WO2019188432A1 - Resin composition and electronic component - Google Patents

Abstract

This resin composition contains an annular olefin polymer (A) having a polar group, and an epoxy resin (B) with an epoxy equivalent of greater than or equal to 500.

Description

Resin composition and electronic component

The present invention relates to a resin composition and an electronic component, and more particularly to a resin composition that can be suitably used for forming an insulating film or the like used for an electronic component and an electronic component including a resin film made of the resin composition. is there.

Various display elements such as organic EL elements and liquid crystal display elements, integrated circuit elements, solid-state imaging elements, color filters, and electronic components such as black matrixes have surface protective films, element surfaces, Various resin films are provided as a planarizing film for planarizing wirings, an interlayer insulating film for insulating between wirings arranged in layers, and the like.

Recently, in order to impart desired properties to the resin film as described above, attempts have been made to improve the resin composition for forming the resin film from various viewpoints. For example, in Patent Document 1, a resin composition containing a binder resin, a radiation-sensitive compound, an epoxy equivalent of 450 or less, a softening point of 30 ° C. or less, and a tetrafunctional or less epoxy crosslinking agent, and an aralkylphenol resin Has been proposed. According to the resin composition according to Patent Document 1, it is possible to form a resin composition that can provide a resin film having high adhesion to the metal layer and excellent in developability and low moisture absorption.

International Publication No. 2015/141717

The resin film obtained by using the resin composition as described above may be used to form a desired pattern shape according to the application. Here, from the viewpoints of improving the yield and improving the performance of electronic components including a resin film, it is necessary that the resin film be capable of forming a pattern shape with good resolution. In order to be able to form a pattern with good resolution, lithography is performed on the resin film to obtain a development pattern, and when the development pattern is cured to obtain a pattern, the pattern shape is changed before and after curing. It is necessary to be able to sufficiently suppress the change. In addition, when the tensile elongation of the resin film is insufficient, that is, when the resin film is poor in extensibility, during continuous operation of an electronic device equipped with an electronic component, when stress is generated in the electronic component, etc. In addition, there is a possibility that a crack occurs in the resin film or the resin film is easily peeled off from the substrate. If a crack occurs in the resin film or the resin film peels from the substrate, it may be difficult for the electronic component to function normally. For this reason, from the viewpoint of providing highly reliable high-performance electronic components, the resin film is also required to have excellent extensibility. However, the resin film obtained using the above conventional resin composition cannot achieve both good resolution and sufficient stretchability.

Accordingly, the present invention provides a resin composition capable of forming a resin film excellent in resolution and extensibility, and a high-performance electronic component including a resin film formed using the resin composition. Objective.

The present inventor has intensively studied for the purpose of solving the above problems. According to the resin composition containing the cyclic olefin polymer having a polar group and the epoxy resin having an epoxy equivalent of a predetermined value or more, the inventor forms a resin film having excellent resolution and extensibility. The present invention has been completed by newly finding the points that can be achieved.

That is, this invention aims at solving the said subject advantageously, The resin composition of this invention is the cyclic olefin polymer (A) which has a polar group, and an epoxy equivalent is 500 or more. It contains an epoxy resin (B). Thus, if the resin composition contains the cyclic olefin polymer (A) having a polar group and the epoxy resin (B) having an epoxy equivalent of 500 or more, a resin film having excellent resolution and extensibility can be obtained. Can be formed.
In addition, an epoxy equivalent represents the gram number (g / eq.) Of resin containing 1 g equivalent of epoxy groups, and can be calculated | required according to JISK7236: 2009.

In the resin composition of the present invention, the epoxy resin (B) preferably contains a flexible skeleton and an aromatic group in the molecule. If the epoxy resin (B) contained in the resin composition contains a flexible skeleton and an aromatic group in the molecule, the resolution and extensibility of the resulting resin film can be further enhanced.
In the resin composition of the present invention, the content of the epoxy resin (B) is preferably 40 parts by mass or more and 100 parts by mass or less per 100 parts by mass of the cyclic olefin polymer (A). If content of an epoxy resin (B) is more than the said lower limit, the extensibility of a resin film can be improved further. Moreover, if content of an epoxy resin (B) is below the said upper limit, the resolution of a resin film can be improved further.

Here, the resin composition of the present invention preferably further contains a crosslinking agent (C) containing a phenolic hydroxyl group and an alkoxymethyl group in the molecule. According to the resin composition further containing a crosslinking agent (C) containing a phenolic hydroxyl group and an alkoxymethyl group in the molecule, a resin film having excellent chemical resistance can be formed.
In the resin composition of the present invention, the content of the crosslinking agent (C) is preferably 1 part by mass or more and 100 parts by mass or less per 100 parts by mass of the cyclic olefin polymer (A). If content of a crosslinking agent (C) is more than the said lower limit, the chemical resistance of a resin film can be improved further. Moreover, if content of a crosslinking agent (C) is below the said upper limit, the extensibility of a resin film can be improved.

Moreover, it is preferable that the resin composition of the present invention further contains a photoacid generator (D). If the resin composition contains a photoacid generator (D), the resin film can be patterned by changing the solubility of the resin film in the developer by the action of the photoacid generator (D). Become.

Further, the present invention is intended to advantageously solve the above-described problems, and the electronic component of the present invention is characterized by including a resin film made of any of the resin compositions described above. Since the resin film formed using the resin composition described above is excellent in resolution and extensibility, an electronic component including the resin film can sufficiently perform its intended function, and thus has high performance. It is.

According to the present invention, it is possible to provide a resin composition capable of forming a resin film excellent in resolution and extensibility, and a high-performance electronic component including a resin film formed using the resin composition. it can.

Hereinafter, embodiments of the present invention will be described in detail. The resin composition of the present invention can be used for forming a resin film. Such a resin film can be used as, for example, a surface protective film, a planarizing film, and an interlayer insulating film in an electronic component manufactured according to the wafer level package technology. And the electronic component of this invention is equipped with the resin film obtained using the resin composition of this invention.

(Resin composition)
The resin composition of the present invention contains a cyclic olefin polymer (A) having a polar group, and an epoxy resin (B) having an epoxy equivalent of 500 or more, optionally, a crosslinking agent (C), and photoacid generation An agent (D) and the like may further be contained.

And since the resin composition of this invention contains the cyclic olefin polymer (A) which has a polar group, and the epoxy resin (B) whose epoxy equivalent is 500 or more, it is excellent in resolution and an extendibility. A resin film can be formed. Conventionally, a resin film having good extensibility often has a high content ratio of a resin component having a low glass transition temperature. Even if a pattern is formed by lithography using the resin film, the resin film is subjected to a thermosetting process or the like. When provided, pattern collapse or the like occurred, and as a result, resolution was sacrificed due to the provision of extensibility. However, in the resin composition of the present invention, in combination with the cyclic olefin polymer (A) having a polar group, the epoxy resin (B) having an epoxy equivalent of 500 or more is blended, whereby resolution and extensibility are obtained. It became possible to achieve both.

<Cyclic olefin polymer having a polar group (A)>
When the cyclic olefin polymer blended in the resin composition has a polar group, the strength of the resulting resin film can be increased. The cyclic olefin polymer (A) having a polar group may have one or more polar groups. Furthermore, it is preferable that the cyclic olefin polymer (A) having a polar group has at least a protic polar group. If the cyclic olefin polymer (A) having a polar group has a protic polar group, it has solubility in a developer (in particular, an alkali developer described later), and the resin composition is When the crosslinking agent (C) described later is included, a resin film excellent in chemical resistance can be formed by being well crosslinked by the crosslinking agent (C).

Here, the protic polar group means a group containing an atom belonging to Group 15 or Group 16 of the periodic table to which a hydrogen atom is directly bonded. The atom belonging to Group 15 or 16 of the periodic table is preferably an atom belonging to Group 1 or 2 of Group 15 or 16 of the periodic table, more preferably an oxygen atom, a nitrogen atom or a sulfur atom. Particularly preferred is an oxygen atom.

Specific examples of such protic polar groups include polar groups having oxygen atoms such as hydroxyl groups, carboxyl groups (hydroxycarbonyl groups), sulfonic acid groups, and phosphoric acid groups; primary amino groups, secondary amino groups A polar group having a nitrogen atom such as a primary amide group or a secondary amide group (imide group); a polar group having a sulfur atom such as a thiol group. Among these, a polar group having an oxygen atom is preferable, and a carboxyl group is more preferable.
In addition, cyclic olefin polymer (A) may have only 1 type of protic polar groups, and may have 2 or more types.

And the method of introducing the above-mentioned protic polar group into the cyclic olefin polymer (A) is not particularly limited. That is, the cyclic olefin polymer (A) includes, for example, a repeating unit derived from the cyclic olefin monomer (a) having a protic polar group, and optionally a repeating derived from the other monomer (b). A polymer containing units may be used, or a polymer obtained by introducing a protic polar group into a cyclic olefin polymer having no protic polar group using a modifier, but the former is preferred. .

[Cyclic olefin monomer having a protic polar group (a)]
The cyclic olefin monomer (a) having a protic polar group is not particularly limited as long as it is a monomer having the above-mentioned protic polar group and a cyclic olefin structure. Preferred examples include a monomer and a cyclic olefin monomer having a hydroxyl group. Preferable examples of these monomers include various monomers described in International Publication No. 2015/141717. Among them, a cyclic olefin monomer having a carboxyl group is preferable from the viewpoint of improving the solubility in a developing solution and improving the adhesion of the resin film to the substrate, and 4-hydroxycarbonyltetracyclo [6.2.1.1]. ^3,6 . 0 ^2,7 ] dodec-9-ene (hereinafter also referred to as “TCDC”) is more preferable. In addition, a cyclic olefin monomer (a) may be used individually by 1 type, or may be used in combination of 2 or more type.

-Cyclic olefin monomer having a carboxyl group-
Examples of the cyclic olefin monomer having a carboxyl group include 2-hydroxycarbonylbicyclo [2.2.1] hept-5-ene, 2-methyl-2-hydroxycarbonylbicyclo [2.2.1] hept- 5-ene, 2-carboxymethyl-2-hydroxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-methoxycarbonylmethylbicyclo [2.2.1] hept-5-ene 2-hydroxycarbonyl-2-ethoxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-propoxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2 -Hydroxycarbonyl-2-butoxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2 Hydroxycarbonyl-2-pentyloxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-hexyloxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2- Hydroxycarbonyl-2-cyclohexyloxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-phenoxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxy Carbonyl-2-naphthyloxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-biphenyloxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxy Carbonyl-2-benzyloxycarbonylmethylbishi [2.2.1] Hept-5-ene, 2-hydroxycarbonyl-2-hydroxyethoxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2,3-dihydroxycarbonylbicyclo [2.2 .1] Hept-5-ene, 2-hydroxycarbonyl-3-methoxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3-ethoxycarbonylbicyclo [2.2.1] hept -5-ene, 2-hydroxycarbonyl-3-propoxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3-butoxycarbonylbicyclo [2.2.1] hept-5-ene 2-hydroxycarbonyl-3-pentyloxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydro Xoxycarbonyl-3-hexyloxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3-cyclohexyloxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl -3-phenoxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3-naphthyloxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3- Biphenyloxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3-benzyloxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3-hydroxyethoxy Carbonyl bicyclo [2.2.1] hept-5-ene, 2-hydro Cycarbonyl-3-hydroxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 3-methyl-2-hydroxycarbonylbicyclo [2.2.1] hept-5-ene, 3-hydroxymethyl-2 -Hydroxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyltricyclo [5.2.1.0 ^2,6 ] deca-3,8-diene, 4-hydroxycarbonyltetracyclo [ 6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-methyl-4-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4,5-dihydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-carboxymethyl-4-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, N- (hydroxycarbonylmethyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (hydroxycarbonylethyl) bicyclo [2 2.1] hept-5-ene-2,3-dicarboximide, N- (hydroxycarbonylpentyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (Dihydroxycarbonylethyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (dihydroxycarbonylpropyl) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (hydroxycarbonylphenethyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2- ( -Hydroxyphenyl) -1- (hydroxycarbonyl) ethyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (hydroxycarbonylphenyl) bicyclo [2.2.1] And hept-5-ene-2,3-dicarboximide. These may be used alone or in combination of two or more.

―Content rate―
And the content rate of the repeating unit derived from the cyclic olefin monomer (a) in the cyclic olefin polymer (A) is preferably 10 mol% or more, assuming that all repeating units are 100 mol%, and 20 mol. % Or more, more preferably 30 mol% or more, preferably 90 mol% or less, more preferably 80 mol% or less, and further preferably 70 mol% or less. preferable. If the ratio of the repeating unit derived from the cyclic olefin monomer (a) is 10 mol% or more, it is possible to increase the sensitivity during patterning using the resin film and to effectively suppress the development residue. If it is 90 mol% or less, the amount of the remaining film after development of the cyclic olefin polymer (A) can be sufficiently secured.

[Other monomer (b)]
The other monomer (b) is not particularly limited as long as it is a monomer copolymerizable with the above-mentioned cyclic olefin monomer (a). As the monomer copolymerizable with the cyclic olefin monomer (a), a cyclic olefin monomer (b1) having a polar group other than a protic polar group, a cyclic olefin monomer having no polar group ( and monomers (b3) other than b2) and cyclic olefins. As the various monomers (b1) to (b3), various monomers described in International Publication No. 2015/141717 can be used. These may be used alone or in combination of two or more. Among these, from the viewpoint of improving the heat resistance of the resin film, for example, other than protic polar groups such as N-substituted imide groups, ester groups, cyano groups, acid anhydride groups, or cyclic olefin monomers having a halogen atom And a cyclic olefin monomer (b1) having a polar group of N-phenyl-bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide (hereinafter also referred to as “NBPI”). And more preferred are cyclic olefin monomers having an N-substituted imide group.

-Cyclic olefin monomer having N-substituted imide group-
Examples of the cyclic olefin monomer having an N-substituted imide group include monomers represented by the following general formula (1) and general formula (2). Among these, a monomer that can be represented by the following general formula (1) is preferable from the viewpoint of improving heat resistance and suppressing pattern flow.

(In the above general formula (1), R ¹ represents a hydrogen atom, a cyclic or chain alkyl group having 1 to 16 carbon atoms, or an aryl group. N represents an integer of 1 to 2.)

(In the above general formula (2), R ² is a divalent alkylene group having 1 to 3 carbon atoms, R ³ is a monovalent alkyl group having 1 to 10 carbon atoms, or a monovalent alkyl group having 1 to 10 carbon atoms. Represents a halogenated alkyl group.)

In the general formula (1), R ¹ is an alkyl group or aryl group having 1 to 16 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, linear alkyl groups such as n-pentadecyl group and n-hexadecyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group Ring such as a group, norbornyl group, bornyl group, isobornyl group, decahydronaphthyl group, tricyclodecanyl group, adamantyl group, etc. Alkyl group; 2-propyl group, 2-butyl group, 2-methyl-1-propyl group, 2-methyl-2-propyl group, 1-methylbutyl group, 2-methylbutyl group, 1-methylpentyl group, 1- And branched alkyl groups such as ethylbutyl group, 2-methylhexyl group, 2-ethylhexyl group, 4-methylheptyl group, 1-methylnonyl group, 1-methyltridecyl group and 1-methyltetradecyl group. Specific examples of the aryl group include a phenyl group and a benzyl group. Among these, an alkyl group and an aryl group having 6 to 14 carbon atoms are preferable, and an alkyl group and an aryl group having 6 to 10 carbon atoms are more preferable because of excellent heat resistance and solubility in an alkali developer. When the carbon number is less than the above lower limit, the compatibility with the crosslinking agent is poor. Further, if the carbon number exceeds the above upper limit value, the heat resistance is inferior, and when the resin film is patterned, the pattern may disappear due to melting by heat.

Specific examples of the monomer represented by the general formula (1) include bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-phenyl-bicyclo [2.2. .1] Hept-5-ene-2,3-dicarboximide, N-methylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-ethylbicyclo [2.2 .1] Hept-5-ene-2,3-dicarboximide, N-propylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-butylbicyclo [2.2 .1] Hept-5-ene-2,3-dicarboximide, N-cyclohexylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-adamantylbicyclo [2.2 .1] Hept-5-ene-2,3-di Ruboxyimide, N- (1-methylbutyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-methylbutyl) -bicyclo [2.2.1] hept- 5-ene-2,3-dicarboximide, N- (1-methylpentyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-methylpentyl) ) -Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-ethylbutyl) -bicyclo [2.2.1] hept-5-ene-2,3- Dicarboximide, N- (2-ethylbutyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-methylhexyl) -bicyclo [2.2.1 ] Hept-5-ene-2,3-dica Boxyimide, N- (2-methylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (3-methylhexyl) -bicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide, N- (1-butylpentyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2- Butylpentyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-methylheptyl) -bicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide, N- (2-methylheptyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (3-methylheptyl) -bicyclo [2 2.1] Hept-5-ene-2,3- Carboximide, N- (4-methylheptyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-ethylhexyl) -bicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide, N- (2-ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (3-ethylhexyl) ) -Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-propylpentyl) -bicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide, N- (2-propylpentyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-methyloctyl) -bicyclo [2.2 .1] Hept-5-ene- 2,3-dicarboximide, N- (2-methyloctyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (3-methyloctyl) -bicyclo [ 2.2.1] Hept-5-ene-2,3-dicarboximide, N- (4-methyloctyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide N- (1-ethylheptyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-ethylheptyl) -bicyclo [2.2.1] hept -5-ene-2,3-dicarboximide, N- (3-ethylheptyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-ethyl Heptyl) -bicyclo [2.2.1] hept-5- -2,3-dicarboximide, N- (1-propylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-propylhexyl)- Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (3-propylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-di Carboximide, N- (1-methylnonyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-methylnonyl) -bicyclo [2.2.1] hept -5-ene-2,3-dicarboximide, N- (3-methylnonyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-methylnonyl) -Bicyclo [2.2.1] hept- -Ene-2,3-dicarboximide, N- (5-methylnonyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-ethyloctyl)- Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-ethyloctyl) -bicyclo [2.2.1] hept-5-ene-2,3-di Carboximide, N- (3-ethyloctyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-ethyloctyl) -bicyclo [2.2.1 ] Hept-5-ene-2,3-dicarboximide, N- (1-methyldecyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1- Methyldodecyl) -bicyclo [2.2.1] hept- 5-ene-2,3-dicarboximide, N- (1-methylundecyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-methyl Dodecyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-methyltridecyl) -bicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide, N- (1-methyltetradecyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-methylpentadecyl) -bicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide, N-phenyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4,5-dicarboximide, N- (2,4-dimethoxyphenyl) -tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4,5-dicarboximide and the like. These may be used alone or in combination of two or more.

On the other hand, in the general formula (2), R ² is a divalent alkylene group having 1 to 3 carbon atoms. Examples of the divalent alkylene group having 1 to 3 carbon atoms include a methylene group, an ethylene group, a propylene group, and An isopropylene group is mentioned. Among these, a methylene group and an ethylene group are preferable because of good polymerization activity.
In the general formula (2), R ³ is a monovalent alkyl group having 1 to 10 carbon atoms or a monovalent halogenated alkyl group having 1 to 10 carbon atoms. Examples of the monovalent alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, hexyl group, and cyclohexyl group. . Examples of the monovalent halogenated alkyl group having 1 to 10 carbon atoms include a fluoromethyl group, a chloromethyl group, a bromomethyl group, a difluoromethyl group, a dichloromethyl group, a difluoromethyl group, a trifluoromethyl group, a trichloromethyl group, Examples include 2,2,2-trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, perfluorobutyl group, and perfluoropentyl group. Among these, because of excellent solubility in alkali developing solution, the R ^3, methyl and ethyl are preferred.

The monomers represented by the above general formulas (1) and (2) can be obtained, for example, by an imidization reaction between a corresponding amine and 5-norbornene-2,3-dicarboxylic acid anhydride. . The obtained monomer can be efficiently isolated by separating and purifying the reaction solution of the imidization reaction by a known method.

―Content rate―
And the content rate of the repeating unit derived from the other monomer (b) in the cyclic olefin polymer (A) is preferably 10 mol% or more, assuming that all repeating units are 100 mol%, and 20 mol. % Or more, more preferably 30 mol% or more, preferably 90 mol% or less, more preferably 80 mol% or less, and further preferably 70 mol% or less. preferable. If the ratio of the repeating unit derived from the other monomer (b) is 10 mol% or more, the dissolution contrast of the exposed part / unexposed part at the time of patterning using the resin film of the cyclic olefin polymer (A). If it is 90 mol% or less, the solubility in a developer, particularly an alkali developer, can be sufficiently secured, and the generation of development residues can be effectively suppressed.

In addition, a cyclic olefin polymer (A) can be prepared by performing the ring-opening polymerization according to a known method, addition polymerization, etc. about the monomer composition containing the various monomers mentioned above. Especially, it is preferable to perform ring-opening polymerization and to obtain a cyclic olefin polymer (A). As the ring-opening polymerization method, a ring-opening metathesis polymerization method according to the method described in International Publication No. 2010/110323 or the like can be suitably employed. Furthermore, in the preparation of the cyclic olefin polymer (A), when the ring-opened polymer is obtained according to the ring-opening polymerization method, the obtained ring-opened polymer is further subjected to hydrogenation reaction, and at least the main A hydrogenated product obtained by hydrogenating at least part of the carbon-carbon double bonds contained in the chain is preferable. When the cyclic olefin polymer (A) is a hydrogenated product, the ratio of hydrogenated carbon-carbon double bonds is preferably 50% or more from the viewpoint of improving the heat resistance of the resin film. 70% or more, more preferably 90% or more, and particularly preferably 95% or more. The “hydrogenation rate” can be measured according to the ¹ H-NMR spectrum measurement method.

<Epoxy resin (B) having an epoxy equivalent of 500 or more>
The epoxy resin (B) having an epoxy equivalent of 500 or more is a component that acts to enhance the resolution and extensibility of the resin film obtained using the resin composition. The epoxy equivalent of the epoxy resin (B) needs to be 500 or more, preferably 900 or more, more preferably 950 or more, preferably 1500 or less, and more preferably 1250 or less. preferable. If the epoxy equivalent of an epoxy resin (B) is 900 or more, the extensibility of the resin film obtained using a resin composition can be improved further. Moreover, if the epoxy equivalent of an epoxy resin (B) is below the said upper limit, while suppressing generation | occurrence | production of the image development residue at the time of patterning of the resin film obtained using a resin composition, resolution can be improved further. it can.

<< Structure of Epoxy Resin (B) >>
The epoxy resin (B) preferably contains a flexible skeleton and an aromatic group in the molecule. When the epoxy resin (B) contains both a flexible skeleton and an aromatic group, it is more effective to impart extensibility and impart resolution to the resulting resin film. It can be compatible. The reason is not clear, but the epoxy resin containing both the flexible skeleton and the aromatic group imparts flexibility to the resin film by the flexible skeleton, and also has heat resistance to the resin film by the aromatic group. It is inferred that this is due to the fact that Furthermore, since the epoxy resin (B) contains both the flexible skeleton and the aromatic group, chemical resistance can be improved in addition to the stretchability and resolution of the resin film. The reason for this is not clear, but due to the intermolecular interaction between the aromatic groups contained in the epoxy resin and / or the aromatic group contained in the epoxy resin and the cyclic olefin polymer (A), This is presumably because the invasion of solvent molecules into the surface is suppressed.

Here, the “flexible skeleton” is not particularly limited as long as it can exhibit flexibility, and includes a divalent linking group that is bonded to the linked structure at both ends. Specifically, examples of the divalent linking group include an alkylene structure having 2 to 20 carbon atoms and an alkylene structure having an ether bond having 2 to 20 carbon atoms. As the alkylene structure having 2 to 20 carbon atoms, an alkylene structure having 2 to 15 carbon atoms is preferable, and an alkylene structure having 2 to 10 carbon atoms is more preferable. The alkylene group may be linear, branched or cyclic. Examples of the alkylene structure include ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, and cyclohexane. A propylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a decahydronaphthanylene group, a norbornanylene group, an adamantanilene group and the like can be mentioned. The alkylene structure is a halogen atom, alkyl group, alkoxy group, alkylidene group, amino group, silyl group, acyl group, acyloxy group, carboxy group, sulfo group, cyano group, nitro group, hydroxy group, mercapto group, oxo group. May have a substituent such as, but preferably does not have a substituent. The carbon number does not include the carbon number of the substituent.

Examples of the alkylene structure having an ether bond having 2 to 20 carbon atoms include an oxyalkylene structure, an alkyleneoxy structure, an oxyalkyleneoxy structure, an alkyleneoxyalkylene structure, and an alkyleneoxyalkyleneoxyalkylene structure. The alkylene structure having an ether bond having 2 to 20 carbon atoms is preferably an alkylene structure having an ether bond having 2 to 15 carbon atoms, more preferably an alkylene structure having an ether bond having 2 to 10 carbon atoms. The alkylene structure may be linear, branched or cyclic. Examples of the alkylene structure having such an ether bond include oxyethylene group, oxypropylene group, oxybutylene group, oxypentylene group, oxyhexylene group, oxyheptylene group, oxyoctylene group, oxynonylene group, oxydecylene group, oxyundecylene. Group, oxide decylene group, oxytridecylene group, oxytetradecylene group, oxypentadecylene group, oxycyclopropylene group, oxycyclobutylene group, oxycyclopentylene group, oxycyclohexylene group, oxydecahydronaphthalene Group, oxynorbornanylene group, oxyadamantanylene group and the like. The oxyalkylene structure includes a halogen atom, alkyl group, alkoxy group, alkylidene group, amino group, silyl group, acyl group, acyloxy group, carboxy group, sulfo group, cyano group, nitro group, hydroxy group, mercapto group, oxo It may have a substituent such as a group, but preferably has no substituent. Here, the carbon number does not include the carbon number of the substituent.

Examples of the aromatic group contained in the epoxy resin (B) include an aromatic hydrocarbon ring group having 6 to 20 carbon atoms, and among them, a phenylene group is preferable.

Furthermore, the epoxy resin (B) is preferably a compound represented by the following general formula (3).

(In the general formula (3), X represents a divalent linking group, Y ¹ and Y ² each independently represent the above-mentioned “flexible skeleton”, and m represents an integer of 1-20. To express.)

Specific examples of the divalent linking group that can be X in the general formula (3) include a single bond, an oxygen atom, a carbon atom, or a sulfur atom. X and Y ¹ are different, and X and Y ² are different. Then, for example, a functional group such as a methyl group, a trifluoromethyl group, a carbonyl group, and a phenyl group may be further bonded to the divalent linking group as X.
Further, Y ¹ in the general formula (3) and Y ² which may be present in plural may be the same or different, but are preferably the same.
Furthermore, m in the general formula (3) is preferably an integer of 1 to 10, more preferably an integer of 3 to 5.

The epoxy resin (B) satisfying the general formula (3) is not particularly limited, and can be synthesized, for example, according to the method disclosed in JP 2010-285627 A. Moreover, as a suitable epoxy resin (B) marketed, it is not specifically limited, For example, "YX7110B80" by Mitsubishi Chemical Corporation can be mentioned.
In addition, as a epoxy resin (B), a kind of compound can be used individually or in combination of 2 or more types.

<< Content of Epoxy Resin (B) >>
The content of the epoxy resin (B) in the resin composition is preferably 40 parts by mass or more, more preferably 60 parts by mass or more, and preferably 100 parts by mass or less, per 100 parts by mass of the cyclic olefin polymer (A). Less than the mass part is more preferable. If content of an epoxy resin (B) is more than the said lower limit, the extensibility of a resin film can be improved further. Moreover, if content of an epoxy resin (B) is below the said upper limit, the resolution of a resin film can be improved further.

<Crosslinking agent (C)>
The crosslinking agent (C) contains a phenolic hydroxyl group and an alkoxymethyl group in the molecule. Such a crosslinking agent (C) can form a crosslinked structure between the crosslinking agent molecules by heating and / or react with the cyclic olefin polymer (A) having a polar group to form a crosslinked structure. Therefore, the chemical resistance of the resin film can be increased by adding the crosslinking agent (C) to the resin composition.

As the crosslinking agent (C), a phenol compound in which two or more alkoxymethyl groups are directly bonded to an aromatic ring is preferable. In addition, as an alkoxymethyl group, a methoxymethyl group is preferable. Examples of the phenol compound in which two or more alkoxymethyl groups are directly bonded to an aromatic ring include dimethoxymethyl such as 2,6-dimethoxymethyl-4-t-butylphenol and 2,6-dimethoxymethyl-p-cresol. Substituted phenol compounds; 3,3 ′, 5,5′-tetramethoxymethyl-4,4′-dihydroxybiphenyl (for example, trade name “TMOM-BP”, manufactured by Honshu Chemical Industry Co., Ltd.), 1,1-bis [3 , 5-di (methoxymethyl) -4-hydroxyphenyl] -1-phenylethane and the like; 4,4 ′, 4 ″-(ethylidene) tris [2,6- (methoxymethyl) phenol ] (For example, trade name “HMOM-TPHAP”, manufactured by Honshu Chemical Industry Co., Ltd.) A compound; Among them, 3,3 ′, 5,5′-tetramethoxymethyl-4,4′- dihydroxybiphenyl (TMOM-BP) and 4,4 ′, 4 ″-(ethylidene) tris [2,6- (methoxymethyl) Phenol] (HMOM-TPHAP) is preferable, and these can be used alone or in combination of two or more.

<< Content of Cross-linking Agent (C) >>
The content of the crosslinking agent (C) in the resin composition is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, per 100 parts by mass of the cyclic olefin polymer (A), and 30 parts by mass. More preferably, the amount is 1 part by mass or more, more preferably 2 parts by mass or more, and still more preferably 5 parts by mass or more. If content of a crosslinking agent (C) is more than the said lower limit, the chemical resistance of a resin film can be improved further. Moreover, if content of a crosslinking agent (C) is below the said upper limit, the extensibility of a resin film can be improved.

<Photoacid generator (D)>
The resin composition preferably further contains a photoacid generator (D). When the resin composition contains a radiation-sensitive compound such as the photoacid generator (D), the resin film developer in the exposed portion is obtained by the action of the photoacid generator (D) when the resin film is exposed. The solubility of the resin film can be changed, whereby the resin film can be patterned. That is, when the resin composition contains a radiation sensitive compound such as the photoacid generator (D), the resin composition can function as a radiation sensitive resin composition.

Examples of the photoacid generator include azide compounds (such as quinonediazide compounds), onium salt compounds, halogenated organic compounds, α, α′-bis (sulfonyl) diazomethane compounds, α-carbonyl-α′-sulfonyldiazomethane compounds , Sulfone compounds, organic acid ester compounds, organic acid amide compounds, organic acid imide compounds, acetophenone compounds, and triarylsulfonium salts, azide compounds are preferred, and quinonediazide compounds are more preferred.

As a quinonediazide compound suitably used as a photoacid generator, for example, an ester compound of a quinonediazidesulfonic acid halide and a compound having a phenolic hydroxyl group can be used.
Examples of the quinonediazide sulfonic acid halide used in the preparation of the ester compound include 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 1,2-naphthoquinonediazide-4-sulfonic acid chloride, and 1,2-benzoquinonediazide-5. -Sulfonic acid chlorides.
Examples of the compound having a phenolic hydroxyl group used for the preparation of the ester compound include 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 ′-[1 -[4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2- Bis (4-hydroxyphenyl) propane, tris (4-hydroxyphenyl) methane, 1,1,1-tris (4-hydroxy-3-methylphenyl) ethane, 1,1,2,2-tetrakis (4-hydroxy) Phenyl) ethane, novolak resin oligomer, compound having one or more phenolic hydroxyl groups and dicyclopentadiene They include oligomers obtained by copolymerizing and. These can be used individually by 1 type or in combination of 2 or more types.

[Content of Photoacid Generator (D)]
The content of the photoacid generator (D) in the resin composition is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and further 25 parts by mass or more per 100 parts by mass of the cyclic olefin polymer (A). Preferably, 100 parts by mass or less is preferable, 70 parts by mass or less is more preferable, and 50 parts by mass or less is still more preferable. When the content of the photoacid generator (D) is within this range, the cyclic olefin polymer in the exposed area and the unexposed area can be obtained with an appropriate exposure intensity when patterning using the resin film made of the resin composition. Since the difference in solubility of the developer (A) in the developer can be sufficiently increased, a clear pattern can be formed with good sensitivity.

<Solvent>
The resin composition of the present invention may contain a solvent. That is, in the resin composition of the present invention, the cyclic olefin polymer (A), the epoxy resin (B), the crosslinking agent (C), and the optionally added photoacid generator (D) are dissolved in the solvent. And / or a resin liquid that is dispersed.
The solvent is not particularly limited, and known solvents for the resin composition, for example, solvents disclosed in International Publication No. 2015/141717 such as diethylene glycols containing diethylene glycol ethyl methyl ether can be used. As a solvent, it can use individually by 1 type or in mixture of multiple types. The content of the solvent in the resin composition of the present invention is preferably 10 parts by mass or more and 10000 parts by mass or less, more preferably 50 parts by mass or more and 5000 parts by mass or less, per 100 parts by mass of the cyclic olefin polymer (A). More preferably, it is the range of 100 to 1000 mass parts.

<Other additives>
In addition, the resin composition of the present invention may contain other additives other than the above, if desired, as long as the effects of the present invention are not inhibited. Examples of such other additives include cross-linking agents other than the cross-linking agent (C), silane coupling agents, surfactants, sensitizers, light stabilizers, antifoaming agents, pigments, dyes, and fillers. (For example, see International Publication No. 2015/141717). Examples of the crosslinking agent other than the crosslinking agent (C) include a crosslinking agent having a methylol group, a crosslinking agent having an oxetane group, and a crosslinking agent having a blocked isocyanate group.

<Method for preparing resin composition>
The preparation method of the resin composition of this invention is not specifically limited, What is necessary is just to mix each component which comprises a resin composition by a well-known method. The mixing method is not particularly limited, but it is preferable to mix a solution or dispersion obtained by dissolving or dispersing each component constituting the resin composition in a solvent. Thereby, the resin composition is obtained in the form of a solution or a dispersion (that is, a state of a resin liquid). The mixing is not particularly limited, and is performed using a known mixer. Moreover, you may filter by a known method after mixing.
And the solid content concentration of the resin liquid which is the resin composition of this invention is 1 mass% or more and 70 mass% or less normally, Preferably they are 5 mass% or more and 60 mass% or less, More preferably, they are 10 mass% or more and 50 mass% or less. It is as follows. If the solid content concentration is within the above-described range, the dissolution stability and coating property of the resin liquid, the film thickness uniformity and flatness of the formed resin film, and the like can be highly balanced.

(Electronic parts)
The electronic component of the present invention includes a resin film made of the above-described resin composition of the present invention. And since the electronic component of this invention is equipped with the resin film which was sufficiently small in the development residue formed from the resin composition of this invention, and was excellent in the extendibility, it is high performance.

<Types of electronic components>
The electronic component of the present invention is not particularly limited, but the resin film made of the resin composition of the present invention is manufactured by wafer level package technology because it has a sufficiently small development residue and excellent extensibility. Electronic components are preferred. In particular, in an electronic component manufactured by the wafer level package technology, an interlayer insulating film (such as a rewiring interlayer insulating film or the like) for insulating between wirings arranged in layers in a resin component made of the resin composition of the present invention. It is more preferable that it is used as what forms a).

<Method of manufacturing electronic component including resin film>
An electronic component including a resin film is not particularly limited, and can be manufactured by forming a resin film on a substrate such as a silicon wafer on which a semiconductor element is mounted. The method for forming the resin film on the substrate is not particularly limited. The resin film includes, for example, a process of forming a film on a substrate (a film forming process) using a resin composition containing a solvent (that is, a resin liquid), and a process of obtaining a resin film by crosslinking the obtained film. (Crosslinking step) can be manufactured. If necessary, a step of exposing the film on the substrate with actinic radiation to obtain an exposure film (exposure step) between the film forming step and the crosslinking step, and developing and developing the exposure film By performing the process of obtaining a film (development process) in this order, a patterned resin film can be obtained. Hereinafter, each step will be described.

[Film formation process]
In the film forming step, a film is formed on the substrate using the resin composition according to a known method such as a coating method or a film lamination method. For example, in the coating method, the resin composition is coated according to a known method such as a spin coating method, and then dried by heating to remove the solvent to obtain a coating film. The heating and drying conditions at this time vary depending on the types and blending ratios of the components, but the heating temperature is usually 30 to 150 ° C., preferably 60 to 120 ° C., and the heating time is usually 0.5 to 90 minutes. , Preferably 1 to 60 minutes, more preferably 1 to 30 minutes. Also, for example, in the film lamination method, the resin composition is applied onto a B-stage film-forming substrate such as a resin film or a metal film, and then the solvent is removed by heat drying to obtain a B-stage film (coating film). Next, this B stage film is laminated on the substrate. The heating and drying conditions at this time can be appropriately selected according to the type and mixing ratio of each component, but the heating temperature is usually 30 to 150 ° C., and the heating time is usually 0.5 to 90 minutes. sell. Film lamination can be performed using a pressure laminator, a press, a vacuum laminator, a vacuum press, a roll laminator or the like.

[Exposure process]
In an exposure step that can be optionally performed, the coating film on the substrate is irradiated with actinic radiation to obtain an exposure film. More specifically, in the exposure step, the coating film is irradiated with actinic radiation to form a latent image pattern. It is preferable that the resin composition used when performing an exposure process contains radiation sensitive compounds, such as a photo-acid generator (D). When the resin composition contains the photoacid generator (D), as described above, the developer of the cyclic olefin polymer (A) in the exposed part and the non-exposed part by the action of the photoacid generator (D). The solubility with respect to can be made different. As a method for obtaining a patterned resin film without blending the photoacid generator (D) into the resin composition, for example, a method using laser processing using a CO ₂ laser, a UV-YAG laser, or the like. Alternatively, a method of forming a mask pattern on the resin film and performing dry etching, and a direct drawing method such as an ink jet method can be used.

The actinic radiation is not particularly limited as long as it can activate the photoacid generator (D) contained in the resin composition and change the solubility of the film in the developer. Specifically, light rays such as ultraviolet rays, single-wavelength ultraviolet rays such as g, h, and i rays, g-h-i mixed rays, KrF excimer laser light, ArF excimer laser light; particle beams such as electron beams; Etc. can be used. As a method of selectively irradiating these actinic radiations in a pattern to form a latent image pattern, a conventional method may be followed. Irradiation conditions are appropriately selected depending on the actinic radiation to be used. For example, when a light beam having a wavelength of 200 to 450 nm is used, the irradiation amount is usually 10 to 5,000 mJ / cm ² , preferably 50 to 2, preferably. The range is 500 mJ / cm ² and is determined according to the irradiation time and illuminance. After irradiation with actinic radiation in this way, the resin film may be heat-treated at a temperature of about 60 to 130 ° C. for about 1 to 2 minutes as necessary.

[Development process]
Next, the latent image pattern formed in the exposure process is developed and made visible. As the developer, an alkali developer can be used. The alkaline developer can be prepared by dissolving an alkaline compound in an aqueous solvent. As the alkaline compound, for example, an alkali metal salt, an amine, or an ammonium salt can be used. The alkaline compound may be an inorganic compound or an organic compound. Specific examples of these compounds include alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate and sodium metasilicate; ammonia water; primary amines such as ethylamine and n-propylamine; diethylamine Secondary amines such as di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide and choline Alcohol alcohols such as dimethylethanolamine and triethanolamine; pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] nona-5 -En, N-Me Cyclic amines such as Rupiroridon; and the like. These alkaline compounds can be used alone or in combination of two or more. As an aqueous solvent for the alkaline aqueous solution, water; water-soluble organic solvents such as methanol and ethanol can be used. The alkaline aqueous solution may have a surfactant added in an appropriate amount.

As a method of bringing the developer into contact with the exposure film having a latent image pattern, for example, a paddle method, a spray method, a dipping method, or the like is used. The development temperature is usually selected from the range of 0 to 100 ° C., preferably 5 to 55 ° C., more preferably 10 to 30 ° C., and the development time is usually appropriately selected from the range of 30 to 180 seconds.

The developing film on which the target pattern is formed in this way can be rinsed with a rinsing liquid as necessary in order to remove development residues. After the rinsing treatment, it is preferable to remove the remaining rinsing liquid with compressed air or compressed nitrogen.
Furthermore, in order to deactivate the photo-acid generator (D) contained in the resin composition as necessary, the development film can be irradiated with actinic radiation as described above. For irradiation with actinic radiation, the method exemplified in the formation of the latent image pattern can be used. The developing film may be heated simultaneously with irradiation or after irradiation. Examples of the heating method include a method of heating an electronic component in a hot plate or an oven. The heating temperature is usually in the range of 80 to 300 ° C, preferably 100 to 200 ° C.

[Crosslinking process]
Then, a crosslinking reaction is performed on the film formed on the substrate in the film forming process or the developed film that has undergone the developing process. Such crosslinking may be appropriately selected depending on the type of the crosslinking agent (C), but is usually performed by heating. The heating method can be performed using, for example, a hot plate or an oven. The heating temperature is usually 180 to 250 ° C., and the heating time is appropriately selected depending on the area and thickness of the film, equipment used, etc. For example, when using a hot plate, an oven is usually used for 5 to 60 minutes. The case is usually in the range of 30 to 240 minutes. Heating may be performed in an inert gas atmosphere as necessary. Any inert gas may be used as long as it does not contain oxygen and does not oxidize the film. Examples thereof include nitrogen, argon, helium, neon, xenon, and krypton. Among these, nitrogen and argon are preferable, and nitrogen is particularly preferable. In particular, an inert gas having an oxygen content of 0.1% by volume or less, preferably 0.01% by volume or less, particularly nitrogen is suitable. These inert gases can be used alone or in combination of two or more.

The thickness of the resin film that can be formed as described above is not particularly limited and may be appropriately set depending on the application, but is preferably 0.1 to 100 μm, more preferably 0.5 to 50 μm. More preferably, the thickness is 0.5 to 30 μm.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the following description, “%” and “part” representing amounts are based on mass unless otherwise specified. In addition, the weight average molecular weight and number average molecular weight of the cyclic olefin polymer obtained according to the following synthesis examples were obtained as polystyrene equivalent values by gel permeation chromatography (GPC) using a solvent such as tetrahydrofuran as an eluent.
Moreover, the epoxy equivalent (g / eq.) Of the epoxy resin used when preparing a resin composition in an Example and a comparative example was calculated | required according to JISK7236: 2009.
Furthermore, the stretchability, chemical resistance, and resolution of the resin films formed using the resin compositions according to the examples and comparative examples were evaluated using the following methods, respectively.

<Extension>
Resin compositions prepared in each of Examples and Comparative Examples on a 4-inch silicon wafer on which a 50 nm-thick aluminum film was formed using a sputtering apparatus (“I-Miller CFS-4EP-LL” manufactured by Shibaura Eletech Co., Ltd.) The material was spin-coated and then pre-baked at 120 ° C. for 2 minutes using a hot plate to form a film made of the resin composition. Subsequently, it was cured by heating at 230 ° C. for 1 hour in nitrogen to obtain a resin film, thereby obtaining a silicon wafer with a resin film having a thickness of 10 μm. This was immersed in a 0.1 mol% hydrochloric acid aqueous solution for 12 hours to etch aluminum, thereby peeling the resin film from the wafer and then drying it in an oven at 150 ° C. for 1 hour. This was cut into a strip shape having a width of 5 mm and a length of 40 mm to obtain a test piece, and the tensile elongation rate was measured by conducting a tensile test on the test piece. Specifically, a tensile test was performed with a tensile tester (manufactured by Shimadzu Corporation, “AGS-10kNX”) at 23 ° C. with a gripping tool spacing of 2 cm and a tensile speed of 2 mm / min, and the elongation at the breaking point was measured. Eight test pieces were tested, and the average value of the top three points was defined as the elongation percentage of the resin film formed using the resin composition obtained in each example. It means that the extensibility of a resin film is so high that the value of elongation rate is large. In addition, since the extensibility of the resin film formed from the resin composition is higher, the resin film formed using the resin composition is less prone to crack and peeling during the temperature cycle test and the drop impact test. preferable.
A: Tensile elongation is 25% or more B: Tensile elongation is more than 15% and less than 25% C: Tensile elongation is 15% or less

<Chemical resistance>
The resin composition produced in each example and each comparative example was spin coated on a silicon wafer and then pre-baked at 120 ° C. for 2 minutes using a hot plate to form a film made of the resin composition. Subsequently, the silicon wafer with a resin film of 10 micrometers thickness was obtained by heating at 230 degreeC in nitrogen for 1 hour. This was immersed in monoethanolamine / dimethyl sulfoxide = 7/3 (mass ratio) at 23 ° C. for 15 minutes, and the formula: (film thickness change (%) = | film thickness after immersion−film thickness before immersion | / immersion The change in film thickness was calculated according to the previous film thickness × 100). Based on the calculated value (%) of the change in film thickness, chemical resistance was evaluated according to the following criteria.
A: There is no crack or peeling in the film, and the film thickness change is less than 10%. B: There is no crack or peeling in the film, and the film thickness change is 10% or more and less than 20%. C: Crack or peeling occurs in the film. More than 20% thickness change

<Resolution>
The resin composition prepared in each example and each comparative example was spin-coated on a silicon wafer and then pre-baked at 120 ° C. for 2 minutes using a hot plate to obtain a 10 μm thick coating film. Next, exposure was carried out with a mask aligner (“PLA501F” manufactured by Canon Inc.) using a g-hi mixed line through a 20 μm hole mask at a predetermined dose, and then 2.38 as an alkali developer. Dip development was performed for 60 seconds with a% tetramethylammonium hydroxide aqueous solution. The amount of irradiation at the time of exposure was set to the amount of irradiation at which 20 μm holes were formed when each coating film was exposed using the mask. Next, rinsing with ultrapure water was performed for 10 seconds to obtain a silicon wafer with a development film in which 20 μm holes were patterned. Using an inert oven, the temperature was raised at 100 ° C. for 30 minutes and then from 100 ° C. to 230 ° C. at a rate of 2 ° C./minute, followed by curing at 230 ° C. for 1 hour. The change rate of the hole diameter before and after curing is calculated according to the formula: (| hole diameter before curing−hole diameter after curing | / hole diameter before curing × 100), and the value (%) of the obtained change rate is calculated. Evaluation was made according to the following criteria.
A: Less than 10% B: 10% or more, less than 20% C: 20% or more

(Synthesis Example 1)
<Preparation of Cyclic Olefin Polymer (A-1)>
N-phenyl-bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide (NBPI) 40 mol% as a cyclic olefin monomer having an N-substituted imide group, and a carboxyl group 4-Hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene (TCDC) 100 parts monomer mixture, 1,5-hexadiene 2.0 parts, (1,3-dimesitylimidazoline-2-ylidene) ( Tricyclohexylphosphine) benzylidene ruthenium dichloride (synthesized by the method described in Org. Lett., Vol. 1, p. 953, 1999) and 200 parts of diethylene glycol ethyl methyl ether made of nitrogen-substituted glass The polymerization reaction liquid was obtained by charging into a pressure-resistant reactor and making it react at 80 degreeC for 4 hours, stirring.
Then, the obtained polymerization reaction liquid is put in an autoclave and stirred for 5 hours at 150 ° C. under a hydrogen pressure of 4 MPa to carry out a hydrogenation reaction, and contains a cyclic olefin polymer (A-1) having a protic polar group A polymer solution was obtained. The resulting cyclic olefin polymer (A-1) having a protic polar group had a polymerization conversion of 99.7%, a polystyrene-equivalent weight average molecular weight of 7,150, a number average molecular weight of 4,690, and a molecular weight distribution of 1 0.52 and the hydrogenation rate was 99.7%. Further, the solid content concentration of the polymer solution of the obtained cyclic olefin polymer (A-1) having a protic polar group was 34.4% by mass.

(Synthesis Example 2)
<Preparation of cyclic olefin polymer (A-2)>
N-phenyl-bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide (NBPI) 16 mol% and N- (2 as cyclic olefin monomers having N-substituted imide groups -Ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide (NEHI) 16 mol%, and 4-hydroxycarbonyltetracyclo as a cyclic olefin monomer having a carboxyl group [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene (TCDC) 100 parts by weight of a monomer mixture, 1.0 part by weight of 1-hexene, (1,3-dimesitylimidazoline-2-ylidene) ( 0.06 part by mass of tricyclohexylphosphine) benzylidene ruthenium dichloride (synthesized by the method described in “Org. Lett., Vol. 1, page 953, 1999”) and 300 parts by mass of diethylene glycol ethyl methyl ether The polymer was charged in a substituted glass pressure-resistant reactor and reacted at 80 ° C. for 4 hours with stirring to obtain a polymerization reaction solution. Then, the obtained polymerization reaction liquid is put in an autoclave and stirred for 5 hours at 150 ° C. under a hydrogen pressure of 4 MPa to carry out a hydrogenation reaction, and contains a cyclic olefin polymer (A-2) having a protic polar group A polymer solution was obtained. The polymerization conversion rate of the obtained cyclic olefin polymer (A-2) having a protic polar group was 99.3% by mass, the polystyrene-equivalent weight average molecular weight was 20,600, the number average molecular weight was 11,500, and the molecular weight distribution was The hydrogenation rate was 1.9.8 mol%, 1.79. Further, the solid content concentration of the polymer solution of the obtained cyclic olefin polymer (A-2) having a protic polar group was 25.3 mass%.

Example 1
<Preparation of resin composition>
As the cyclic olefin polymer (A), 291 parts of a polymer solution of the cyclic olefin polymer (A-1) having a protic polar group obtained in Synthesis Example 1 (100 parts as the cyclic olefin polymer (A-1)) ), 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2 as photoacid generator (D) -Mixture of 30 parts of condensate with naphthoquinonediazide-5-sulfonic acid chloride (2.5 mol), epoxy resin (B) having an epoxy equivalent of 1124 and methyl ethyl ketone (MEK) ("YX7110B80" manufactured by Mitsubishi Chemical Corporation) 63 parts (50 parts as an epoxy resin (B)) and 53 parts of diethylene glycol ethyl methyl ether as a solvent were mixed and dissolved. The resin composition was prepared by filtration through a polytetrafluoroethylene filter having a pore diameter of 0.45 μm.
And various evaluation was performed according to the above using the obtained resin composition. The results are shown in Table 1.
In addition, “YX7110B80” manufactured by Mitsubishi Chemical Co., Ltd. used as an epoxy resin (B) having an epoxy equivalent of 500 or more has an aromatic group and a flexible skeleton in the molecule, and has an aromatic group. As a result, it was confirmed by ¹ H-NMR and ¹³ C-NMR that it had at least a phenylene group. More specifically, it was confirmed that “YX7110B80” has a structure that satisfies the above-described general formula (3).

(Example 2)
In Example 1, the crosslinking agent (C) (HMOM-TPHAP, 4,4 ′, 4 ″-(ethylidene) tris [2,6- (methoxymethyl) phenol] containing a phenolic hydroxyl group and an alkoxymethyl group in the molecule Further, 50 parts of a 20% solution of γ-butyrolactone of the following formula (α) (“HMOM-TPHAP-GB” manufactured by Honshu Chemical Co., Ltd.) (10 parts as a crosslinking agent (C)) is further blended, and diethylene glycol ethyl as a solvent A resin composition was prepared in the same manner as in Example 1 except that the amount of methyl ether was changed from 53 parts to 28 parts, and various evaluations were performed. The results are shown in Table 1.

Example 3
In Example 1, the mixture of epoxy resin (B) and MEK (Mitsubishi Chemical Co., Ltd., “YX7110B80”) was changed from 63 parts to 81 parts (65 parts as epoxy resin (B)), and the phenolic hydroxyl group in the molecule And an alkoxymethyl group-containing crosslinking agent (C) (“TMOM-BP” manufactured by Honshu Chemical Co., Ltd., 3,3 ′, 5,5′-tetramethoxymethyl-4,4′-dihydroxybiphenyl, the following formula (β) The resin composition was prepared in the same manner as in Example 1 except that 10 parts were further blended and the amount of diethylene glycol ethyl methyl ether as the solvent was changed from 53 parts to 86 parts, and various evaluations were performed. The results are shown in Table 1.

Example 4
In Example 1, the mixture of epoxy resin (B) and MEK (manufactured by Mitsubishi Chemical Corporation, YX7110B80) was changed from 63 parts to 94 parts (75 parts as epoxy resin (B)), and γ-butyrolactone 20 of HMOM-TPHAP was changed. % Solution (Honshu Chemical Co., Ltd., “HMOM-TPHAP-GB”) 100 parts (20 parts as a cross-linking agent (C)) was added, and diethylene glycol ethyl methyl ether was changed from 53 parts to 31 parts. In the same manner as in Example 1, resin compositions were prepared and subjected to various evaluations. The results are shown in Table 1.

(Example 5)
As the cyclic olefin polymer (A), 232 parts of a polymer solution of the cyclic olefin polymer (A-1) having a protic polar group obtained in Synthesis Example 1 (80 parts as the cyclic olefin polymer (A-1)) And 79 parts of a polymer solution of the cyclic olefin polymer (A-2) having a protic polar group obtained in Synthesis Example 2 (20 parts as the cyclic olefin polymer (A-2)), a photoacid generator As (D), 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinonediazide-5- 35 parts of a condensate with sulfonic acid chloride (2.5 mol), 88 parts of a mixture of epoxy resin (B) and MEK (manufactured by Mitsubishi Chemical Corporation, YX7110B80) (70 parts as epoxy resin (B)), HMOM-TPHAP γ-butyrolactone 20% solution (Honshu Chemical Co., Ltd., “HMOM-TPHAP-GB”) 50 parts (10 parts as a crosslinking agent (C)) and 38 parts of diethylene glycol ethyl methyl ether as a solvent were mixed. After dissolution, the resin composition was prepared by filtering through a polytetrafluoroethylene filter having a pore diameter of 0.45 μm, and various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 1)
As the cyclic olefin polymer (A), 291 parts of a polymer solution of the cyclic olefin polymer (A-1) obtained in Synthesis Example 1 (100 parts as the cyclic olefin polymer (A-1)), a photoacid generator As (D), 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinonediazide-5- 30 parts of a condensate with sulfonic acid chloride (2.5 mol), 70 parts of a resin having an epoxy equivalent of 487 (manufactured by Mitsubishi Chemical Corporation, “YX7105”), and γ-butyrolactone 20 of HMOM-TPHAP % Solution (Honshu Chemical Co., Ltd., “HMOM-TPHAP-GB”) 50 parts (10 parts as a crosslinking agent (C)) and 39 parts of diethylene glycol ethyl methyl ether as a solvent were mixed and dissolved. After, filtered with a polytetrafluoroethylene filter with a pore size of 0.45μm resin composition was prepared, it was carried out the same evaluation tests as in Example 1. The results are shown in Table 1. YX7105 used as the other epoxy resin had an aromatic group and a flexible skeleton.

(Comparative Example 2)
As the cyclic olefin polymer (A), 291 parts of a polymer solution of the cyclic olefin polymer (A-1) obtained in Synthesis Example 1 (100 parts as the cyclic olefin polymer (A-1)), a photoacid generator As (D), 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinonediazide-5- 30 parts of a condensate with sulfonic acid chloride (2.5 mol), 70 parts of a resin having an epoxy equivalent of 440 (manufactured by Mitsubishi Chemical Corporation, “YX7400”) as another epoxy resin, and diethylene glycol ethylmethyl as a solvent After 39 parts of ether were mixed and dissolved, a resin composition was prepared by filtering through a polytetrafluoroethylene filter having a pore diameter of 0.45 μm. It was evaluated in the same manner as. The results are shown in Table 1. YX7400, which is an epoxy resin, did not have an aromatic group and had a flexible skeleton.

(Comparative Example 3)
As a cyclic olefin polymer (A), 100 parts of a copolymer of hydroxystyrene and methyl methacrylate (manufactured by Maruzen Petrochemical Co., Ltd., “CMM”) and 4,4 ′-[ 1- [4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.5 mol) 93.75 parts (75 parts as epoxy resin (B)) of a mixture of 30 parts of condensate, epoxy resin (B) having an epoxy equivalent of 1124 and MEK (manufactured by Mitsubishi Chemical Co., YX7110B80), crosslinking agent (C) ( 10 parts of “TMOM-BP” manufactured by Honshu Chemical Co., Ltd.) and 288 parts of diethylene glycol ethyl methyl ether as a solvent were mixed and dissolved, and then the pore diameter was 0.45 μm. A resin composition was prepared by filtration through a polytetrafluoroethylene filter. In order to evaluate extensibility in the same manner as in Example 1, preparation of a test piece was attempted. However, since the resin film was brittle and could not be peeled off from the wafer, the test piece could not be prepared and evaluated. I couldn't. About the other item, the same evaluation as Example 1 was performed. The results are shown in Table 1.

From Table 1, according to the resin composition containing the cyclic olefin polymer (A) having a polar group and the epoxy resin (B) having an epoxy equivalent of 500 or more, a resin film excellent in resolution and extensibility is obtained. It can be seen that it was possible to form. In addition, from Table 1, in the resin composition of Comparative Example 1 using an epoxy resin having both a flexible skeleton and an aromatic group but having an epoxy equivalent of less than 500, the resulting resin film has extensibility and resolution. It turns out that both of these could not be provided. Moreover, in the resin composition of Comparative Example 2 using an epoxy resin having a flexible skeleton but having no aromatic group and having an epoxy equivalent of less than 500, it is possible to impart resolution to the resulting resin film. I understand that I couldn't. Furthermore, it can be seen that in the resin composition of Comparative Example 3 using a resin other than the cyclic olefin polymer having a polar group, the resolution and extensibility could not be imparted to the resulting resin film.

According to the resin composition of the present invention, a resin film excellent in resolution and extensibility can be formed.
Moreover, according to the present invention, a high-performance electronic component can be provided.

Claims (7)

1. Resin composition containing the cyclic olefin polymer (A) which has a polar group, and the epoxy resin (B) whose epoxy equivalent is 500 or more.
2. The resin composition according to claim 1, wherein the epoxy resin (B) contains a flexible skeleton and an aromatic group in the molecule.
3. The resin composition according to claim 1 or 2, further comprising a crosslinking agent (C) containing a phenolic hydroxyl group and an alkoxymethyl group in the molecule.
4. The resin composition according to any one of claims 1 to 3, further comprising a photoacid generator (D).
5. The resin composition according to any one of claims 1 to 4, wherein the content of the epoxy resin (B) is 40 parts by mass or more and 100 parts by mass or less per 100 parts by mass of the cyclic olefin polymer (A). .
6. The resin composition according to any one of claims 1 to 5, wherein the content of the crosslinking agent (C) is 1 part by mass or more and 100 parts by mass or less per 100 parts by mass of the cyclic olefin polymer (A). .
7. An electronic component comprising a resin film made of the resin composition according to any one of claims 1 to 6.