KR20200138210A - Resin composition and electronic component - Google Patents

Abstract

It is a resin composition containing a cyclic olefin polymer (A) having a polar group and an epoxy resin (B) having an epoxy equivalent of 500 or more.

Description

Resin composition and electronic component

TECHNICAL FIELD The present invention relates to a resin composition and an electronic component, and in particular, to a resin composition that can be suitably used for formation of an insulating film used for an electronic component, and an electronic component including a resin film made of the resin composition.

For various display elements such as organic EL elements and liquid crystal display elements, integrated circuit elements, solid-state imaging elements, color filters, and electronic parts such as black matrix, surface protective films to prevent deterioration or damage, and element surfaces or wiring are planarized. Various resin films are formed as a planarization film for forming a layer, an interlayer insulating film for insulating wirings arranged in layers, and the like.

In recent years, in order to impart desired properties to the resin film as described above, improvement has been attempted from various viewpoints of the resin composition for forming the resin film. 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-based crosslinking agent, and an aralkylphenol resin is proposed. have. According to the resin composition according to Patent Document 1, it is possible to form a resin composition capable of providing a resin film having high adhesion to a metal layer and excellent in developability and low hygroscopicity.

International Publication No. 2015/141717

The resin film obtained by using the above resin composition may be used in order to form a desired pattern shape according to the application. Here, from the viewpoint of improving the yield and improving the performance of the electronic component provided with the resin film, it is required that the resin film is capable of forming a pattern shape having good resolution. In order to be able to form a pattern with good resolution, it is necessary to sufficiently suppress the change in pattern shape before and after curing when obtaining a developed pattern by performing lithography or the like on a resin film, and curing such a developing pattern to obtain a pattern. There is. In addition, when the tensile elongation of the resin film is insufficient, that is, when the resin film is insufficient in extensibility, cracks occur in the resin film during continuous operation of an electronic device including electronic components, and when stress is generated in the electronic component. There is a possibility that it may occur, or the resin film may be easily peeled off from the substrate. When a crack occurs in the resin film or the resin film is peeled off from the substrate, there is a fear that it becomes difficult for the electronic component to function normally. For this reason, from the viewpoint of providing a highly reliable high-performance electronic component, the resin film is required to have excellent extensibility. However, in the resin film obtained by using the above conventional resin composition, it was not possible to achieve both good resolution and maintaining sufficient extensibility.

Accordingly, an object of the present invention is to provide a high-performance electronic component comprising a resin composition capable of forming a resin film excellent in resolution and extensibility, and a resin film formed by using the resin composition.

The present inventor has conducted intensive examination for the purpose of solving the above problems. And, the present inventors newly discovered that a resin film having excellent resolution and extensibility can be formed according to a resin composition containing a cyclic olefin polymer having a polar group and an epoxy resin having an epoxy equivalent of a predetermined value or more, The present invention was completed.

That is, the present invention aims to advantageously solve the above problems, and 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. Characterized in that. Thus, when the resin composition contains a cyclic olefin polymer (A) having a polar group and an epoxy resin (B) having an epoxy equivalent of 500 or more, a resin film excellent in resolution and extensibility can be formed.

On the other hand, the epoxy equivalent represents the number of grams (g/eq.) of a resin containing 1 g equivalent of an epoxy group, and can be obtained according to JIS K 7236:2009.

Further, in the resin composition of the present invention, it is preferable that the epoxy resin (B) contains a flexible skeleton and an aromatic group in a molecule. When the epoxy resin (B) contained in the resin composition contains a flexible skeleton and an aromatic group in its molecule, the resolution and extensibility of the obtained resin film can be further improved.

In addition, 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). When the content of the epoxy resin (B) is more than the above lower limit, the extensibility of the resin film can be further improved. In addition, when the content of the epoxy resin (B) is equal to or less than the above upper limit, the resolution of the resin film can be further improved.

Here, it is preferable that the resin composition of the present invention 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 excellent in chemical resistance can be formed.

In addition, 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). When the content of the crosslinking agent (C) is more than the above lower limit, the chemical resistance of the resin film can be further improved. In addition, when the content of the crosslinking agent (C) is equal to or less than the upper limit, the extensibility of the resin film can be improved.

In addition, it is preferable that the resin composition of the present invention further contains a photoacid generator (D). When the resin composition contains the photoacid generator (D), it becomes possible to pattern the resin film by changing the solubility of the resin film in the developer by the action of the photoacid generator (D).

Moreover, this invention aims at solving the said subject advantageously, and the electronic component of this invention is characterized by including the resin film which consists of any one of the resin compositions mentioned above. Since the resin film formed using the above-described resin composition is excellent in resolution and extensibility, the electronic component provided with the resin film can sufficiently exhibit a desired function, and thus has high performance.

ADVANTAGE OF THE INVENTION According to this invention, a high-performance electronic component provided with the resin composition which can form a resin film excellent in resolution and extensibility, and the resin film formed using the said resin composition can be provided.

Hereinafter, an embodiment of the present invention will be described in detail. The resin composition of the present invention can be used for formation of a resin film. In addition, such a resin film can be used, for example, as a surface protective film, a planarization film, an interlayer insulating film, and the like in an electronic component manufactured according to a wafer level package technology. And the electronic component of this invention is equipped with the resin film obtained by 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, and optionally, a crosslinking agent (C), a photoacid generator (D), etc. It may contain.

In addition, since 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, a resin film excellent in resolution and extensibility 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, and even if a pattern is formed by performing lithography using a resin film, pattern collapse, etc., when subjected to a thermosetting process of a resin film, etc. As a result, resolution was sacrificed by imparting extensibility. However, in the resin composition of the present invention, by mixing an epoxy resin (B) having an epoxy equivalent of 500 or more in addition to the cyclic olefin polymer (A) having a polar group, it has become possible to achieve both resolution and extensibility.

<Cyclic olefin polymer (A) having a polar group>

When the cyclic olefin polymer blended in the resin composition has a polar group, the strength of the obtained resin film can be increased. The cyclic olefin polymer (A) having a polar group may have one or more types of polar groups. In addition, it is preferable that the cyclic olefin polymer (A) having a polar group has at least a protic polar group. When the cyclic olefin polymer (A) having a polar group has a protic polar group, it has solubility in a developer (particularly, an alkali developer described later), and the resin composition contains a crosslinking agent (C) described later In this case, it is possible to form a resin film excellent in chemical resistance by being crosslinked favorably with such a crosslinking agent (C).

Here, the protic polar group refers to a group containing an atom belonging to Group 15 or 16 of the periodic table to which a hydrogen atom is directly bonded. As the atoms belonging to Group 15 or 16 of the periodic table, an atom belonging to the first or second cycle of Group 15 or 16 of the periodic table is preferable, more preferably an oxygen atom, a nitrogen atom, or a sulfur atom, It is particularly preferably an oxygen atom.

Specific examples of such a protic polar group include a polar group having an oxygen atom such as a hydroxyl group, a carboxyl group (hydroxycarbonyl group), a sulfonic acid group, and a phosphoric acid group; Polar groups having a nitrogen atom such as a primary amino group, a secondary amino group, a primary amide group, and a secondary amide group (imide group); Polar groups having a sulfur atom such as a thiol group; and the like. Among these, a polar group having an oxygen atom is preferable, and a carboxyl group is more preferable.

On the other hand, the cyclic olefin polymer (A) may have only one type of protic polar group, or may have two or more types.

In addition, the method of introducing the protonic polar group described above 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 a cyclic olefin monomer (a) having a protic polar group, and optionally, a repeating unit derived from another monomer (b). It may be a polymer containing 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 preferable.

[Cyclic olefin monomer (a) having a protic polar group]

The cyclic olefin monomer (a) having a protic polar group is not particularly limited as long as it is a monomer having the aforementioned protic polar group and a cyclic olefin structure. For example, a cyclic olefin monomer having a carboxyl group, a ring having a hydroxyl group Type olefin monomers are mentioned suitably. Suitable examples of these monomers include various monomers described in International Publication No. 2015/141717. Among them, from the viewpoint of enhancing the solubility in a developer and improving the adhesion of the resin film to the substrate, a cyclic olefin monomer having a carboxyl group is preferable, and 4-hydroxycarbonyltetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]Dodeca-9-ene (hereinafter, also referred to as "TCDC" in some cases) is more preferable. On the other hand, cyclic olefin monomer (a) may be used individually by 1 type, and may be used in combination of 2 or more types.

-Cyclic olefin monomer having a carboxyl group-

As a cyclic olefin monomer having a carboxyl group, for example, 2-hydroxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-methyl-2-hydroxycarbonylbicyclo[2.2.1] Hepto-5-ene, 2-carboxymethyl-2-hydroxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-2-methoxycarbonylmethylbicyclo[2.2.1 ]Hepto-5-ene, 2-hydroxycarbonyl-2-ethoxycarbonylmethylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-2-propoxycarbonylmethylbicyclo [2.2.1]Hepto-5-ene, 2-hydroxycarbonyl-2-butoxycarbonylmethylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-2-pentyloxycar Bornylmethylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-2-hexyloxycarbonylmethylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl- 2-cyclohexyloxycarbonylmethylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-2-phenoxycarbonylmethylbicyclo[2.2.1]hepto-5-ene, 2 -Hydroxycarbonyl-2-naphthyloxycarbonylmethylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-2-biphenyloxycarbonylmethylbicyclo[2.2.1]hepto -5-ene, 2-hydroxycarbonyl-2-benzyloxycarbonylmethylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-2-hydroxyethoxycarbonylmethylbicyclo [2.2.1]Hepto-5-ene, 2,3-dihydroxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-3-methoxycarbonylbicyclo[2.2 .1]Hepto-5-ene, 2-hydroxycarbonyl-3-ethoxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-3-propoxycarbonylbicyclo [2.2.1]Hepto-5-ene, 2-hydroxycarbonyl-3-butoxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-3-pentyloxycarbo Nylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-3-hexyloxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-3-cyclohex Siloxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-3-phenoxycarbonylbicy Chlo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-3-naphthyloxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-3-biphenyl Oxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-3-benzyloxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-3 -Hydroxyethoxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-3-hydroxycarbonylmethylbicyclo[2.2.1]hepto-5-ene, 3-methyl -2-hydroxycarbonylbicyclo[2.2.1]hepto-5-ene, 3-hydroxymethyl-2-hydroxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycar Bonyltricyclo[5.2.1.0 ^2,6 ]deca-3,8-diene, 4-hydroxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodeca-9-ene, 4-methyl -4-hydroxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodeca-9-ene, 4,5-dihydroxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^{2 ,7} ]dodeca-9-ene, 4-carboxymethyl-4-hydroxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodeca-9-ene, N-(hydroxycarbonyl Methyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(hydroxycarbonylethyl)bicyclo[2.2.1]hepto-5-ene-2,3-di Carboximide, N-(hydroxycarbonylpentyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(dihydroxycarbonylethyl)bicyclo[2.2.1] Hepto-5-ene-2,3-dicarboximide, N-(dihydroxycarbonylpropyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(hydroxy Carbonylphenethyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(2-(4-hydroxyphenyl)-1-(hydroxycarbonyl)ethyl) ratio Cyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(hydroxycarbonylphenyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide Can be lifted. In addition, these may be used individually, respectively, and may be used in combination of 2 or more types.

-Content ratio-

In addition, the content ratio of the repeating unit derived from the cyclic olefin monomer (a) in the cyclic olefin polymer (A) is preferably 10 mol% or more, with all repeating units being 100 mol%, and 20 mol% It is more preferable that it is more preferably, it is more preferable that it is 30 mol% or more, it is preferable that it is 90 mol% or less, it is more preferable that it is 80 mol% or less, and it is still more preferable that it is 70 mol% or less. If the proportion of the repeating unit derived from the cyclic olefin monomer (a) is 10 mol% or more, the sensitivity at the time of patterning using a resin film can be increased, while the occurrence of the developing residue can be effectively suppressed, and if it is 90 mol% or less, the ring The amount of the remaining film after development of the type olefin polymer (A) can be sufficiently ensured.

[Other monomers (b)]

The other monomer (b) is not particularly limited as long as it is a monomer copolymerizable with the cyclic olefin monomer (a) described above. As a monomer copolymerizable with a 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 (b2), and a monomer other than a cyclic olefin ( b3) is mentioned. As the various monomers (b1) to (b3), various monomers described in International Publication No. 2015/141717 can be used, respectively. These may be used individually by 1 type, and may be used in combination of 2 or more types. Among them, from the viewpoint of improving the heat resistance of the resin film, for example, polar groups 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 A cyclic olefin monomer (b1) having a is preferable, and N-phenyl-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide (hereinafter, also referred to as "NBPI" in some cases.) Cyclic olefin monomers having an N-substituted imide group such as the like are more preferable.

-N-cyclic olefin monomer having a substituted imide group-

As a cyclic olefin monomer which has an N-substituted imide group, the monomer represented by the following general formula (1) and general formula (2) is mentioned, for example. Among them, a monomer which can be represented by the following general formula (1) is preferable from the viewpoint of improving heat resistance and suppressing pattern flow.

[Formula 1]

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

[Formula 2]

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

In the general formula (1), R ¹ is an alkyl group or aryl group having 1 to 16 carbon atoms, and specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, 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, n-pentade Straight-chain alkyl groups such as a practical group and an n-hexadecyl group; Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, norbornyl group, bornyl group, isobornyl group , Cyclic alkyl groups such as decahydronaphthyl group, tricyclodecanyl group, and adamantyl 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-ethylbutyl Branched alkyl groups such as group, 2-methylhexyl group, 2-ethylhexyl group, 4-methylheptyl group, 1-methylnonyl group, 1-methyltridecyl group, and 1-methyltetradecyl group; And the like. Moreover, as a specific example of the aryl group, a phenyl group, a benzyl group, etc. are mentioned. Among these, from the viewpoint of more excellent heat resistance and solubility in an alkali developer, 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. When the number of carbon atoms is less than the lower limit, compatibility with the crosslinking agent is inferior. Further, if the number of carbon atoms exceeds the above upper limit, heat resistance is poor, and when the resin film is patterned, it may be melted by heat and the pattern may be lost.

Specific examples of the monomer represented by the general formula (1) include bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, and N-phenyl-bicyclo[2.2.1]hepto-5 -Ene-2,3-dicarboximide, N-methylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-ethylbicyclo[2.2.1]hepto-5-ene -2,3-dicarboximide, N-propylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-butylbicyclo[2.2.1]hepto-5-ene-2 ,3-dicarboximide, N-cyclohexylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-adamantylbicyclo[2.2.1]hepto-5-ene-2 ,3-dicarboximide, N-(1-methylbutyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(2-methylbutyl)-bicyclo[2.2 .1]Hepto-5-ene-2,3-dicarboximide, N-(1-methylpentyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-( 2-Methylpentyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(1-ethylbutyl)-bicyclo[2.2.1]hepto-5-ene-2 ,3-dicarboximide, N-(2-ethylbutyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(1-methylhexyl)-bicyclo[2.2 .1]Hepto-5-ene-2,3-dicarboximide, N-(2-methylhexyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-( 3-Methylhexyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(1-butylpentyl)-bicyclo[2.2.1]hepto-5-ene-2 ,3-dicarboximide, N-(2-butylpentyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(1-methylheptyl)-bicyclo[2.2 .1]Hepto-5-ene-2,3-dicarboximide, N-(2-methylheptyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-( 3-Methylheptyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(4-methylheptyl)-bicyclo[2.2.1]hepto-5-ene-2 ,3-dicarboximide, N-(1-ethylhexyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dica Reboximide, N-(2-ethylhexyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(3-ethylhexyl)-bicyclo[2.2.1] Hepto-5-ene-2,3-dicarboximide, N-(1-propylpentyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(2-propyl Pentyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(1-methyloctyl)-bicyclo[2.2.1]hepto-5-ene-2,3- Dicarboximide, N-(2-methyloctyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(3-methyloctyl)-bicyclo[2.2.1] Hepto-5-ene-2,3-dicarboximide, N-(4-methyloctyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(1-ethyl Heptyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(2-ethylheptyl)-bicyclo[2.2.1]hepto-5-ene-2,3- Dicarboximide, N-(3-ethylheptyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(4-ethylheptyl)-bicyclo[2.2.1] Hepto-5-ene-2,3-dicarboximide, N-(1-propylhexyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(2-propyl Hexyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(3-propylhexyl)-bicyclo[2.2.1]hepto-5-ene-2,3- Dicarboximide, N-(1-methylnonyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(2-methylnonyl)-bicyclo[2.2.1] Hepto-5-ene-2,3-dicarboximide, N-(3-methylnonyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(4-methyl Nonyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(5-methylnonyl)-bicyclo[2.2.1]hepto-5-ene-2,3- Dicarboximide, N-(1-ethyloctyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(2-ethyloctyl)-bicyclo[2.2.1] Hepto-5-ene-2,3-dicarboximide, N-(3-ethyloctyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide , N-(4-ethyloctyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(1-methyldecyl)-bicyclo[2.2.1]hepto-5 -Ene-2,3-dicarboximide, N-(1-methyldodecyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(1-methylundecyl )-Bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(1-methyldodecyl)-bicyclo[2.2.1]hepto-5-ene-2,3- Dicarboximide, N-(1-methyltridecyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(1-methyltetradecyl)-bicyclo[2.2. 1]Hepto-5-ene-2,3-dicarboximide, N-(1-methylpentadecyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-phenyl -Tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodeca-9-ene-4,5-dicarboximide, N-(2,4-dimethoxyphenyl)-tetracyclo[6.2.1.1 ^{3 ,6} .0 ^2,7 ]dodeca-9-ene-4,5-dicarboximide, etc. are mentioned. In addition, these may be used individually, respectively, and may be used combining 2 or more types.

On the other hand, in the general formula (2), R ² is a C1-C3 divalent alkylene group, and examples of the C1-C3 divalent alkylene group include a methylene group, an ethylene group, a propylene group, and an isopropylene group. I can. Among these, since the polymerization activity is good, a methylene group and an ethylene group are preferable.

Further, 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 fluoromethyl group, chloromethyl group, bromomethyl group, difluoromethyl group, dichloromethyl group, difluoromethyl group, trifluoromethyl group, trichloromethyl group, 2 , 2,2-trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, perfluorobutyl group, perfluoropentyl group, and the like. Among these, a methyl group and an ethyl group are preferable as R ³ because solubility in an alkali developer is excellent.

On the other hand, the monomer represented by the general formulas (1) and (2) can be obtained, for example, by imidation reaction of a corresponding amine and 5-norbornene-2,3-dicarboxylic anhydride. . In addition, the obtained monomer can be isolated efficiently by separating and purifying the reaction solution of the imidation reaction by a known method.

-Content ratio-

And, the content ratio of the repeating units derived from other monomers (b) in the cyclic olefin polymer (A) is preferably 10 mol% or more, with all repeating units being 100 mol%, and 20 mol% or more. It is more preferable, it is more preferable that it is 30 mol% or more, it is preferable that it is 90 mol% or less, it is more preferable that it is 80 mol% or less, and it is still more preferable that it is 70 mol% or less. When the ratio of the repeating unit derived from the other monomer (b) is 10 mol% or more, when patterning using the resin film of the cyclic olefin polymer (A), the dissolution contrast of the exposed portion/unexposed portion can be sufficiently secured. If it is not more than mol%, the solubility in a developer, particularly an alkali developer, is sufficiently secured, and the occurrence of a developing residue can be effectively suppressed.

On the other hand, the cyclic olefin polymer (A) can be prepared by performing ring-opening polymerization and addition polymerization according to a known method with respect to a monomer composition containing the various monomers described above. Among these, it is preferable to perform ring-opening polymerization 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. In addition, in the preparation of the cyclic olefin polymer (A), when a ring-opening polymer is obtained by the ring-opening polymerization method, the obtained ring-opening polymer is further subjected to a hydrogenation reaction, and at least the carbon-carbon double bonds contained in the main chain are It is preferable to use a hydrogenated product obtained by adding at least a part of hydrogen. On the other hand, when the cyclic olefin polymer (A) is a hydrogenated product, the ratio of hydrogenated carbon-carbon double bonds is preferably 50% or more, more preferably 70% or more, from the viewpoint of improving the heat resistance of the resin film, It is more preferably 90% or more, and particularly preferably 95% or more. In addition, the "hydrogen addition 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 increase the resolution and extensibility of the resin film obtained by 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. When the epoxy equivalent of the epoxy resin (B) is 900 or more, the extensibility of the resin film obtained by using the resin composition can be further improved. In addition, when the epoxy equivalent of the epoxy resin (B) is equal to or less than the above upper limit, the occurrence of a developing residue during patterning of a resin film obtained using a resin composition can be suppressed and resolution can be further improved.

<<Structure of epoxy resin (B)>>

It is preferable that the epoxy resin (B) contains a flexible skeleton and an aromatic group in a molecule. When the epoxy resin (B) contains both a flexible skeleton and an aromatic group, it is possible to more effectively achieve both extensibility and resolution of the resulting resin film. The reason is not clear, but it is speculated that the epoxy resin containing both a flexible skeleton and an aromatic group imparts flexibility to the resin film by the flexible skeleton, and at the same time imparts heat resistance to the resin film by an aromatic group. do. Further, when the epoxy resin (B) contains both a flexible skeleton and an aromatic group, in addition to the extensibility and resolution of the resin film, chemical resistance can be improved. The reason is not clear, but the invasion of solvent molecules into the resin film due to intermolecular interactions between the aromatic groups contained in the epoxy resin and/or the aromatic groups contained in the epoxy resin and the cyclic olefin polymer (A). It is speculated that this is because it is suppressed.

Here, the "flexible skeleton" is not particularly limited as long as it can exhibit flexibility, and a divalent linking group that is bonded to the structure to be connected at both ends may be mentioned. 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 a C2-C20 alkylene structure, a C2-C15 alkylene structure is preferable, and a C2-C10 alkylene structure 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, cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, decahydronaphtanylene group, norbornanylene group, and adamantanylene group. In addition, the alkylene structure is a halogen atom, an alkyl group, an alkoxy group, an alkylidene group, an amino group, a silyl group, an acyl group, an acyloxy group, a carboxyl group, a sulfo group, a cyano group, a nitro group, a hydroxy group, a mercapto group, Although it may have a substituent such as an oxo group, it is preferable not to have a substituent. On the other hand, the carbon number of the substituent does not include the carbon number of the substituent.

Examples of the alkylene structure having an ether bond of 2 to 20 carbon atoms include an oxyalkylene structure, an alkyleneoxy structure, an oxyalkyleneoxy structure, an alkyleneoxyalkylene structure, an alkyleneoxyalkyleneoxyalkylene structure, etc. I can. The alkylene structure having an ether bond of 2 to 20 carbon atoms is preferably an alkylene structure having an ether bond of 2 to 15 carbon atoms, and more preferably an alkylene structure having an ether bond of 2 to 10 carbon atoms. The alkylene structure may be linear, branched or cyclic. As an alkylene structure having such an ether bond, an oxyethylene group, an oxypropylene group, an oxybutylene group, an oxypentylene group, an oxyhexylene group, an oxyheptylene group, an oxyoctylene group, an oxynonylene group, an oxydecylene group, and an oxy Undecylene group, oxidodecylene group, oxytridecylene group, oxytetradecylene group, oxypentadecylene group, oxycyclopropylene group, oxycyclobutylene group, oxycyclopentylene group, oxycyclohexylene group, oxydeca Hydronaphtanylene group, oxynorbornanylene group, oxyadamantanylene group, etc. are mentioned. In addition, the oxyalkylene structure is a halogen atom, an alkyl group, an alkoxy group, an alkylidene group, an amino group, a silyl group, an acyl group, an acyloxy group, a carboxyl group, a sulfo group, a cyano group, a nitro group, a hydroxy group, a mercapto group. And may have a substituent such as an oxo group, but it is preferable not to have a substituent. Here, the carbon number of the substituent does not include the number of carbon atoms.

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.

In addition, it is preferable that the epoxy resin (B) is a compound represented by the following general formula (3).

[Formula 3]

(In the general formula (3), X represents a divalent linking group, Y ¹ and Y ² each independently represent the above-described "flexible skeleton", and m represents an integer of 1 to 20.)

Specific examples of the divalent linking group which may be X in the general formula (3) include a single bond, an oxygen atom, a carbon atom, or a sulfur atom. On the other hand, X and Y ¹ are different, and X and Y ² are different. In addition, functional groups 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.

In addition, although Y ¹ in the said general formula (3) and Y ² which may exist in multiple may be the same or different, the same is preferable.

In addition, m in the said general formula (3) becomes like this. Preferably it is an integer of 1-10, More preferably, it is an integer of 3-5.

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 Japanese Laid-Open Patent Publication No. 2010-285627. In addition, it does not specifically limit as a commercially available suitable epoxy resin (B), For example, "YX7110B80" manufactured by Mitsubishi Chemical Co., Ltd. is mentioned.

On the other hand, as the epoxy resin (B), one type of compound can be used alone or in combination of two or more.

<<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), It is more preferably 80 parts by mass or less. When the content of the epoxy resin (B) is more than the above lower limit, the extensibility of the resin film can be further improved. In addition, when the content of the epoxy resin (B) is equal to or less than the above upper limit, the resolution of the resin film can be further improved.

<Crosslinking agent (C)>

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

As the crosslinking agent (C), a phenol compound formed by directly bonding two or more alkoxymethyl groups to an aromatic ring is preferable. On the other hand, as the alkoxymethyl group, a methoxymethyl group is preferable. As a phenolic compound formed by directly bonding two or more alkoxymethyl groups to an aromatic ring, for example, 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, etc. Dimethoxymethyl substituted phenol compound; 3,3',5,5'-tetramethoxymethyl-4,4'-dihydroxybiphenyl (for example, brand name "TMOM-BP", manufactured by Honshu Chemical Industries, Ltd.), 1,1-bis[3 Tetramethoxymethyl substituted biphenyl compounds such as ,5-di(methoxymethyl)-4-hydroxyphenyl]-1-phenylethane; Hexamethoxymethyl substitution tree, such as 4,4',4"-(ethylidene)tris[2,6-(methoxymethyl)phenol] (for example, brand name "HMOM-TPHAP", manufactured by Honshu Chemical Industries, Ltd.) Phenyl compounds; 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. These can be used alone or in combination of two or more.

<<Content of crosslinking 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, and 30 parts by mass or less per 100 parts by mass of the cyclic olefin polymer (A). It is more preferable to use, more preferably 1 part by mass or more, more preferably 2 parts by mass or more, and still more preferably 5 parts by mass or more. When the content of the crosslinking agent (C) is more than the above lower limit, the chemical resistance of the resin film can be further improved. In addition, when the content of the crosslinking agent (C) is equal to or less than the upper limit, the extensibility of the resin film can be improved.

<mine generator (D)>

It is preferable that the resin composition further contains a photoacid generator (D). Since the resin composition contains a radiation-sensitive compound such as the photoacid generator (D), the solubility of the resin film in the exposed portion in the developer can be changed by the action of the photoacid generator (D) when the resin film is exposed. And thereby it becomes possible to pattern the resin film. That is, when the resin composition contains a radiation-sensitive compound such as the photoacid generator (D), such a resin composition can function as a radiation-sensitive resin composition.

Examples of the photoacid generator include azide compounds (quinone diazide compounds, etc.), 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, but an azide compound is preferred, and a quinonediazide compound This is more preferable.

As a quinone diazide compound suitably used as a photoacid generator, an ester compound of a quinone diazide sulfonic acid halide and a compound having a phenolic hydroxyl group can be used, for example.

Examples of the quinone diazide sulfonic acid halide used in the preparation of the ester compound include 1,2-naphthoquinone diazide-5-sulfonic acid chloride, 1,2-naphthoquinone diazide-4-sulfonic acid chloride, 1,2-benzoquinonediazide-5-sulfonic acid chloride.

As a compound having a phenolic hydroxyl group used in the preparation of the ester compound, for example, 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-hydroxyphenyl)ethane, oligomers of novolac resins, and oligomers obtained by copolymerizing dicyclopentadiene with a compound having one or more phenolic hydroxyl groups. These can be used alone or in combination of two or more.

[Content of mine 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 even more preferably 25 parts by mass or more per 100 parts by mass of the cyclic olefin polymer (A). And 100 parts by mass or less are preferable, 70 parts by mass or less are more preferable, and 50 parts by mass or less are still more preferable. When the content of the photoacid generator (D) is in this range, when patterning using a resin film made of a resin composition, at an appropriate exposure intensity, the cyclic olefin polymer (A) in the exposed portion and the unexposed portion is used as a developer. Since the difference in solubility can be made sufficiently large, 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, a cyclic olefin polymer (A), an epoxy resin (B), a crosslinking agent (C), and an optionally added photoacid generator (D) are dissolved and/or dispersed in a solvent. Resin liquid may be sufficient.

The solvent is not particularly limited, and known as a solvent for the resin composition, for example, a solvent disclosed in International Publication No. 2015/141717 such as diethylene glycol containing diethylene glycol ethylmethyl ether can be used. have. As a solvent, 1 type can be used individually or multiple types can be mixed and used. On the other hand, the content of the solvent in the resin composition of the present invention is per 100 parts by mass of the cyclic olefin polymer (A), 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. , More preferably 100 parts by mass or more and 1000 parts by mass or less.

<Other additives>

Further, the resin composition of the present invention may contain other additives other than the above as desired, as long as the effect of the present invention is not impaired. Examples of such other additives include crosslinking agents other than the crosslinking agent (C), silane coupling agents, surfactants, sensitizers, light stabilizers, antifoaming agents, pigments, dyes, and fillers (for example , See International Publication No. 2015/141717). On the other hand, examples of crosslinking agents 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 block isocyanate group.

<Preparation method of resin composition>

The method for preparing the resin composition of the present invention is not particularly limited, and each component constituting the resin composition may be mixed by a known method. The method of mixing 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 dispersion (that is, in the state of a resin liquid). The mixing is not particularly limited and is performed using a known mixer. Further, after mixing, filtration may be performed by a known method.

And, the solid content concentration of the resin liquid which is the resin composition of the present invention is usually 1% by mass or more and 70% by mass or less, preferably 5% by mass or more and 60% by mass or less, more preferably 10% by mass or more and 50% by mass or less. . When the solid content concentration is within the above-described range, the dissolution stability and coatability of the resin solution, and the film thickness uniformity and flatness of the formed resin film can be highly balanced.

(Electronic parts)

The electronic component of the present invention is provided with a resin film made of the resin composition of the present invention described above. In addition, the electronic component of the present invention has a sufficiently small amount of developing residues formed from the resin composition of the present invention and has a resin film excellent in extensibility, so it is high performance.

<Types of electronic components>

The electronic component of the present invention is not particularly limited, but since the resin film made of the resin composition of the present invention has a sufficiently small amount of developing residue and has excellent extensibility, electronic components manufactured by wafer-level package technology are suitable. Do. In particular, the resin film made of the resin composition of the present invention is used to form an interlayer insulating film (interlayer insulating film for rewiring, etc.) for insulating between wirings arranged in layers in an electronic component manufactured by wafer level package technology. It is more suitable to be.

<Method of manufacturing electronic component with resin film>

The electronic component provided with a resin film is not specifically limited, For example, it can manufacture by forming a resin film on a substrate, such as a silicon wafer on which a semiconductor element is mounted. The method of forming the resin film on the substrate is not particularly limited. The resin film includes, for example, a step of forming a film on a substrate (film formation step) using a resin composition (i.e., a resin liquid) containing a solvent, and a step of crosslinking the obtained film to obtain a resin film (crosslinking step). Can be manufactured through On the other hand, if necessary, between the film formation process and the crosslinking process, a process of irradiating a film on a substrate with active radiation to obtain an exposure film (exposure process) and a process of developing the exposure film to obtain a developing film (development process) are performed. By carrying out in order, a patterned resin film can be obtained. Hereinafter, each process is demonstrated.

[Film formation process]

In the film forming step, a film is formed on a substrate using a resin composition according to a known method such as a coating method or a film lamination method. For example, in the coating method, a resin composition is applied according to a known method such as a spin coating method, and then dried by heating to remove a solvent to obtain a coating film. The heating and drying conditions at this time vary depending on the type and mixing ratio of each component, 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 Can be 1 to 60 minutes, more preferably 1 to 30 minutes. In addition, in the film lamination method, for example, after applying the resin composition on a substrate for forming a B stage film such as a resin film or a metal film, the solvent is removed by heat drying to obtain a B stage film (coating film), and then , This B-stage film is laminated on a substrate. The heating and drying conditions at this time can be appropriately selected depending on the type and blending ratio of each component, but the heating temperature is usually 30 to 150°C, and the heating time can be usually 0.5 to 90 minutes. Film lamination can be performed using a compression machine such as a pressure laminator, a press, a vacuum laminator, a vacuum press, and a roll laminator.

[Exposure process]

In an optional exposure step, an exposure film is obtained by irradiating the coating film on the substrate with active radiation. More specifically, in the exposure step, a latent image pattern is formed by irradiating the coating film with actinic radiation. It is preferable that the resin composition used in the case of performing the exposure step contains a radiation-sensitive compound such as a photoacid generator (D). When the resin composition contains the photoacid generator (D), as described above, by the action of the photoacid generator (D), the developer of the cyclic olefin polymer (A) in the exposed portion and the non-exposed portion The solubility can be varied. On the other hand, as a method for obtaining a patterned resin film without mixing the photoacid generator (D) in the resin composition, for example, a method using laser processing using a CO ₂ laser or a UV-YAG laser, or a resin film A method of forming a mask pattern on the image and performing dry etching, and further, a direct drawing method such as an ink jet method, and the like may be mentioned.

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

[Development process]

Next, the latent image pattern formed in the exposure process is developed and made visible. As a developer, an alkali developer can be used. An alkali developer can be prepared by dissolving an alkaline compound in an aqueous solvent. As an alkaline compound, an alkali metal salt, an amine, and an ammonium salt can be used, for example. 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; Primary amines such as ethylamine and n-propylamine; Secondary amines such as diethylamine and di-n-propylamine; Tertiary amines such as triethylamine and methyldiethylamine; Quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide and choline; Alcohol amines such as dimethylethanolamine and triethanolamine; Pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]undeca-7-ene, 1,5-diazabicyclo[4.3.0]nona-5-ene, N-methylpyrrolidone, etc. Cyclic amines of; And the like. These alkaline compounds can be used individually or in combination of two or more, respectively. As the aqueous solvent of the alkaline aqueous solution, water; Water-soluble organic solvents such as methanol and ethanol can be used. The alkaline aqueous solution may be obtained by adding an appropriate amount of a surfactant or the like.

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

In this way, the developing film on which the target pattern is formed may be rinsed with a rinse solution, if necessary, to remove the development residue. After the rinse treatment, it is preferable to remove the remaining rinse liquid with compressed air or compressed nitrogen.

Further, if necessary, in order to deactivate the photoacid generator (D) contained in the resin composition, the developing film may be irradiated with active radiation as described above. For irradiation of active radiation, the method exemplified for formation of the latent image pattern can be used. Simultaneously with or after irradiation, the developing film may be heated. As a heating method, a method of heating an electronic component in a hot plate or an oven is mentioned, for example. The heating temperature is usually 80 to 300°C, preferably 100 to 200°C.

[Crosslinking process]

Then, a crosslinking reaction is performed with respect to the film formed on the substrate in the film formation step or the developing film that has been subjected to the development step. Such crosslinking may be appropriately selected depending on the type of 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 or thickness of the film, the equipment used, etc. For example, when using a hot plate, usually 5 to 60 minutes, using an oven. In the case, it is usually in the range of 30 to 240 minutes. Heating may be performed in an inert gas atmosphere as necessary. Examples of the inert gas that do not contain oxygen and that do not oxidize the film include nitrogen, argon, helium, neon, xenon, krypton, and the like. 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. Each of 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 according to the application, but is preferably 0.1 to 100 μm, more preferably 0.5 to 50 μm, and even more preferably 0.5. ~30 μm.

[Example]

Hereinafter, the present invention will be described in detail based on Examples, but the present invention is not limited to these Examples. In addition, in the following description, "%" and "parts" indicating amounts are based on mass unless otherwise noted. On the other hand, the weight average molecular weight and number average molecular weight of the cyclic olefin polymer obtained according to the following Synthesis Example were determined as polystyrene conversion values by gel permeation chromatography (GPC) using a solvent such as tetrahydrofuran as an eluent. I did.

In addition, the epoxy equivalent (g/eq.) of the epoxy resin used when preparing the resin composition in Examples and Comparative Examples was determined according to JIS K 7236:2009.

In addition, extensibility, chemical resistance, and resolution of resin films formed using the resin compositions according to Examples and Comparative Examples were evaluated using the following methods, respectively.

<Elongation>

A sputtering device (manufactured by Shibaura eletech, ``i-Miller CFS-4EP-LL'') was used to form an aluminum film with a thickness of 50 nm on a 4 inch silicon wafer, which was produced in each example and each comparative example. After spin-coating the resin composition, it was prebaked 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 in nitrogen at 230° C. for 1 hour to obtain a resin film, and a silicone wafer with a resin film thickness of 10 μm was obtained. This was immersed in 0.1 mol% aqueous hydrochloric acid solution for 12 hours to perform etching of aluminum to remove the resin film from the wafer, and then dried in an oven at 150°C for 1 hour. This was cut out into a rectangle having a width of 5 mm and a length of 40 mm to obtain a test piece, and the tensile elongation was measured by performing a tensile test on the test piece. Specifically, a tensile test was performed at 23°C with a tensile tester (manufactured by Shimadzu Corporation, "AGS-10kNX") at a grip distance 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 upper three points was taken as the elongation rate of the resin film formed using the resin composition obtained in each example. The larger the value of the elongation, the higher the elongation of the resin film. On the other hand, the higher the extensibility of the resin film formed from the resin composition, the more preferable the resin film formed by using the resin composition is difficult to cause cracking or peeling during a temperature cycle test or a drop impact test.

A: tensile elongation of 25% or more

B: Tensile elongation is more than 15% and less than 25%

C: tensile elongation of 15% or less

<Chemical resistance>

After spin-coating the resin composition prepared in each Example and each comparative example on a silicon wafer, it was prebaked for 2 minutes at 120°C using a hot plate to form a film made of the resin composition. Subsequently, by heating at 230°C for 1 hour in nitrogen, a silicon wafer with a thickness of 10 μm was obtained. This was immersed in monoethanolamine/dimethyl sulfoxide = 7/3 (mass ratio) for 15 minutes at 23°C, and the formula: (film thickness change (%) = |film thickness after immersion-film thickness before immersion|/film thickness before immersion) × 100), the film thickness change was calculated. 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 change in film thickness 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, or the change in film thickness is 20% or more

<Resolution>

After spin-coating the resin composition prepared in each Example and each Comparative Example on a silicon wafer, it was prebaked at 120°C for 2 minutes using a hot plate to obtain a coating film having a thickness of 10 μm. Subsequently, through a mask with a 20 μm hole, exposure was performed at a predetermined irradiation amount using a ghi mixing line with a mask aligner (manufactured by Canon, ``PLA501F''), and then, for 60 seconds with a 2.38% tetramethylammonium hydroxide aqueous solution as an alkali developer. , Dip development was performed. The amount of irradiation at the time of exposure was set to the amount of irradiation at which a 20 μm hole was formed for each coating film when exposure was performed using the mask. Subsequently, by rinsing with ultrapure water for 10 seconds, a silicon wafer with a developing film patterned with 20 μm holes was obtained. After raising the temperature in nitrogen at 100°C for 30 minutes and then from 100°C to 230°C at a rate of 2°C/min using an inner oven, curing was performed at 230°C for 1 hour. Formula: (|hole diameter before hardening-hole diameter after hardening|/hole diameter before hardening × 100), according to the rate of change of the hole diameter before and after hardening, and the value of the obtained change rate (%) was evaluated according to the following criteria. I did.

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]hepto-5-ene-2,3-dicarboximide (NBPI) 40 mol% as a cyclic olefin monomer having an N-substituted imide group, and a cyclic olefin having a carboxyl group 100 parts of a monomer mixture consisting of 60 mol% of 4-hydroxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodeca-9-ene (TCDC) as a monomer, 2.0 parts of 1,5-hexadiene , (1,3-dimethylimidazoline-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride (Org. Lett., Vol. 1, p. 953, synthesized by the method described in 1999. Then) 0.02 parts and 200 parts of diethylene glycol ethylmethyl ether were put into a nitrogen-substituted glass pressure-resistant reactor, and reacted at 80° C. for 4 hours while stirring to obtain a polymerization reaction solution.

Then, the obtained polymerization reaction solution was put in an autoclave, stirred for 5 hours at 150° C. and 4 MPa hydrogen pressure to perform hydrogenation, thereby preparing a polymer solution containing a cyclic olefin polymer (A-1) having a protic polar group. Got it. The polymerization conversion ratio of the obtained cyclic olefin polymer (A-1) having a protic polar group was 99.7%, the weight average molecular weight in terms of polystyrene was 7,150, the number average molecular weight was 4,690, the molecular weight distribution was 1.52, and the hydrogenation rate was 99.7%. In addition, 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]hepto-5-ene-2,3-dicarboxyimide (NBPI) 16 mol% and N-(2-ethylhexyl) as cyclic olefin monomers having an N-substituted imide group )-Bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide (NEHI) 16 mol%, and 4-hydroxycarbonyltetracyclo[6.2.1.1] as a cyclic olefin monomer having a carboxyl group ^3,6 .0 ^2,7 ]Dodeca-9-ene (TCDC) 100 parts by mass of a monomer mixture consisting of 68 mol%, 1-hexene 1.0 parts by mass, (1,3-dimethylimidazoline-2- Ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride (synthesized by the method described in ``Org. Lett., Vol. 1, p. 953, 1999'') 0.06 parts by mass, and diethylene glycol ethyl methyl ether 300 parts by mass was put into a nitrogen-substituted glass pressure-resistant reactor, and reacted at 80°C for 4 hours while stirring to obtain a polymerization reaction solution. Then, the obtained polymerization reaction solution was put into an autoclave, stirred at 150° C. and 4 MPa hydrogen pressure for 5 hours to perform hydrogenation, thereby obtaining a polymer solution containing a cyclic olefin polymer (A-2) having a protic polar group. Got it. The polymerization conversion ratio of the obtained cyclic olefin polymer (A-2) having a protic polar group was 99.3% by mass, the weight average molecular weight in terms of polystyrene was 20,600, the number average molecular weight was 11,500, the molecular weight distribution was 1.79, and the hydrogenation rate was 99.8 mol%. In addition, the solid content concentration of the polymer solution of the obtained cyclic olefin polymer (A-2) having a protic polar group was 25.3% by mass.

(Example 1)

<Preparation of resin composition>

As a 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 a cyclic olefin polymer (A-1)), photoacid generation As agent (D), 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1 mol) and 1,2-naphtho 30 parts of a condensate of quinonediazide-5-sulfonic acid chloride (2.5 moles), 63 parts of a mixture of an epoxy resin (B) having an epoxy equivalent of 1124 and methyl ethyl ketone (MEK) (manufactured by Mitsubishi Chemical, ``YX7110B80'') (50 parts as an epoxy resin (B)), and 53 parts of diethylene glycol ethylmethyl ether as a solvent were mixed and dissolved, and then filtered through a filter made of polytetrafluoroethylene having a pore diameter of 0.45 μm to prepare a resin composition.

And various evaluations were performed according to the above using the obtained resin composition. Table 1 shows the results.

On the other hand, manufactured by Mitsubishi Chemical Co., Ltd., "YX7110B80" using an epoxy equivalent of 500 or more epoxy resin (B) has, in the molecule, it will have an aromatic group, and a flexible skeleton, also, ^one that has an at least-phenylenediamine as an aromatic group It was confirmed using H-NMR and ¹³ C-NMR. In more detail, it was confirmed that "YX7110B80" has a structure that satisfies the above-described general formula (3).

(Example 2)

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

[Formula 4]

(Example 3)

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

[Formula 5]

(Example 4)

In Example 1, the mixture of the epoxy resin (B) and MEK (manufactured by Mitsubishi Chemical, YX7110B80) was changed from 63 parts to 94 parts (75 parts as epoxy resin (B)), and γ-buty of HMOM-TPHAP Except having added 100 parts of lolactone 20% solution (manufactured by Honshu Chemical Co., Ltd., ``HMOM-TPHAP-GB'') (20 parts as crosslinking agent (C)) and changing diethylene glycol ethylmethyl ether from 53 parts to 31 parts In the same manner as in Example 1, a resin composition was prepared, and various evaluations were performed. Table 1 shows the results.

(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 a cyclic olefin polymer (A-1)), and synthesis 79 parts of a polymer solution of the cyclic olefin polymer (A-2) having a protic polar group obtained in Example 2 (20 parts as a cyclic olefin polymer (A-2)), as a photoacid generator (D), 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) of 35 parts of condensate, 88 parts of a mixture of epoxy resin (B) and MEK (manufactured by Mitsubishi Chemical, YX7110B80) (70 parts as an epoxy resin (B)), 20% of γ-butyrolactone of HMOM-TPHAP 50 parts of a solution (manufactured by Honshu Chemical Co., Ltd., ``HMOM-TPHAP-GB'') (10 parts as a crosslinking agent (C)), and 38 parts of diethylene glycol ethylmethyl ether as a solvent were mixed and dissolved, then polytetra with a pore diameter of 0.45 μm It filtered with a fluoroethylene filter to prepare a resin composition, and various evaluations were performed in the same manner as in Example 1. Table 1 shows the results.

(Comparative Example 1)

As a 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 a cyclic olefin polymer (A-1)), as a photoacid generator (D) , 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1 mol) and 1,2-naphthoquinonediazide-5 -30 parts of a condensation product of sulfonic acid chloride (2.5 mol), 70 parts of a resin having an epoxy equivalent of 487 (manufactured by Mitsubishi Chemical, ``YX7105'') as other epoxy resins, and a 20% solution of γ-butyrolactone of HMOM-TPHAP (Honshu Chemical Corporation make, ``HMOM-TPHAP-GB'') 50 parts (10 parts as a crosslinking agent (C)), and 39 parts of diethylene glycol ethylmethyl ether as a solvent were mixed and dissolved, then polytetrafluoro with a pore diameter of 0.45 μm. It filtered with a filter made of ethylene and prepared a resin composition, and various evaluations were performed in the same manner as in Example 1. Table 1 shows the results. On the other hand, YX7105 used as another epoxy resin had an aromatic group and a flexible skeleton.

(Comparative Example 2)

As a 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 a cyclic olefin polymer (A-1)), as a photoacid generator (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 of sulfonic acid chloride (2.5 mol), 70 parts of a resin having an epoxy equivalent of 440 (manufactured by Mitsubishi Chemical Co., Ltd., ``YX7400'') as other epoxy resins, and 39 parts of diethylene glycol ethyl methyl ether as a solvent are mixed Then, after dissolving, it was filtered through a filter made of polytetrafluoroethylene having a pore diameter of 0.45 μm to prepare a resin composition, and the same evaluation as in Example 1 was performed. Table 1 shows the results. On the other hand, 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, "CMM"), as a photoacid generator (D), 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) A mixture of 30 parts of the condensate, an epoxy resin (B) having an epoxy equivalent of 1124 and MEK (manufactured by Mitsubishi Chemical, YX7110B80) was added to 93.75 parts (75 parts as an epoxy resin (B)), crosslinking agent (C) (manufactured by Honshu Chemical, "TMOM-BP") 10 parts and 288 parts of diethylene glycol ethylmethyl ether as a solvent were mixed and dissolved, and then filtered through a filter made of polytetrafluoroethylene having a pore diameter of 0.45 μm to prepare a resin composition. In order to evaluate the extensibility in the same manner as in Example 1, preparation of a test piece was attempted. However, since the resin film had become soft and could not be peeled off from the wafer, the test piece could not be prepared and evaluated. For other items, the same evaluation as in Example 1 was performed. Table 1 shows the results.

From Table 1, it can be seen that according to the resin composition containing a cyclic olefin polymer (A) having a polar group and an epoxy resin (B) having an epoxy equivalent of 500 or more, a resin film excellent in resolution and extensibility was possible. . Further, from Table 1, it can be seen that in the resin composition of Comparative Example 1 in which an epoxy resin having a flexible skeleton and an aromatic group together, but an epoxy equivalent of less than 500 was used, both extensibility and resolution could not be imparted to the obtained resin film. . Further, it can be seen that in the resin composition of Comparative Example 2 in which an epoxy resin having a flexible skeleton but no aromatic group and an epoxy equivalent of less than 500 was used, resolution could not be imparted to the obtained resin film. In addition, in the resin composition of Comparative Example 3 in which resins other than the cyclic olefin polymer having a polar group were used, it was found that resolution and extensibility could not be imparted to the obtained resin film.

[Industrial availability]

According to the resin composition of the present invention, a resin film excellent in resolution and extensibility can be formed.

Further, according to the present invention, a high-performance electronic component can be provided.

Claims (7)

A resin composition containing a cyclic olefin polymer (A) having a polar group and an epoxy resin (B) having an epoxy equivalent of 500 or more. The method of claim 1,
The resin composition, wherein the epoxy resin (B) contains a flexible skeleton and an aromatic group in a molecule. The method according to claim 1 or 2,
A resin composition further containing a crosslinking agent (C) containing a phenolic hydroxyl group and an alkoxymethyl group in a molecule. The method according to any one of claims 1 to 3,
A resin composition further containing a photoacid generator (D). The method according to any one of claims 1 to 4,
The resin composition, 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). The method according to any one of claims 1 to 5,
The resin composition, 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). An electronic component provided with a resin film made of the resin composition according to any one of claims 1 to 6.