JP2018172558A - Polymer and polymer composition - Google Patents

Abstract

Provided are a polymer that can be suitably used for obtaining a resin film having a low tensile elastic modulus and excellent developability and tensile elongation, and a polymer composition containing the polymer. A 2,5-dimethylenecyclopentane structural unit and an oxy group which may have an organic group at a 3,4-position, or may form a part of a ring at a 3,4-position. A polymer having a structural unit having an ethylene group bonded to the α, ω-position of alkylene and / or a structural unit having an alkyl group at the ω-position and an ethylene group at the α-position of oxyalkylene. [Selection figure] None

Description

  The present invention relates to a polymer and a polymer composition, and in particular, a polymer that has a low tensile elastic modulus and can be suitably used to obtain a resin film excellent in developability and tensile elongation, and a polymer containing the polymer. The present invention relates to a combined composition.

Conventionally, a crosslinked cyclic olefin resin film obtained by metathesis polymerization of a cyclic olefin monomer has been developed (see, for example, Patent Documents 1 and 2), but has a low tensile elastic modulus and excellent developability and tensile elongation. A resin film has not been found, and development of such a resin film has been strongly demanded.
Conventionally, a ring-opening polymer obtained by metathesis polymerization of a cyclic olefin monomer and a hydride thereof have been used for various applications (see, for example, Patent Documents 1 to 3). Specifically, for example, in Patent Documents 1 and 2, metathesis polymerization is performed in the presence of a crosslinking agent having two or more polymerizable unsaturated bonds, as an electrically insulating material for insulating a wiring layer of a printed wiring board. It is disclosed that a crosslinked cyclic olefin resin (ring-opening polymer) obtained in this manner is used. Further, for example, in Patent Document 3, it is obtained by metathesis polymerization of a cyclic olefin monomer as a resin film that can be used for manufacturing electronic components such as display elements, integrated circuit elements, solid-state imaging elements, color filters, and black matrices. A resin film having excellent alkali development characteristics, which is formed using a polymer composition containing a hydride of a ring-opening polymer and a photosensitizer such as a photoacid generator, is disclosed.

JP 2014-101447 A JP 2014-1009009 A International Publication No. 2015/141717

  However, conventional polymers such as ring-opened polymers and hydrides thereof described in Patent Documents 1 to 3 have all of the tensile modulus, developability and tensile elongation of a resin film formed using the polymer. There was room for improvement in terms of parallelism at a high level.

  Accordingly, an object of the present invention is to provide a polymer that can be suitably used for obtaining a resin film having a low tensile elastic modulus and excellent developability and tensile elongation, and a polymer composition containing the polymer. To do.

The inventor has intensively studied to achieve the above object. And this inventor is represented by the structural unit (A) represented by the following general formula (I), the structural unit (B) represented by the following general formula (II), and / or the following general formula (III). It was found that the polymer having the structural unit (C) to be used can be suitably used for obtaining a resin film having a low tensile elastic modulus and excellent in developability and tensile elongation, thereby completing the present invention.

〔式（Ｉ）中、ＸおよびＹは、それぞれ独立して、水素原子または有機基を表し、互いに結合して環を形成していてもよい。〕

〔式（ＩＩ）中、Ｒ_ａは、炭素数２以上４以下のアルキレン基を表し、ｎは、２以上１００以下の整数である。なお、複数のＲ_ａは互いに同一であってもよく、それぞれが異なっていてもよい。〕

〔式（ＩＩＩ）中、Ｒ_ｂは、炭素数２以上４以下のアルキレン基を表し、Ｒ_１は、水素原子またはアルキル基を表し、ｍは、２以上１００以下の整数である。なお、複数のＲ_ｂは互いに同一であってもよく、それぞれが異なっていてもよい。〕
上記一般式（Ｉ）で表される構造単位（Ａ）と、上記一般式（ＩＩ）で表される構造単位（Ｂ）および／または上記一般式（ＩＩＩ）で表される構造単位（Ｃ）と、を有する重合体は、引張弾性率が低く、現像性および引張伸びに優れた樹脂膜を得るために好適に使用し得る。 That is, this invention aims at solving the said subject advantageously, The polymer of this invention has the structural unit (A) represented by the following general formula (I), the following general formula ( II) and / or a structural unit (C) represented by the following general formula (III).

[In Formula (I), X and Y each independently represent a hydrogen atom or an organic group, and may be bonded to each other to form a ring. ]

[In Formula (II), R _a represents an alkylene group having 2 to 4 carbon atoms, and n is an integer of 2 to 100. In addition, several _Ra may mutually be the same and each may differ. ]

[In the formula (III), R _b represents an alkylene group having 2 to 4 carbon atoms, R ₁ represents a hydrogen atom or an alkyl group, and m is an integer of 2 to 100. In addition, several _Rb may mutually be the same and each may differ. ]
The structural unit (A) represented by the general formula (I), the structural unit (B) represented by the general formula (II) and / or the structural unit (C) represented by the general formula (III). And a polymer having a low tensile elastic modulus and can be suitably used to obtain a resin film excellent in developability and tensile elongation.

Here, the polymer of the present invention, the _{R a is, -CH 2 -CH 2 -, -} CH 2 -C (CH 3) H-, _{or, -C (CH 3) H-} CH 2 - represents a It is preferable. Wherein _{R a is, -CH 2 -CH 2 -, -} CH 2 -C (CH 3) H-, _{or, -C (CH 3) H-} CH 2 - a representative polymer, the tensile modulus is low, It can be suitably used for reliably obtaining a resin film excellent in developability and tensile elongation.

In the polymer of the present invention, R _b may represent —CH ₂ —CH ₂ —, —CH ₂ —C (CH ₃ ) H—, or —C (CH ₃ ) H—CH ₂ —. preferable. Wherein _{R b is, -CH 2 -CH 2 -, -} CH 2 -C (CH 3) H-, or _{-C (CH 3) H-CH} 2 - a representative polymer, the tensile modulus is low, development In order to reliably obtain a resin film excellent in properties and tensile elongation, it can be suitably used.

Furthermore, in the polymer of the present invention, R ₁ preferably represents a hydrogen atom, a methyl group, or an n-butyl group. The polymer in which R ₁ represents a hydrogen atom, a methyl group, or an n-butyl group can be suitably used for reliably obtaining a resin film having a low tensile elastic modulus and excellent in developability and tensile elongation.

  Here, the polymer of the present invention preferably has a weight average molecular weight of 5,000 or more and 50,000 or less. If the weight average molecular weight is 5000 or more and 50000 or less, the balance of tensile elastic modulus, tensile elongation, and developability of the obtained resin film can be maintained high.

  In the polymer of the present invention, the total proportion of the structural unit (B) and the structural unit (C) in all the structural units in the polymer is preferably 5% by mass or more and 50% by mass or less. When the total proportion of the structural unit (B) and the structural unit (C) in all the structural units in the polymer is 5% by mass or more and 50% by mass or less, the tensile elasticity modulus and tensile elongation of the resulting resin film , And the balance of developability can be maintained high.

  Here, in the polymer of the present invention, the structural unit (A) preferably has a polar group. If the structural unit (A) has a polar group, the developability of the resulting resin film can be improved.

  In the polymer of the present invention, the structural unit (A) preferably includes a structural unit A1 having a protic polar group and / or a structural unit A2 having a polar group other than a protic polar group. If the structural unit (A) includes the structural unit A1 having a protic polar group and / or the structural unit A2 having a polar group other than the protic polar group, the developability of the resulting resin film can be improved. .

前記構造単位（Ａ）が、上記一般式（ＩＶ）で表される構造単位（Ｄ）および／または上記一般式（Ｖ）で表される構造単位（Ｅ）を含む重合体は、引張弾性率がより低く、現像性および引張伸びにより優れた樹脂膜を得るために好適に使用し得る。 Further, in the polymer of the present invention, the structural unit (A) is a structural unit (D) represented by the following general formula (IV) and / or a structural unit (E) represented by the following general formula (V). It is preferable to contain.

The polymer in which the structural unit (A) includes the structural unit (D) represented by the general formula (IV) and / or the structural unit (E) represented by the general formula (V) has a tensile modulus. Can be suitably used to obtain a resin film having a lower developability and tensile elongation.

  Another object of the present invention is to advantageously solve the above problems, and the polymer composition of the present invention comprises any of the above-mentioned polymers, a crosslinking agent, and a solvent. And If any of the above-described polymers, a crosslinking agent, and a solvent are contained, a resin film having a low tensile modulus and excellent developability and tensile elongation can be formed.

  Here, it is preferable that the polymer composition of the present invention further contains a photosensitizer. If a photosensitizer is further included, a resin film having photosensitivity useful as a resist film or the like can be formed.

The polymer of the present invention can be suitably used for obtaining a resin film having a low tensile modulus and excellent developability and tensile elongation.
Moreover, according to the polymer composition of the present invention, a resin film having a low tensile elastic modulus and excellent in developability and tensile elongation can be formed.

Hereinafter, embodiments of the present invention will be described in detail.
Here, the polymer of the present invention can be suitably used for obtaining a resin film having a low tensile elastic modulus and excellent in developability and tensile elongation. The polymer composition of the present invention contains the polymer of the present invention, and forms a resin film having a low tensile elastic modulus and excellent developability and tensile elongation.

〔式（Ｉ）中、ＸおよびＹは、それぞれ独立して、水素原子または有機基を表し、互いに結合して環を形成していてもよい。〕
で表される構造単位（Ａ）と、
下記の一般式（ＩＩ）：

〔式（ＩＩ）中、Ｒ_ａは、炭素数２以上４以下のアルキレン基を表し、ｎは、２以上１００以下の整数である。なお、複数のＲ_ａは互いに同一であってもよく、それぞれが異なっていてもよい。
で表される構造単位（Ｂ）、および／または、
下記一般式（ＩＩＩ）：

〔式（ＩＩＩ）中、Ｒ_ｂは、炭素数２以上４以下のアルキレン基を表し、Ｒ_１は、水素原子またはアルキル基を表し、ｍは、２以上１００以下の整数である。なお、複数のＲ_ｂは互いに同一であってもよく、それぞれが異なっていてもよい。〕
で表される構造単位（Ｃ）と、を有する。
そして、本発明の重合体は、上記一般式（Ｉ）で表される構造単位（Ａ）と、上記一般式（ＩＩ）で表される構造単位（Ｂ）および／または上記一般式（ＩＩＩ）で表される構造単位（Ｃ）と、を有するので、引張弾性率が低く、現像性および引張伸びに優れた樹脂膜を形成することができる。 (Polymer)
The polymer of the present invention has the following general formula (I):

[In Formula (I), X and Y each independently represent a hydrogen atom or an organic group, and may be bonded to each other to form a ring. ]
A structural unit (A) represented by:
The following general formula (II):

[In Formula (II), R _a represents an alkylene group having 2 to 4 carbon atoms, and n is an integer of 2 to 100. In addition, several _Ra may mutually be the same and each may differ.
A structural unit (B), and / or
The following general formula (III):

[In the formula (III), R _b represents an alkylene group having 2 to 4 carbon atoms, R ₁ represents a hydrogen atom or an alkyl group, and m is an integer of 2 to 100. In addition, several _Rb may mutually be the same and each may differ. ]
And a structural unit (C) represented by
The polymer of the present invention comprises the structural unit (A) represented by the general formula (I), the structural unit (B) represented by the general formula (II) and / or the general formula (III). Therefore, it is possible to form a resin film having a low tensile modulus and excellent developability and tensile elongation.

  The polymer preferably has a weight average molecular weight of 5000 or more, more preferably 8000 or more, particularly preferably 15000 or more, preferably 50000 or less, more preferably 35000 or less. preferable. If the weight average molecular weight is 5000 or more and 50000 or less, the balance of tensile elastic modulus, tensile elongation, and developability of the obtained resin film can be maintained high.

〔式（Ｉ−１）中、ＸおよびＹは、それぞれ独立して、水素原子または有機基を表し、互いに結合して環を形成していてもよい。〕 <Structural unit (A)>
The structural unit (A) is a structural unit represented by the general formula (I), and is derived from the monomer (a) represented by the following general formula (I-1) (cyclic olefin). Monomer-derived structural unit). Specifically, the structural unit (A) is obtained by subjecting the monomer composition containing the monomer (a) to ring-opening metathesis polymerization and then hydrogenating the carbon-carbon double bond of the resulting ring-opening metathesis polymer. It is a structural unit formed when Moreover, 1 type may be sufficient as the structural unit (A) contained in a polymer, and 2 or more types may be sufficient as it.

[In Formula (I-1), X and Y each independently represent a hydrogen atom or an organic group, and may be bonded to each other to form a ring. ]

Here, as an organic group in X and Y in Formula (I) and Formula (I-1), it is preferable that it is a C1-C20 organic group, and it is a C1-C10 organic group. Is more preferable.
Examples of the ring that can be formed by combining X and Y in formula (I) and formula (I-1) with each other include, for example, an aliphatic hydrocarbon ring that may have a substituent, and a substituent. An aliphatic heterocyclic ring that may have, and a bicyclic structure that may have a substituent (for example, X and Y are bonded to each other to form a bicyclic structure, and the above formula (I-1) And the monomer (a) represented by formula (I) becomes a compound represented by the following formula (I-1-1)). The aliphatic hydrocarbon ring is not particularly limited, and examples thereof include a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a norbornane ring, and the like, and for example, represented by the above formula (I-1). As in the case where the monomer (a) becomes a compound represented by the following formula (I-1-2), a part of the aliphatic hydrocarbon ring may have a double bond. In addition, the aliphatic heterocyclic ring is not particularly limited, and examples thereof include a pyrrolidine ring, a tetrahydrofuran ring, and a tetrahydrothiophene ring. Furthermore, the substituent that these rings may have is not particularly limited, and examples thereof include an alkyl group, a carboxyl group, a hydroxyl group, a halogen atom, ═O, a phenyl group, a benzyl group, and a tolyl group.

  The structural unit (A) and the monomer (a) have a polar group (a protic polar group and / or a polar group other than the protic polar group) from the viewpoint of improving the developability of the resulting resin film. The polymer preferably includes the structural unit A1 having a protic polar group and / or the structural unit A2 having a polar group other than the protic polar group, and the structural unit A1 having a protic polar group and the proticity It is more preferable to include the structural unit A2 having a polar group other than the polar group. That is, the organic group represented by X and / or Y in Formula (I) and Formula (I-1), or the ring formed by combining X and Y with each other has a polar group. It is preferable.

<< Polar group >>
The polar group is not particularly limited as long as it is a polar functional group, and may be either a protic polar group or a polar group other than a protic polar group.

-Protic polar group-
Here, the protic polar group refers to a group containing an atomic group in which a hydrogen atom is directly bonded to an atom belonging to Group 15 or 16 of the periodic table. Among atoms belonging to Group 15 or Group 16 of the periodic table, atoms belonging to Group 1 or 2 of Group 15 or Group 16 of the Periodic Table are preferable, and more preferably oxygen atom, nitrogen atom or sulfur An atom, particularly preferably an oxygen atom.

  Specific examples of such protic polar groups include polar groups having oxygen atoms such as hydroxyl groups, carboxy groups (hydroxycarbonyl groups), sulfonic acid groups, 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, those having an oxygen atom are preferable, and a carboxy group is more preferable.

-Structural unit A1-
Examples of the structural unit A1 include a structural unit derived from a cyclic olefin monomer having a protic polar group, which is a specific example below.
Specific examples of the cyclic olefin monomer having a protic polar group include, for example, (i) 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] he To-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-hydroxycarbonyl-2-naphthyloxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-biphenyloxycarbonylmethylbicyclo [2.2.1] hept -5-ene, 2-hydroxycarbonyl-2-benzyloxyca Bonylmethylbicyclo [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-hydroxycarbonyl-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-Hydroxyethoxycarbonylbicyclo [2.2.1] hept-5 Ene, 2-hydroxycarbonyl-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, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylic acid, N- (hydroxycarbonylmethyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (hydroxycarbonyl) Ethyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (hydroxycarbonylpentyl) bicyclo [2.2.1] hept-5-ene-2,3-di Carboximide, 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-dicarboxyimi N- (2- (4-hydroxyphenyl) -1- (hydroxycarbonyl) ethyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (hydroxycarbonylphenyl) Carboxy group-containing cyclic olefins such as bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide; (ii) 2- (4-hydroxyphenyl) bicyclo [2.2.1] hept- 5-ene, 2-methyl-2- (4-hydroxyphenyl) bicyclo [2.2.1] hept-5-ene, 2-hydroxybicyclo [2.2.1] hept-5-ene, 2-hydroxy Methylbicyclo [2.2.1] hept-5-ene, 2-hydroxyethylbicyclo [2.2.1] hept-5-ene, 2-methyl-2-hydroxymethylbicyclo [2.2. 1] hept-5-ene, 2,3-dihydroxymethylbicyclo [2.2.1] hept-5-ene, 2- (hydroxyethoxycarbonyl) bicyclo [2.2.1] hept-5-ene, 2 -Methyl-2- (hydroxyethoxycarbonyl) bicyclo [2.2.1] hept-5-ene, 2- (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) bicyclo [2 2.1] hept-5-ene, 2- (2-hydroxy-2-trifluoromethyl-3,3,3-trifluoropropyl) bicyclo [2.2.1] hept-5-ene, N- (Hydroxyethyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (hydroxyphenyl) bicyclo [2.2.1] hept-5-ene-2,3- Dikarboki Hydroxyl group-containing cyclic olefin such as imide; and the like.

  The number of protic polar groups in the structural unit A1 is not particularly limited, and different types of protic polar groups may be included.

-Polar groups other than protic polar groups-
Examples of polar groups other than protic polar groups include N-substituted imide groups, ester groups, cyano groups, acid anhydride groups, and halogen atoms.

-Structural unit A2-
Examples of the structural unit A2 include a structural unit derived from a cyclic olefin monomer having a polar group other than the protic polar group, which is shown as a specific example below.
Specific examples of the cyclic olefin monomer having a polar group other than the protic polar group include, for example, (i) 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-ethyl Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-propylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-butyl Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-cyclohexylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-adamantyl Bicyclo [ 2.1] hept-5-ene-2,3-dicarboximide, 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-dicarboximide, 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-dicarboximide, N- (4-methylheptyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imido, 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-di Carboximide, 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-ethylhept ) -Bicyclo [2.2.1] hept-5-ene-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-dicarboximide, 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-methyl Nonyl) -bicyclo [2.2.1] hept-5-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-dicarboximide, 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-methyl Decyl) -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-methyldodecyl) -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-dicarboxy Imido, N- (1-methylpentadecyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, 4-phenyl-4-azatricyclo [5.2.1.0 ^{2 , 6} ] N- such as deca-8-ene-3,5-dione A cyclic olefin having a substituted imide group; (ii) 2-acetoxybicyclo [2.2.1] hept-5-ene, 2-acetoxymethylbicyclo [2.2.1] hept-5-ene, 2-methoxycarbonyl Bicyclo [2.2.1] hept-5-ene, 2-ethoxycarbonylbicyclo [2.2.1] hept-5-ene, 2-propoxycarbonylbicyclo [2.2.1] hept-5-ene, 2-butoxycarbonylbicyclo [2.2.1] hept-5-ene, 2-cyclohexyloxycarbonylbicyclo [2.2.1] hept-5-ene, 2-methyl-2-methoxycarbonylbicyclo [2.2 .1] Hept-5-ene, 2-methyl-2-ethoxycarbonylbicyclo [2.2.1] hept-5-ene, 2-methyl-2-propoxycarbonyl Cyclo [2.2.1] hept-5-ene, 2-methyl-2-butoxycarbonylbicyclo [2.2.1] hept-5-ene, 2-methyl-2-cyclohexyloxycarbonylbicyclo [2.2 .1] Hept-5-ene, 2- (2,2,2-trifluoroethoxycarbonyl) bicyclo [2.2.1] hept-5-ene, 2-methyl-2- (2,2,2- Cyclic olefins having ester groups such as (trifluoroethoxycarbonyl) bicyclo [2.2.1] hept-5-ene; (iii) 2-cyanobicyclo [2.2.1] hept-5-ene, 2- Cyclic olefins having a cyano group such as methyl-2-cyanobicyclo [2.2.1] hept-5-ene, 2,3-dicyanobicyclo [2.2.1] hept-5-ene; (iv) bicyclo [2.2 1] cyclic having an acid anhydride group such as hept-5-ene-2,3-dicarboxylic acid anhydride, 2-carboxymethyl-2-hydroxycarbonylbicyclo [2.2.1] hept-5-ene anhydride (V) 2-chlorobicyclo [2.2.1] hept-5-ene, 2-chloromethylbicyclo [2.2.1] hept-5-ene, 2- (chlorophenyl) bicyclo [2.2] .1] cyclic olefins having a halogen atom such as hept-5-ene;

  The number of polar groups other than the protic polar group in the structural unit A2 is not particularly limited, and polar groups other than different types of protic polar groups may be included.

Specific examples of the structural unit (A) include, for example, a structural unit (D) represented by the following general formula (IV), a structural unit (E) represented by the following general formula (V), and the like. Can be mentioned. The polymer in which the structural unit (A) includes the structural unit (D) and / or the structural unit (E) has a lower tensile elastic modulus, and is suitable for obtaining a resin film excellent in developability and tensile elongation. Can be used.

As a specific example of the structural unit (A1), a structural unit in which X and Y are bonded to form an aliphatic hydrocarbon ring having a substituent is preferably exemplified, and represented by the following structural formula (X). A structural unit (D) derived from a cyclic olefin monomer is particularly preferred. As a specific example of the structural unit (A2), a structural unit in which X and Y are bonded to form an aliphatic heterocyclic ring having a substituent is preferably exemplified, and represented by the following structural formula (Y). Particularly preferred is the structural unit (E) derived from the cyclic olefin monomer.

  The proportion of the structural unit (A) in all the structural units in the polymer is preferably 50% by mass or more, more preferably 55% by mass or more, and particularly preferably 60% by mass or more. , 95% by mass or less, more preferably 92% by mass or less, and particularly preferably 90% by mass or less.

〔式（ＩＩ−１）中、Ｒ_ａは、炭素数２以上４以下のアルキレン基を表し、ｎは、２以上１００以下の整数である。なお、複数のＲ_ａは互いに同一であってもよく、それぞれが異なっていてもよい。〕 <Structural unit (B)>
The structural unit (B) is a structural unit represented by the general formula (II) and is derived from the monomer (b) represented by the following general formula (II-1) (allylation). A structural unit derived from polyalkylene glycol (polyalkylene glycol diallyl ether). Specifically, the structural unit (B) is obtained when the carbon-carbon double bond of the produced metathesis polymer is hydrogenated after metathesis polymerization of the monomer composition containing the monomer (b). A structural unit to be formed. Moreover, 1 type may be sufficient as the structural unit (B) contained in a polymer, and 2 or more types may be sufficient as it.

[In formula (II-1), R _a represents an alkylene group having 2 to 4 carbon atoms, and n is an integer of 2 to 100. In addition, several _Ra may mutually be the same and each may differ. ]

The _Ra includes ethylene group, n-propylene group, 1-methylethylene group, 2-methylethylene group, n-butylene group, 1-methylpropylene group, 2-methylpropylene group, 3-methylpropylene group, 1 , 1-dimethylethylene group, 1,2-dimethylethylene group, 2,2-dimethylethylene group, 1-ethylethylene group, 2-ethylethylene group and the like. Among them, _{R a is,} -CH ₂ -CH 2 - (ethylene _{group), - CH 2 -C (CH} 3) H- (2- methylethylene), _{or, -C (CH 3) H-} CH ₂ - preferably represents a (1-methylethylene group). Wherein _{R a is, -CH 2 -CH 2 -, -} CH 2 -C (CH 3) H-, _{or, -C (CH 3) H-} CH 2 - a representative polymer, the tensile modulus is low, It can be suitably used for reliably obtaining a resin film excellent in developability and tensile elongation.

〔式（ＩＩ−２）中、Ｒは、−ＣＨ_２−Ｃ（ＣＨ_３）Ｈ−、または、−Ｃ（ＣＨ_３）Ｈ−ＣＨ_２−を表し、ｎは、２以上１００以下の整数である。なお、複数のＲは互いに同一であってもよく、それぞれが異なっていてもよい。〕

〔式（ＩＩ−３）中、ｎは、２以上１００以下の整数である。〕 Specific examples of the structural unit (B) include, for example, a structural unit (F) represented by the following general formula (II-2), a structural unit (G) represented by the following general formula (II-3), Etc. are preferable. The polymer in which the structural unit (B) includes the structural unit (F) and / or the structural unit (G) is suitable for reliably obtaining a resin film having a low tensile elastic modulus and excellent developability and tensile elongation. Can be used for

[In Formula (II-2), R represents —CH ₂ —C (CH ₃ ) H— or —C (CH ₃ ) H—CH ₂ —, and n represents an integer of 2 or more and 100 or less. is there. In addition, several R may mutually be the same and each may differ. ]

[In Formula (II-3), n is an integer of 2 or more and 100 or less. ]

〔式（ａ）中、Ｒは、−ＣＨ_２−Ｃ（ＣＨ_３）Ｈ−、または、−Ｃ（ＣＨ_３）Ｈ−ＣＨ_２−を表し、ｎは、２以上１００以下の整数である。なお、複数のＲは互いに同一であってもよく、それぞれが異なっていてもよい。〕

〔式（ｂ）中、ｎは、２以上１００以下の整数である。〕
なお、一般式（ａ）で表される化合物の化学名は、ポリプロピレングリコール−ジアリルエーテルであり、一般式（ｂ）で表される化合物の化学名は、ポリエチレングリコール−ジアリルエーテルである。 The monomer (b) represented by the general formula (II-1) is preferably represented by the following general formula (a) or (b).

Wherein (a), R _{is, -CH 2 -C (CH 3)} H-, _{or, -C (CH 3) H-} CH 2 - represents, n is 2 or more and 100 or less integer. In addition, several R may mutually be the same and each may differ. ]

[In formula (b), n is an integer of 2 or more and 100 or less. ]
The chemical name of the compound represented by the general formula (a) is polypropylene glycol-diallyl ether, and the chemical name of the compound represented by the general formula (b) is polyethylene glycol-diallyl ether.

〔式（ＩＩＩ−１）中、Ｒ_ｂは、炭素数２以上４以下のアルキレン基を表し、Ｒ_１は、水素原子またはアルキル基を表し、ｍは、２以上１００以下の整数である。なお、複数のＲ_ｂは互いに同一であってもよく、それぞれが異なっていてもよい。〕 <Structural unit (C)>
The structural unit (C) is a structural unit represented by the above general formula (III), and is derived from the monomer (c) represented by the following general formula (III-1) (allylation) A structural unit derived from polyalkylene glycol (polyalkylene glycol monoallyl ether). Specifically, the structural unit (C) is obtained when the carbon-carbon double bond of the produced metathesis polymer is hydrogenated after metathesis polymerization of the monomer composition containing the monomer (c). A structural unit to be formed. Moreover, 1 type may be sufficient as the structural unit (C) contained in a polymer, and 2 or more types may be sufficient as it.

[In Formula (III-1), R _b represents an alkylene group having 2 to 4 carbon atoms, R ₁ represents a hydrogen atom or an alkyl group, and m is an integer of 2 to 100. In addition, several _Rb may mutually be the same and each may differ. ]

Examples of R _b include ethylene, n-propylene, 1-methylethylene, 2-methylethylene, n-butylene, 1-methylpropylene, 2-methylpropylene, 3-methylpropylene, , 1-dimethylethylene group, 1,2-dimethylethylene group, 2,2-dimethylethylene group, 1-ethylethylene group, 2-ethylethylene group and the like. Among them, _{R b is,} -CH ₂ -CH 2 - (ethylene _{group), - CH 2 -C (CH} 3) H- (2- methylethylene), or _{-C (CH 3) H-CH} 2 It preferably represents-(1-methylethylene group). Wherein _{R b is, -CH 2 -CH 2 -, -} CH 2 -C (CH 3) H-, or _{-C (CH 3) H-CH} 2 - a representative polymer, the tensile modulus is low, development In order to reliably obtain a resin film excellent in properties and tensile elongation, it can be suitably used.

The alkyl group for R ₁ is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, a 1-methylethyl group, a 2-methylethyl group, an n-butyl group, and an n-pentyl group. And an alkyl group having 1 to 6 carbon atoms such as an n-hexyl group. Among these, R ₁ preferably represents a hydrogen atom, a methyl group, or an n-butyl group. The polymer in which R ₁ represents a hydrogen atom, a methyl group, or an n-butyl group can be suitably used for reliably obtaining a resin film having a low tensile elastic modulus and excellent in developability and tensile elongation.

〔式（ＩＩＩ−２）中、ｍは、２以上１００以下の整数である。〕

〔式（ＩＩＩ−３）中、ｍは、２以上１００以下の整数である。〕

〔式（ＩＩＩ−４）中、Ｒは、−ＣＨ_２−Ｃ（ＣＨ_３）Ｈ−、または、−Ｃ（ＣＨ_３）Ｈ−ＣＨ_２−を表し、ｍ１およびｍ２は、それぞれ１以上の整数であって、合計が２以上１００以下となる整数である。なお、Ｒが複数の場合、複数のＲは互いに同一であってもよく、それぞれが異なっていてもよい。〕

〔式（ＩＩＩ−５）中、Ｒは、−ＣＨ_２−Ｃ（ＣＨ_３）Ｈ−、または、−Ｃ（ＣＨ_３）Ｈ−ＣＨ_２−を表し、ｍは、２以上１００以下の整数である。なお、複数のＲは互いに同一であってもよく、それぞれが異なっていてもよい。〕

〔式（ＩＩＩ−６）中、Ｒは、−ＣＨ_２−Ｃ（ＣＨ_３）Ｈ−、または、−Ｃ（ＣＨ_３）Ｈ−ＣＨ_２−を表し、ｍ１およびｍ２は、それぞれ１以上の整数であって、合計が２以上１００以下となる整数である。なお、Ｒが複数の場合、複数のＲは互いに同一であってもよく、それぞれが異なっていてもよい。〕 Specific examples of the structural unit (C) include, for example, a structural unit (H) represented by the following general formula (III-2), a structural unit (I) represented by the following general formula (III-3), Structural unit (J) represented by the following general formula (III-4), Structural unit (K) represented by the following general formula (III-5), Structural unit represented by the following general formula (III-6) (L) etc. are mentioned suitably. The polymer in which the structural unit (C) includes at least one of the structural units (H) to (L) is suitable for reliably obtaining a resin film having a low tensile elastic modulus and excellent developability and tensile elongation. Can be used for

[In Formula (III-2), m is an integer of 2 or more and 100 or less. ]

[In Formula (III-3), m is an integer of 2 or more and 100 or less. ]

[In the formula (III-4), R represents —CH ₂ —C (CH ₃ ) H— or —C (CH ₃ ) H—CH ₂ —, wherein m1 and m2 each represents an integer of 1 or more. It is an integer whose total is 2 or more and 100 or less. When there are a plurality of Rs, the plurality of Rs may be the same as each other or different from each other. ]

[In Formula (III-5), R represents —CH ₂ —C (CH ₃ ) H— or —C (CH ₃ ) H—CH ₂ —, and m represents an integer of 2 or more and 100 or less. is there. In addition, several R may mutually be the same and each may differ. ]

[In the formula (III-6), R represents —CH ₂ —C (CH ₃ ) H— or —C (CH ₃ ) H—CH ₂ —, and m1 and m2 each represents an integer of 1 or more. It is an integer whose total is 2 or more and 100 or less. When there are a plurality of Rs, the plurality of Rs may be the same as each other or different from each other. ]

〔式（ｃ）中、ｍは、２以上１００以下の整数である。〕

〔式（ｄ）中、ｍは、２以上１００以下の整数である。〕

〔式（ｅ）中、Ｒは、−ＣＨ_２−Ｃ（ＣＨ_３）Ｈ−、または、−Ｃ（ＣＨ_３）Ｈ−ＣＨ_２−を表し、ｍ１およびｍ２は、それぞれ１以上の整数であって、合計が２以上１００以下となる整数である。なお、Ｒが複数の場合、複数のＲは互いに同一であってもよく、それぞれが異なっていてもよい。〕

〔式（ｆ）中、Ｒは、−ＣＨ_２−Ｃ（ＣＨ_３）Ｈ−、または、−Ｃ（ＣＨ_３）Ｈ−ＣＨ_２−を表し、ｍは、２以上１００以下の整数である。なお、複数のＲは互いに同一であってもよく、それぞれが異なっていてもよい。〕

〔式（ｇ）中、Ｒは、−ＣＨ_２−Ｃ（ＣＨ_３）Ｈ−、または、−Ｃ（ＣＨ_３）Ｈ−ＣＨ_２−を表し、ｍ１およびｍ２は、それぞれ１以上の整数であって、合計が２以上１００以下となる整数である。なお、Ｒが複数の場合、複数のＲは互いに同一であってもよく、それぞれが異なっていてもよい。〕
なおここで、一般式（ｃ）で表される化合物の化学名は、ポリエチレングリコール−アリルエーテルであり、一般式（ｄ）で表される化合物の化学名は、メトキシ−ポリエチレングリコール−アリルエーテルであり、一般式（ｅ）で表される化合物の化学名は、ポリエチレングリコール−ポリプロピレングリコール−アリルエーテルであり、一般式（ｆ）で表される化合物の化学名は、ポリプロピレングリコール−アリルエーテルであり、一般式（ｇ）で表される化合物の化学名は、ブトキシ−ポリエチレングリコール−ポリプロピレングリコール−アリルエーテルである。 The monomer (c) represented by the general formula (III-1) is preferably represented by any one of the following general formulas (c) to (g).

[In Formula (c), m is an integer of 2-100. ]

[In Formula (d), m is an integer of 2-100. ]

[In the formula (e), R represents —CH ₂ —C (CH ₃ ) H— or —C (CH ₃ ) H—CH ₂ —, and m1 and m2 each represents an integer of 1 or more. Thus, the total is an integer of 2 or more and 100 or less. When there are a plurality of Rs, the plurality of Rs may be the same as each other or different from each other. ]

Wherein (f), R _{is, -CH 2 -C (CH 3)} H-, _{or, -C (CH 3) H-} CH 2 - represents, m is 2 or more and 100 or less integer. In addition, several R may mutually be the same and each may differ. ]

[In the formula (g), R represents —CH ₂ —C (CH ₃ ) H— or —C (CH ₃ ) H—CH ₂ —, and m1 and m2 each represents an integer of 1 or more. Thus, the total is an integer of 2 or more and 100 or less. When there are a plurality of Rs, the plurality of Rs may be the same as each other or different from each other. ]
Here, the chemical name of the compound represented by the general formula (c) is polyethylene glycol-allyl ether, and the chemical name of the compound represented by the general formula (d) is methoxy-polyethylene glycol-allyl ether. Yes, the chemical name of the compound represented by the general formula (e) is polyethylene glycol-polypropylene glycol-allyl ether, and the chemical name of the compound represented by the general formula (f) is polypropylene glycol-allyl ether. The chemical name of the compound represented by the general formula (g) is butoxy-polyethylene glycol-polypropylene glycol-allyl ether.

  The total proportion of the structural unit (B) and the structural unit (C) in all the structural units in the polymer is preferably 5% by mass or more, more preferably 8% by mass or more. It is particularly preferably at least mass%, more preferably at most 50 mass%, more preferably at most 45 mass%, particularly preferably at most 40 mass%. If the total proportion of the structural unit (B) and the structural unit (C) in all the structural units in the polymer is 5% by mass or more and 50% by mass or less, the tensile elastic modulus, tensile elongation, and development of the resulting resin film The balance of sex can be kept high.

<Polymer production mechanism>
The polymer having the structural unit described above can be obtained by metathesis polymerizing the above-described monomer and hydrogenating the polymer obtained by the metathesis polymerization. As the metathesis polymerization catalyst, those described in International Publication No. 2015/141717, International Publication No. 2010/110323 and the like can be used. Reaction conditions can be performed under the conditions described in International Publication No. 2015/141717, International Publication No. 2010/110323, and the like.
Specifically, in the metathesis reaction, in addition to the reaction between the cyclic olefin monomers that form the structure represented by the following structural formula (1), the cyclic olefin monomer that forms the structure represented by the following structural formula (2) A reaction with a polyalkylene glycol diallyl ether, a reaction between polyalkylene glycol diallyl ethers that form a structure represented by the following structural formula (3), a cyclic olefin monomer that forms a structure represented by the following structural formula (4), and It occurs in combination with the reaction with polyalkylene glycol monoallyl ether and at least one of the reaction of polyalkylene glycol diallyl ether and polyalkylene glycol monoallyl ether in which the structure represented by the following structural formula (5) is formed , Which has multiple carbon-carbon double bonds in the molecule. Polymer is obtained. And a double bond is hydrogenated by hydrogenation reaction, The polymer of this invention which has the structural unit mentioned above is obtained. When the structure represented by the following structural formula (1) is hydrogenated, a structure in which two structural units (A) are arranged, and when the structure represented by the following structural formula (2) is hydrogenated, When the unit (A) and the structural unit (B) are arranged, and the structure represented by the following structural formula (3) is hydrogenated, two structural units (B) are arranged, and the following structural formula ( When the structure represented by 4) is hydrogenated, the structural unit (A) and the structural unit (C) are arranged side by side. When the structure represented by the following structural formula (5) is hydrogenated, the structural unit ( B) and the structural unit (C) are arranged. In the following structural formulas (1) to (5), the portion where the wavy line is described (double bond) is a bond with another structure or a polymer terminal.

  Thus, since the polymerization in the present specification is a metathesis polymerization different from the addition polymerization, the polymerization proceeds while the double bond is changed.

(Polymer composition)
The polymer composition of the present invention includes the polymer of the present invention, a crosslinking agent, and a solvent, and further includes a photosensitizer and other components as necessary.

<Polymer>
As the polymer, the above-described polymer of the present invention is used. Since the polymer of the present invention is used, a resin film having a low tensile elastic modulus and excellent developability and tensile elongation can be obtained.

<Crosslinking agent>
There is no restriction | limiting in particular as a crosslinking agent, For example, an epoxy-type crosslinking agent, a methoxymethyl group containing crosslinking agent, etc. are mentioned.

<< Epoxy-based crosslinking agent >>
Specific examples of the epoxy-based crosslinking agent include, for example, 4,5-epoxycyclohexane-1,2-dicarboxylate bis (3,4-epoxycyclohexylmethyl) modified ε-caprolactone (aliphatic cyclic trifunctional epoxy resin). , Butanetetracarboxylic acid tetra (3,4-epoxycyclohexylmethyl) modified ε-caprolactone (aliphatic cyclic tetrafunctional epoxy resin), 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, ε-caprolactone-modified 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1,2: 8,9-diepoxylimonene, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. Epoxy compound having alicyclic structure of A type epoxy compound, bisphenol F type epoxy compound, hydrogenated bisphenol A type epoxy compound, long chain bisphenol A type epoxy resin, EO modified bisphenol A type epoxy compound, phenol novolac type polyfunctional epoxy compound, 1,6-bis ( 2,3-epoxypropan-1-yloxy) polyfunctional epoxy compounds having a naphthalene skeleton such as naphthalene, tricyclodecane dimethanol diglycidyl ether, glycidylamine type epoxy resin, chain alkyl polyfunctional epoxy compound, polyfunctional epoxy polybutadiene And glycidyl polyether compounds of glycerin, diglycerin polyglycidyl ether compounds, and epoxy compounds having no alicyclic structure such as γ-glycidoxypropyltrimethylsilane;
These can also be used individually by 1 type and can also be used in combination of 2 or more type.
Among these, from the viewpoint of tensile elongation and developability of the resin film, 4,5-epoxycyclohexane-1,2-dicarboxylate bis (3,4-epoxycyclohexylmethyl) modified ε-caprolactone, butanetetracarboxylate tetra (3,4-epoxycyclohexylmethyl) modified ε-caprolactone, 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, ε-caprolactone modified 3 ′, 4′-epoxycyclohexylmethyl-3,4 -Epoxycyclohexanecarboxylate is preferred.

<< Methoxymethyl group-containing crosslinking agent >>
Specific examples of the methoxymethyl group-containing crosslinking agent include, for example, dimethoxymethyl-substituted phenol compounds such as 2,6-dimethoxymethyl-4-t-butylphenol and 2,6-dimethoxymethyl-p-cresol; Tetramethoxymethyl-substituted biphenyl such as 5,5′-tetramethoxymethyl-4,4′-dihydroxybiphenyl, 1,1-bis [3,5-di (methoxymethyl) -4-hydroxyphenyl] -1-phenylethane Compound; Hexamethoxymethyl-substituted triphenyl compound such as hexamethoxymethyl-substituted compound of 4,4 ′, 4 ″-(ethylidene) trisphenol; N, N′-dimethoxymethylmelamine, N, N ′, N ″- Trimethoxymethylmelamine, N, N, N ′, N ″ -tetramethoxymethylmelamine, N, N, N ′, N ′, N ″ -pe A melamine compound in which an amino group is substituted with two or more methoxymethyl groups, such as tamethoxymethylmelamine, N, N, N ′, N ′, N ″, N ″ -hexamethoxymethylmelamine; .
These can be used singly or in combination of two or more.
Among these, N, N, N ′, N ′, N ″, N ″ -hexamethoxymethylmelamine is preferable from the viewpoint of reactivity.

  The content of the crosslinking agent in the polymer composition of the present invention is preferably 1 part by mass or more, more preferably 5 parts by mass or more, particularly preferably 10 parts by mass or more, based on 100 parts by mass of the polymer, and 80 parts by mass. Part or less, more preferably 75 parts by weight or less, and particularly preferably 70 parts by weight or less. When the content of the crosslinking agent in the polymer composition of the present invention is 5 parts by mass or more with respect to 100 parts by mass of the polymer, the tensile elongation of the resin film can be improved. When it exists, developability can be improved.

<Solvent>
The solvent is not particularly limited, and is a known polymer composition solvent such as acetone, methyl ethyl ketone, cyclopentanone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, Linear ketones such as 2-octanone, 3-octanone, 4-octanone; alcohols such as n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, cyclohexanol; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dioxane, etc. Ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propyl formate, butyl formate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyrate Esters such as methyl, ethyl butyrate, methyl lactate, and ethyl lactate; cellosolve esters such as cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate; propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether Propylene glycols such as acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether; diethylene glycol such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether Saturated γ-lactones such as γ-butyrolactone, γ-valerolactone, γ-caprolactone and γ-caprolactone; halogenated hydrocarbons such as trichloroethylene; aromatic hydrocarbons such as toluene and xylene; dimethylacetamide , Polar solvents such as dimethylformamide and N-methylacetamide;
These can also be used individually by 1 type and can also be used in combination of 2 or more type.

  The content of the solvent in the polymer composition of the present invention is preferably 10 parts by mass or more, more preferably 50 parts by mass or more, particularly preferably 100 parts by mass or more, based on 100 parts by mass of the polymer, and 10000 parts by mass. The following is preferable, 5000 parts by mass or less is more preferable, and 1000 parts by mass or less is particularly preferable.

  A method for dissolving or dispersing each component constituting the polymer composition in a solvent may follow a conventional method. Specifically, stirring using a stirrer and a magnetic stirrer, a high-speed homogenizer, a disper, a planetary stirrer, a twin-screw stirrer, a ball mill, a three-roll, etc. can be used. Further, after each component is dissolved or dispersed in a solvent, it may be filtered using, for example, a filter having a pore size of about 0.5 μm.

<Photosensitive agent>
A photosensitizer is a compound that can cause a chemical reaction when irradiated with radiation such as ultraviolet rays or electron beams. The photosensitive agent is preferably one that can control the alkali solubility of the resin film formed from the polymer composition, and it is particularly preferable to use a photoacid generator.

  Such a photosensitizer is not particularly limited and includes, for example, acetophenone compounds, triarylsulfonium salts, azide compounds such as quinonediazide compounds, and the like, preferably azide compounds, and more preferably quinonediazide compounds. preferable.

  There is no restriction | limiting in particular as a quinonediazide compound, For example, the ester compound of the compound which has a quinonediazidesulfonic acid halide and a phenolic hydroxyl group can be used. Specific examples of the quinonediazide sulfonic acid halide include 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-benzoquinonediazide-5-sulfonic acid chloride, and the like. Is mentioned. Representative examples of the compound having a phenolic hydroxyl group include 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 ′-[1- [4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, and the like. Other compounds having a phenolic hydroxyl group include 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2-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, novolac resin oligomer, phenolic And an oligomer obtained by copolymerizing a compound having one or more hydroxyl groups with dicyclopentadiene.

In addition to quinonediazide compounds, photoacid generators include onium salts, halogenated organic compounds, α, α′-bis (sulfonyl) diazomethane compounds, α-carbonyl-α′-sulfonyldiazomethane compounds, sulfone compounds, Known compounds such as organic acid ester compounds, organic acid amide compounds, and organic acid imide compounds can be used.
These can also be used individually by 1 type and can also be used in combination of 2 or more type.

  The content of the photosensitizer in the polymer composition of the present invention is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, particularly preferably 25 parts by mass or more, and 100 parts by mass with respect to 100 parts by mass of the polymer. Part or less, more preferably 70 parts by weight or less, and particularly preferably 50 parts by weight or less. When the content of the photosensitizer in the polymer composition of the present invention is 10 parts by mass or more with respect to 100 parts by mass of the polymer, the solubility of the polymer in the exposed area in the exposed region by irradiation with actinic radiation. Is sufficiently increased, and the occurrence of development residue can be suppressed. When the amount is 100 parts by mass or less, the solubility of the polymer in the unexposed region in the developer is not increased, and the resolution is excellent. Pattern shapes can be formed.

<Other ingredients>
In addition, the polymer composition of the present invention may be a compound having an acidic group or a heat-latent acidic group, a surfactant, a sensitizer, a light stabilizer, as long as the effect of the present invention is not inhibited. Other compounding agents such as antifoaming agents, pigments, dyes, fillers and the like may be contained. Among these, for example, as the compound having an acidic group or a heat-latent acidic group, those described in JP-A-2014-29766 can be used, and surfactants, sensitizers, photostabilizers, and the like can be used. As the agent, those described in JP 2011-75609 A can be used.

<Preparation method>
The preparation method of the polymer composition of this invention is not specifically limited, What is necessary is just to mix each component which comprises a polymer 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 polymer composition in a solvent. Thereby, the polymer composition is obtained in the form of a solution or a dispersion.

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 Examples and Comparative Examples, resins A to C were prepared by the following methods, and tensile elongation, tensile elastic modulus, and developability were measured and evaluated by the following methods.

次に、テトラシクロ［６．２．１．１^３，６．０^２，７］ドデカ−９−エン−４−カルボン酸５１．３部、４−フェニル−４−アザトリシクロ［５．２．１．０^２，６］デカ−８−エン−３，５−ジオン４０．１部、ユニオックスＡＡ−８００：８．６部、（１，３−ジメシチルイミダゾリン−２−イリデン）（トリシクロヘキシルホスフィン）ベンジリデンルテニウムジクロリド（Ｏｒｇ．Ｌｅｔｔ．，第１巻，９５３頁，１９９９年に記載された方法で合成した）０．０７部、およびテトラヒドロフラン４００部を、窒素置換したガラス製耐圧反応器に仕込み、５０℃にて２時間撹拌して共重合することにより、共重合体Ａ溶液を得た。 Example 1
<Preparation of Resin A (hydrogenated product of copolymer A of cyclic olefin monomer and polyethylene glycol diallyl ether monomer)>
[Preparation of copolymer A]
First, (i) tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylic acid, and (ii) 4-phenyl-4-azatricyclo [5.2.1.0 ^2,6 ] deca represented by the following structural formula (Y) -8-ene-3,5-dione and (iii) polyethylene glycol diallyl ether represented by the following general formula (b) (“trade name: UNIOX AA-800 (where n is 16 in the formula (b)) Prepared by NOF Corporation))).

Next, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylic acid 51.3 parts, 4-phenyl-4-azatricyclo [5.2.1.0 ^2,6 ] dec-8-ene-3,5-dione 40.1 parts, UNIOX AA-800: 8.6 parts, (1,3-dimesityrylimidazoline-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride (Org. Lett., Vol. 1, page 953) 0.07 parts synthesized by the method described in 1999) and 400 parts of tetrahydrofuran were charged into a nitrogen pressure-replaced glass pressure-resistant reactor, and stirred at 50 ° C. for 2 hours to carry out copolymerization. A polymer A solution was obtained.

[Hydrogenation (hydrogenation) of copolymer A]
The obtained copolymer A solution was put into an autoclave and stirred for 1 hour at 150 ° C. and a hydrogen pressure of 5.5 MPa to conduct a hydrogenation reaction. The resulting solution was poured into a large amount of normal hexane. The precipitated solid is collected by filtration and vacuum-dried at 120 ° C. for 16 hours, whereby the structural unit represented by the following general formula (IV), the structural unit represented by the following general formula (V), and the following general formula Resin A having the structural unit represented by (h) was obtained.
Resin A had a polystyrene-reduced weight average molecular weight (Mw) of 18700 by gel permeation chromatography (GPC), and the hydrogenation rate measured by ¹ H-NMR was 99%. The ratio of “the structural unit represented by the following general formula (h) derived from the polyethylene glycol diallyl ether monomer represented by the general formula (b)” in all the structural units in the resin A was 8.3% by mass.

次に、テトラシクロ［６．２．１．１^３，６．０^２，７］ドデカ−９−エン−４−カルボン酸の量を４４．１部に変え、４−フェニル−４−アザトリシクロ［５．２．１．０^２，６］デカ−８−エン−３，５−ジオンの量を３４．４部に変え、ユニオックスＡＡ−８００：８．６部をユニオックスＰＫＡ−５００５：２１．５部に代えたこと以外は、実施例１と同様にして共重合することにより、共重合体Ｂ溶液を得た。 (Example 2)
<Preparation of resin B (hydrogenated product of copolymer B of cyclic olefin monomer and polyethylene glycol monoallyl ether monomer)>
[Preparation of copolymer B]
First, (i) tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylic acid, and (ii) 4-phenyl-4-azatricyclo [5.2.1.0 ^2,6 ] deca represented by the above structural formula (Y). -8-ene-3,5-dione, and (iii) a polyethylene glycol monoallyl ether monomer represented by the following general formula (c) (“trade name: UNIOX PKA— wherein m in the formula (c) is 33” 5005 (manufactured by NOF Corporation) ").

Next, tetracyclo [6.2.1.1 ^3,6 . The amount of 0 ^2,7 ] dodec-9-ene-4-carboxylic acid was changed to 44.1 parts and 4-phenyl-4-azatricyclo [5.2.1.0 ^2,6 ] dec-8-ene- Example 1 except that the amount of 3,5-dione was changed to 34.4 parts and UNIOX AA-800: 8.6 parts were replaced by UNIOX PKA-5005: 21.5 parts. Copolymer B solution was obtained by copolymerization.

[Hydrogenation of copolymer B (hydrogenation)]
The obtained copolymer B solution was hydrogenated (hydrogenated) in the same manner as in Example 1 to obtain a structural unit represented by the above general formula (IV), represented by the above general formula (V). And a resin B having a structural unit represented by the following general formula (i).
The obtained resin B had a polystyrene-reduced weight average molecular weight (Mw) of 30500 by gel permeation chromatography (GPC), and the hydrogenation rate measured by ¹ H-NMR was 99%. The ratio of “the polyethylene glycol monoallyl ether monomer structural unit represented by the following general formula (i) derived from the polyethylene glycol monoallyl ether monomer represented by the following general formula (c)” in all the structural units in the resin B is 21. It was 3 mass%.

(Comparative Example 1)
<Preparation of Resin C>
[Preparation of copolymer C]
First, (i) tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylic acid, and (ii) 4-phenyl-4-azatricyclo [5.2.1.0 ^2,6 ] deca represented by the above structural formula (Y). -8-ene-3,5-dione and (iii) 1-hexene (manufacturing company name: Tokyo Chemical Industry Co., Ltd., trade name: 1-hexene) were prepared.
Next, tetracyclo [6.2.1.1 ^3,6 . The amount of 0 ^2,7 ] dodec-9-ene-4-carboxylic acid was changed to 56.1 parts and 4-phenyl-4-azatricyclo [5.2.1.0 ^2,6 ] dec-8-ene- Copolymerization was carried out in the same manner as in Example 1 except that the amount of 3,5-dione was changed to 43.8 parts and UNIOX AA-800: 8.6 parts were replaced with 1-hexene: 0.8 parts. As a result, a copolymer C solution was obtained.

[Hydrogenation of copolymer C (hydrogenation)]
The obtained copolymer C solution was hydrogenated (hydrogenated) in the same manner as in Example 1 to express the structural unit represented by the general formula (IV) and the general formula (V). Resin C having a structural unit was obtained.
The obtained resin C had a polystyrene-reduced weight average molecular weight (Mw) by gel permeation chromatography (GPC) of 30700, and the hydrogenation rate measured by ¹ H-NMR was 99%.

<Tensile elongation, tensile modulus>
Using a sputtering apparatus, the polymer composition prepared in each Example and each Comparative Example was spin-coated on a silicon wafer on which an aluminum thin film was formed to a thickness of 100 nm, and then at 120 ° C. using a hot plate. By heating for 2 minutes and then curing at 180 ° C. for 60 minutes under a nitrogen atmosphere, a 10 μm-thick resin film was formed to obtain a laminate. And after cutting the obtained laminated body into a predetermined magnitude | size, the aluminum thin film was dissolved and peeled in 1 mol / L hydrochloric acid aqueous solution, and the resin film was obtained by drying the peeled film. And about the obtained resin film, the test piece (5 mm x 50 mm) was cut out, the tensile elongation and the tensile elasticity modulus were measured by performing a tensile test with the following procedures about this test piece. That is, by using an autograph (manufactured by Shimadzu Corporation, AGS-5kNG), a tensile test was performed under the conditions of a distance between chucks of 20 mm, a tensile speed of 2 mm / min, and a measurement temperature of 23 ° C. (%) And tensile modulus (GPa) were measured. In addition, all the characteristics are average values of the values measured for each test piece after cutting out five test pieces from each of the resin films.
The tensile modulus (GPa) was evaluated according to the following evaluation criteria. Here, the lower the tensile elastic modulus, the more preferable it is when used as a resist, since the occurrence of warpage after baking can be suppressed.
[Evaluation criteria for tensile modulus]
A: Tensile modulus is less than 2 GPa B: Tensile modulus is 2 GPa or more, less than 2.2 GPa C: Tensile modulus is 2.2 GPa or more

<Developability>
A polymer composition prepared in each of Examples and Comparative Examples was spin coated on a silicon wafer, and then pre-baked at 120 ° C. for 2 minutes using a hot plate to form a resin film having a thickness of 3 μm. Next, exposure was performed at 400 mJ / cm ² using a high-pressure mercury lamp that emits light with wavelengths of g-line (436 nm), h-line (405 nm), and i-line (365 nm). Then, the exposed sample was immersed in a 2.38% tetramethylammonium hydroxide aqueous solution (alkaline developer) at 23 ° C. for 3 minutes, rinsed with ultrapure water for 30 seconds, and the surface state of the developed sample was changed. Visual observation was performed, and developability was evaluated according to the following criteria. A resin film that does not dissolve or swell does not have excellent developability as a positive resin film.
A: The resin film was completely dissolved.
C: The resin film was not dissolved at all or was swollen.

(Example 3)
100 parts of resin A obtained in Example 1, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) as a photosensitizer And 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2 mol) (manufacturer name: Toyo Gosei Co., Ltd., trade name: TS200) 30 parts, as a crosslinking agent, butanetetracarboxylic acid tetra (3,3) 4-Epoxycyclohexylmethyl) -modified ε-caprolactone (manufacturer name: Daicel Corporation, trade name: Epolide GT401) 30 parts, and 300 parts of cyclopentanone as a solvent were mixed and dissolved at 23 ° C. A polymer composition was prepared by filtration through a 0.45 μm polytetrafluoroethylene filter. Using the prepared polymer composition, the tensile elongation, tensile elastic modulus, and developability were measured or evaluated. The results are shown in Table 1.

Example 4
In Example 3, a polymer composition was prepared in the same manner as in Example 3 except that Resin B was used instead of Resin A, and measured for tensile elongation, tensile elastic modulus, and developability. Thorough evaluation. The results are shown in Table 1.

(Comparative Example 2)
In Example 3, a polymer composition was prepared in the same manner as in Example 3 except that Resin C was used instead of Resin A, and measured for tensile elongation, tensile elastic modulus, and developability. Thorough evaluation. The results are shown in Table 1.

(Comparative Example 3)
In Comparative Example 2, instead of using only resin C as the polymer, resin C and polyethylene glycol (PEG) (“trade name: polyethylene glycol 1,540 (manufactured by Wako Pure Chemical Industries, Ltd., average molecular weight 1500)”) were used. A polymer composition was prepared in the same manner as in Comparative Example 2 except that it was used in the proportions shown in Table 1, and the tensile elongation, tensile elastic modulus, and developability were measured or evaluated. The results are shown in Table 1.

  In Table 1, “PEG” represents polyethylene glycol (manufacturer name: Wako Pure Chemical Industries, Ltd., trade name: polyethylene glycol 1,540), and “photoacid generator” as a photosensitizer is 4 , 4 ′-[1- [4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2 mol) ) And a condensate (manufacturer name: Toyo Gosei Kogyo Co., Ltd., trade name: TS200). Caprolactone (manufacturer name: Daicel Corporation, trade name: Epolide GT401), “solvent” is cyclopentanone (manufacturer name: Kyocera Chemical Industry Co., Ltd., product name: show the cyclopentanone).

From Table 1, resin A having a structural unit (A) derived from a cyclic olefin monomer, a structural unit (B) derived from a polyethylene glycol diallyl ether monomer and / or a structural unit (C) derived from a polyethylene glycol monoallyl ether monomer, and Resin films prepared using B (Examples 3 and 4) were prepared from resin C having no structural unit (B) derived from a polyethylene glycol diallyl ether monomer and no structural unit (C) derived from a polyethylene glycol monoallyl ether monomer. It was found that the tensile elastic modulus was lower than that of the resin films produced by using (Comparative Examples 2 and 3), and the developability and tensile elongation were excellent.
Furthermore, from Table 1, the resin film (Example 4) produced using the resin B having a weight average molecular weight of 30500 is more than the resin film (Example 3) produced using the resin A having a weight average molecular weight of 18700. It was found that the tensile elongation was excellent.
Further, from Table 1, the resin film produced using resin C and polyethylene glycol (PEG) (Comparative Example 3) has a lower tensile elastic modulus than the resin film produced using only resin C (Comparative Example 2). It turned out that it was not enough.

  According to the polymer and polymer composition of the present invention, it is possible to provide a resin film having a low tensile elastic modulus and excellent developability and tensile elongation.

Claims (11)

A structural unit (A) represented by the following general formula (I);
A polymer having a structural unit (B) represented by the following general formula (II) and / or a structural unit (C) represented by the following general formula (III).

[In Formula (I), X and Y each independently represent a hydrogen atom or an organic group, and may be bonded to each other to form a ring. ]

[In Formula (II), R _a represents an alkylene group having 2 to 4 carbon atoms, and n is an integer of 2 to 100. In addition, several _Ra may mutually be the same and each may differ. ]

[In the formula (III), R _b represents an alkylene group having 2 to 4 carbon atoms, R ₁ represents a hydrogen atom or an alkyl group, and m is an integer of 2 to 100. In addition, several _Rb may mutually be the same and each may differ. ] Wherein _{R a is, -CH 2 -CH 2 -, -} CH 2 -C (CH 3) H-, _{or, -C (CH 3) H-} CH 2 - represents a polymer of claim 1. Wherein _{R b is, -CH 2 -CH 2 -, -} CH 2 -C (CH 3) H-, or _{-C (CH 3) H-CH} 2 - represents a polymer according to claim 1 or 2 . The polymer according to any one of claims 1 to 3, wherein R ₁ represents a hydrogen atom, a methyl group, or an n-butyl group.   The polymer according to any one of claims 1 to 4, wherein the weight average molecular weight is from 5,000 to 50,000.   The weight according to any one of claims 1 to 5, wherein a total ratio of the structural unit (B) and the structural unit (C) in all the structural units in the polymer is 5% by mass or more and 50% by mass or less. Coalescence.   The polymer according to any one of claims 1 to 6, wherein the structural unit (A) has a polar group.   The polymer according to any one of claims 1 to 7, wherein the structural unit (A) includes a structural unit A1 having a protic polar group and / or a structural unit A2 having a polar group other than a protic polar group. The structural unit (A) includes the structural unit (D) represented by the following general formula (IV) and / or the structural unit (E) represented by the following general formula (V). The polymer in any one.

  A polymer composition comprising the polymer according to claim 1, a crosslinking agent, and a solvent.   The polymer composition according to claim 10, further comprising a photosensitizer.