TW202409728A - Curable resin composition, resin cured film, printed circuit board, semiconductor package, and display device - Google Patents

Curable resin composition, resin cured film, printed circuit board, semiconductor package, and display device Download PDF

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TW202409728A
TW202409728A TW112130679A TW112130679A TW202409728A TW 202409728 A TW202409728 A TW 202409728A TW 112130679 A TW112130679 A TW 112130679A TW 112130679 A TW112130679 A TW 112130679A TW 202409728 A TW202409728 A TW 202409728A
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内田一幸
渋谷佳佑
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日商日鐵化學材料股份有限公司
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/46Polymerisation initiated by wave energy or particle radiation
    • C08F2/48Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10Esters
    • C08F222/1006Esters of polyhydric alcohols or polyhydric phenols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10Esters
    • C08F222/1006Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106Esters of polycondensation macromers
    • C08F222/1067Esters of polycondensation macromers of alcohol terminated epoxy functional polymers, e.g. epoxy(meth)acrylates
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/03Use of materials for the substrate
    • H05K1/0313Organic insulating material

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

An object of the present invention is to provide a curable resin composition that suppresses pollutions caused by a polymerization initiator or decomposed products thereof and also ensures a bonding strength, a resin cured film, a printed circuit board, a semiconductor package, and a display device. The curable resin composition includes: (A) a specific unsaturated group-containing alkali-soluble resin having a fluorine skeleton, (B) a polymerizable compound having at least two unsaturated groups, (C) a specific photopolymerization initiator having a fluorine skeleton, and (D) a solvent. With respect to 100 parts by mass of the unsaturated group-containing alkali-soluble resin (A) and the polymerizable compound (B), the content of the photopolymerization initiator (C) is 1 part by mass or more and 15 parts by mass or less.

Description

硬化性樹脂組成物、樹脂硬化膜、印刷基板、半導體封裝體及顯示裝置Curable resin composition, cured resin film, printed circuit board, semiconductor package and display device

本發明是有關於一種硬化性樹脂組成物、樹脂硬化膜、印刷基板、半導體封裝體及顯示裝置。The present invention relates to a curable resin composition, a resin cured film, a printed circuit board, a semiconductor package and a display device.

在製造印刷基板、半導體封裝體及顯示裝置等時,使用用於使各種材料黏接的黏接劑。對於此種黏接劑,為了使微細的零件彼此黏接,有時要求微細圖案化,因此,有時使用包含能夠進行鹼顯影的樹脂、賦予硬化性的聚合性化合物及用於使聚合性化合物硬化的聚合起始劑的組成物(專利文獻1)。When manufacturing printed circuit boards, semiconductor packages, display devices, etc., adhesives are used to bond various materials. For this kind of adhesive, in order to bond fine parts to each other, fine patterning is sometimes required. Therefore, a resin that can be developed by alkali, a polymerizable compound that imparts curability, and a polymerizable compound that imparts curability are sometimes used. A composition of a hardened polymerization initiator (Patent Document 1).

例如,在專利文獻1中記載有一種黏接劑組成物,其包含鹼可溶性的聚合物、聚合性化合物及聚合起始劑。在專利文獻1中,使用豔佳固(Irgacure)907作為聚合起始劑。For example, Patent Document 1 describes an adhesive composition comprising an alkali-soluble polymer, a polymerizable compound, and a polymerization initiator. In Patent Document 1, Irgacure 907 is used as the polymerization initiator.

[現有技術文獻] [專利文獻] [專利文獻1]日本專利特開2003-176343號公報 [Prior art documents] [Patent Document] [Patent Document 1] Japanese Patent Application Laid-Open No. 2003-176343

[發明所要解決的問題] 基於本發明人等人的研究,若想要使用如專利文獻1中記載那樣的黏接劑將各種構件黏接,則所黏接的裝置等有時會被聚合起始劑或其分解物污染。另一方面,若使用不易產生由分解物造成的污染的聚合起始劑,則黏接強度並不充分,且非常難兼顧抑制由分解物造成的污染與確保黏接強度。 [Problem to be solved by the invention] Based on the research of the inventors and others, if one wants to use an adhesive as described in Patent Document 1 to bond various components, the bonded devices may be contaminated by the polymerization initiator or its decomposition products. On the other hand, if a polymerization initiator that is not easily contaminated by decomposition products is used, the bonding strength is not sufficient, and it is very difficult to balance the suppression of contamination by decomposition products and the assurance of bonding strength.

本發明是鑒於所述問題而成,其目的在於提供一種能兼顧抑制由聚合起始劑或其分解物造成的污染與確保黏接強度的硬化性樹脂組成物、使所述硬化性樹脂組成物硬化而獲得的樹脂硬化膜、以及將所述硬化性樹脂組成物用作黏接劑的印刷基板、半導體封裝體及顯示裝置。 [解決問題的技術手段] The present invention has been made in view of the above problems, and an object thereof is to provide a curable resin composition that can suppress contamination caused by a polymerization initiator or its decomposed products and ensure adhesive strength. A resin cured film obtained by curing, and a printed circuit board, a semiconductor package, and a display device using the curable resin composition as an adhesive. [Technical means to solve problems]

用於解決所述課題的本發明的一實施方式涉及下述[1]~[5]的硬化性樹脂組成物。 [1]一種硬化性樹脂組成物,包含:(A)下述通式(1)所表示的含不飽和基的鹼可溶性樹脂、 (B)具有至少兩個不飽和基的聚合性化合物、 (C)下述通式(9)所表示的光聚合起始劑、及 (D)溶劑, 相對於所述(A)含不飽和基的鹼可溶性樹脂與所述(B)聚合性化合物的合計100質量份,所述(C)光聚合起始劑的含量為1質量份以上且15質量份以下。 One embodiment of the present invention for solving the above problems relates to the curable resin compositions of the following [1] to [5]. [1] A curable resin composition containing: (A) an unsaturated group-containing alkali-soluble resin represented by the following general formula (1), (B) Polymeric compounds having at least two unsaturated groups, (C) A photopolymerization initiator represented by the following general formula (9), and (D) Solvent, The content of the (C) photopolymerization initiator is 1 part by mass or more and 15 parts by mass relative to a total of 100 parts by mass of the (A) unsaturated group-containing alkali-soluble resin and the (B) polymerizable compound. portion or less.

[化1] ···通式(1) [Chemistry 1] ···General formula (1)

式(1)中,Ar 1分別獨立地為碳數6以上且14以下的芳香族烴基,所鍵結的氫原子的一部分可經選自由碳數1以上且10以下的烷基、碳數6以上且10以下的芳基或芳基烷基、碳數3以上且10以下的環烷基或環烷基烷基、碳數1以上且5以下的烷氧基及鹵素基所組成的群組中的取代基取代。R 1分別獨立地為碳數2以上且4以下的伸烷基,l分別獨立地為0以上且3以下的數。G分別獨立地為(甲基)丙烯醯基、下述通式(2)或下述通式(3)所表示的取代基,Y為四價的羧酸殘基。Z分別獨立地為氫原子或下述通式(4)所表示的取代基,一個以上為下述通式(4)所表示的取代基。n是平均值為1以上且20以下的數。 In formula (1), Ar 1 is independently an aromatic alkyl group having 6 to 14 carbon atoms, and a portion of the hydrogen atoms to which it is bonded may be substituted by a substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group or an arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or a cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen group. R 1 is independently an alkylene group having 2 to 4 carbon atoms, and l is independently a number of 0 to 3. G is independently a (meth)acryloyl group, a substituent represented by the following general formula (2) or the following general formula (3), and Y is a tetravalent carboxylic acid residue. Z is independently a hydrogen atom or a substituent represented by the following general formula (4), and one or more of them are substituents represented by the following general formula (4). n is a number whose average value is greater than or equal to 1 and less than or equal to 20.

[化2] ···通式(2) [Chemicalization 2] ···General formula (2)

[化3] ···通式(3) [Chemistry 3] ···General formula (3)

式(2)、式(3)中,R 2為氫原子或甲基,R 3為碳數2以上且10以下的二價的伸烷基或烷基伸芳基,R 4為碳數2以上且20以下的二價的飽和或不飽和的烴基,p為0以上且10以下的數。*表示與通式(1)所示的化合物的鍵結部位。 In formula (2) and formula (3), R2 is a hydrogen atom or a methyl group, R3 is a divalent alkylene group or an alkylarylene group having 2 to 10 carbon atoms, R4 is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number of 0 to 10. * represents a bonding site with the compound represented by general formula (1).

[化4] ···通式(4) [Chemical 4] ···General formula (4)

式(4)中,W為二價或三價的羧酸殘基,m為1或2的數。*表示與通式(1)所示的化合物的鍵結部位。In formula (4), W is a divalent or trivalent carboxylic acid residue, and m is 1 or 2. * represents a bonding site with the compound represented by general formula (1).

[化5] ···通式(9) [Chemistry 5] ···General formula (9)

通式(9)中, A為氫原子、鹵素原子、硝基、碳數1以上且20以下的直鏈狀或可具有分支鏈的烷基、碳數3以上且10以下的環烷基、碳數4以上且10以下的烷基環烷基、碳數4以上且10以下的環烷基烷基、-N(R 9) 2、-COR 10或-CO-CR 6R 7R 8所表示的取代基。此外,這些取代基所具有的伸甲基(-CH 2-)也可經-O-、-N-、-S-或-C(=O)-取代。 R 5獨立地表示氫原子、鹵素原子、碳數1以上且20以下的直鏈狀或可具有分支鏈的烷基、碳數3以上且20以下的環烷基烷基或碳數2以上且20以下的烯基。此外,這些官能基所具有的伸甲基(-CH 2-)也可經-O-、-N-、-S-或-C(=O)-取代。另外,兩個R 5也可相互鍵結而形成環。 R 6及R 7獨立地表示碳數1以上且20以下的直鏈狀或可具有分支鏈的烷基、碳數3以上且20以下的環烷基、碳數4以上且20以下的環烷基烷基、碳數4以上且20以下的烷基環烷基、碳數6以上且20以下的芳基或碳數7以上且20以下的烷基芳基。此外,這些官能基所具有的氫原子中的一個或多個可獨立地經碳數1以上且20以下的直鏈狀或可具有分支鏈的烷基、鹵素原子、羥基或硝基取代。另外,這些官能基所具有的伸甲基(-CH 2-)也可經-O-、-N-、-S-或-C(=O)-取代。R 6及R 7可相互鍵結而形成環。 或者,也可為,R 6為碳數1以上且20以下的直鏈狀或可具有分支鏈的烷基、或者碳數2以上且20以下的直鏈狀或可具有分支鏈的烯基,且R 7為下述通式(10)~通式(12)所表示的官能基中的任一個。 In the general formula (9), A is a hydrogen atom, a halogen atom, a nitro group, a linear or optionally branched alkyl group having a carbon number of 1 to 20, a cycloalkyl group having a carbon number of 3 to 10, Alkylcycloalkyl group with 4 or more carbon atoms and 10 or less carbon atoms, cycloalkylalkyl group with 4 or more carbon atoms and 10 or less carbon atoms, -N(R 9 ) 2 , -COR 10 or -CO-CR 6 R 7 R 8 represents the substituent. In addition, the methylene group (-CH 2 -) of these substituents may be substituted by -O-, -N-, -S- or -C(=O)-. R 5 independently represents a hydrogen atom, a halogen atom, a linear or optionally branched alkyl group with a carbon number of 1 to 20, a cycloalkylalkyl group with a carbon number of 3 to 20, or a cycloalkylalkyl group with a carbon number of 2 or more and Alkenyl group below 20. In addition, the methylene group (-CH 2 -) of these functional groups may be substituted by -O-, -N-, -S- or -C(=O)-. In addition, two R 5 may be bonded to each other to form a ring. R 6 and R 7 independently represent a linear or optionally branched alkyl group having a carbon number of 1 to 20, a cycloalkyl group having a carbon number of 3 to 20, or a cycloalkyl having a carbon number of 4 to 20. alkylalkyl group, an alkylcycloalkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms. In addition, one or more of the hydrogen atoms of these functional groups may be independently substituted with a linear or branched alkyl group having a carbon number of 1 to 20, a halogen atom, a hydroxyl group, or a nitro group. In addition, the methylene group (-CH 2 -) of these functional groups may be substituted by -O-, -N-, -S- or -C(=O)-. R 6 and R 7 may bond with each other to form a ring. Alternatively, R 6 may be a linear or optionally branched alkyl group having a carbon number of 1 to 20, or a linear or optionally branched alkenyl group having a carbon number of 2 to 20, And R 7 is any one of the functional groups represented by the following general formula (10) to general formula (12).

[化6] ···通式(10) [Chemical 6] ···General formula (10)

通式(10)中,R 13表示氫原子、碳數1以上且8以下的直鏈狀或可具有分支鏈的烷基、或者苯基,R 14、R 15及R 16獨立地表示氫原子、或者碳數1以上且4以下的直鏈狀或可具有分支鏈的烷基。*表示與通式(9)所示的化合物的鍵結部位。 In the general formula (10), R 13 represents a hydrogen atom, a linear or optionally branched alkyl group having a carbon number of 1 to 8, or a phenyl group, and R 14 , R 15 and R 16 independently represent a hydrogen atom. , or a linear or optionally branched alkyl group having 1 to 4 carbon atoms. * indicates the bonding site with the compound represented by general formula (9).

[化7] ···通式(11) [Chemistry 7] ···General formula (11)

通式(11)中,s為0以上且4以下的數。*表示與通式(9)所示的化合物的鍵結部位。In the general formula (11), s is a number of 0 or more and 4 or less. * represents a bonding site with the compound represented by the general formula (9).

[化8] ···通式(12) [Chemistry 8] ···General formula (12)

通式(12)中,Ar 2表示均可經取代的苯基、萘基、呋喃基、噻吩基或吡啶基。*表示與通式(9)所示的化合物的鍵結部位。 In the general formula (12), Ar 2 represents a phenyl group, a naphthyl group, a furyl group, a thienyl group or a pyridyl group which may be substituted. * represents a bonding site with the compound represented by the general formula (9).

R 8表示N-嗎啉基、N-呱啶基、N-吡咯基或N-二烷基。此外,這些官能基所具有的氫原子中的一個或多個可獨立地經鹵素原子或羥基取代。 R 9獨立地表示碳數1以上且20以下的直鏈狀或可具有分支鏈的烷基、碳數3以上且20以下的環烷基、碳數2以上且20以下的直鏈狀或可具有分支鏈的烯基、碳數6以上且20以下的芳基或碳數7以上且20以下的烷基芳基。此外,這些官能基所具有的氫原子中的一個或多個可獨立地經碳數1以上且20以下的直鏈狀或可具有分支鏈的烷基、鹵素原子、羥基或硝基取代。另外,這些取代基所具有的伸甲基(-CH 2-)也可經-O-取代。另外,兩個R 9也可相互鍵結而形成環,此時,所述環可為經由-O-、-S-、-NH-而形成的五員環或六員環。 R 10表示碳數1以上且20以下的直鏈狀或可具有分支鏈的烷基、碳數3以上且20以下的環烷基、碳數4以上且10以下的烷基環烷基、碳數2以上且20以下的直鏈狀或可具有分支鏈的烯基、碳數6以上且20以下的芳基或碳數7以上且20以下的烷基芳基。此外,這些官能基所具有的伸甲基(-CH 2-)也可經-O-或-S-取代。這些官能基所具有的氫原子中的一個或多個可獨立地經碳數1以上且20以下的直鏈狀或可具有分支鏈的烷基、鹵素原子、硝基、氰基、-SR 11或-OR 12取代。 R 11及R 12獨立地表示氫原子、或者碳數1以上且20以下的直鏈狀或可具有分支鏈的烷基。 R 8 represents N-morpholinyl, N-piridyl, N-pyrrolyl or N-dialkyl. In addition, one or more of the hydrogen atoms possessed by these functional groups may be independently substituted with a halogen atom or a hydroxyl group. R 9 independently represents a linear or optionally branched alkyl group having a carbon number of 1 or more and 20 or less, a cycloalkyl group having a carbon number of 3 or more and 20 or less, a linear or optionally branched alkyl group having a carbon number of 2 or more and 20 or less. An alkenyl group having a branched chain, an aryl group having 6 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms. In addition, one or more of the hydrogen atoms of these functional groups may be independently substituted with a linear or branched alkyl group having a carbon number of 1 to 20, a halogen atom, a hydroxyl group, or a nitro group. In addition, the methylene group (-CH 2 -) of these substituents may be substituted with -O-. In addition, two R 9s may be bonded to each other to form a ring. In this case, the ring may be a five-membered ring or a six-membered ring formed through -O-, -S-, or -NH-. R 10 represents a linear or optionally branched alkyl group having a carbon number of 1 to 20, a cycloalkyl group having a carbon number of 3 to 20, an alkylcycloalkyl group having a carbon number of 4 to 10, a carbon A linear or optionally branched alkenyl group having a number of 2 or more and 20 or less, an aryl group having a carbon number of 6 or more and 20 or less, or an alkylaryl group having a carbon number of 7 or more and 20 or less. In addition, the methylene group (-CH 2 -) of these functional groups may be substituted with -O- or -S-. One or more of the hydrogen atoms of these functional groups may be independently modified by a linear or branched alkyl group having a carbon number of 1 to 20, a halogen atom, a nitro group, a cyano group, -SR 11 OR -OR 12 replaced. R 11 and R 12 independently represent a hydrogen atom or a linear or optionally branched alkyl group having 1 to 20 carbon atoms.

[2]根據[1]所述的硬化性樹脂組成物,其中,所述(A)含不飽和基的鹼可溶性樹脂的重量平均分子量為1000以上且40000以下且酸值為50 mgKOH/g以上且200 mgKOH/g以下。 [3]根據[1]或[2]所述的硬化性樹脂組成物,包含(E)增感劑。 [4]根據[3]所述的硬化性樹脂組成物,其中,所述(E)增感劑包含二苯甲酮衍生物或硫雜蒽酮衍生物。 [5]根據[1]至[4]中任一項所述的硬化性樹脂組成物,包含(F)具有兩個以上的環氧基的環氧化合物。 [2] The curable resin composition according to [1], wherein the weight average molecular weight of the unsaturated group-containing alkali-soluble resin (A) is 1,000 to 40,000 and the acid value is 50 to 200 mgKOH/g. [3] The curable resin composition according to [1] or [2], comprising (E) a sensitizer. [4] The curable resin composition according to [3], wherein the (E) sensitizer comprises a benzophenone derivative or a thioxanthrone derivative. [5] The curable resin composition according to any one of [1] to [4], comprising (F) an epoxy compound having two or more epoxy groups.

用於解決所述課題的本發明的一實施方式涉及下述[6]的樹脂硬化膜。 [6]一種樹脂硬化膜,是使根據[1]至[5]中任一項所述的硬化性樹脂組成物硬化而成。 One embodiment of the present invention for solving the above problems relates to the resin cured film of the following [6]. [6] A resin cured film obtained by curing the curable resin composition according to any one of [1] to [5].

用於解決所述課題的本發明的一實施方式涉及下述[7]~[9]的印刷基板、半導體封裝體及顯示裝置。 [7]一種印刷基板,包含根據[6]所述的樹脂硬化膜作為絕緣膜。 [8]一種半導體封裝體,包含根據[6]所述的樹脂硬化膜作為絕緣膜。 [9]一種顯示裝置,包含根據[6]所述的樹脂硬化膜作為絕緣膜。 [發明的效果] One embodiment of the present invention for solving the above problems relates to the printed circuit board, semiconductor package, and display device of the following [7] to [9]. [7] A printed circuit board including the resin cured film according to [6] as an insulating film. [8] A semiconductor package including the resin cured film according to [6] as an insulating film. [9] A display device including the resin cured film according to [6] as an insulating film. [Effects of the invention]

通過本發明,可提供一種能兼顧抑制由聚合起始劑或其分解物造成的污染與確保黏接強度的硬化性樹脂組成物、使所述硬化性樹脂組成物硬化而獲得的樹脂硬化膜、以及將所述硬化性樹脂組成物用作黏接劑的印刷基板、半導體封裝體及顯示裝置。According to the present invention, it is possible to provide a curable resin composition capable of both suppressing contamination caused by a polymerization initiator or its decomposed products and ensuring adhesive strength, and a resin cured film obtained by curing the curable resin composition. And printed circuit boards, semiconductor packages and display devices using the curable resin composition as an adhesive.

以下,對本發明的實施方式進行說明,但本發明並不限定於以下的實施方式。此外,在本發明中,關於各成分的含量,在小數第一位為0時,有時省略小數點以後的表述。另外,關於之後例示的化合物或者官能基或結構,只要未特別提及,則可僅使用所例示者中的一種,也可並用多種。The following describes the embodiments of the present invention, but the present invention is not limited to the following embodiments. In addition, in the present invention, when the first decimal place is 0, the expression after the decimal point is sometimes omitted. In addition, as for the compounds, functional groups or structures exemplified below, only one of the exemplified ones may be used, or multiple ones may be used in combination unless otherwise specified.

1.硬化性樹脂組成物 用於解決所述第一課題的本發明的一實施方式涉及一種硬化性樹脂組成物,包含: (A)通式(1)所表示的含不飽和基的鹼可溶性樹脂、 (B)具有至少兩個不飽和基的聚合性化合物、 (C)通式(9)所表示的光聚合起始劑、及 (D)溶劑, 相對於所述(A)含不飽和基的鹼可溶性樹脂與所述(B)聚合性化合物的合計100質量份,所述(C)光聚合起始劑的含量為1質量份以上且15質量份以下。 1. Curable resin composition One embodiment of the present invention for solving the first problem relates to a curable resin composition, comprising: (A) an alkali-soluble resin containing an unsaturated group represented by general formula (1), (B) a polymerizable compound having at least two unsaturated groups, (C) a photopolymerization initiator represented by general formula (9), and (D) a solvent, wherein the content of the photopolymerization initiator (C) is 1 part by mass or more and 15 parts by mass or less relative to 100 parts by mass of the total of the alkali-soluble resin containing an unsaturated group (A) and the polymerizable compound (B).

(A)1-1.通式(1)所表示的含不飽和基的鹼可溶性樹脂 (A)通式(1)所表示的含不飽和基的鹼可溶性樹脂(以下,也簡稱為「(A)成分」)為在分子中具有聚合性不飽和基與用於表現出鹼可溶性的酸性基,並通過光或熱的刺激而使聚合性不飽和基產生聚合反應來進行硬化的化合物。 (A) 1-1. Unsaturated group-containing alkali-soluble resin represented by general formula (1) (A) The unsaturated group-containing alkali-soluble resin represented by the general formula (1) (hereinafter, also referred to as "(A) component") has a polymerizable unsaturated group in the molecule and is used to express alkali solubility. A compound that has an acidic group and hardens by polymerizing the polymerizable unsaturated group through stimulation by light or heat.

[化9] ···通式(1) [Chemical 9] ···General formula (1)

通式(1)中,Ar 1獨立地為碳數6以上且14以下的芳香族烴基,構成Ar 1的氫原子的一部分可經碳數1以上且10以下的烷基、碳數6以上且10以下的芳基或芳基烷基、碳數3以上且10以下的環烷基或環烷基烷基、碳數1以上且5以下的烷氧基或鹵素基取代。R 1獨立地為碳數2以上且4以下的伸烷基。l獨立地為0以上且3以下的數。G獨立地為(甲基)丙烯醯基、或者下述通式(2)或下述通式(3)所表示的取代基。Y為四價的羧酸殘基。Z獨立地為氫原子或下述通式(4)所表示的取代基,Z的至少一個為下述通式(4)所表示的取代基。n是平均值為1以上且20以下的數。 In the general formula (1), Ar 1 is independently an aromatic hydrocarbon group having a carbon number of 6 or more and 14 or less. A part of the hydrogen atoms constituting Ar 1 may be an alkyl group having a carbon number of 1 or more and 10 or less, or an alkyl group having a carbon number of 6 or more and 14 or less. Substituted with an aryl group or arylalkyl group having 10 or less carbon atoms, a cycloalkyl group or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group or a halogen group having 1 to 5 carbon atoms. R 1 is independently an alkylene group having 2 to 4 carbon atoms. l is independently a number from 0 to 3. G is independently a (meth)acrylyl group or a substituent represented by the following general formula (2) or the following general formula (3). Y is a tetravalent carboxylic acid residue. Z is independently a hydrogen atom or a substituent represented by the following general formula (4), and at least one of Z is a substituent represented by the following general formula (4). n is a number whose average value is 1 or more and 20 or less.

此外,「(甲基)丙烯醯基」是丙烯醯基及甲基丙烯醯基的總稱,所謂「(甲基)丙烯酸」是丙烯酸及甲基丙烯酸的總稱,所謂(甲基)丙烯酸酯是丙烯酸酯及甲基丙烯酸酯的總稱,均是指這些中的一者或兩者。In addition, "(meth)acrylyl" is the general term for acrylic and methacrylic groups, "(meth)acrylic acid" is the general term for acrylic acid and methacrylic acid, and (meth)acrylate is the general term for acrylic acid. The general terms of ester and methacrylate refer to one or both of these.

[化10] ···通式(2) [Chemistry 10] ···General formula (2)

[化11] ···通式(3) [Chemistry 11] ···General formula (3)

通式(2)及通式(3)中,R 2為氫原子或甲基,R 3為碳數2以上且10以下的伸烷基或烷基伸芳基,R 4為碳數2以上且20以下的飽和或不飽和的烴基,p為0以上且10以下的數。*表示與通式(1)所示的化合物的鍵結部位。 In general formula (2) and general formula (3), R 2 is a hydrogen atom or a methyl group, R 3 is an alkylene group or alkyl aryl group having 2 or more carbon atoms and 10 or less carbon atoms, and R 4 is an alkylene group having 2 or more carbon atoms and 10 or less carbon atoms. 20 or less saturated or unsaturated hydrocarbon groups, p is a number from 0 to 10. * indicates the bonding site with the compound represented by general formula (1).

[化12] ···通式(4) [Chemistry 12] ···General formula (4)

通式(4)中,W為二價或三價的羧酸殘基,m為1或2的數。*表示與通式(1)所示的化合物的鍵結部位。In the general formula (4), W is a divalent or trivalent carboxylic acid residue, and m is a number of 1 or 2. * indicates the bonding site with the compound represented by general formula (1).

通式(1)所表示的樹脂可利用以下的方法來合成。The resin represented by the general formula (1) can be synthesized by the following method.

首先,使下述通式(5)所表示的、在一分子內可具有若干個環氧烷改性基的、具有雙芳基茀骨架的環氧化合物(a-1)(以下,也簡稱為「環氧化合物(a-1)」)與(甲基)丙烯酸、下述通式(6)所表示的(甲基)丙烯酸衍生物及下述通式(7)所表示的(甲基)丙烯酸衍生物的至少一種反應,獲得作為(甲基)丙烯酸環氧酯的二醇化合物。此外,所述雙芳基茀骨架較佳為雙萘酚茀骨架或雙苯酚茀骨架。First, an epoxy compound (a-1) (hereinafter, also referred to as abbreviated as "Epoxy compound (a-1)") and (meth)acrylic acid, a (meth)acrylic acid derivative represented by the following general formula (6) and (methyl) represented by the following general formula (7) ) at least one reaction of an acrylic acid derivative to obtain a diol compound as (meth)acrylic acid epoxy ester. In addition, the bisaryl fluoride skeleton is preferably a bis-naphthol fluoride skeleton or a bisphenol fluoride skeleton.

[化13] ···通式(5) [Chemistry 13] ···General formula (5)

通式(5)中,Ar 1分別獨立地為碳數6以上且14以下的芳香族烴基,構成Ar 1的氫原子的一部分可經碳數1以上且10以下的烷基、碳數6以上且10以下的芳基或芳基烷基、碳數3以上且10以下的環烷基或環烷基烷基、碳數1以上且5以下的烷氧基或鹵素基取代。R 1獨立地為碳數2以上且4以下的伸烷基。l獨立地為0以上且3以下的數。 In the general formula (5), Ar 1 is independently an aromatic alkyl group having 6 to 14 carbon atoms, and a portion of the hydrogen atoms constituting Ar 1 may be substituted by an alkyl group having 1 to 10 carbon atoms, an aryl group or an arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or a cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group or a halogen group having 1 to 5 carbon atoms. R 1 is independently an alkylene group having 2 to 4 carbon atoms. l is independently a number of 0 to 3.

[化14] ···通式(6) [Chemical 14] ···General formula (6)

[化15] ···通式(7) [Chemistry 15] ···General formula (7)

通式(6)、通式(7)中,R 2為氫原子或甲基,R 3為碳數2以上且10以下的伸烷基或烷基伸芳基,R 4為碳數2以上且20以下的飽和或不飽和的烴基,p為0以上且10以下的數。 In the general formula (6) and the general formula (7), R 2 is a hydrogen atom or a methyl group, R 3 is an alkylene group or alkyl aryl group having a carbon number of 2 or more and 10 or less, and R 4 is an alkyl aryl group having a carbon number of 2 or more and 10 or less. 20 or less saturated or unsaturated hydrocarbon groups, p is a number from 0 to 10.

所述環氧化合物(a-1)與(甲基)丙烯酸或其衍生物的反應可使用公知的方法。例如,在日本專利特開平4-355450號公報中記載有:通過相對於具有兩個環氧基的環氧化合物1莫耳而使用約2莫耳的(甲基)丙烯酸,可獲得含有聚合性不飽和基的二醇化合物。在本實施方式中,通過所述反應而獲得的化合物為下述通式(8)所表示的含有聚合性不飽和基的二醇(d)(以下,也簡稱為「二醇(d)」)。The reaction of the epoxy compound (a-1) with (meth)acrylic acid or a derivative thereof can be carried out by a known method. For example, Japanese Patent Publication No. 4-355450 states that a diol compound containing a polymerizable unsaturated group can be obtained by using about 2 mol of (meth)acrylic acid per 1 mol of an epoxy compound having two epoxy groups. In the present embodiment, the compound obtained by the reaction is a diol (d) containing a polymerizable unsaturated group represented by the following general formula (8) (hereinafter also referred to as "diol (d)").

[化16] ···通式(8) [Chemistry 16] ···General formula (8)

通式(8)中,Ar 1分別獨立地為碳數6以上且14以下的芳香族烴基,構成Ar 1的氫原子的一部分可經碳數1以上且10以下的烷基、碳數6以上且10以下的芳基或芳基烷基、碳數3以上且10以下的環烷基或環烷基烷基、碳數1以上且5以下的烷氧基或鹵素基取代。G分別獨立地為(甲基)丙烯醯基、通式(2)或通式(3)所表示的取代基,R 1獨立地為碳數2以上且4以下的伸烷基。l獨立地為0以上且3以下的數。 In the general formula (8), Ar 1 is independently an aromatic alkyl group having 6 to 14 carbon atoms, and a portion of the hydrogen atoms constituting Ar 1 may be substituted by an alkyl group having 1 to 10 carbon atoms, an aryl group or an arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or a cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group or a halogen group having 1 to 5 carbon atoms. G is independently a (meth)acryloyl group, a substituent represented by the general formula (2) or the general formula (3), and R 1 is independently an alkylene group having 2 to 4 carbon atoms. l is independently a number of 0 to 3.

[化17] ···通式(2) [Chemistry 17] ···General formula (2)

[化18] ···通式(3) [Chemical 18] ···General formula (3)

通式(2)及通式(3)中,R 2為氫原子或甲基,R 3為碳數2以上且10以下的伸烷基或烷基伸芳基,R 4為碳數2以上且20以下的飽和或不飽和的烴基,p為0以上且10以下的數。*表示與通式(1)所示的化合物的鍵結部位。 In general formula (2) and general formula (3), R 2 is a hydrogen atom or a methyl group, R 3 is an alkylene group or alkyl aryl group having 2 or more carbon atoms and 10 or less carbon atoms, and R 4 is an alkylene group having 2 or more carbon atoms and 10 or less carbon atoms. 20 or less saturated or unsaturated hydrocarbon groups, p is a number from 0 to 10. * indicates the bonding site with the compound represented by general formula (1).

其次,使所述獲得的二醇(d)、二羧酸或三羧酸或者其酸單酐(b)及四羧酸或其酸二酐(c)反應,可獲得通式(1)所表示的在一分子內具有羧基及聚合性不飽和基的含不飽和基的硬化性樹脂。Next, the obtained diol (d), dicarboxylic acid or tricarboxylic acid or its monoanhydride (b) and tetracarboxylic acid or its dianhydride (c) are reacted to obtain an unsaturated group-containing curable resin represented by the general formula (1) having a carboxyl group and a polymerizable unsaturated group in one molecule.

所述酸成分為可與二醇(d)分子中的羥基反應的多元酸成分。為了獲得通式(1)所表示的樹脂,需要並用二羧酸或三羧酸或者它們的酸單酐(b)及四羧酸或其酸二酐(c)。所述酸成分的羧酸殘基可為飽和烴基或不飽和烴基的任一種。另外,在這些羧酸殘基中也可包含-O-、-S-、羰基等含有異質元素的鍵。The acid component is a polyacid component that can react with the hydroxyl group in the diol (d) molecule. In order to obtain the resin represented by the general formula (1), it is necessary to use a dicarboxylic acid or a tricarboxylic acid or their acid monoanhydride (b) and a tetracarboxylic acid or its acid dianhydride (c). The carboxylic acid residue of the acid component can be any of a saturated hydrocarbon group and an unsaturated hydrocarbon group. In addition, these carboxylic acid residues can also contain bonds containing heterogeneous elements such as -O-, -S-, and carbonyl groups.

在所述二羧酸或三羧酸或者它們的酸單酐(b)的例子中包含:鏈式烴二羧酸或三羧酸、脂環式烴二羧酸或三羧酸、芳香族烴二羧酸或三羧酸及它們的酸單酐等。Examples of the dicarboxylic acid or tricarboxylic acid or their monoanhydrides (b) include chain hydrocarbon dicarboxylic acids or tricarboxylic acids, alicyclic hydrocarbon dicarboxylic acids or tricarboxylic acids, aromatic hydrocarbon dicarboxylic acids or tricarboxylic acids and their monoanhydrides.

在所述鏈式烴二羧酸或三羧酸的例子中包含:琥珀酸、乙醯基琥珀酸、馬來酸、己二酸、衣康酸、壬二酸、檸蘋酸(citramalic acid)、丙二酸、戊二酸、檸檬酸、酒石酸、氧代戊二酸、庚二酸、癸二酸、辛二酸及二甘醇酸等、以及導入有任意的取代基的這些二羧酸或三羧酸等。Examples of the chain alkyl dicarboxylic acid or tricarboxylic acid include succinic acid, acetyl succinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid and diglycolic acid, as well as these dicarboxylic acids or tricarboxylic acids into which any substituents are introduced.

在所述脂環式烴二羧酸或三羧酸的例子中包含:環丁烷二羧酸、環戊烷二羧酸、六氫鄰苯二甲酸、四氫鄰苯二甲酸、甲基四氫鄰苯二甲酸、甲基內伸甲基四氫鄰苯二甲酸、氯菌酸、六氫偏苯三甲酸及降冰片烷二羧酸等、以及導入有任意的取代基的這些二羧酸或三羧酸等。Examples of the alicyclic alkyl dicarboxylic acids or tricarboxylic acids include cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methylendometriyltetrahydrophthalic acid, chlorendic acid, hexahydrotrimellitic acid and norbornanedicarboxylic acid, as well as these dicarboxylic acids or tricarboxylic acids into which any substituents are introduced.

在所述芳香族烴二羧酸或三羧酸的例子中包含:鄰苯二甲酸、間苯二甲酸、1,8-萘二羧酸、2,3-萘二羧酸及偏苯三甲酸等、以及導入有任意的取代基的這些二羧酸或三羧酸。Examples of the aromatic hydrocarbon dicarboxylic acid or tricarboxylic acid include: phthalic acid, isophthalic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid and trimellitic acid etc., and these dicarboxylic acids or tricarboxylic acids introduced with optional substituents.

這些中,所述二羧酸或三羧酸較佳為琥珀酸、衣康酸、四氫鄰苯二甲酸、六氫偏苯三甲酸、鄰苯二甲酸及偏苯三甲酸,更佳為琥珀酸、衣康酸及四氫鄰苯二甲酸。Among these, the dicarboxylic acid or tricarboxylic acid is preferably succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid and trimellitic acid, and more preferably amber acid, itaconic acid and tetrahydrophthalic acid.

所述二羧酸或三羧酸較佳為使用其酸單酐。The dicarboxylic acid or tricarboxylic acid is preferably its acid monoanhydride.

在所述四羧酸或其酸二酐(c)的例子中包含:鏈式烴四羧酸、脂環式烴四羧酸、芳香族烴四羧酸及它們的酸二酐等。Examples of the tetracarboxylic acid or its acid dianhydride (c) include chain hydrocarbon tetracarboxylic acid, alicyclic hydrocarbon tetracarboxylic acid, aromatic hydrocarbon tetracarboxylic acid and their acid dianhydride, and the like.

在所述鏈式烴四羧酸的例子中包含:丁烷四羧酸、戊烷四羧酸、己烷四羧酸、以及導入有脂環式烴基及不飽和烴基等取代基的這些鏈式烴四羧酸等。Examples of the chain alkane tetracarboxylic acid include butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, and these chain alkane tetracarboxylic acids into which a substituent such as an alicyclic alkyl group and an unsaturated alkyl group is introduced.

在所述脂環式烴四羧酸的例子中包含:環丁烷四羧酸、環戊烷四羧酸、環己烷四羧酸、環庚烷四羧酸及降冰片烷四羧酸、以及導入有鏈式烴基及不飽和烴基等取代基的這些脂環式四羧酸等。Examples of the alicyclic hydrocarbon tetracarboxylic acid include: cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid and norbornane tetracarboxylic acid, and these alicyclic tetracarboxylic acids in which substituents such as chain hydrocarbon groups and unsaturated hydrocarbon groups are introduced.

在所述芳香族烴四羧酸的例子中包含:均苯四甲酸、二苯甲酮四羧酸、聯苯四羧酸、二苯基醚四羧酸、二苯基碸四羧酸、萘-1,4,5,8-四羧酸及萘-2,3,6,7-四羧酸等。Examples of the aromatic tetracarboxylic acid include pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenylsulfone tetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, and naphthalene-2,3,6,7-tetracarboxylic acid.

這些中,所述四羧酸較佳為聯苯四羧酸、二苯甲酮四羧酸及二苯基醚四羧酸,更佳為聯苯四羧酸及二苯基醚四羧酸。Among these, the tetracarboxylic acid is preferably biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid and diphenyl ether tetracarboxylic acid, and more preferably biphenyltetracarboxylic acid and diphenyl ether tetracarboxylic acid.

所述四羧酸較佳為使用其酸二酐。As the tetracarboxylic acid, its acid dianhydride is preferably used.

另外,也可使用雙偏苯三甲酸酐芳基酯類來代替所述四羧酸或其酸二酐(c)。所謂雙偏苯三甲酸酐芳基酯類例如為通過國際公開第2010/074065號中所記載的方法而製造的化合物,在結構上為芳香族二醇(萘二醇、聯苯酚及三聯苯二醇等)的兩個羥基與二分子的偏苯三甲酸酐的羧基分別反應並進行酯鍵結的形態的酸二酐。In addition, trimellitic anhydride aryl esters may be used instead of the tetracarboxylic acid or its acid dianhydride (c). The so-called trimellitic anhydride aryl esters are compounds produced by the method described in International Publication No. 2010/074065, for example, and are structurally aromatic diols (naphthalenediol, biphenol and terphenyldiol). It is an acid dianhydride in the form in which two hydroxyl groups of two molecules of trimellitic anhydride react with each other and form an ester bond with the carboxyl groups of two molecules of trimellitic anhydride.

二醇(d)與酸成分(b)及酸成分(c)的反應方法並無特別限定,可採用公知的方法。例如,在日本專利特開平9-325494號公報中記載有在反應溫度為90℃~140℃下使(甲基)丙烯酸環氧酯與四羧酸二酐反應的方法。The reaction method of diol (d) with acid component (b) and acid component (c) is not particularly limited, and a known method can be adopted. For example, Japanese Patent Laid-Open No. 9-325494 describes a method of reacting epoxy (meth)acrylate with tetracarboxylic dianhydride at a reaction temperature of 90° C. to 140° C.

此時,為了使化合物的末端成為羧基,較佳為以(甲基)丙烯酸環氧酯(二醇(d))、二羧酸或三羧酸或者它們的酸單酐(b)及四羧酸二酐(c)的莫耳比成為(d):(b):(c)=1.0:0.01~1.0:0.2~1.0的方式進行反應。At this time, in order to make the terminal of the compound a carboxyl group, it is preferred to react in a manner such that the molar ratio of (meth) acrylate epoxy ester (diol (d)), dicarboxylic acid or tricarboxylic acid or their acid monoanhydride (b) and tetracarboxylic dianhydride (c) becomes (d): (b): (c) = 1.0: 0.01 to 1.0: 0.2 to 1.0.

例如,在使用酸單酐(b)、酸二酐(c)的情況下,較佳為以酸成分的量[(b)/2+(c)]相對於二醇(d)的莫耳比[[(b)/2+(c)]/(d)]大於0.5且為1.0以下的方式進行反應。若所述莫耳比為1.0以下,則通式(1)所表示的含不飽和基的硬化性樹脂的末端不會成為酸酐,因此可抑制未反應酸二酐的含量增大,從而提高各組成物的經時穩定性。另外,若所述莫耳比大於0.5,則可抑制含有聚合性不飽和基的二醇(d)中未反應的成分的殘存量增大,從而提高各組成物的經時穩定性。此外,出於調整通式(1)所表示的含不飽和基的硬化性樹脂的酸值、分子量的目的,可將(b)、(c)及(d)各成分的莫耳比在所述範圍內任意地變更。For example, when an acid monoanhydride (b) or an acid dianhydride (c) is used, it is preferred to react such that the molar ratio of the amount of the acid component [(b)/2+(c)] to the diol (d) [[(b)/2+(c)]/(d)] is greater than 0.5 and less than 1.0. If the molar ratio is less than 1.0, the terminal of the unsaturated group-containing curable resin represented by the general formula (1) will not become an acid anhydride, thereby suppressing the increase in the content of the unreacted acid dianhydride, thereby improving the temporal stability of each composition. In addition, if the molar ratio is greater than 0.5, the increase in the residual amount of the unreacted component in the diol (d) containing a polymerizable unsaturated group can be suppressed, thereby improving the temporal stability of each composition. In order to adjust the acid value and molecular weight of the unsaturated group-containing curable resin represented by the general formula (1), the molar ratio of the components (b), (c) and (d) can be arbitrarily changed within the above range.

此外,二醇(d)的合成及其後的多元羧酸或其酸酐的反應通常是在溶媒中視需要使用催化劑來進行。The synthesis of the diol (d) and the subsequent reaction of the polycarboxylic acid or its anhydride are usually carried out in a solvent using a catalyst as necessary.

在所述溶媒的例子中包含:乙基溶纖劑乙酸酯及丁基溶纖劑乙酸酯等溶纖劑系溶媒、二乙二醇二甲醚、乙基卡必醇乙酸酯、丁基卡必醇乙酸酯、及丙二醇單甲醚乙酸酯等高沸點的醚系或酯系的溶媒、以及環己酮及二異丁基酮等酮系溶媒等。此外,關於所使用的溶媒、催化劑等的反應條件,並無特別限制,例如較佳為將不具有羥基、且具有比反應溫度高的沸點的溶媒用作反應溶媒。Examples of the solvent include solvent-based solvents such as ethyl solvent acetate and butyl solvent acetate, high-boiling-point ether-based or ester-based solvents such as diethylene glycol dimethyl ether, ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate, and ketone-based solvents such as cyclohexanone and diisobutyl ketone. In addition, there are no particular restrictions on the reaction conditions of the solvent, catalyst, etc. used, for example, it is preferred to use a solvent that does not have a hydroxyl group and has a boiling point higher than the reaction temperature as a reaction solvent.

另外,環氧基與羧基或羥基的反應較佳為使用催化劑來進行。作為所述催化劑,在日本專利特開平9-325494號公報中記載有溴化四乙基銨、氯化三乙基苄基銨等銨鹽、三苯基膦及三(2,6-二甲氧基苯基)膦等膦類等。The reaction of the epoxy group with the carboxyl group or the hydroxyl group is preferably carried out using a catalyst. As the catalyst, ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, and phosphines such as triphenylphosphine and tri(2,6-dimethoxyphenyl)phosphine are described in Japanese Patent Publication No. 9-325494.

(A)成分的酸值較佳為50 mgKOH/g以上且200 mgKOH/g以下,更佳為60 mgKOH/g以上且150 mgKOH/g以下。若酸值為50 mgKOH/g以上,則鹼顯影時不易殘留殘渣,若為200 mgKOH/g以下,則鹼性顯影液的滲透不會變得過快,因此可抑制剝離顯影。此外,酸值可使用電位差滴定裝置「COM-1600」(平沼產業股份有限公司製造),並利用1/10N-KOH水溶液進行滴定來求出。The acid value of component (A) is preferably 50 mgKOH/g or more and 200 mgKOH/g or less, and more preferably 60 mgKOH/g or more and 150 mgKOH/g or less. If the acid value is 50 mgKOH/g or more, residue is less likely to remain during alkaline development, and if it is 200 mgKOH/g or less, the penetration of the alkaline developer does not become too fast, thereby suppressing peeling development. The acid value can be determined by titrating with a 1/10N-KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

(A)成分的基於膠體滲透層析儀(gel permeation chromatograph,GPC)測定(HLC-8220GPC,東曹(Tosoh)股份有限公司製造)所得的聚苯乙烯換算的重量平均分子量(Mw)較佳為1000以上且40000以下,更佳為1500以上且30000以下,更佳為2000以上且15000以下。若重量平均分子量(Mw)為1000以上,則可提高支撐體與被黏附體的密合性。另外,若重量平均分子量(Mw)為40000以下,則容易調整為適於塗布的組成物的溶液黏度,對支撐體或被黏附體的表面的塗布不需要太長時間,更容易提高對被黏附體的黏接性。在重視黏接強度的情況下,重量平均分子量(Mw)較佳為1000以上且5000以下。The weight average molecular weight (Mw) of the component (A) in terms of polystyrene as measured by gel permeation chromatograph (GPC) (HLC-8220GPC, manufactured by Tosoh Corporation) is preferably 1,000 to 40,000, more preferably 1,500 to 30,000, and even more preferably 2,000 to 15,000. If the weight average molecular weight (Mw) is 1,000 or more, the adhesion between the support and the adherend can be improved. If the weight average molecular weight (Mw) is 40,000 or less, it is easy to adjust the solution viscosity of the composition suitable for coating, and coating on the surface of the support or the adherend does not require too much time, making it easier to improve the adhesion to the adherend. When emphasis is placed on adhesive strength, the weight average molecular weight (Mw) is preferably 1,000 or more and 5,000 or less.

(A)成分其自身不易熱分解,與其他樹脂相比較,不易產生分解物的揮發。另外,(A)成分具有與後述的(C)成分相同的茀骨架,因此可抑制(C)成分或其分解物的揮發。另外,(A)成分提高使硬化性樹脂組成物硬化而成的樹脂硬化膜的玻璃化轉變溫度,抑制由熱造成的黏接性的降低。(A) The component itself is not easily decomposed by heat, and is less likely to volatilize decomposed products compared to other resins. In addition, since component (A) has the same fluorine skeleton as component (C) described later, volatilization of component (C) or its decomposition products can be suppressed. In addition, the component (A) increases the glass transition temperature of the resin cured film obtained by curing the curable resin composition and suppresses a decrease in adhesiveness caused by heat.

相對於固體成分的總質量,(A)成分的含量較佳為10質量%以上且90質量%以下,更佳為20質量%以上且80質量%以下,在重視圖案化特性的情況下,進而佳為40質量%以上且80質量%以下。若(A)成分的所述含量為10質量%以上,則能夠充分抑制(C)成分或其分解物的揮發,且能夠形成高分辨率的圖案。The content of component (A) is preferably 10% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 80% by mass or less, relative to the total mass of the solid components. When the content of component (A) is 10% by mass or more, the volatility of component (C) or its decomposition product can be sufficiently suppressed, and a high-resolution pattern can be formed.

1-2.(B)具有至少兩個不飽和基的聚合性化合物 (B)具有至少兩個不飽和基的聚合性化合物(以下,也簡稱為「(B)成分」)為具有兩個以上的聚合性不飽和基,並通過光或熱的刺激而產生聚合反應的不具有鹼可溶性基的化合物。 1-2. (B) Polymerizable compound having at least two unsaturated groups (B) A polymerizable compound having at least two unsaturated groups (hereinafter, also referred to as "(B) component") has two or more polymerizable unsaturated groups and causes a polymerization reaction by stimulation with light or heat. Compounds that do not have alkali-soluble groups.

(B)成分除可提高使各組成物硬化而成的硬化膜對被黏附體或基材的黏附強度及耐溶劑性以外,還可使硬化時的感度及顯影性良好。The component (B) can improve the adhesion strength and solvent resistance of the cured film formed by curing the respective components to the adherend or substrate, and can also improve the sensitivity and developability during curing.

(B)成分只要具有至少兩個以上的能與(A)成分所具有的聚合性不飽和基反應(聚合)的聚合性不飽和基即可。所述聚合性不飽和基較佳為(甲基)丙烯醯基。此外,(B)成分可為單體,也可為寡聚物、聚合物。The component (B) only needs to have at least two polymerizable unsaturated groups that can react (polymerize) with the polymerizable unsaturated groups possessed by the component (A). The polymerizable unsaturated groups are preferably (meth)acryloyl groups. In addition, the component (B) may be a monomer, an oligomer, or a polymer.

在(B)成分的例子中包含:乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、四伸甲基二醇二(甲基)丙烯酸酯、丙三醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、三羥甲基乙烷三(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇四(甲基)丙烯酸酯、丙三醇三(甲基)丙烯酸酯、山梨糖醇五(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、山梨糖醇六(甲基)丙烯酸酯、磷腈(phosphazene)的環氧烷改性六(甲基)丙烯酸酯、己內酯改性二季戊四醇六(甲基)丙烯酸酯等(甲基)丙烯酸酯類、作為具有乙烯性雙鍵的化合物的具有(甲基)丙烯酸基的樹枝狀聚合物等。可僅單獨使用這些聚合性化合物的一種,也可並用兩種以上。(B)成分只要可起到使(A)成分的分子彼此交聯的作用即可,就進一步充分發揮所述功能的觀點而言,較佳為使用具有三個以上的不飽和鍵的成分。另外,聚合性化合物的分子量除以一分子中的(甲基)丙烯酸基的數量而得的丙烯酸基當量較佳為50以上且300以下,更佳為80以上且200以下。此外,(B)成分不具有游離的羧基。Examples of the component (B) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylethylene glycol di(meth)acrylate, glycerol di(meth)acrylate, trihydroxymethylpropane tri(meth)acrylate, trihydroxymethylethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol (Meth)acrylates such as glycerol tetra(meth)acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, phosphazene epoxide-modified hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and dendrimers having (meth)acrylic groups as compounds having ethylene double bonds. Only one of these polymerizable compounds may be used alone, or two or more may be used in combination. Component (B) may be used as long as it can crosslink the molecules of component (A). From the viewpoint of further fully exerting the above function, it is preferred to use a component having three or more unsaturated bonds. The acrylic acid group equivalent obtained by dividing the molecular weight of the polymerizable compound by the number of (meth)acrylic acid groups in one molecule is preferably 50 to 300, more preferably 80 to 200. Component (B) does not have a free carboxyl group.

另外,(B)成分較佳為環氧烷改性物。作為環氧烷改性物的(B)成分可對樹脂硬化膜賦予適度的柔軟性,進一步提高對被黏附體的黏接性或形成圖案時的對基板的密合性。In addition, the component (B) is preferably a modified alkylene oxide. The component (B) being a modified alkylene oxide can impart appropriate flexibility to the cured resin film, thereby further improving the adhesion to the adherend or the adhesion to the substrate when forming a pattern.

(A)成分與(B)成分的調配比例以質量比(A)/(B)計而較佳為30/70~90/10,更佳為40/60~80/20。若(A)成分與(B)成分的調配比例為30/70以上,則不易產生製作具有所期望的硬度的樹脂硬化膜時的(C)成分或其分解物的揮發,硬化後的硬化物不易變脆,另外,在未硬化部中塗膜的酸值不易變低,因此可抑制對於鹼性顯影液的溶解性的降低。因此,不易產生圖案邊緣產生毛邊或變得不鮮明等不良情況。另外,若(A)成分與(B)成分的調配比例為90/10以下,則聚合性官能基在樹脂中所占的比例充分,因此可進行所期望的交聯結構的形成。另外,由於樹脂成分的酸值度不會過高,因此硬化部對於鹼性顯影液的溶解性不易變高,因此可抑制所形成的圖案變得比目標線寬細或圖案的缺失。The mixing ratio of component (A) to component (B) is preferably 30/70 to 90/10, more preferably 40/60 to 80/20, in terms of the mass ratio (A)/(B). If the mixing ratio of component (A) to component (B) is 30/70 or more, it is less likely that component (C) or its decomposition product will volatilize when producing a resin cured film having the desired hardness, and the cured product will not become brittle after curing. In addition, the acid value of the coating film in the uncured part will not become low, so that the solubility in the alkaline developer can be suppressed. Therefore, it is less likely that the edge of the pattern will be burred or become unclear. In addition, if the mixing ratio of component (A) to component (B) is 90/10 or less, the proportion of the polymerizable functional group in the resin is sufficient, so that the desired cross-linked structure can be formed. In addition, since the acid value of the resin component is not too high, the solubility of the hardened portion in the alkaline developer is not likely to increase, thereby preventing the formed pattern from becoming thinner than the target line width or the pattern from being lost.

1-3.(C)通式(9)所表示的光聚合起始劑 (C)通式(9)所表示的光聚合起始劑(以下,也簡稱為「(C)成分」)在照射光時使(A)成分及(B)成分引發聚合,使顯影時的硬化的部分的溶解性降低而形成所期望的微細圖案。 1-3. (C) Photopolymerization initiator represented by general formula (9) (C) The photopolymerization initiator represented by the general formula (9) (hereinafter also referred to as "component (C)") initiates polymerization of the component (A) and the component (B) when irradiated with light, thereby causing the The solubility of the hardened part is reduced and a desired fine pattern is formed.

[化19] ···通式(9) [Chemical 19] ···General formula (9)

通式(9)中,A為氫原子、鹵素原子、硝基、碳數1以上且20以下的直鏈狀或可具有分支鏈的烷基、碳數3以上且10以下的環烷基、碳數4以上且10以下的烷基環烷基、碳數4以上且10以下的環烷基烷基、-N(R 9) 2、-COR 10或-CO-CR 6R 7R 8所表示的取代基。此外,這些取代基所具有的伸甲基(-CH 2-)也可經-O-、-N-、-S-或-C(=O)-取代。 In the general formula (9), A is a hydrogen atom, a halogen atom, a nitro group, a linear or optionally branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, Alkylcycloalkyl group with 4 or more carbon atoms and 10 or less carbon atoms, cycloalkylalkyl group with 4 or more carbon atoms and 10 or less carbon atoms, -N(R 9 ) 2 , -COR 10 or -CO-CR 6 R 7 R 8 represents the substituent. In addition, the methylene group (-CH 2 -) of these substituents may be substituted by -O-, -N-, -S- or -C(=O)-.

R 5獨立地表示氫原子、鹵素原子、碳數1以上且20以下的直鏈狀或可具有分支鏈的烷基、碳數3以上且20以下的環烷基烷基或碳數2以上且20以下的烯基。此外,這些官能基所具有的伸甲基(-CH 2-)也可經-O-、-N-、-S-或-C(=O)-取代。另外,兩個R 5也可相互鍵結而形成環。這些中,較佳為碳數1以上且8以下的直鏈狀或可具有分支鏈的烷基。 R 5 independently represents a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkylalkyl group having 3 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms. In addition, the methyl group (-CH 2 -) possessed by these functional groups may be substituted by -O-, -N-, -S-, or -C(=O)-. In addition, two R 5 groups may be bonded to each other to form a ring. Among these, a linear or branched alkyl group having 1 to 8 carbon atoms is preferred.

R 6及R 7獨立地表示碳數1以上且20以下的直鏈狀或可具有分支鏈的烷基、碳數3以上且20以下的環烷基、碳數4以上且20以下的環烷基烷基、碳數4以上且20以下的烷基環烷基、碳數6以上且20以下的芳基或碳數7以上且20以下的烷基芳基。此外,這些官能基所具有的氫原子中的一個或多個可獨立地經碳數1以上且20以下的直鏈狀或可具有分支鏈的烷基、鹵素原子、羥基或硝基取代。另外,這些官能基所具有的伸甲基(-CH 2-)也可經-O-、-N-、-S-或-C(=O)-取代。R 6及R 7可相互鍵結而形成環。 R6 and R7 independently represent a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkylalkyl group having 4 to 20 carbon atoms, an alkylcycloalkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms. In addition, one or more of the hydrogen atoms possessed by these functional groups may be independently substituted by a linear or branched alkyl group having 1 to 20 carbon atoms, a halogen atom, a hydroxyl group, or a nitro group. In addition, the methylene group ( -CH2- ) possessed by these functional groups may be substituted by -O-, -N-, -S-, or -C(=O)-. R6 and R7 may be bonded to each other to form a ring.

或者,也可為,R 6為碳數1以上且20以下的直鏈狀或可具有分支鏈的烷基、或者碳數2以上且20以下的直鏈狀或可具有分支鏈的烯基,且R 7為下述式(10)~式(12)所表示的官能基中的任一個。 Alternatively, R 6 may be a linear or optionally branched alkyl group having a carbon number of 1 to 20, or a linear or optionally branched alkenyl group having a carbon number of 2 to 20, And R 7 is any one of the functional groups represented by the following formula (10) to formula (12).

[化20] ···通式(10) [Chemistry 20] ···General formula (10)

通式(10)中,R 13表示氫原子、碳數1以上且8以下的直鏈狀或可具有分支鏈的烷基、或者苯基,R 14、R 15及R 16獨立地表示氫原子、或者碳數1以上且4以下的直鏈狀或可具有分支鏈的烷基。*表示與通式(9)所表示的化合物的鍵結部位。 In the general formula (10), R13 represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a phenyl group, and R14 , R15 , and R16 independently represent a hydrogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms. * represents a bonding site to the compound represented by the general formula (9).

[化21] ···通式(11) [Chemistry 21] ···General formula (11)

通式(11)中,s為0以上且4以下的數。*表示與通式(9)所示的化合物的鍵結部位。In general formula (11), s is a number from 0 to 4. * indicates the bonding site with the compound represented by general formula (9).

[化22] ···通式(12) [Chemistry 22] ···General formula (12)

通式(12)中,Ar 2表示均可經取代的苯基、萘基、呋喃基、噻吩基或吡啶基。*表示與通式(9)所示的化合物的鍵結部位。 In the general formula (12), Ar 2 represents phenyl, naphthyl, furyl, thienyl or pyridyl, which may be substituted. * indicates the bonding site with the compound represented by general formula (9).

R 8表示N-嗎啉基、N-呱啶基、N-吡咯基或N-二烷基。這些中,較佳為N-嗎啉基。此外,這些官能基所具有的氫原子中的一個或多個可獨立地經鹵素原子或羥基取代。 R 8 represents N-morpholinyl, N-piridyl, N-pyrrolyl or N-dialkyl. Among these, N-morpholinyl is preferred. In addition, one or more of the hydrogen atoms possessed by these functional groups may be independently substituted with a halogen atom or a hydroxyl group.

R 9獨立地表示碳數1以上且20以下的直鏈狀或可具有分支鏈的烷基、碳數3以上且20以下的環烷基、碳數2以上且20以下的直鏈狀或可具有分支鏈的烯基、碳數6以上且20以下的芳基或碳數7以上且20以下的烷基芳基。此外,這些官能基所具有的氫原子中的一個或多個可獨立地經碳數1以上且20以下的直鏈狀或可具有分支鏈的烷基、鹵素原子、羥基或硝基取代。另外,這些取代基所具有的伸甲基(-CH 2-)也可經-O-取代。另外,兩個R 9也可相互鍵結而形成環,此時,所述環可為經由-O-、-S-、-NH-而形成的五員環或六員環。 R 9 independently represents a linear or optionally branched alkyl group having a carbon number of 1 or more and 20 or less, a cycloalkyl group having a carbon number of 3 or more and 20 or less, a linear or optionally branched alkyl group having a carbon number of 2 or more and 20 or less. An alkenyl group having a branched chain, an aryl group having 6 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms. In addition, one or more of the hydrogen atoms of these functional groups may be independently substituted with a linear or branched alkyl group having a carbon number of 1 to 20, a halogen atom, a hydroxyl group, or a nitro group. In addition, the methylene group (-CH 2 -) of these substituents may be substituted with -O-. In addition, two R 9s may be bonded to each other to form a ring. In this case, the ring may be a five-membered ring or a six-membered ring formed through -O-, -S-, or -NH-.

R 10表示碳數1以上且20以下的直鏈狀或可具有分支鏈的烷基、碳數3以上且20以下的環烷基、碳數4以上且10以下的烷基環烷基、碳數2以上且20以下的直鏈狀或可具有分支鏈的烯基、碳數6以上且20以下的芳基或碳數7以上且20以下的烷基芳基。此外,這些官能基所具有的伸甲基(-CH 2-)也可經-O-或-S-取代。這些官能基所具有的氫原子中的一個或多個可獨立地經碳數1以上且20以下的直鏈狀或可具有分支鏈的烷基、鹵素原子、硝基、氰基、-SR 11或-OR 12取代。 R 10 represents a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkylcycloalkyl group having 4 to 10 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms. In addition, the methylene group (-CH 2 -) possessed by these functional groups may be substituted by -O- or -S-. One or more of the hydrogen atoms possessed by these functional groups may be independently substituted by a linear or branched alkyl group having 1 to 20 carbon atoms, a halogen atom, a nitro group, a cyano group, -SR 11 , or -OR 12 .

R 11及R 12獨立地表示氫原子、或者碳數1以上且20以下的直鏈狀或可具有分支鏈的烷基。 R 11 and R 12 independently represent a hydrogen atom, or a linear or branched alkyl group having 1 to 20 carbon atoms.

在(C)成分的具體例中包含日本專利特表2020-507664號公報中記載的各化合物。Specific examples of the component (C) include compounds described in Japanese Patent Application Publication No. 2020-507664.

(C)成分具有茀結構,因此其自身不易揮發,另外,其分解物也不易揮發。在本實施方式中,使用同樣地具有茀結構的樹脂作為(A)成分,因此可通過(A)成分與(C)成分的分解物的親和性而不易產生分解物的揮發。因此,(C)成分在本實施方式中用於黏接劑時不易產生被黏附體等的污染。此外,基於本發明人等人的研究,在肟酯系的起始劑等中存在同樣地不易揮發的光聚合起始劑,但此種起始劑的硬化性過高,因此會使硬化性樹脂組成物過硬化,在用於黏接劑時,無法充分提高黏接性。相對於此,(C)成分具有適度的硬化性,因此也可充分提高用於黏接劑時的黏接性。Component (C) has a fluorene structure, so it itself is not easy to volatilize, and its decomposition products are also not easy to volatilize. In this embodiment, a resin having a fluorene structure is used as component (A), so the volatility of the decomposition products can be difficult to occur due to the affinity between component (A) and the decomposition products of component (C). Therefore, when component (C) is used in an adhesive in this embodiment, it is not easy to cause contamination of the adherend, etc. In addition, based on the research of the inventors and others, there is a photopolymerization initiator that is also not easy to volatilize in the initiator of oxime ester system, but the curability of this initiator is too high, so it will cause the curable resin composition to over-cure, and when used in an adhesive, the adhesion cannot be fully improved. In contrast, component (C) has moderate curability, so it can also fully improve the adhesion when used in an adhesive.

相對於(A)成分與(B)成分的合計100質量份,(C)成分的含量為1質量份以上且15質量份以下,較佳為2質量份以上且10質量份以下。若(C)成分的含量為所述下限值以上,則具有適度的光聚合速度,因此可確保充分的感度。另外,若(C)成分的含量為所述上限值以下,則可再現忠實於遮罩的線寬,並且可使圖案邊緣鮮明。The content of component (C) is 1 to 15 parts by mass, preferably 2 to 10 parts by mass, based on 100 parts by mass of the total of components (A) and (B). If the content of component (C) is equal to or higher than the lower limit, a moderate photopolymerization speed is obtained, and therefore sufficient sensitivity can be ensured. In addition, when the content of component (C) is equal to or less than the upper limit, line widths faithful to the mask can be reproduced and pattern edges can be made clear.

1-4.(D)溶劑 (D)溶劑(以下,也簡稱為「(D)成分」)使硬化性樹脂組成物中所含的各成分溶解或分散並提高各組成物的塗布性。 1-4. (D) Solvent The (D) solvent (hereinafter, also referred to as "(D) component") dissolves or disperses each component contained in the curable resin composition and improves the coatability of each composition.

在(D)成分的例子中包含:甲醇、乙醇、正丙醇、異丙醇、乙二醇、丙二醇、3-甲氧基-1-丁醇、乙二醇單丁醚、3-羥基-2-丁酮及二丙酮醇等醇類;α-萜品醇或β-萜品醇等萜烯類;丙酮、甲基乙基酮、環己酮及N-甲基-2-吡咯烷酮等酮類;甲苯、二甲苯及四甲基苯等芳香族烴類;溶纖劑、甲基溶纖劑、乙基溶纖劑、卡必醇、甲基卡必醇、乙基卡必醇、丁基卡必醇、二乙二醇乙基甲基醚、丙二醇單甲醚、丙二醇單乙醚、二丙二醇單甲醚、二丙二醇單乙醚、三乙二醇單甲醚及三乙二醇單乙醚等二醇醚類;乙酸乙酯、乙酸丁酯、乳酸乙酯、3-甲氧基丁基乙酸酯、3-甲氧基-3-丁基乙酸酯、3-甲氧基-3-甲基-1-丁基乙酸酯、溶纖劑乙酸酯、乙基溶纖劑乙酸酯、丁基溶纖劑乙酸酯、卡必醇乙酸酯、乙基卡必醇乙酸酯、丁基卡必醇乙酸酯、丙二醇單甲醚乙酸酯及丙二醇單乙醚乙酸酯等酯類等。Examples of component (D) include: methanol, ethanol, n-propanol, isopropyl alcohol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy- Alcohols such as 2-butanone and diacetone alcohol; terpenes such as α-terpineol or β-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone and N-methyl-2-pyrrolidone Class; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl Carbitol, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether and triethylene glycol monoethyl ether, etc. Glycol ethers; ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, 3-methoxy-3- Methyl-1-butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, Esters such as butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate, etc.

(D)成分的含量是根據目標黏度而變化,相對於硬化性樹脂組成物的總質量,較佳為30質量%以上且90質量%以下。若(D)成分的含量為30質量%以上,則可形成容易將硬化性樹脂組成物塗布於基板上的黏度,若為90質量%以下,則可縮短將硬化性樹脂組成物塗布於基板上後的乾燥所需的時間。The content of the component (D) varies depending on the target viscosity, and is preferably 30% by mass or more and 90% by mass or less relative to the total mass of the curable resin composition. If the content of the component (D) is 30% by mass or more, a viscosity that allows the curable resin composition to be easily applied to a substrate can be formed, and if it is 90% by mass or less, the time required for drying the curable resin composition after it is applied to the substrate can be shortened.

1-5.(E)增感劑 硬化性樹脂組成物也可包含(E)增感劑(以下,也簡稱為「(E)成分」)。 1-5. (E) Sensitizer The curable resin composition may contain (E) sensitizer (hereinafter, also referred to as "(E) component").

(E)成分可使(C)成分更有效率地開裂而有效率地進行聚合反應,由此進一步提高樹脂硬化膜對基板的密合性。The component (E) can cause the component (C) to cleave more efficiently and to efficiently carry out the polymerization reaction, thereby further improving the adhesion of the cured resin film to the substrate.

在(E)成分的例子中包含:三乙醇胺、三異丙醇胺、二苯甲酮、4,4'-雙二甲基胺基二苯甲酮(米氏酮)、4-苯基二苯甲酮、4,4'-二氯二苯甲酮、羥基二苯甲酮、4,4'-二乙基胺基二苯甲酮等二苯甲酮類;苯乙酮、2,2-二乙氧基苯乙酮、對二甲基胺基苯乙酮、對二甲基胺基苯丙酮、二氯苯乙酮、三氯苯乙酮、對第三丁基苯乙酮、苯偶醯二甲基縮酮等苯乙酮類;安息香、安息香甲醚、安息香異丙醚、安息香異丁醚等安息香醚類;2-二甲基胺基乙基苯甲酸、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸(正丁氧基)乙酯、4-二甲基胺基苯甲酸異戊酯、4-二甲基胺基苯甲酸2-乙基己酯、2,4-二異丙基硫雜蒽酮、4-苯甲醯基-4'-甲基-二苯基硫醚;丙烯醯化二苯甲酮、3,3',4,4'-四(第三丁基過氧化羰基)二苯甲酮、3,3'-二甲基-4-甲氧基二苯甲酮等二苯甲酮系;硫雜蒽酮、2-氯硫雜蒽酮、2-甲基硫雜蒽酮、2-異丙基硫雜蒽酮、4-異丙基硫雜蒽酮、2,4-二甲基硫雜蒽酮、2,4-二乙基硫雜蒽酮、2,4-二氯硫雜蒽酮、1-氯-4-丙氧基硫雜蒽酮等硫雜蒽酮系;4,4'-雙二乙基胺基二苯甲酮等胺基二苯甲酮系;10-丁基-2-氯吖啶酮、2-乙基蒽醌、9,10-菲醌、樟腦醌等。此外,這些增感劑可僅單獨使用其中一種,也可並用兩種以上。Examples of the component (E) include benzophenones such as triethanolamine, triisopropanolamine, benzophenone, 4,4'-bis(dimethylamino)benzophenone (Michler's ketone), 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, and 4,4'-diethylaminobenzophenone; acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, and p-dimethylamine. Acetophenones such as acetophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, and dimethyl benzoate; benzoin ethers such as benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; 2-dimethylaminoethylbenzoic acid, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid (n-butoxy) ethyl ester, 4-dimethylaminobenzoic acid isopentyl ester, 4- 2-Ethylhexyl dimethylaminobenzoate, 2,4-diisopropylthioxanthrone, 4-benzoyl-4'-methyl-diphenyl sulfide; benzophenone series such as acryloyl benzophenone, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 3,3'-dimethyl-4-methoxybenzophenone; thioxanthrone, 2-chlorothioxanthrone, 2-methylthioxanthrone, 2 - isopropylthioanthrone, 4-isopropylthioanthrone, 2,4-dimethylthioanthrone, 2,4-diethylthioanthrone, 2,4-dichlorothioanthrone, 1-chloro-4-propoxythioanthrone and other thioanthrone series; 4,4'-bisdiethylaminobenzophenone and other aminobenzophenone series; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone and the like. In addition, these sensitizers may be used alone or in combination of two or more.

(E)成分較佳為包含二苯甲酮衍生物或硫雜蒽酮衍生物。這些增感劑可使(C)成分進一步有效率地開裂,因此提高樹脂硬化膜對基板的密合性的效果顯著。The component (E) preferably contains a benzophenone derivative or a thioxanthrone derivative. These sensitizers can make the component (C) cleave more efficiently, thereby significantly improving the adhesion of the cured resin film to the substrate.

在將(C)成分的總質量設為100質量份時,(E)成分的含量較佳為0.5質量份以上且400質量份以下,更佳為1質量份以上且300質量份以下。若增感劑的所述含量為0.5質量份以上,則可提高光聚合起始劑的感度,並加快光聚合速度。另外,若增感劑的所述含量為400質量份以下,則可抑制感度的過度提高,在通過光的照射而使組成物硬化時,不易產生燒焦、剝離殘渣等。When the total mass of component (C) is 100 parts by mass, the content of component (E) is preferably from 0.5 parts by mass to 400 parts by mass, more preferably from 1 part by mass to 300 parts by mass. If the content of the sensitizer is 0.5 parts by mass or more, the sensitivity of the photopolymerization initiator can be increased and the photopolymerization speed can be accelerated. In addition, if the content of the sensitizer is 400 parts by mass or less, an excessive increase in sensitivity can be suppressed, and when the composition is cured by irradiation with light, burning, peeling residue, etc. are less likely to occur.

1-6.(F)具有兩個以上的環氧基的環氧化合物 硬化性樹脂組成物也可包含(F)具有兩個以上的環氧基的環氧化合物(以下,也簡稱為「(F)成分」)。 1-6. (F) Epoxy compound having two or more epoxy groups The curable resin composition may also contain (F) an epoxy compound having two or more epoxy groups (hereinafter, also referred to as "(F) component").

(F)成分可對樹脂硬化膜賦予適度的柔軟性,進一步提高對被黏附體的黏接性或形成圖案時的對基板的密合性。另外,(F)成分也可減少來自硬化膜的(C)成分或其分解物的揮發量。The component (F) can impart appropriate flexibility to the resin cured film, further improving the adhesion to the adherend or the adhesion to the substrate when forming a pattern. In addition, the component (F) can also reduce the volatility of the component (C) or its decomposition products from the cured film.

在(F)成分的例子中包含:雙酚A型環氧化合物、雙酚F型環氧化合物、雙苯酚茀型環氧化合物、雙萘酚茀型環氧化合物、二苯基茀型環氧化合物、苯酚酚醛清漆型環氧化合物、甲酚酚醛清漆型環氧化合物、苯酚芳烷基型環氧化合物、包含萘骨架的苯酚酚醛清漆化合物(例如,NC-7000L:日本化藥股份有限公司製造)、聯苯型環氧化合物(例如,jER YX4000:三菱化學股份有限公司製造,「jER」是所述公司的註冊商標)、萘酚芳烷基型環氧化合物、三苯酚甲烷型環氧化合物(例如,EPPN-501H:日本化藥股份有限公司製造)、四苯酚乙烷型環氧化合物、多元醇的縮水甘油醚、多元羧酸的縮水甘油酯、甲基丙烯酸與甲基丙烯酸縮水甘油酯的共聚物所代表的包含(甲基)丙烯酸縮水甘油酯作為單元的具有(甲基)丙烯酸基的單體的共聚物、3',4'-環氧環己基甲基3,4-環氧環己烷羧酸酯(例如,賽羅西德(Celloxide)2021P:大賽璐(Daicel)股份有限公司製造,「賽羅西德(Celloxide)」是所述公司的註冊商標)、丁烷四羧酸四(3,4-環氧環己基甲基)修飾ε-己內酯(例如,艾波利得(EPOLEAD)GT401:大賽璐(Daicel)股份有限公司製造,「艾波利得(EPOLEAD)」是所述公司的註冊商標)、具有環氧環己基的環氧化合物(例如,HiREM-1:四國化成工業股份有限公司製造)、具有二環戊二烯骨架的多官能環氧化合物(例如,HP7200系列:迪愛生(DIC)股份有限公司製造)、2,2-雙(羥基甲基)-1-丁醇的1,2-環氧-4-(2-氧雜環丙基)環己烷加成物(例如,EHPE3150:大賽璐(Daicel)股份有限公司製造)、環氧化聚丁二烯(例如,尼索(NISSO)-PB JP-100:日本曹達股份有限公司製造,「尼索(NISSO)-PB」是所述公司的註冊商標)、具有矽酮骨架的環氧化合物等。此外,這些化合物可僅使用其中一種化合物,也可並用兩種以上。Examples of the component (F) include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol fluorene type epoxy compounds, bisnaphthol fluorene type epoxy compounds, diphenyl fluorene type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, phenol aralkyl type epoxy compounds, phenol novolac compounds containing a naphthalene skeleton (for example, NC-7000L: manufactured by Nippon Kayaku Co., Ltd.), biphenyl type epoxy compounds (for example, jER YX4000: manufactured by Mitsubishi Chemical Co., Ltd., "jER" is a registered trademark of the company), naphthol aralkyl type epoxy compounds, triphenol methane type epoxy compounds (for example, EPPN-501H: manufactured by Nippon Kayaku Co., Ltd.), tetraphenol ethane type epoxy compounds, glycidyl ethers of polyols, glycidyl esters of polycarboxylic acids, copolymers of monomers having (meth) acrylic acid groups represented by copolymers of methacrylic acid and glycidyl methacrylate containing (meth) acrylic acid glycidyl ester as units, 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (for example, Celloxide 2021P: manufactured by Daicel Co., Ltd., "Celloxide" is a registered trademark of the company), butane oxadiazine tetracarboxylic acid tetra(3,4-epoxyepoxyhexylmethyl) modified ε-caprolactone (e.g., EPOLEAD GT401: manufactured by Daicel Co., Ltd., "EPOLEAD" is a registered trademark of the company), epoxy compounds having an epoxyepoxy group (e.g., HiREM-1: manufactured by Shikoku Chemical Industries, Ltd.), polyfunctional epoxy compounds having a dicyclopentadiene skeleton (e.g., HP7200 series: manufactured by DIC Corporation), 1,2-epoxy-4-(2-oxohexacyclopropyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (e.g., EHPE3150: manufactured by Daicel Co., Ltd.), epoxidized polybutadiene (e.g., NISSO-PB JP-100: manufactured by Nippon Soda Co., Ltd., "NISSO-PB" is a registered trademark of the company), epoxy compounds having a silicone skeleton, etc. In addition, only one of these compounds may be used, or two or more thereof may be used in combination.

這些中,較佳為雙酚A型環氧化合物、雙酚F型環氧化合物、雙苯酚茀型環氧化合物、雙萘酚茀型環氧化合物、苯酚酚醛清漆型環氧化合物、甲酚酚醛清漆型環氧化合物、聯苯型環氧化合物,更佳為聯苯型環氧化合物。通過使用聯苯型的環氧化合物,可兼顧符合要求特性的硬化物的機械強度或耐化學品性、硬化時的硬化性樹脂組成物的圖案化性,並且可增大設計硬化性樹脂組成物的自由度。Among these, preferred are bisphenol A-type epoxy compounds, bisphenol F-type epoxy compounds, bisphenol-type epoxy compounds, bis-naphthol-type epoxy compounds, phenol novolac-type epoxy compounds, and cresol novolac-type epoxy compounds. Varnish type epoxy compound, biphenyl type epoxy compound, more preferably biphenyl type epoxy compound. By using a biphenyl-type epoxy compound, it is possible to achieve both the mechanical strength and chemical resistance of a cured product that meets required characteristics and the patternability of the curable resin composition during curing, and the design of the curable resin composition can be increased. degree of freedom.

(F)成分的環氧當量較佳為100 g/eq以上且300 g/eq以下,更佳為100 g/eq以上且250 g/eq以下。另外,(F)成分的數量平均分子量(Mn)較佳為100以上且5000以下。若所述環氧當量為100 g/eq以上且所述環氧化合物的數量平均分子量(Mn)為100以上,則能形成具有良好的耐溶劑性的硬化膜,若環氧當量為300 g/eq以下且數量平均分子量(Mn)為5000以下,則即便在後續步驟中使用鹼性藥液的情況下也可維持充分的耐鹼性。The epoxy equivalent of the component (F) is preferably from 100 g/eq to 300 g/eq, more preferably from 100 g/eq to 250 g/eq. In addition, the number average molecular weight (Mn) of component (F) is preferably from 100 to 5,000. If the epoxy equivalent is 100 g/eq or more and the number average molecular weight (Mn) of the epoxy compound is 100 or more, a cured film with good solvent resistance can be formed. If the epoxy equivalent is 300 g/eq. eq or less and the number average molecular weight (Mn) is 5000 or less, sufficient alkali resistance can be maintained even when an alkaline chemical solution is used in the subsequent step.

此外,(F)成分的環氧當量可使用電位差滴定裝置「COM-1600」(平沼產業股份有限公司製造)並利用1/10N-高氯酸溶液進行滴定來求出。另外,(F)成分的數量平均分子量(Mn)例如可利用所述膠體滲透層析儀(gel permeation chromatograph,GPC)「HLC-8220GPC」(東曹(Tosoh)股份有限公司製造)來求出。In addition, the epoxy equivalent of component (F) can be determined by titrating with a 1/10N-perchloric acid solution using a potentiometric titration device "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.). In addition, the number average molecular weight (Mn) of the component (F) can be determined using, for example, the above-mentioned gel permeation chromatograph (GPC) "HLC-8220GPC" (manufactured by Tosoh Co., Ltd.).

在使用(F)成分時,可並用硬化劑及硬化促進劑。When using component (F), a hardener and a hardening accelerator may be used together.

在所述硬化劑的例子中包含:胺系化合物、多元羧酸系化合物、酚樹脂、胺基樹脂、二氰二胺及路易斯酸錯合化合物等。Examples of the curing agent include amine compounds, polycarboxylic acid compounds, phenol resins, amino resins, dicyandiamide, and Lewis acid complex compounds.

在所述硬化促進劑的例子中包含:有助於環氧樹脂的硬化促進的三級胺、四級銨鹽、三級膦、四級鏻鹽、硼酸酯、路易斯酸、有機金屬化合物及咪唑類等。在所述熱聚合抑制劑及抗氧化劑的例子中包含:對苯二酚、對苯二酚單甲醚、連苯三酚、第三丁基兒茶酚、吩噻嗪及受阻酚系化合物等。在所述塑化劑的例子中包含:鄰苯二甲酸二丁酯、鄰苯二甲酸二辛酯及磷酸三甲苯酯等。在所述填充劑的例子中包含:玻璃纖維、二氧化矽、雲母及氧化鋁等。在所述消泡劑及流平劑的例子中包含矽酮系、氟系及丙烯酸系的化合物。在所述表面活性劑的例子中包含氟系表面活性劑及矽酮系表面活性劑等。在所述偶合劑的例子中包含:3-(縮水甘油基氧基)丙基三甲氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、3-異氰酸基丙基三乙氧基矽烷及3-脲基丙基三乙氧基矽烷等。Examples of the curing accelerator include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, borates, Lewis acids, organic metal compounds, and imidazoles that help accelerate the curing of epoxy resins. Examples of the thermal polymerization inhibitor and antioxidant include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, and hindered phenol compounds. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate. Examples of the filler include glass fiber, silicon dioxide, mica, and aluminum oxide. Examples of the defoamer and leveling agent include silicone, fluorine, and acrylic compounds. Examples of the surfactant include fluorine surfactants and silicone surfactants. Examples of the coupling agent include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane.

相對於固體成分的總質量,(F)成分的含量較佳為1質量%以上且30質量%以下,更佳為3質量%以上且25質量%以下。若將(F)成分的所述含量設為1質量%以上,則可進一步提高樹脂硬化膜的耐化學品性及耐濕密合性。若將(F)成分的所述含量設為30質量%以下,則可進一步提高樹脂硬化膜對基板的密合性。The content of the component (F) is preferably 1% by mass or more and 30% by mass or less, and more preferably 3% by mass or more and 25% by mass or less, relative to the total mass of the solid components. When the content of the component (F) is 1% by mass or more, the chemical resistance and moisture resistance of the cured resin film can be further improved. When the content of the component (F) is 30% by mass or less, the adhesion of the cured resin film to the substrate can be further improved.

1-7.其他成分 硬化性樹脂組成物可調配通式(1)所表示的化合物以外的含不飽和基的鹼可溶性樹脂、通式(9)所表示的化合物以外的光聚合起始劑、熱聚合起始劑、聚合抑制劑、抗氧化劑、鏈轉移劑、塑化劑、填充劑、流平劑、顏料及染料、消泡劑、表面活性劑及偶合劑等。 1-7.Other ingredients The curable resin composition may contain an unsaturated group-containing alkali-soluble resin other than the compound represented by the general formula (1), a photopolymerization initiator and a thermal polymerization initiator other than the compound represented by the general formula (9), Polymerization inhibitors, antioxidants, chain transfer agents, plasticizers, fillers, leveling agents, pigments and dyes, defoaming agents, surfactants and coupling agents, etc.

在聚合抑制劑及抗氧化劑的例子中包含:對苯二酚、對苯二酚單甲醚、連苯三酚、第三丁基兒茶酚、吩噻嗪、受阻酚系化合物等。Examples of the polymerization inhibitor and antioxidant include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, hindered phenol compounds, and the like.

在鏈轉移劑的例子中包含:2-巰基苯並咪唑、2-巰基苯並噁唑、2-巰基苯並噻唑、β-巰基丙酸、2-乙基己基-3-巰基丙酸酯、正辛基-3-巰基丙酸酯、甲氧基丁基-3-巰基丙酸酯、硬脂基-3-巰基丙酸酯、三羥甲基丙烷三(3-巰基丙酸酯)、三-[(3-巰基丙醯基氧基)-乙基]-異氰脲酸酯、季戊四醇四(3-巰基丁酸酯)、季戊四醇四(3-巰基丙酸酯)、四乙二醇雙(3-巰基丙酸酯)、二季戊四醇六(3-巰基丙酸酯)、3,3'-硫代二丙酸、二硫代二丙酸、月桂基硫代丙酸等硫醇化合物等。Examples of chain transfer agents include: 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, β-mercaptopropionic acid, 2-ethylhexyl-3-mercaptopropionate, n-Octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, stearyl-3-mercaptopropionate, trimethylolpropane tris(3-mercaptopropionate), Tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol Thiol compounds such as bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), 3,3'-thiodipropionic acid, dithiodipropionic acid, laurylthiopropionic acid, etc. wait.

在塑化劑的例子中包含:鄰苯二甲酸二丁酯、鄰苯二甲酸二辛酯、磷酸三甲苯酯等。在填充劑的例子中包含:玻璃纖維、二氧化矽、雲母、氧化鋁等。Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like. Examples of fillers include: glass fiber, silica, mica, alumina, etc.

在消泡劑或流平劑的例子中包含矽酮系、氟系、丙烯酸系的化合物。Examples of defoaming agents and leveling agents include silicone-based, fluorine-based, and acrylic-based compounds.

在表面活性劑的例子中包含氟系表面活性劑、矽酮系表面活性劑等。Examples of surfactants include fluorine-based surfactants, silicone-based surfactants, and the like.

在偶合劑的例子中包含:3-(縮水甘油基氧基)丙基三甲氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、3-異氰酸基丙基三乙氧基矽烷、3-脲基丙基三乙氧基矽烷等。Examples of the coupling agent include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, and the like.

1-8.硬化性樹脂組成物的製造 硬化性樹脂組成物可通過將所述各成分混合來獲得。 1-8. Preparation of hardening resin composition The hardening resin composition can be obtained by mixing the above-mentioned components.

2.用途 所述硬化性樹脂組成物可用於通過放射線的照射而形成樹脂硬化膜的包含絕緣材、黏接劑及保護膜等在內的各種用途。另外,硬化性樹脂組成物通過包含鹼可溶性樹脂而能夠在曝光後或加熱後進行顯影,因此也可適宜地用於形成細線圖案的用途。 2. Applications The curable resin composition can be used for various applications including insulating materials, adhesives, and protective films that form a resin cured film by irradiation with radiation. In addition, since the curable resin composition contains an alkali-soluble resin, it can be developed after exposure or heating, and can therefore be suitably used for the purpose of forming a fine line pattern.

作為黏接劑用途,特別是在圖案形成後也具有高的黏接強度,因此可用於黏接適於製作微機電系統(microelectromechanical system,MEMS)封裝體或LED等半導體封裝體的各種構件。As an adhesive, it has high bonding strength especially after pattern formation, so it can be used to bond various components suitable for making microelectromechanical system (MEMS) packages or semiconductor packages such as LEDs.

作為絕緣材用途,特別是具有高的密合性、耐濕性及耐酸性,因此可適宜地用於製作印刷配線基板及半導體封裝體用的絕緣膜、例如阻焊劑層、鍍敷抗蝕劑層、蝕刻抗蝕劑層、緩衝層、再配線層、層間絕緣層等。在本申請中,半導體封裝體除是指倒裝芯片封裝體、晶片級封裝體等以外,還是指包括如例如將倒裝芯片封裝體層疊於中介層(Interposer)上而成者等那樣形成為包含半導體芯片且可封裝於印刷基板上的形態者在內的封裝體。除此以外,也可用於製作塗料或油墨的面塗層、塑料類的硬塗層及金屬類的防銹膜等。As an insulating material, it has particularly high adhesion, moisture resistance, and acid resistance, so it can be suitably used to produce insulating films for printed wiring boards and semiconductor packages, such as solder resist layers and plating resists. layer, etching resist layer, buffer layer, rewiring layer, interlayer insulating layer, etc. In this application, the semiconductor package refers to a flip-chip package, a wafer-level package, etc., as well as a package formed by laminating a flip-chip package on an interposer. A package including a semiconductor chip that can be mounted on a printed circuit board. In addition, it can also be used to make top coats for paints or inks, hard coats for plastics, and anti-rust films for metals.

例如,在製成多層印刷配線時,例如通過浸漬法、噴霧法、旋塗法、輥塗法、簾塗法及絲網印刷法等方法,在預先形成有導體配線(第一導體配線)的基板的表面塗布硬化性樹脂組成物而形成濕潤塗膜。其後,在60℃~120℃左右的溫度下使(D)成分(溶劑)揮發,從而使濕潤塗膜乾燥。此外,也可在聚酯等的支撐體的表面塗布硬化性樹脂組成物並使其乾燥而形成乾薄膜,將經乾燥的塗膜從所述乾薄膜轉印至基板。For example, when forming multi-layer printed wiring, a conductor wiring (first conductor wiring) is formed in advance by a method such as a dipping method, a spray method, a spin coating method, a roller coating method, a curtain coating method, or a screen printing method. A curable resin composition is applied to the surface of the substrate to form a wet coating film. Thereafter, component (D) (solvent) is volatilized at a temperature of about 60°C to 120°C to dry the wet coating film. Alternatively, the curable resin composition may be applied to the surface of a support such as polyester and dried to form a dry film, and the dried coating film may be transferred from the dry film to the substrate.

其後,介隔負型遮罩對塗膜進行曝光而使其局部光硬化。曝光只要通過可見光線、紫外線、遠紫外線、電子束及X射線等公知的放射線的照射來進行即可。這些放射線中,較佳為紫外線。所照射的放射線的波長較佳為250 nm以上且400 nm以下。放射線的曝光量較佳為25 mJ/cm 2以上且3000 mJ/cm 2以下。此外,在使用乾薄膜時,也可在轉印前利用乾薄膜對塗膜進行曝光。 Thereafter, the coating is exposed through a negative mask to partially photoharden it. Exposure can be performed by irradiation with known radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam and X-ray. Among these radiations, ultraviolet light is preferred. The wavelength of the irradiated radiation is preferably greater than 250 nm and less than 400 nm. The exposure amount of the radiation is preferably greater than 25 mJ/ cm2 and less than 3000 mJ/ cm2 . In addition, when using a dry film, the coating can also be exposed using the dry film before transfer.

其次,對塗膜進行鹼顯影並將未曝光的部分去除。在顯影方法的例子中包含:噴淋顯影法、噴霧顯影法、浸漬(dip)顯影法及水坑式(puddle)(覆液)顯影法等。另外,在顯影中使用的顯影液的例子中包含:氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸鉀、碳酸鋰、矽酸鈉、偏矽酸鈉、氨、乙胺、正丙胺、二乙胺、二乙基胺基乙醇、二正丙胺、三乙胺、甲基二乙胺、二甲基乙醇胺、三乙醇胺、氫氧化四甲基銨、氫氧化四乙基銨、吡咯、呱啶、1,8-二氮雜雙環[5.4.0]-7-十一烯及1,5-二氮雜雙環[4.3.0]-5-壬烯等鹼(鹼性化合物)的水溶液等。顯影條件根據硬化性樹脂組成物而不同,較佳為在20℃~30℃的溫度下進行10秒~120秒。此外,所述顯影可使用市售的顯影機或超聲波清洗機等來進行。Next, the coating is developed with alkaline to remove the unexposed portion. Examples of developing methods include shower developing, mist developing, dip developing, and puddle developing. In addition, examples of the developer used in the development include aqueous solutions of alkalis (alkaline compounds) such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene and 1,5-diazabicyclo[4.3.0]-5-nonene, etc. The developing conditions vary depending on the curable resin composition, but are preferably performed at a temperature of 20°C to 30°C for 10 seconds to 120 seconds. The development can be performed using a commercially available developer or ultrasonic cleaning machine or the like.

所述曝光及顯影是以將多層印刷配線中的供通孔形成的位置處的塗膜去除的方式進行。The exposure and development are performed in such a manner that the coating film is removed at the position where the through hole is to be formed in the multi-layer printed wiring.

其後,對顯影後的曝光部進行熱處理而使硬化性樹脂組成物正式硬化(後烘烤)。後烘烤可通過公知的方法(利用烘箱、熱風送風機、加熱板、紅外線加熱器等的加熱、真空乾燥或它們的組合)等來進行。關於加熱條件,若為樹脂硬化膜進行正式硬化(後烘烤)的溫度,則並無特別限制,較佳為在180℃~250℃的溫度下進行20分鐘~120分鐘。Thereafter, the exposed part after development is heat-treated to cure the curable resin composition (post-baking). Post-baking can be performed by a known method (heating with an oven, hot air blower, heating plate, infrared heater, etc., vacuum drying, or a combination thereof). Regarding the heating conditions, there are no particular restrictions as long as the temperature for the resin cured film to be cured (post-baked) is achieved, but it is preferably performed at a temperature of 180°C to 250°C for 20 minutes to 120 minutes.

其後,可利用加成法等公知的方法來製作形成於樹脂硬化膜的表面的導體配線(第二導體配線)、及被覆無通孔的表面並將第一導體配線與第二導體配線連接的孔鍍敷,從而獲得形成有多層印刷配線的印刷配線基板。Thereafter, a conductor wiring (second conductor wiring) formed on the surface of the resin cured film and a via plating that covers the surface without through-holes and connects the first conductor wiring and the second conductor wiring can be produced by a known method such as an additive method, thereby obtaining a printed wiring board having a multi-layer printed wiring.

此外,所述製造方法只不過示出硬化性樹脂組成物的用途的一例,也可設為並非多層結構的單層的印刷配線基板。The above-described manufacturing method is merely an example of the use of the curable resin composition, and a single-layer printed wiring board instead of a multi-layer structure may be used.

另外,在用於黏接劑用途時等,也可不介隔負型遮罩而對整個塗膜進行曝光。此時,不需要鹼顯影。另外,在不進行圖案化而用作半導體元件或不同種材料的黏接劑的情況下,也可通過加熱使塗膜熱硬化,來代替通過曝光使塗膜光硬化。In addition, when used for adhesive purposes, the entire coating can be exposed without a negative mask. In this case, alkaline development is not required. In addition, when it is used as an adhesive for semiconductor devices or different materials without patterning, the coating can be thermally cured by heating instead of photocuring by exposure.

另外,所述印刷配線基板或半導體封裝體也可與其他功能零件等組合而製成半導體裝置或顯示裝置。 [實施例] In addition, the printed wiring substrate or semiconductor package can also be combined with other functional parts to form a semiconductor device or display device. [Example]

以下,基於實施例及比較例對本發明的實施方式進行具體說明,但本發明並不限定於這些。Hereinafter, the implementation mode of the present invention will be specifically described based on embodiments and comparative examples, but the present invention is not limited to these.

首先,從作為(A)成分的含不飽和基的鹼可溶性樹脂的合成例開始進行說明,但只要無說明,則這些合成例中的樹脂的評價是如以下那樣進行。First, the synthesis examples of the unsaturated group-containing alkali-soluble resin as the component (A) will be described. However, unless otherwise specified, the evaluation of the resins in these synthesis examples was performed as follows.

此外,關於各種測定設備,在使用同一機型的情況下,從第二處開始省略設備製造商名稱。另外,在實施例中,測定用帶有硬化膜的基板的製作中使用的玻璃基板全部實施相同的處理後使用。另外,關於各成分的含量,在小數第一位為0時,有時省略小數點以後的表述。In addition, when the same model is used for various measuring equipment, the equipment manufacturer name is omitted from the second place. In addition, in the embodiment, all glass substrates used in the production of the substrate with a cured film for measurement are subjected to the same treatment before use. In addition, when the first decimal place of the content of each component is 0, the expression after the decimal point may be omitted.

[固體成分濃度] 根據使合成例中所獲得的樹脂溶液1 g含浸於玻璃濾光片[重量:W 0(g)]中並秤量後的重量[W 1(g)]、與在160℃下加熱2小時後的重量[W 2(g)]並利用下式來求出。 固體成分濃度(重量%)=100×(W 2-W 0)/(W 1-W 0[Solid content concentration] The solid content concentration was calculated by using the following formula: 1 g of the resin solution obtained in the synthesis example was impregnated into a glass filter [weight: W 0 (g)] and the weight [W 1 (g)] after heating at 160°C for 2 hours [W 2 (g)]. Solid content concentration (weight %) = 100 × (W 2 - W 0 ) / (W 1 - W 0 )

[酸值] 使樹脂溶液溶解於二噁烷中,使用電位差滴定裝置「COM-1600」(平沼產業股份有限公司製造),並利用1/10N-KOH水溶液進行滴定來求出。 [Acid value] Dissolve the resin solution in dioxane and use a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.) to titrate with a 1/10N-KOH aqueous solution to determine the acid value.

[分子量] 利用膠體滲透層析儀(gel permeation chromatograph,GPC)「HLC-8220GPC」(東曹(Tosoh)股份有限公司製造,溶媒:四氫呋喃,管柱:TSKgelSuper H-2000(2根)+TSKgelSuper H-3000(1根)+TSKgelSuper H-4000(1根)+TSKgelSuper H-5000(1根)(東曹(Tosoh)股份有限公司製造),溫度:40℃,速度:0.6 ml/min)進行測定,並作為標準聚苯乙烯(東曹(Tosoh)股份有限公司製造,PS-寡聚物套組)換算值來求出重量平均分子量(Mw)。 [Molecular weight] Measured using a gel permeation chromatograph (GPC) "HLC-8220GPC" (manufactured by Tosoh Co., Ltd., solvent: tetrahydrofuran, columns: TSKgelSuper H-2000 (2 columns) + TSKgelSuper H-3000 (1 column) + TSKgelSuper H-4000 (1 column) + TSKgelSuper H-5000 (1 column) (manufactured by Tosoh Co., Ltd.), temperature: 40°C, speed: 0.6 ml/min) and the weight average molecular weight (Mw) was calculated as a conversion value of standard polystyrene (manufactured by Tosoh Co., Ltd., PS-oligomer set).

合成例中記載的簡稱如下所述。 BPFE     :雙苯酚茀型環氧樹脂(通式(1)中Ar 1為苯環且l為0的環氧樹脂,環氧當量256 g/eq) AA              :丙烯酸(acrylic acid,AA) TPP             :三苯基膦(triphenyl phosphine,TPP) PGMEA       :丙二醇單甲醚乙酸酯(propylene glycol monomethyl ether acetate,PGMEA) BPDA         :3,3',4,4'-聯苯四羧酸二酐(3,3',4,4'-biphenyl tetracarboxylic dianhydride,BPDA) THPA          :1,2,3,6-四氫鄰苯二甲酸酐(1,2,3,6-tetrahydrophthalic anhydride,THPA) DCPMA      :甲基丙烯酸二環戊烷基酯(dicyclopentanyl methacrylate,DCPMA) GMA           :甲基丙烯酸縮水甘油酯(glycidyl methacrylate,GMA) St                :苯乙烯(styrene,St) AIBN          :偶氮雙異丁腈(azobisisobutyronitrile,AIBN) TDMAMP  :三-二甲基胺基甲基苯酚(tris-dimethyl amino methyl phenol,TDMAMP) HQ              :對苯二酚(hydroquinone,HQ) SA              :琥珀酸酐(succinic anhydride,SA) TEA            :三乙胺(triethyl amine,TEA) The abbreviations described in the synthesis examples are as follows. BPFE: bisphenol-type epoxy resin (epoxy resin in which Ar 1 is a benzene ring and l is 0 in the general formula (1), epoxy equivalent 256 g/eq) AA: acrylic acid (AA) TPP: tri Triphenyl phosphine (TPP) PGMEA: propylene glycol monomethyl ether acetate (PGMEA) BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride (3,3 ',4,4'-biphenyl tetracarboxylic dianhydride (BPDA) THPA: 1,2,3,6-tetrahydrophthalic anhydride (THPA) DCPMA: dimethacrylic acid Cyclopentyl ester (dicyclopentanyl methacrylate, DCPMA) GMA: glycidyl methacrylate (GMA) St: styrene (St) AIBN: azobisisobutyronitrile (AIBN) TDMAMP: tri -tris-dimethyl amino methyl phenol (TDMAMP) HQ: hydroquinone (HQ) SA: succinic anhydride (SA) TEA: triethyl amine (TEA) )

[合成例1] 在帶有回流冷卻機的250 mL的四口燒瓶中投入BPFE(50.00 g、0.10 mol)、AA(14.07 g、0.20 mol)、TPP(0.26 g)及PGMEA(40.00 g),在100℃~105℃下攪拌12小時,獲得反應生成物。其後,在所述反應生成物中加入PGMEA(25.00 g)並調整為固體成分為50質量%。 [Synthesis example 1] Put BPFE (50.00 g, 0.10 mol), AA (14.07 g, 0.20 mol), TPP (0.26 g) and PGMEA (40.00 g) into a 250 mL four-necked flask with a reflux cooler, and heat it at 100°C to 105 The mixture was stirred for 12 hours at ℃ to obtain a reaction product. Thereafter, PGMEA (25.00 g) was added to the reaction product to adjust the solid content to 50 mass%.

繼而,在所獲得的反應生成物中加入BPDA(14.37 g、0.05 mol)及THPA(7.43 g、0.05 mol),在115℃~120℃下攪拌6小時,獲得含不飽和基的鹼可溶性樹脂(A)-1。所獲得的樹脂溶液的固體成分濃度為57.0質量%,酸值(固體成分換算)為96 mgKOH/g,基於GPC分析所得的Mw為3600。Next, BPDA (14.37 g, 0.05 mol) and THPA (7.43 g, 0.05 mol) were added to the obtained reaction product, and the mixture was stirred at 115°C to 120°C for 6 hours to obtain an unsaturated group-containing alkali-soluble resin (A)-1. The obtained resin solution had a solid content concentration of 57.0 mass %, an acid value (solid content conversion) of 96 mgKOH/g, and a Mw of 3600 based on GPC analysis.

[合成例2] 在帶有回流冷卻機的250 mL的四口燒瓶中投入BPFE(50.00 g、0.10 mol)、AA(14.07 g、0.20 mol)、TPP(0.26 g)及PGMEA(40.00 g),在100℃~105℃下攪拌12小時,獲得反應生成物。其後,在所述反應生成物中加入PGMEA(25.00 g)並調整為固體成分為50質量%。 [Synthesis Example 2] BPFE (50.00 g, 0.10 mol), AA (14.07 g, 0.20 mol), TPP (0.26 g) and PGMEA (40.00 g) were placed in a 250 mL four-necked flask equipped with a reflux cooler, and stirred at 100°C to 105°C for 12 hours to obtain a reaction product. Thereafter, PGMEA (25.00 g) was added to the reaction product and adjusted to a solid content of 50% by mass.

繼而,在所獲得的反應生成物中加入BPDA(10.06 g、0.03 mol)及THPA(11.89 g、0.08 mol),在115℃~120℃下攪拌6小時,獲得含不飽和基的硬化性樹脂(A)-2。所獲得的樹脂溶液的固體成分濃度為57.0質量%,酸值(固體成分換算)為98 mgKOH/g,基於GPC分析所得的Mw為2300。Then, BPDA (10.06 g, 0.03 mol) and THPA (11.89 g, 0.08 mol) were added to the obtained reaction product, and stirred at 115°C to 120°C for 6 hours to obtain an unsaturated group-containing curable resin ( A)-2. The solid content concentration of the obtained resin solution was 57.0 mass%, the acid value (solid content conversion) was 98 mgKOH/g, and the Mw based on GPC analysis was 2300.

[合成例3] 在帶有回流冷卻機的250 mL的四口燒瓶中投入BPFE(50.00 g、0.10 mol)、AA(14.07 g、0.20 mol)、TPP(0.26 g)及PGMEA(40.00 g),在100℃~105℃下攪拌12小時,獲得反應生成物。其後,在所述反應生成物中加入PGMEA(25.00 g)並調整為固體成分為50質量%。 [Synthesis example 3] Put BPFE (50.00 g, 0.10 mol), AA (14.07 g, 0.20 mol), TPP (0.26 g) and PGMEA (40.00 g) into a 250 mL four-necked flask with a reflux cooler, and heat it at 100°C to 105 The mixture was stirred for 12 hours at ℃ to obtain a reaction product. Thereafter, PGMEA (25.00 g) was added to the reaction product to adjust the solid content to 50 mass%.

繼而,在所獲得的反應生成物中加入BPDA(19.25 g、0.07 mol)及THPA(0.30 g、0.002 mol),在115℃~120℃下攪拌6小時,獲得含不飽和基的硬化性樹脂(A)-3。所獲得的樹脂溶液的固體成分濃度為56.3質量%,酸值(固體成分換算)為97 mgKOH/g,基於GPC分析所得的Mw為4700。Next, BPDA (19.25 g, 0.07 mol) and THPA (0.30 g, 0.002 mol) were added to the obtained reaction product, and the mixture was stirred at 115°C to 120°C for 6 hours to obtain a hardening resin (A)-3 containing an unsaturated group. The obtained resin solution had a solid content concentration of 56.3% by mass, an acid value (solid content conversion) of 97 mgKOH/g, and a Mw of 4700 based on GPC analysis.

[合成例4] 在帶有回流冷卻機的250 mL的四口燒瓶中投入BPFE(50.00 g、0.09 mol)、AA(12.82 g、0.20 mol)、TPP(0.23 g)及PGMEA(40.00 g),在100℃~105℃下攪拌12小時,獲得反應生成物。其後,在所述反應生成物中加入PGMEA(25.00 g)並調整為固體成分為50質量%。 [Synthesis Example 4] BPFE (50.00 g, 0.09 mol), AA (12.82 g, 0.20 mol), TPP (0.23 g) and PGMEA (40.00 g) were placed in a 250 mL four-necked flask equipped with a reflux cooler, and stirred at 100°C to 105°C for 12 hours to obtain a reaction product. Thereafter, PGMEA (25.00 g) was added to the reaction product and adjusted to a solid content of 50% by mass.

繼而,在所獲得的反應生成物中加入1,2,3,4-丁烷四羧酸二酐(9.67 g、0.05 mol)及THPA(7.43 g、0.05 mol),在115℃~120℃下攪拌6小時,獲得含不飽和基的鹼可溶性樹脂(A)-4。所獲得的樹脂溶液的固體成分濃度為56.0質量%,酸值(固體成分換算)為106 mgKOH/g,基於GPC分析所得的Mw為3300。Then, 1,2,3,4-butanetetracarboxylic dianhydride (9.67 g, 0.05 mol) and THPA (7.43 g, 0.05 mol) were added to the obtained reaction product, and the mixture was heated at 115°C to 120°C. Stir for 6 hours to obtain unsaturated group-containing alkali-soluble resin (A)-4. The solid content concentration of the obtained resin solution was 56.0 mass%, the acid value (solid content conversion) was 106 mgKOH/g, and the Mw based on GPC analysis was 3300.

[合成例5] 在帶有回流冷卻機的1 L的四口燒瓶中放入PGMEA(300 g),對燒瓶體系內進行氮氣置換後,升溫至120℃。從滴加漏斗向燒瓶內歷時2小時滴加如下混合物,即將AIBN(10 g)溶解於單體混合物(DCPMA(77.1 g、0.35 mol)、GMA(49.8 g、0.35 mol)、St(31.2 g、0.30 mol))中而成的混合物,進而,在120℃下攪拌2小時,獲得共聚物溶液。 [Synthesis Example 5] PGMEA (300 g) was placed in a 1 L four-necked flask equipped with a reflux cooler, and the flask system was replaced with nitrogen, and the temperature was raised to 120°C. A mixture of AIBN (10 g) dissolved in a monomer mixture (DCPMA (77.1 g, 0.35 mol), GMA (49.8 g, 0.35 mol), St (31.2 g, 0.30 mol)) was added dropwise from a dropping funnel to the flask over 2 hours, and then stirred at 120°C for 2 hours to obtain a copolymer solution.

繼而,將燒瓶體系內置換為空氣後,在所獲得的共聚物溶液中加入AA(24.0 g、縮水甘油基的95%)、TDMAMP(0.8 g)及HQ(0.15 g),在120℃下攪拌6小時,獲得含聚合性不飽和基的共聚物溶液。在所獲得的含聚合性不飽和基的共聚物溶液中加入SA(30.0 g、AA添加莫耳數的90%)、TEA(0.5 g),在120℃下反應4小時,獲得含聚合性不飽和基的鹼可溶性共聚物樹脂溶液(A)'-5。樹脂溶液的固體成分濃度為46.0質量%,酸值(固體成分換算)為76 mgKOH/g,基於GPC分析所得的Mw為5300。Then, after replacing the flask system with air, AA (24.0 g, 95% of glycidyl groups), TDMAMP (0.8 g), and HQ (0.15 g) were added to the obtained copolymer solution, and the mixture was stirred at 120°C. After 6 hours, a copolymer solution containing polymerizable unsaturated groups was obtained. Add SA (30.0 g, 90% of the molar number of AA added) and TEA (0.5 g) to the obtained copolymer solution containing polymerizable unsaturated groups, and react at 120°C for 4 hours to obtain polymerizable unsaturated group-containing copolymer solution. Saturated alkali-soluble copolymer resin solution (A)'-5. The solid content concentration of the resin solution is 46.0 mass%, the acid value (solid content conversion) is 76 mgKOH/g, and the Mw based on GPC analysis is 5300.

以表1及表2中記載的調配量(單位為質量%)來製備實施例1~實施例10、比較例1~比較例8的硬化性樹脂組成物。表1中使用的調配成分如以下所述。The curable resin compositions of Examples 1 to 10 and Comparative Examples 1 to 8 were prepared with the blending amounts (unit: mass %) listed in Tables 1 and 2. The blending components used in Table 1 are as follows.

(含不飽和基的鹼可溶性樹脂) (A)-1:合成例1中所獲得的樹脂溶液(固體成分濃度57.0質量%) (A)-2:合成例2中所獲得的樹脂溶液(固體成分濃度57.0質量%) (A)-3:合成例3中所獲得的樹脂溶液(固體成分濃度56.3質量%) (A)-4:合成例4中所獲得的樹脂溶液(固體成分濃度56.0質量%) (A)'-5:合成例5中所獲得的樹脂溶液(固體成分濃度46.0質量%) (Alkaline-soluble resin containing unsaturated groups) (A)-1: Resin solution obtained in Synthesis Example 1 (solid content concentration 57.0 mass%) (A)-2: Resin solution obtained in Synthesis Example 2 (solid content concentration 57.0 mass%) (A)-3: Resin solution obtained in Synthesis Example 3 (solid content concentration 56.3 mass%) (A)-4: Resin solution obtained in Synthesis Example 4 (solid content concentration 56.0 mass%) (A)'-5: Resin solution obtained in Synthesis Example 5 (solid content concentration 46.0 mass%)

(聚合性化合物) (B)-1:二季戊四醇五丙烯酸酯與六丙烯酸酯的混合物(DPHA,日本化藥股份有限公司製造) (B)-2:三羥甲基丙烷三丙烯酸酯的環氧乙烷6莫耳加成物(阿羅尼斯(Aronix)M-360,東亞合成股份有限公司製造) (Polymerizable compound) (B)-1: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) (B)-2: An ethylene oxide 6-mole adduct of trihydroxymethylpropane triacrylate (Aronix M-360, manufactured by Toagosei Co., Ltd.)

(光聚合起始劑) (C)-1:1-(9,9-二丁基-9H-茀-2-基)-2-甲基-2-嗎啉-4-基-丙烷-1-酮(強力(TRONLY)公司製造,「TR-NPI-20400」(通式(9)中兩個R 5均為直鏈狀的碳數4的烷基、R 6及R 7均為甲基且R 8為N-嗎啉基的化合物)) (C)'-2:2-[4-(甲硫基)苯甲醯基]-2-(4-嗎啉基)丙烷(IGM樹脂(IGM Resins)B.V.公司製造,「歐姆尼拉德(Omnirad)907」(「歐姆尼拉德(Omnirad)」是所述公司的註冊商標)) (C)'-3:1,2-辛二酮,1-[4-(苯硫基)苯基]-,2-(O-苯甲醯基肟)(巴斯夫(BASF)公司製造,「豔佳固(Irgacure)OXE-01」「豔佳固(Irgacure)」是所述公司的註冊商標) (C)'-4:乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-哢唑-3-基]-,1-(O-乙醯基肟)(巴斯夫(BASF)公司製造,豔佳固(Irgacure)OXE-02) (C)'-5:1-(聯苯-4-基)-2-甲基-2-嗎啉-4-基-丙烷-1-酮(有尾(YOUWEI)公司製造,APi-307) (Photopolymerization initiator) (C)-1: 1-(9,9-dibutyl-9H-fluoren-2-yl)-2-methyl-2-morpholin-4-yl-propane-1-one (manufactured by Tronly Corporation, "TR-NPI-20400" (a compound in which both R5s in the general formula (9) are linear alkyl groups having 4 carbon atoms, R6 and R7 are both methyl groups, and R8 is N-morpholinyl)) (C)'-2: 2-[4-(methylthio)benzoyl]-2-(4-morpholinyl)propane (manufactured by IGM Resins BV, "Omnirad 907"("Omnirad" is a registered trademark of the aforementioned company)) (C)'-3: 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyl oxime) (manufactured by BASF, "Irgacure OXE-01" and "Irgacure" are registered trademarks of the aforementioned company) (C)'-4: Ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-oxazol-3-yl]-, 1-(O-acetyl oxime) (manufactured by BASF, Irgacure OXE-02) (C)'-5: 1-(biphenyl-4-yl)-2-methyl-2-oxolin-4-yl-propane-1-one (manufactured by YOUWEI, APi-307)

(溶劑) (D):丙二醇單甲醚乙酸酯(PGMEA) (solvent) (D): Propylene glycol monomethyl ether acetate (PGMEA)

(增感劑) (E)-1:米氏酮 (E)-2:2,4-二乙基硫雜蒽酮 (E)-3:9,10-二丁氧基蒽 (Sensitizer) (E)-1: Michler's ketone (E)-2: 2,4-diethylthioxanthrone (E)-3: 9,10-dibutoxyanthracene

(環氧化合物) (F)-1:聯苯型環氧樹脂(jER YX4000,三菱化學股份有限公司製造,「jER」是所述公司的註冊商標,環氧當量180 g/eq~192 g/eq) (F)-2:雙酚A型環氧樹脂(jER 828,三菱化學股份有限公司製造,環氧當量120 g/eq~150 g/eq) (Epoxy compounds) (F)-1: Biphenyl type epoxy resin (jER YX4000, manufactured by Mitsubishi Chemical Co., Ltd., "jER" is a registered trademark of the company, epoxy equivalent 180 g/eq to 192 g/eq) (F)-2: Bisphenol A type epoxy resin (jER 828, manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent 120 g/eq to 150 g/eq)

[表1] 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 1 2 3 4 5 6 7 8 9 10 (A)-1 63.9 63.8 63.8 63.8 63.8 54.2 54.2 (A)-2 64.7 (A)-3 63.9 (A)-4 65.0 (A)'-5 (B)-1 12.1 12.1 12.1 12.1 12.1 12.1 12.1 10.3 10.3 (B)-2 12.1 (C)-1 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 (C)'-2 (C)'-3 (C)'-4 (C)'-5 (D) 22.5 21.7 22.5 21.4 22.5 22.5 22.5 22.5 26.6 26.6 (E)-1 0.1 0.1 0.1 0.1 (E)-2 0.1 (E)-3 0.1 (F)-1 7.3 (F)-2 7.3 [Table 1] Example Example Example Example Example Example Example Example Example Example 1 2 3 4 5 6 7 8 9 10 (A)-1 63.9 63.8 63.8 63.8 63.8 54.2 54.2 (A)-2 64.7 (A)-3 63.9 (A)-4 65.0 (A)'-5 (B)-1 12.1 12.1 12.1 12.1 12.1 12.1 12.1 10.3 10.3 (B)-2 12.1 (C)-1 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 (C)'-2 (C)'-3 (C)'-4 (C)'-5 (D) 22.5 21.7 22.5 21.4 22.5 22.5 22.5 22.5 26.6 26.6 (E)-1 0.1 0.1 0.1 0.1 (E)-2 0.1 (E)-3 0.1 (F)-1 7.3 (F)-2 7.3

[表2] 比較例 比較例 比較例 比較例 比較例 比較例 比較例 比較例 1 2 3 4 5 6 7 8 (A)-1 63.9 63.9 63.9 63.9 54.2 54.2 54.2 (A)-2 (A)-3 (A)-4 (A)'-5 79.1 (B)-1 12.1 12.1 12.1 12.1 10.3 10.3 12.1 10.3 (B)-2 (C)-1 1.5 (C)'-2 1.5 1.5 (C)'-3 1.5 1.5 (C)'-4 1.5 (C)'-5 1.5 1.5 (D) 22.5 22.5 22.5 22.5 26.6 26.6 7.3 26.7 (E)-1 0.1 0.1 (E)-2 (E)-3 (F)-1 7.3 7.3 7.3 (F)-2 [Table 2] Comparative example Comparative example Comparative example Comparative example Comparative example Comparative example Comparative example Comparative example 1 2 3 4 5 6 7 8 (A)-1 63.9 63.9 63.9 63.9 54.2 54.2 54.2 (A)-2 (A)-3 (A)-4 (A)'-5 79.1 (B)-1 12.1 12.1 12.1 12.1 10.3 10.3 12.1 10.3 (B)-2 (C)-1 1.5 (C)'-2 1.5 1.5 (C)'-3 1.5 1.5 (C)'-4 1.5 (C)'-5 1.5 1.5 (D) 22.5 22.5 22.5 22.5 26.6 26.6 7.3 26.7 (E)-1 0.1 0.1 (E)-2 (E)-3 (F)-1 7.3 7.3 7.3 (F)-2

[評價] 使用使所述硬化性樹脂組成物硬化而成的硬化膜,進行以下的評價。 [Evaluation] The following evaluation was performed using a cured film formed by curing the curable resin composition.

[氣體產生性評價] (氣體產生性評價用的樹脂膜粉末的製作) 使用旋塗機將表1及表2中所示的硬化性樹脂組成物以加熱硬化處理後的膜厚成為20.0 μm的方式塗布於玻璃基板「#1737」上,使用加熱板在110℃下進行5分鐘預烘烤來製作乾燥膜。繼而,在所述乾燥膜上利用i射線照度30 mW/cm 2的超高壓水銀燈照射1000 mJ/cm 2的紫外線,進行乾燥膜的光硬化反應。 [Evaluation of gas generation] (Preparation of resin film powder for evaluation of gas generation) The curable resin composition shown in Table 1 and Table 2 was applied to a glass substrate "#1737" using a spin coater so that the film thickness after heat curing was 20.0 μm, and pre-baked at 110°C for 5 minutes using a hot plate to prepare a dry film. Then, the dry film was irradiated with ultraviolet rays of 1000 mJ/ cm2 using an ultra-high pressure mercury lamp with an i-ray irradiance of 30 mW/ cm2 to perform a photocuring reaction of the dry film.

繼而,針對經曝光的所述曝光膜,利用23℃的2.38%氫氧化四甲基銨(tetramethylammonium hydroxide,TMAH)顯影液以1 kgf/cm 2的噴淋壓進行60秒的顯影處理後,進行5 kgf/cm 2的噴霧水洗,獲得實施例1~實施例10、比較例1~比較例8的帶有樹脂膜的基板。其後,削取所獲得的樹脂膜,獲得氣體產生性評價用的樹脂膜粉末。 Then, the exposed film was developed using 2.38% tetramethylammonium hydroxide (TMAH) developer at 23°C and a spray pressure of 1 kgf/cm 2 for 60 seconds, and then The substrates with resin films of Examples 1 to 10 and Comparative Examples 1 to 8 were obtained by spray water washing at 5 kgf/cm 2 . Thereafter, the obtained resin film was scraped off to obtain resin film powder for gas generation property evaluation.

(評價方法) 針對所獲得的樹脂膜的粉末,使用熱重/差熱分析(Thermogravimetry/Differential Thermal Analysis,TG/DTA)裝置「TG/DTA6200」(精工儀器(Seiko Instruments)股份有限公司製造),在空氣中以升溫速度10℃/min從30℃升溫至120℃,在120℃下靜置5分鐘後,以升溫速度10℃/min從120℃升溫至230℃。繼而,在230℃下靜置30分鐘後,以升溫速度10℃/min從230℃升溫至260℃,最後,在260℃下靜置3分鐘。沿著所述溫度曲線來測定樹脂膜的重量減少率。此外,將△以上設為合格。 (evaluation method) The powder of the obtained resin film was analyzed in the air using a thermogravimetry/differential thermal analysis (TG/DTA) device "TG/DTA6200" (manufactured by Seiko Instruments Co., Ltd.). The temperature was increased from 30°C to 120°C at a heating rate of 10°C/min, and after standing at 120°C for 5 minutes, the temperature was increased from 120°C to 230°C at a heating rate of 10°C/min. Then, after leaving it still at 230°C for 30 minutes, the temperature was raised from 230°C to 260°C at a temperature rising rate of 10°C/min, and finally, it was left still at 260°C for 3 minutes. The weight reduction rate of the resin film was measured along the temperature curve. In addition, △ or more was considered a pass.

(評價基準) ◎:重量減少率為96%以上 ○:重量減少率為94%以上且未滿96% △:重量減少率為92%以上且未滿94% ×:重量減少率未滿92% (Evaluation criteria) ◎: Weight reduction rate is over 96% ○: Weight reduction rate is 94% or more and less than 96% △: Weight reduction rate is more than 92% and less than 94% ×: Weight reduction rate is less than 92%

[剪切強度(黏接強度)評價] (剪切強度(黏接強度)評價用的帶有樹脂硬化膜的基板的製作) 使用旋塗機將表1及表2中所示的硬化性樹脂組成物以加熱硬化處理後的膜厚成為10.0 μm的方式塗布於玻璃基板「#1737」上,使用加熱板在110℃下進行5分鐘預烘烤來製作乾燥膜。繼而,在所述乾燥膜上利用i射線照度30 mW/cm 2的超高壓水銀燈照射500 mJ/cm 2的紫外線,進行乾燥膜中感光部分的光硬化反應。 [Evaluation of shear strength (adhesion strength)] (Preparation of a substrate with a resin cured film for evaluation of shear strength (adhesion strength)) Use a spin coater to apply the curable resins shown in Tables 1 and 2 The composition was applied on the glass substrate "#1737" so that the film thickness after heat-hardening treatment became 10.0 μm, and prebaked at 110°C for 5 minutes using a hot plate to produce a dry film. Then, the dry film was irradiated with ultraviolet light of 500 mJ/cm 2 using an ultra-high-pressure mercury lamp with an i-ray illumination of 30 mW/cm 2 to perform a photohardening reaction on the photosensitive part of the dry film.

繼而,針對經曝光的所述曝光膜,利用23℃的2.38%TMAH(氫氧化四甲基銨)顯影液以1 kgf/cm 2的噴淋壓進行60秒的顯影處理後,進行5 kgf/cm 2的噴霧水洗,將曝光膜的未曝光部分去除而在玻璃基板上形成2 mm×2 mm的圖案。繼而,在圖案上放置切割成2 mm×2 mm的玻璃基板「#1737」,在110℃的加熱板上加熱1分鐘並進行暫時黏接。其後,使用熱風乾燥機在230℃下正式硬化(後烘烤)30分鐘,獲得剪切強度(黏接強度)評價用的帶有樹脂硬化膜的基板。 Next, the exposed film was developed for 60 seconds using a 2.38% TMAH (tetramethylammonium hydroxide) developer at 23°C with a spray pressure of 1 kgf/ cm2 , and then washed with a spray of 5 kgf/ cm2 to remove the unexposed portion of the exposed film and form a 2 mm×2 mm pattern on the glass substrate. Next, a glass substrate "#1737" cut into 2 mm×2 mm was placed on the pattern, and temporarily bonded by heating on a heating plate at 110°C for 1 minute. After that, a hot air dryer was used to formally cure (post-bake) at 230°C for 30 minutes to obtain a substrate with a resin cured film for shear strength (adhesive strength) evaluation.

(評價方法) 針對黏接於所獲得的帶有樹脂硬化膜的基板的2 mm×2 mm的玻璃基板「#1737」,利用芯片剪切測試儀(阿克泰科(Ark tech)公司製造)來測定剪切強度(黏接強度)。此外,將△以上設為合格。 (evaluation method) The shear was measured using a chip shear tester (manufactured by Ark Tech) on a 2 mm × 2 mm glass substrate "#1737" bonded to the obtained resin cured film-attached substrate. Strength (bonding strength). In addition, △ or more was considered a pass.

(評價基準) ◎:剪切強度(黏接強度)為20 MPa以上 ○:剪切強度(黏接強度)為18 MPa以上且未滿20 MPa △:剪切強度(黏接強度)為16 MPa以上且未滿18 MPa ×:剪切強度(黏接強度)未滿16 MPa (Evaluation criteria) ◎: Shear strength (adhesive strength) is 20 MPa or more ○: Shear strength (adhesive strength) is 18 MPa or more and less than 20 MPa △: Shear strength (adhesive strength) is 16 MPa or more and less than 18 MPa ×: Shear strength (adhesive strength) is less than 16 MPa

[顯影密合性評價] (顯影密合性評價用的帶有樹脂硬化膜的基板的製作) 使用旋塗機將表1及表2中所示的硬化性樹脂組成物以加熱硬化處理後的膜厚成為10.0 μm的方式塗布於玻璃基板「#1737」上,使用加熱板在110℃下進行5分鐘預烘烤來製作乾燥膜。繼而,在所述乾燥膜上利用i射線照度30 mW/cm 2的超高壓水銀燈照射500 mJ/cm 2的紫外線,進行乾燥膜的光硬化反應。 [Development Adhesion Evaluation] (Preparation of a substrate with a resin cured film for development adhesion evaluation) The curable resin composition shown in Table 1 and Table 2 was applied to a glass substrate "#1737" using a spin coater so that the film thickness after heat curing treatment was 10.0 μm, and a dry film was prepared by pre-baking at 110°C for 5 minutes using a hot plate. Then, the dry film was irradiated with ultraviolet rays of 500 mJ/ cm2 using an ultra-high pressure mercury lamp with an i-ray irradiance of 30 mW/ cm2 to perform a photocuring reaction of the dry film.

繼而,針對經曝光的所述曝光膜,利用23℃的2.38%TMAH(氫氧化四甲基銨)顯影液以1 kgf/cm 2的噴淋壓進行60秒的顯影處理後,進行5 kgf/cm 2的噴霧水洗,將未曝光部去除而形成10 μm的點圖案。最後,使用熱風乾燥機在230℃下正式硬化(後烘烤)30分鐘,獲得顯影密合性評價用的帶有樹脂硬化膜的基板。 Then, the exposed film was developed using a 2.38% TMAH (tetramethylammonium hydroxide) developer at 23°C and a spray pressure of 1 kgf/ cm for 60 seconds, and then 5 kgf/cm2 was developed. cm 2 spray water washing to remove the unexposed parts and form a 10 μm dot pattern. Finally, the substrate was formally cured (post-baked) at 230° C. for 30 minutes using a hot air dryer to obtain a substrate with a resin cured film for development adhesion evaluation.

(評價方法) 使用光學顯微鏡對所獲得的帶有樹脂硬化膜的基板的樹脂硬化膜的10 μm的點圖案進行觀察,並判定圖案有無剝離。此外,將△以上設為合格。 (evaluation method) The 10 μm dot pattern of the resin cured film of the obtained resin cured film-attached substrate was observed using an optical microscope, and the presence or absence of peeling in the pattern was determined. In addition, △ or more was considered a pass.

(評價基準) ◎:未看到圖案剝離 ○:看到圖案的極小一部分剝離 △:圖案的一半剝離 ×:圖案的大部分剝離 (Evaluation criteria) ◎: No pattern peeling was observed ○: A very small part of the pattern peeled off △: Half of the pattern peeled off ×: Most of the pattern peeled off

[玻璃化轉變溫度評價] (玻璃化轉變溫度評價用的樹脂硬化膜的製作) 使用旋塗機將表1及表2中所示的硬化性樹脂組成物以加熱硬化處理後的膜厚成為30.0 μm的方式塗布於脫模鋁箔「賽帕尼烏木(Sepanium)」(東洋鋁股份有限公司製造)上,使用加熱板在110℃下進行5分鐘預烘烤來製作乾燥膜。繼而,在所述乾燥膜上利用i射線照度30 mW/cm 2的超高壓水銀燈照射500 mJ/cm 2的紫外線,進行乾燥膜的光硬化反應。 [Evaluation of Glass Transition Temperature] (Preparation of Resin Cured Film for Evaluation of Glass Transition Temperature) The curable resin composition shown in Table 1 and Table 2 was heated and cured using a spin coater so that the film thickness became 30.0 μm is applied to the release aluminum foil "Sepanium" (manufactured by Toyo Aluminum Co., Ltd.), and prebaked at 110°C for 5 minutes using a hot plate to produce a dry film. Then, the dry film was irradiated with ultraviolet light of 500 mJ/cm 2 using an ultra-high-pressure mercury lamp with an i-ray illumination of 30 mW/cm 2 to perform a photohardening reaction of the dry film.

繼而,針對經曝光的所述曝光膜,利用23℃的2.38%TMAH(氫氧化四甲基銨)顯影液以1 kgf/cm 2的噴淋壓進行60秒的顯影處理後,進行5 kgf/cm 2的噴霧水洗,將未曝光部去除而形成100 mm×5 mm的圖案。最後,使用熱風乾燥機在230℃下正式硬化(後烘烤)30分鐘,將樹脂硬化膜從脫模鋁箔剝離,獲得玻璃化轉變溫度評價用的樹脂硬化膜。 Next, the exposed film was developed with a 2.38% TMAH (tetramethylammonium hydroxide) developer at 23°C at a spray pressure of 1 kgf/ cm2 for 60 seconds, and then washed with a spray of 5 kgf/ cm2 to remove the unexposed portion and form a 100 mm×5 mm pattern. Finally, a hot air dryer was used for formal curing (post-baking) at 230°C for 30 minutes, and the resin cured film was peeled off from the release aluminum foil to obtain a resin cured film for glass transition temperature evaluation.

(評價方法) 使用動態黏彈性(動態熱機械分析(Dynamic mechanical analysis,DMA))測定裝置(TA儀器(TA Instrument)股份有限公司製造的RSA-G2),以夾頭間長度成為22 mm的方式設置寬度5 mm的硬化薄膜,在30℃至300℃的溫度範圍內測定玻璃化轉變溫度。此外,將△以上設為合格。 (Evaluation method) Using a dynamic viscoelasticity (dynamic mechanical analysis (DMA)) measuring device (RSA-G2 manufactured by TA Instruments, Inc.), a 5 mm wide cured film was set so that the length between the chucks was 22 mm, and the glass transition temperature was measured in the temperature range of 30°C to 300°C. In addition, △ or above was regarded as passing.

(評價基準) ◎:玻璃化轉變溫度為180℃以上 ○:玻璃化轉變溫度為160℃以上且未滿180℃ △:玻璃化轉變溫度為140℃以上且未滿160℃ ×:玻璃化轉變溫度未滿140℃ (Evaluation criteria) ◎: Glass transition temperature is above 180℃ ○: Glass transition temperature is 160℃ or more and less than 180℃ △: Glass transition temperature is 140℃ or more and less than 160℃ ×: Glass transition temperature is less than 140℃

[表3] 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 1 2 3 4 5 6 7 8 9 10 氣體產生性 剪切強度 (黏接強度) 顯影密合性 玻璃化轉變溫度 [table 3] Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment 1 2 3 4 5 6 7 8 9 10 Gas generation Shear strength (adhesive strength) Development adhesion Glass transition temperature

[表4] 比較例 比較例 比較例 比較例 比較例 比較例 比較例 比較例 1 2 3 4 5 6 7 8 氣體產生性 × × × × × 剪切強度 (黏接強度) × × × 顯影密合性 × 玻璃化轉變溫度 [Table 4] Comparative example Comparative example Comparative example Comparative example Comparative example Comparative example Comparative example Comparative example 1 2 3 4 5 6 7 8 Gas generating property × × × × × Shear strength (bonding strength) × × × development adhesion × glass transition temperature

根據表3及表4而明確,當使用(A)通式(1)所表示的含不飽和基的鹼可溶性樹脂與(C)通式(9)所表示的光聚合起始劑時,來自使硬化性樹脂組成物硬化而獲得的樹脂硬化膜的氣體產生性降低,且可提高與被黏附體的黏接強度。此外,在使用通式(9)所表示的光聚合起始劑時,當使用不具有茀基的含不飽和基的鹼可溶性樹脂作為(A)成分時,(A)成分的分解物也容易揮發且(A)成分也無法抑制通式(9)所表示的光聚合起始劑的分解物的揮發,因此無法充分提高氣體產生性。 [產業上的可利用性] As is clear from Tables 3 and 4, when (A) an unsaturated group-containing alkali-soluble resin represented by general formula (1) and (C) a photopolymerization initiator represented by general formula (9) are used, the gas generation of the resin cured film obtained by curing the curable resin composition is reduced, and the bonding strength to the adherend can be improved. In addition, when the photopolymerization initiator represented by general formula (9) is used, when an unsaturated group-containing alkali-soluble resin without a fluorene group is used as the (A) component, the decomposition product of the (A) component is also easy to volatilize and the (A) component cannot suppress the volatility of the decomposition product of the photopolymerization initiator represented by general formula (9), so the gas generation cannot be fully improved. [Industrial Applicability]

通過本發明,可抑制由來自樹脂硬化膜的揮發物造成的被黏附體的污染。因此,本發明進一步擴展硬化性黏接劑的用途,被期待有助於所述技術領域的進一步發展。According to the present invention, contamination of an adherend caused by volatile matter from the resin cured film can be suppressed. Therefore, the present invention further expands the uses of curable adhesives and is expected to contribute to further development of the technical field.

Claims (9)

一種硬化性樹脂組成物,包括: (A)含不飽和基的鹼可溶性樹脂,由下述通式(1)表示、 (B)聚合性化合物,具有至少兩個不飽和基、 (C)光聚合起始劑,由下述通式(9)表示、及 (D)溶劑, 相對於所述(A)含不飽和基的鹼可溶性樹脂與所述(B)聚合性化合物的合計100質量份,所述(C)光聚合起始劑的含量為1質量份以上且15質量份以下; ···通式(1) 式(1)中,Ar 1分別獨立地為碳數6以上且14以下的芳香族烴基,所鍵結的氫原子的一部分可經選自由碳數1以上且10以下的烷基、碳數6以上且10以下的芳基或芳基烷基、碳數3以上且10以下的環烷基或環烷基烷基、碳數1以上且5以下的烷氧基及鹵素基所組成的群組中的取代基取代;R 1分別獨立地為碳數2以上且4以下的伸烷基,l分別獨立地為0以上且3以下的數;G分別獨立地為(甲基)丙烯醯基、下述通式(2)或下述通式(3)所表示的取代基,Y為四價的羧酸殘基;Z分別獨立地為氫原子或下述通式(4)所表示的取代基,一個以上為下述通式(4)所表示的取代基;n是平均值為1以上且20以下的數, ···通式(2) ···通式(3) 式(2)、式(3)中,R 2為氫原子或甲基,R 3為碳數2以上且10以下的二價的伸烷基或烷基伸芳基,R 4為碳數2以上且20以下的二價的飽和或不飽和的烴基,p為0以上且10以下的數;*表示與通式(1)所示的化合物的鍵結部位, ···通式(4) 式(4)中,W為二價或三價的羧酸殘基,m為1或2的數;*表示與通式(1)所示的化合物的鍵結部位, ···通式(9) 通式(9)中, A為氫原子、鹵素原子、硝基、碳數1以上且20以下的直鏈狀或可具有分支鏈的烷基、碳數3以上且10以下的環烷基、碳數4以上且10以下的烷基環烷基、碳數4以上且10以下的環烷基烷基、-N(R 9) 2、-COR 10或-CO-CR 6R 7R 8所表示的取代基;此外,這些取代基所具有的-CH 2-也可經-O-、-N-、-S-或-C(=O)-取代; R 5獨立地表示氫原子、鹵素原子、碳數1以上且20以下的直鏈狀或可具有分支鏈的烷基、碳數3以上且20以下的環烷基烷基或碳數2以上且20以下的烯基;此外,這些官能基所具有的-CH 2-也可經-O-、-N-、-S-或-C(=O)-取代;另外,兩個R 5也可相互鍵結而形成環; R 6及R 7獨立地表示碳數1以上且20以下的直鏈狀或可具有分支鏈的烷基、碳數3以上且20以下的環烷基、碳數4以上且20以下的環烷基烷基、碳數4以上且20以下的烷基環烷基、碳數6以上且20以下的芳基或碳數7以上且20以下的烷基芳基;此外,這些官能基所具有的氫原子中的一個或多個可獨立地經碳數1以上且20以下的直鏈狀或可具有分支鏈的烷基、鹵素原子、羥基或硝基取代;另外,這些官能基所具有的-CH 2-也可經-O-、-N-、-S-或-C(=O)-取代;R 6及R 7可相互鍵結而形成環; 或者,也可為,R 6為碳數1以上且20以下的直鏈狀或可具有分支鏈的烷基、或者碳數2以上且20以下的直鏈狀或可具有分支鏈的烯基,且R 7為下述通式(10)~通式(12)所表示的官能基中的任一個, ···通式(10) 通式(10)中,R 13表示氫原子、碳數1以上且8以下的直鏈狀或可具有分支鏈的烷基、或者苯基,R 14、R 15及R 16獨立地表示氫原子、或者碳數1以上且4以下的直鏈狀或可具有分支鏈的烷基;*表示與通式(9)所示的化合物的鍵結部位, ···通式(11) 通式(11)中,s為0以上且4以下的數;*表示與通式(9)所示的化合物的鍵結部位, ···通式(12) 通式(12)中,Ar 2表示均可經取代的苯基、萘基、呋喃基、噻吩基或吡啶基;*表示與通式(9)所示的化合物的鍵結部位; R 8表示N-嗎啉基、N-呱啶基、N-吡咯基或N-二烷基;此外,這些官能基所具有的氫原子中的一個或多個可獨立地經鹵素原子或羥基取代; R 9獨立地表示碳數1以上且20以下的直鏈狀或可具有分支鏈的烷基、碳數3以上且20以下的環烷基、碳數2以上且20以下的直鏈狀或可具有分支鏈的烯基、碳數6以上且20以下的芳基或碳數7以上且20以下的烷基芳基;此外,這些官能基所具有的氫原子中的一個或多個可獨立地經碳數1以上且20以下的直鏈狀或可具有分支鏈的烷基、鹵素原子、羥基或硝基取代;另外,這些取代基所具有的-CH 2-也可經-O-取代;另外,兩個R 9也可相互鍵結而形成環,此時,所述環可為經由-O-、-S-、-NH-而形成的五員環或六員環; R 10表示碳數1以上且20以下的直鏈狀或可具有分支鏈的烷基、碳數3以上且20以下的環烷基、碳數4以上且10以下的烷基環烷基、碳數2以上且20以下的直鏈狀或可具有分支鏈的烯基、碳數6以上且20以下的芳基或碳數7以上且20以下的烷基芳基;此外,這些官能基所具有的-CH 2-也可經-O-或-S-取代;這些官能基所具有的氫原子中的一個或多個可獨立地經碳數1以上且20以下的直鏈狀或可具有分支鏈的烷基、鹵素原子、硝基、氰基、-SR 11或-OR 12取代; R 11及R 12獨立地表示氫原子、或者碳數1以上且20以下的直鏈狀或可具有分支鏈的烷基。 A curable resin composition comprises: (A) an alkali-soluble resin containing an unsaturated group, represented by the following general formula (1), (B) a polymerizable compound having at least two unsaturated groups, (C) a photopolymerization initiator, represented by the following general formula (9), and (D) a solvent, wherein the content of the photopolymerization initiator (C) is 1 part by mass or more and 15 parts by mass or less relative to 100 parts by mass of the total of the (A) alkali-soluble resin containing an unsaturated group and the (B) polymerizable compound; ···General formula (1) In formula (1), Ar 1 is independently an aromatic alkyl group having 6 to 14 carbon atoms, and a portion of the hydrogen atoms to which it is bonded may be substituted by a substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group or an arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or a cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen group; R 1 is independently an alkylene group having 2 or more and 4 or less carbon atoms; l is independently a number of 0 or more and 3 or less; G is independently a (meth)acryloyl group, a substituent represented by the following general formula (2) or the following general formula (3); Y is a tetravalent carboxylic acid residue; Z is independently a hydrogen atom or a substituent represented by the following general formula (4); at least one of them is a substituent represented by the following general formula (4); n is a number having an average value of 1 or more and 20 or less; ···General formula (2) ···General formula (3) In formula (2) and formula (3), R2 is a hydrogen atom or a methyl group, R3 is a divalent alkylene group or alkylarylene group having 2 to 10 carbon atoms, R4 is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number from 0 to 10; * represents a bonding site with the compound represented by general formula (1), ···General formula (4) In formula (4), W is a divalent or trivalent carboxylic acid residue, m is 1 or 2; * represents the bonding site with the compound represented by general formula (1), ···General formula (9) In general formula (9), A is a hydrogen atom, a halogen atom, a nitro group, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkylcycloalkyl group having 4 to 10 carbon atoms, a cycloalkylalkyl group having 4 to 10 carbon atoms, -N(R 9 ) 2 , -COR 10 or -CO-CR 6 R 7 R 8 ; in addition, -CH 2 - in these substituents may be substituted by -O-, -N-, -S- or -C(=O)-; R R 5 independently represents a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms; in addition, the -CH 2 - in these functional groups may be substituted by -O-, -N-, -S-, or -C(=O)-; in addition, two R 5 may be bonded to each other to form a ring; R 6 and R R7 independently represents a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkylalkyl group having 4 to 20 carbon atoms, an alkylcycloalkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms; one or more of the hydrogen atoms possessed by these functional groups may independently be substituted by a linear or branched alkyl group having 1 to 20 carbon atoms, a halogen atom, a hydroxyl group, or a nitro group; -CH2- possessed by these functional groups may be substituted by -O-, -N-, -S-, or -C(=O)-; R6 and R7 may be bonded to each other to form a ring; or, R R6 is a linear or branched alkyl group having 1 to 20 carbon atoms, or a linear or branched alkenyl group having 2 to 20 carbon atoms, and R7 is any one of the functional groups represented by the following general formulae (10) to (12), ···General formula (10) In general formula (10), R 13 represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a phenyl group; R 14 , R 15 , and R 16 independently represent a hydrogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms; * represents a bonding site with the compound represented by general formula (9); ···General formula (11) In the general formula (11), s is a number of 0 or more and 4 or less; * represents a bonding site with the compound represented by the general formula (9), ···General formula (12) In general formula (12), Ar2 represents a phenyl group, a naphthyl group, a furyl group, a thienyl group or a pyridyl group which may be substituted; * represents the bonding site with the compound represented by general formula (9); R8 represents an N-morpholinyl group, an N-piperidinyl group, an N-pyrrolyl group or an N-dialkyl group; in addition, one or more of the hydrogen atoms possessed by these functional groups may be independently substituted by a halogen atom or a hydroxyl group; R R 9 independently represents a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms; one or more of the hydrogen atoms possessed by these functional groups may independently be substituted by a linear or branched alkyl group having 1 to 20 carbon atoms, a halogen atom, a hydroxyl group, or a nitro group; -CH 2 - possessed by these substituents may be substituted by -O-; two R 9 may be bonded to each other to form a ring, in which case the ring may be a five-membered or six-membered ring formed via -O-, -S-, or -NH-; R R10 represents a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkylcycloalkyl group having 4 to 10 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms; in addition, -CH2- in these functional groups may be substituted with -O- or -S-; one or more of the hydrogen atoms in these functional groups may be independently substituted with a linear or branched alkyl group having 1 to 20 carbon atoms, a halogen atom, a nitro group, a cyano group, -SR11 , or -OR12 ; R11 and R12 independently represent a hydrogen atom, or a linear or branched alkyl group having 1 to 20 carbon atoms. 如請求項1所述的硬化性樹脂組成物,其中, 所述(A)含不飽和基的鹼可溶性樹脂的重量平均分子量為1000以上且40000以下且酸值為50 mgKOH/g以上且200 mgKOH/g以下。 The curable resin composition as described in claim 1, wherein the weight average molecular weight of the unsaturated group-containing alkali-soluble resin (A) is 1000 or more and 40000 or less and the acid value is 50 mgKOH/g or more and 200 mgKOH/g or less. 如請求項1或2所述的硬化性樹脂組成物,其包含(E)增感劑。The hardening resin composition according to claim 1 or 2, further comprising (E) a sensitizer. 如請求項3所述的硬化性樹脂組成物,其中, 所述(E)增感劑包含二苯甲酮衍生物或硫雜蒽酮衍生物。 The curable resin composition according to claim 3, wherein, The (E) sensitizer contains a benzophenone derivative or a thioxanthone derivative. 如請求項1或2所述的硬化性樹脂組成物,其包含(F)具有兩個以上的環氧基的環氧化合物。The curable resin composition according to claim 1 or 2, which contains (F) an epoxy compound having two or more epoxy groups. 一種樹脂硬化膜,是使如請求項1至5中任一項所述的硬化性樹脂組成物硬化而成。A resin cured film obtained by curing the curable resin composition according to any one of claims 1 to 5. 一種印刷基板,包含如請求項6所述的樹脂硬化膜作為絕緣膜。A printed circuit board including the resin cured film according to claim 6 as an insulating film. 一種半導體封裝體,包含如請求項6所述的樹脂硬化膜作為絕緣膜。A semiconductor package comprises the resin hardening film as claimed in claim 6 as an insulating film. 一種顯示裝置,包含如請求項6所述的樹脂硬化膜作為絕緣膜。A display device including the resin cured film according to claim 6 as an insulating film.
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