the air pressure to 13 hPa or less, and then performing pressure bonding at 100° C. for 30 seconds and a pressure of 0.74 MPa. The superimposed photosensitive film with the support was laminated on a laminate (no copper foil, substrate thickness 0.2 mm, manufactured by Hitachi Chemical Co., Ltd.) using a batch vacuum pressure laminator (MVLP-500, manufactured by Meiki Co., Ltd.). , 679FG) on both sides. The lamination system was performed by reducing the pressure for 30 seconds to reduce the air pressure to 13 hPa or less, and then performing pressure bonding at 100° C. for 30 seconds and a pressure of 0.74 MPa. Next, the mold release PET of the photosensitive film with a support was peeled off, and the photosensitive resin composition layer was hardened by the hardening conditions of 190 degreeC and 90 minutes, and the laminated body was formed. The obtained laminate (thickness of about 360 μm) was cut to a size of 12.7 mm×127 mm and the edge was 1.27 mm, and after being treated in an oven at 70±1° C. for 168 hours, it was left to cool in a desiccator for more than 4 hours to obtain test piece. According to the flame retardant test UL-94V, the burner was moved to just below the test piece, the flame was ignited in the center of the lower end of the test piece for 10 seconds, and the burning time after that was measured. The flame was lit again for 10 seconds, and the burning time after that was measured. This was repeated 5 times and evaluated according to the following criteria. V0: There is no falling of the inflammable material, the test piece is completely burned, and the burning time of the test piece is less than 50 seconds. V1: There is no falling of the inflammable material, no burning of the test piece, and the burning time of the test piece is 50 seconds or more and 250 seconds or less. ×: The falling of the burning material, the complete burning of the test piece, or the burning time of the test piece exceeds 250 seconds.

＜平均線膨脹率及玻璃轉移溫度之測定＞ (評估用硬化物之形成) 　　於實施例、比較例製作之附支持體之感光性薄膜的感光性樹脂組成物層以100mJ/cm2 之紫外線進行曝光使組成物層光硬化。然後，於感光性樹脂組成物層的全面，將作為顯影液之30℃之1質量%碳酸鈉水溶液在噴灑壓0.2MPa進行2分鐘噴灑顯影。噴灑顯影後，進行1J/cm2 之紫外線照射，進而進行190℃、90分鐘之加熱處理，使感光性樹脂組成物層硬化，形成硬化物。然後，剝離支持體，成為評估用硬化物。<Measurement of Average Linear Expansion Coefficient and Glass Transition Temperature> (Formation of hardened product for evaluation) The photosensitive resin composition layer of the photosensitive film with a support prepared in Examples and Comparative Examples was subjected to ultraviolet rays of 100 mJ/cm 2 . Exposure photohardens the composition layer. Then, on the entire surface of the photosensitive resin composition layer, a 1 mass % sodium carbonate aqueous solution at 30° C. as a developer was subjected to spray development at a spray pressure of 0.2 MPa for 2 minutes. After the spray development, 1 J/cm 2 of ultraviolet rays were irradiated, and further heat treatment was performed at 190° C. for 90 minutes to harden the photosensitive resin composition layer to form a hardened product. Then, the support was peeled off to obtain a hardened product for evaluation.

(平均線熱膨脹率之測定及評估) 　　將評估用硬化物切成寬5mm、長度15mm之試驗片，使用熱機械分析裝置(理學公司製、Thermo Plus TMA8310)，以拉伸加重法進行熱機械分析。將試驗片安裝在前述裝置後，在荷重1g、昇溫速度5℃/分鐘之測定條件連續測定2次。算出在第2次之測定從25℃至150℃為止之平均線熱膨脹率(ppm)。(Measurement and Evaluation of Average Linear Thermal Expansion Coefficient) The cured product for evaluation was cut into test pieces with a width of 5 mm and a length of 15 mm, and a thermomechanical analysis was performed by a tensile weight method using a thermomechanical analyzer (Thermo Plus TMA8310, manufactured by Rigaku Corporation). . After the test piece was attached to the above-mentioned apparatus, the measurement was carried out twice continuously under the measurement conditions of a load of 1 g and a temperature increase rate of 5°C/min. The average coefficient of linear thermal expansion (ppm) from 25°C to 150°C in the second measurement was calculated.

(玻璃轉移溫度之測定) 　　將評估用硬化物切成寬約5mm、長度約15mm之試驗片，使用動態黏彈性測定裝置(EXSTAR6000、SIINanotechnology公司製)，以拉伸加重法進行熱機械分析。將試驗片安裝在前述裝置後，在荷重200mN、昇溫速度2℃/分鐘之測定條件測定。將所得之tanδ之峰值頂作為玻璃轉移溫度(℃)算出。(Measurement of glass transition temperature) The cured product for evaluation was cut into test pieces of about 5 mm in width and about 15 mm in length, and thermomechanical analysis was carried out by the tensile weighting method using a dynamic viscoelasticity measuring device (EXSTAR6000, manufactured by SIINanotechnology). After the test piece was attached to the aforementioned apparatus, the measurement was performed under the measurement conditions of a load of 200 mN and a temperature increase rate of 2°C/min. The peak top of the obtained tanδ was calculated as the glass transition temperature (°C).

＜解析性及抗裂性之評估＞ (評估用層合體之形成) 　　對於圖型化厚度18μm之銅層的電路所形成之玻璃環氧基板(覆銅層合板)的銅層，在藉由包含有機酸之表面處理劑(CZ8100、Mec公司製)之處理實施粗糙化。其次，藉由實施例、比較例所得之附支持體之感光性薄膜的感光性樹脂組成物層以與銅電路表面接合的方式配置，使用真空層壓機(日光材料公司製、VP160)進行層合，形成以前述覆銅層合板、與前述感光性樹脂組成物層、與前述支持體順序層合之層合體。壓接條件定為抽真空之時間30秒、壓接溫度80℃、壓接壓力0.7MPa、加壓時間30秒。將該層合體室溫靜置30分鐘以上，從該層合體之支持體上，使用圓孔圖型，使用圖型形成裝置，以紫外線進行曝光。曝光圖型係使用描繪開口：50μm/60μm/70μm/80μm/90μm/100μm之圓孔、L/S(線/空間)：50μm/50μm、60μm/60μm、70μm/70μm、80μm/80μm、90μm/90μm、100μm/100μm之線和空間的石英玻璃遮罩。在室溫靜置30分鐘後，從前述層合體剝離支持體。於該層合板上之感光性樹脂組成物層的全面，將作為顯影液之30℃之1質量%碳酸鈉水溶液在噴灑壓0.2MPa進行2分鐘噴灑顯影。噴灑顯影後，進行1J/cm2 之紫外線照射，進而進行180℃、30分鐘之加熱處理，使感光性樹脂組成物層硬化，於該層合體上形成具有開口部之絕緣層。將此作為評估用層合體。<Evaluation of Analytical Properties and Crack Resistance> (Formation of Laminate for Evaluation) For the copper layer of the glass epoxy substrate (copper clad laminate) formed by patterning the circuit of the copper layer with a thickness of 18 μm, by including The surface treatment agent (CZ8100, made by Mec Corporation) of organic acid was roughened. Next, the photosensitive resin composition layers of the photosensitive films with supports obtained in Examples and Comparative Examples were arranged so as to be bonded to the surface of the copper circuit, and were layered using a vacuum laminator (manufactured by Nikko Materials Co., Ltd., VP160). A laminate is formed in which the copper-clad laminate, the photosensitive resin composition layer, and the support are laminated in this order. The crimping conditions were set as a vacuuming time of 30 seconds, a crimping temperature of 80° C., a crimping pressure of 0.7 MPa, and a pressing time of 30 seconds. The laminate was allowed to stand at room temperature for more than 30 minutes, and the support of the laminate was exposed to ultraviolet rays using a circular hole pattern using a pattern forming apparatus. The exposure pattern is drawn with openings: 50μm/60μm/70μm/80μm/90μm/100μm round holes, L/S (line/space): 50μm/50μm, 60μm/60μm, 70μm/70μm, 80μm/80μm, 90μm/ Quartz glass mask for 90μm, 100μm/100μm lines and spaces. After standing at room temperature for 30 minutes, the support was peeled off from the aforementioned laminate. On the entire surface of the photosensitive resin composition layer on the laminate, a 1 mass % sodium carbonate aqueous solution at 30° C. as a developer was spray developed at a spray pressure of 0.2 MPa for 2 minutes. After spray development, 1 J/cm 2 of ultraviolet light was irradiated, and further heat treatment was performed at 180° C. for 30 minutes to harden the photosensitive resin composition layer, and an insulating layer with openings was formed on the laminate. This was used as a laminate for evaluation.

(解析性之評估) 　　相對於評估用層合體，將經圖型化形成之圓孔以SEM觀察(倍率1000倍)，測定無殘渣之最小貫孔徑、無裝填或剝離之最小L/S。將無樹脂裝填或剝離之無最小L/S的情況定為「×」。又，L/S形狀以下述基準評估。 　　○：觀察三點之L/S，全部L/S之間無剝離或裝填。 　　×：觀察三點之L/S，任一個L/S之間觀察到樹脂裝填或剝離。(Evaluation of Analytical Properties) With respect to the laminate for evaluation, the circular holes formed by patterning were observed by SEM (magnification of 1000 times), and the minimum through hole diameter without residue and the minimum L/S without filling or peeling were measured. The case where there was no minimum L/S without resin filling or peeling was designated as "X". In addition, the L/S shape was evaluated according to the following criteria. ○: Observe the L/S of three points, there is no peeling or filling between all L/S. ×: The L/S of three points was observed, and resin filling or peeling was observed between any one of the L/S.

(抗裂性(TCT耐性)之評估) 　　進行重複500次將評估用層合體於-65℃之大氣中曝露15分鐘後，以180℃/分鐘之昇溫速度進行昇溫，接著，於150℃之大氣中曝露15分鐘後，以180℃/分鐘之降溫速度進行降溫之藉由熱循環之處理的試驗。試驗後，將評估用層合體之裂紋及剝離程度藉由光學顯微鏡(尼康公司製、「LV-100ND」)進行觀察，用以下之基準評估。 　　○：未觀察到裂紋及剝離。 　　×：觀察到裂紋及剝離。(Evaluation of crack resistance (TCT resistance)) After 500 repetitions of exposing the laminate for evaluation to the atmosphere of -65°C for 15 minutes, the temperature was increased at a temperature increase rate of 180°C/min, and then, the temperature was increased to 150°C in the atmosphere After 15 minutes of exposure to the medium, the test of the temperature-lowering treatment by thermal cycling was performed at a temperature-lowering rate of 180° C./min. After the test, the degree of cracking and peeling of the laminate for evaluation was observed with an optical microscope (manufactured by Nikon Corporation, "LV-100ND"), and evaluated by the following criteria. ○: No crack or peeling was observed. ×: Cracks and peeling were observed.

Figure 02_image009
Figure 02_image009

表中之簡稱等係如以下。 (A)成分 　　･ZAR-2000：雙酚A型環氧基丙烯酸酯(日本化藥公司製、酸價99mgKOH/g、不揮發分約70%) 　　･A-1：於合成例1合成之A-1成分(不揮發分70%) (B)成分 　　･SC4050：相對於熔融二氧化矽(Admatex公司製、平均粒徑1.0μm)100質量份，以胺基矽烷(信越化學公司製、「KBM573」)0.5質量份表面處理者 (C)成分 　　･HCA-HQ(1)：平均粒徑為2.19μm之HCA-HQ(三光公司製) 　　･HCA-HQ(2)：平均粒徑為1.50μm之HCA-HQ(三光公司製) 　　･HCA-HQ(3)：平均粒徑為0.80μm之HCA-HQ(三光公司製) 　　･HCA-HQ(4)：平均粒徑為0.65μm之HCA-HQ(三光公司製) 　　･HCA=NQ：平均粒徑為1.65μm之HCA=NQ(三光公司製) 　　･SPS-100：環狀苯氧基磷腈(大塚化學公司製、非含有活性基、P含量13質量%) (D)成分 　　･IrgacureOXE-02：乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯肟)(BASF公司製) (E)成分 　　･NC3000H：聯苯型環氧樹脂(日本化藥公司製、環氧基當量約272) 　　･1031S：四苯基乙烷型環氧樹脂(三菱化學公司製、環氧基當量約220) (F)成分 　　･DPHA：二季戊四醇六丙烯酸酯(日本化藥公司製、丙烯醯基當量約96) (G)成分 　　･EDGAc：乙基二甘醇乙酸酯 　　･MEK：甲基乙基酮 其他 　　･吩噻嗪：東京化成工業公司製 　　･(B)成分的含量：將感光性樹脂組成物之固形分全體定為100質量%時之(B)成分的含量 　　･磷原子含量：將感光性樹脂組成物之樹脂成分定為100質量%時之磷原子的含量The abbreviations in the table are as follows. (A) Component ･ ZAR-2000: Bisphenol A type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 99 mgKOH/g, non-volatile content about 70%) ･A-1: A synthesized in Synthesis Example 1 -1 component (70% non-volatile content) (B) component: SC4050: With respect to 100 parts by mass of fused silica (manufactured by Admatex, average particle size 1.0 μm), aminosilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573 ”) 0.5 parts by mass of Surface Treated (C) Component ･HCA-HQ (1): HCA-HQ (manufactured by Sanko Co., Ltd.) with an average particle size of 2.19 μm ･HCA-HQ (2): with an average particle size of 1.50 μm HCA-HQ (manufactured by Sanko Corporation) ･HCA-HQ(3): HCA-HQ (manufactured by Sanko Corporation) with an average particle size of 0.80 μm ･HCA-HQ(4): HCA-HQ with an average particle size of 0.65 μm ( Sanko Co., Ltd.) ･HCA=NQ: HCA=NQ with an average particle size of 1.65 μm (Sanko Corporation) ･SPS-100: Cyclic phenoxyphosphazene (manufactured by Otsuka Chemical Co., Ltd., non-active group, P content 13 Mass %) (D) Component･IrgacureOXE-02:Ethanone,1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1-( O-acetoxime) (manufactured by BASF Corporation) (E) Component ･NC3000H: Biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., epoxy group equivalent is about 272) ･1031S: Tetraphenylethane type epoxy resin (manufactured by Mitsubishi Chemical Corporation, about 220 epoxy equivalent) (F) Component・DPHA: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., about 96 acryl equivalent) (G) Component・EDGAc: Ethyl diglycerol Alcohol acetate・MEK: Methyl ethyl ketone and others ・Phenothiazine: manufactured by Tokyo Chemical Industry Co., Ltd. ) component content・phosphorus atom content: the content of phosphorus atoms when the resin component of the photosensitive resin composition is 100% by mass

由上述表之結果，瞭解到於使用本發明之感光性樹脂組成物的實施例，具有阻燃性、解析性、裂紋性，且平均線熱膨脹率低，且玻璃轉移溫度高。From the results of the above table, it is understood that the examples using the photosensitive resin composition of the present invention have flame retardancy, analytical properties, cracking properties, a low average linear thermal expansion coefficient, and a high glass transition temperature.

另一方面，於比較例1，由於使用平均粒徑超過2.0μm之(C)成分，(C)成分之溶解性劣化，其結果，使得最小貫孔徑超過100μm等解析性惡化，並非可作為感光性樹脂組成物使用者。於比較例2，由於使用平均粒徑未滿0.7μm之(C)成分，即使進行光照射亦無法固化感光性樹脂組成物，其結果，使得解析性惡化，並非可作為感光性樹脂組成物使用者。未含有(C)成分之比較例3、比較例5與實施例進行比較，阻燃性惡化，並非可作為感光性樹脂組成物使用者。又，取代(C)成分，改含有SPS-100之比較例4，解析性及抗裂性惡化，並非可作為感光性樹脂組成物使用者。On the other hand, in Comparative Example 1, since the component (C) with an average particle diameter exceeding 2.0 μm was used, the solubility of the component (C) was deteriorated, and as a result, the resolution was deteriorated, such as the minimum penetrating diameter exceeding 100 μm, and it was not suitable as a photosensitive material. Sexual resin composition users. In Comparative Example 2, since the component (C) having an average particle diameter of less than 0.7 μm was used, the photosensitive resin composition could not be cured even if it was irradiated with light, and as a result, the resolution was deteriorated, and it was not usable as a photosensitive resin composition. By. In Comparative Example 3 and Comparative Example 5 not containing the component (C), the flame retardancy was deteriorated in comparison with the Examples, and they were not usable as a photosensitive resin composition. Moreover, in the comparative example 4 which replaced with (C)component and contained SPS-100, the analytical property and crack resistance deteriorated, and it was not usable as a photosensitive resin composition.

在各實施例，確認即使未含有(F)～(G)成分等的情況，儘管程度有差，但有與上述實施例相同的結果。In each example, even when components (F) to (G) and the like were not contained, it was confirmed that the same results as those of the above-mentioned examples were obtained, although the degree was inferior.

Claims (13)

一種感光性樹脂組成物，其係含有：(A)含有乙烯性不飽和基及羧基的樹脂，(B)平均粒徑為0.5μm以上2.5μm以下的無機填充材，(C)平均粒徑為0.7μm以上2.0μm以下的粒子，且含有下述一般式(1)或下述一般式(2)表示之磷化合物的粒子，(D)光聚合起始劑及(E)環氧樹脂的感光性樹脂組成物，其特徵為將感光性樹脂組成物的固形分全體定為100質量%時，(B)成分的含量為60質量%以上85質量%以下，其中(B)成分的平均粒徑為藉由雷射繞射散射式粒度分布測定裝置之測定所得之以體積基準之粒度分布的中位徑，(C)成分的平均粒徑為藉由雷射繞射式粒度分布測定裝置測定所得之粒度分布所算出的平均粒徑，
Figure 107108397-A0305-02-0052-1
 (一般式(1)及一般式(2)中，n表示1或2)。 A photosensitive resin composition comprising: (A) a resin containing an ethylenically unsaturated group and a carboxyl group, (B) an inorganic filler having an average particle size of 0.5 μm or more and 2.5 μm or less, and (C) an average particle size of Particles of 0.7 μm or more and 2.0 μm or less, and particles containing a phosphorus compound represented by the following general formula (1) or the following general formula (2), (D) photopolymerization initiator and (E) photosensitive epoxy resin A photosensitive resin composition characterized in that when the total solid content of the photosensitive resin composition is 100% by mass, the content of the component (B) is 60% by mass to 85% by mass, wherein the average particle size of the component (B) is The median diameter of the particle size distribution on a volume basis obtained by measurement by a laser diffraction-type particle size distribution analyzer, and the average particle size of the component (C) is determined by a laser diffraction-type particle size distribution analyzer. The average particle size calculated from the particle size distribution,
Figure 107108397-A0305-02-0052-1
 (In general formula (1) and general formula (2), n represents 1 or 2). 如請求項1之感光性樹脂組成物，其中，(E)成分係含有聯苯型環氧樹脂及四苯基乙烷型環氧樹脂之至少任一種。 The photosensitive resin composition according to claim 1, wherein the component (E) contains at least one of a biphenyl-type epoxy resin and a tetraphenylethane-type epoxy resin. 如請求項1之感光性樹脂組成物，其中，(A)成分係具有萘骨架。 The photosensitive resin composition according to claim 1, wherein the component (A) has a naphthalene skeleton. 如請求項1之感光性樹脂組成物，其中，(A)成分係含有含酸改質萘骨架之環氧(甲基)丙烯酸酯。 The photosensitive resin composition according to claim 1, wherein the component (A) contains an acid-modified naphthalene skeleton-containing epoxy (meth)acrylate. 如請求項1之感光性樹脂組成物，其中，將感光性樹脂組成物之樹脂成分定為100質量%時，磷原子的含量為0.1質量%以上1.2質量%以下。 The photosensitive resin composition according to claim 1, wherein the content of phosphorus atoms is 0.1 mass % or more and 1.2 mass % or less when the resin component of the photosensitive resin composition is 100 mass %. 如請求項1之感光性樹脂組成物，其中，將感光性樹脂組成物的固形分全體定為100質量%時，(C)成分的含量為0.1質量%以上10質量%以下。 The photosensitive resin composition according to claim 1, wherein the content of the component (C) is 0.1 mass % or more and 10 mass % or less when the total solid content of the photosensitive resin composition is 100 mass %. 如請求項1之感光性樹脂組成物，其係光硬化感光性樹脂組成物後，以190℃熱硬化90分鐘時在25℃~150℃之平均線熱膨脹率為50ppm以下。 The photosensitive resin composition according to claim 1, after photocuring the photosensitive resin composition, has an average linear thermal expansion rate of 50 ppm or less at 25°C to 150°C when thermally cured at 190°C for 90 minutes. 如請求項1之感光性樹脂組成物，其中，(B)成分係包含二氧化矽。 The photosensitive resin composition according to claim 1, wherein the component (B) contains silica. 一種感光性薄膜，其係含有如請求項1~8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 8. 一種附支持體之感光性薄膜，其係具有支持體，與設置在該支持體上之包含如請求項1~8中任一項之感光性樹脂組成物的感光性樹脂組成物層。 A photosensitive film with a support, comprising a support, and a photosensitive resin composition layer comprising the photosensitive resin composition according to any one of claims 1 to 8 provided on the support. 一種印刷電路板，其係包含藉由如請求項1~8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 circuit board including an insulating layer formed of a cured product of the photosensitive resin composition according to any one of claims 1 to 8. 如請求項11之印刷電路板，其中，絕緣層為阻焊劑。 The printed circuit board of claim 11, wherein the insulating layer is a solder resist. 一種半導體裝置，其係包含如請求項11之印刷電路板。A semiconductor device comprising the printed circuit board of claim 11.
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