JP2014149477A - Radiation-sensitive resin compositions and electronic components - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide radiation-sensitive resin compositions which have excellent storage stability and high exposure sensitivity and can provide a resin film having high transparency even after firing in an oxidizing atmosphere.SOLUTION: Provided is a radiation-sensitive resin composition comprising a binder resin (A), a radiation-sensitive compound (B), and an antioxidant (C) represented by the specified general formula (1). (In the specified general formula (1), Ris a hydrogen atom or a C1-C9 alkyl group that may have a substituent.)

Description

  The present invention relates to a radiation-sensitive resin composition and an electronic component including a resin film made of the radiation-sensitive resin composition. More specifically, the present invention is excellent in storage stability, high exposure sensitivity, and fired in an oxidizing atmosphere. The present invention relates to a radiation sensitive resin composition capable of providing a resin film having high transparency later and an electronic component including a resin film made of the radiation sensitive resin composition.

  Various display elements such as organic EL elements and liquid crystal display elements, integrated circuit elements, solid-state imaging elements, color filters, black matrices, and other electronic parts are provided with protective films, element surfaces and wiring to prevent their deterioration and damage. Various resin films are provided as a planarization film for planarization, an electrical insulation film for maintaining electrical insulation, and the like. In addition, the organic EL element is provided with a resin film as a pixel separation film in order to separate the light-emitting body portion. Further, in an element such as a display element for thin film transistor type liquid crystal or an integrated circuit element, the organic EL element is layered. A resin film as an interlayer insulating film is provided to insulate between the arranged wirings.

  Conventionally, thermosetting resin materials such as epoxy resins have been widely used as resin materials for forming these resin films. In recent years, with the increase in the density of wiring and devices, development of new resin materials excellent in electrical characteristics such as low dielectric properties has been demanded for these resin materials.

  In order to meet these requirements, for example, Patent Document 1 discloses a radiation-sensitive resin composition comprising a cyclic olefin polymer, a crosslinking agent, a radiation-sensitive compound, a phenol-based antioxidant and a non-phenolic antioxidant. Things are disclosed. However, according to the radiation-sensitive resin composition described in Patent Document 1, although a resin film having high transparency can be obtained even after baking in an oxidizing atmosphere, the obtained resin film has an exposure sensitivity to radiation. Therefore, improvement has been desired from the viewpoint of improving productivity.

JP 2005-292278 A

  The present invention provides a radiation-sensitive resin composition having excellent storage stability, high exposure sensitivity, and capable of providing a resin film having high transparency even after baking in an oxidizing atmosphere, and such radiation-sensitive resin. It aims at providing an electronic component provided with the resin film which consists of a resin composition.

  As a result of intensive studies to achieve the above object, the present inventors have found that the above object can be achieved by blending a specific antioxidant containing sulfur together with a binder resin and a radiation sensitive compound, The present invention has been completed.

（上記一般式（１）中、Ｒ^１は、水素原子又は置換基を有していてもよい炭素数１〜９のアルキル基である。）
〔２〕架橋剤（Ｄ）をさらに含有する前記〔１〕に記載の感放射線樹脂組成物、
〔３〕酸性基又は熱潜在性酸性基を有する化合物（Ｅ）をさらに含有する前記〔１〕又は〔２〕に記載の感放射線樹脂組成物、
〔４〕前記〔１〕〜〔３〕のいずれかに記載の感放射線樹脂組成物からなる樹脂膜を備える電子部品、ならびに、
〔５〕前記感放射線樹脂組成物からなる樹脂膜を形成し、前記樹脂膜をパターン化した後に、酸化雰囲気で焼成する工程を経て製造される前記〔４〕に記載の電子部品、
が提供される。 That is, according to the present invention,
[1] A radiation-sensitive resin composition comprising a binder resin (A), a radiation-sensitive compound (B), and an antioxidant (C) represented by the following general formula (1):

(In the general formula (1), R ¹ is a hydrogen atom or an alkyl group having 1 to 9 carbon atoms which may have a substituent.)
[2] The radiation sensitive resin composition according to [1], further including a crosslinking agent (D),
[3] The radiation-sensitive resin composition according to [1] or [2], further including a compound (E) having an acidic group or a heat-latent acidic group,
[4] An electronic component comprising a resin film comprising the radiation-sensitive resin composition according to any one of [1] to [3], and
[5] The electronic component according to [4], wherein a resin film made of the radiation-sensitive resin composition is formed, the resin film is patterned, and then manufactured through a step of firing in an oxidizing atmosphere.
Is provided.

  According to the present invention, a radiation-sensitive resin composition that is excellent in storage stability, has high exposure sensitivity, and can provide a resin film having high transparency even after baking in an oxidizing atmosphere, and the radiation-sensitive resin An electronic component including a resin film made of the composition can be provided.

  The radiation sensitive resin composition of the present invention comprises a binder resin (A), a radiation sensitive compound (B), and an antioxidant (C) represented by the general formula (1) described later.

(Binder resin (A))
Although it does not specifically limit as binder resin (A) used by this invention, The cyclic olefin polymer (A1), acrylic resin (A2), polyimide (A3), cardo resin (A4), or polysiloxane which has a protic polar group (A5) is preferred, and among these, a cyclic olefin polymer (A1) having a protic polar group is particularly preferred.
These binder resins (A) may be used alone or in combination of two or more.

  The cyclic olefin polymer (A1) having a protic polar group (hereinafter simply referred to as “cyclic olefin polymer (A1)”) is a polymer of one or more cyclic olefin monomers, or 1 Or a copolymer of two or more cyclic olefin monomers and a monomer copolymerizable therewith. In the present invention, a monomer for forming the cyclic olefin polymer (A1). It is preferable to use a cyclic olefin monomer (a) having at least a protic polar group.

  Here, the protic polar group refers to a group containing an atom 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.
In the present invention, the number of protic polar groups bonded to the cyclic olefin resin having a protic polar group is not particularly limited, and different types of protic polar groups may be included.

Specific examples of the cyclic olefin monomer (a) having a protic polar group (hereinafter, appropriately referred to as “monomer (a)”) include 2-hydroxycarbonylbicyclo [2.2.1] hept- 5-ene, 2-methyl-2-hydroxycarbonylbicyclo [2.2.1] hept-5-ene, 2-carboxymethyl-2-hydroxycarbonylbicyclo [2.2.1] hept-5-ene, 2 -Hydroxycarbonyl-2-methoxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-ethoxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxy Carbonyl-2-propoxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-butoxycarbonyl Tyrbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-pentyloxycarbonylmethyl bicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-hexyloxycarbonylmethyl Bicyclo [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-hydroxyca Bonyl-2-benzyloxycarbonylmethylbicyclo [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-pentyloxycarbonylbi Cyclo [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-hydroxyethoxycarbonylbi Chlo [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, 2-hydroxycarbonyltricyclo [5.2.1.0 ^2,6 ] Deca-3,8-diene, 4-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-methyl-4-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4,5-dihydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-carboxymethyl-4-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, N- (hydroxycarbonylmethyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (hydroxycarbonylethyl) bicyclo [2 2.1] hept-5-ene-2,3-dicarboximide, N- (hydroxycarbonylpentyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (Dihydroxycarbonylethyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (dihydroxycarbonylpropyl) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (hydroxycarbonylphenethyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2- ( -Hydroxyphenyl) -1- (hydroxycarbonyl) ethyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (hydroxycarbonylphenyl) bicyclo [2.2.1] Carboxy group-containing cyclic olefins such as hept-5-ene-2,3-dicarboximide; 2- (4-hydroxyphenyl) bicyclo [2.2.1] hept-5-ene, 2-methyl-2- ( 4-hydroxyphenyl) bicyclo [2.2.1] hept-5-ene, 4- (4-hydroxyphenyl) tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-methyl-4- (4-hydroxyphenyl) tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 2-hydroxybicyclo [2.2.1] hept-5-ene, 2-hydroxymethylbicyclo [2.2.1] hept-5-ene, 2-hydroxyethyl Bicyclo [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-trifluoro Mechi 3,3,3-trifluoropropyl) bicyclo [2.2.1] hept-5-ene, 3-hydroxy-tricyclo [5.2.1.0 ^{2, 6]} deca-4,8-diene, 3-hydroxymethyltricyclo [5.2.1.0 ^2,6 ] deca-4,8-diene, 4-hydroxytetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-hydroxymethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4,5-dihydroxymethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4- (hydroxyethoxycarbonyl) tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-methyl-4- (hydroxyethoxycarbonyl) tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, N- (hydroxyethyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (hydroxyphenyl) bicyclo [2.2 .1] Hydroxyl-containing cyclic olefins such as hept-5-ene-2,3-dicarboximide and the like. Among these, a carboxy group-containing cyclic olefin is preferable from the viewpoint that the obtained resin film has high adhesion, and 4-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene is particularly preferred. These monomers (a) may be used alone or in combination of two or more.

  The content ratio of the monomer (a) unit in the cyclic olefin polymer (A1) is preferably 10 to 90 mol%, preferably 20 to 80 mol%, more preferably relative to the total monomer units. Is 30-70 mol%. If the content ratio of the monomer (a) unit is too small, the radiation sensitivity may be insufficient or a dissolution residue may be generated during development. If it is too much, the cyclic olefin polymer (A1). There is a possibility that the solubility in the polar solvent becomes insufficient.

  The cyclic olefin polymer (A1) used in the present invention is obtained by copolymerizing a cyclic olefin monomer (a) having a protic polar group and a monomer (b) copolymerizable therewith. It may be a copolymer. Examples of such copolymerizable monomers include cyclic olefin monomers (b1) having polar groups other than protic polar groups, cyclic olefin monomers having no polar groups (b2), and cyclic olefins. Monomer (b3) (hereinafter referred to as “monomer (b1)”, “monomer (b2)”, “monomer (b3)” as appropriate).

  Examples of the cyclic olefin monomer (b1) having a polar group other than the protic polar group include N-substituted imide groups, ester groups, cyano groups, acid anhydride groups, and cyclic olefins having a halogen atom.

（上記一般式（２）中、Ｒ^２は水素原子もしくは炭素数１〜１６のアルキル基又はアリール基を表す。ｎは１ないし２の整数を表す。）

（上記一般式（３）中、Ｒ^３は炭素数１〜３の２価のアルキレン基、Ｒ^４は、炭素数１〜１０の１価のアルキル基、又は、炭素数１〜１０の１価のハロゲン化アルキル基を表す。） Examples of the cyclic olefin having an N-substituted imide group include a monomer represented by the following general formula (2) or a monomer represented by the following general formula (3).

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

(In the general formula (3), R ³ is a divalent alkylene group having 1 to ³ carbon atoms, R ⁴ is a monovalent alkyl group having 1 to 10 carbon atoms, or monovalent having 1 to 10 carbon atoms. Represents a halogenated alkyl group.)

In the general formula (2), R ² is an alkyl group having 1 to 16 carbon atoms or an aryl group. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, linear alkyl groups such as n-pentadecyl group and n-hexadecyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group Ring such as a group, norbornyl group, bornyl group, isobornyl group, decahydronaphthyl group, tricyclodecanyl group, adamantyl group, etc. Alkyl group; 2-propyl group, 2-butyl group, 2-methyl-1-propyl group, 2-methyl-2-propyl group, 1-methylbutyl group, 2-methylbutyl group, 1-methylpentyl group, 1- And branched alkyl groups such as ethylbutyl group, 2-methylhexyl group, 2-ethylhexyl group, 4-methylheptyl group, 1-methylnonyl group, 1-methyltridecyl group, 1-methyltetradecyl group, and the like. Specific examples of the aryl group include a benzyl group. Among these, since it is excellent in heat resistance and solubility in a polar solvent, a C6-C14 alkyl group and an aryl group are preferable, and a C6-C10 alkyl group and an aryl group are more preferable. When the carbon number is 4 or less, the solubility in a polar solvent is poor, when the carbon number is 17 or more, the heat resistance is poor, and when the resin film is patterned, the pattern is lost by melting with heat. There is a problem.

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

On the other hand, in the above general formula (3), R ³ is a divalent alkylene group having 1 to ³ carbon atoms. Examples of the divalent alkylene group having 1 to 3 carbon atoms include a methylene group, an ethylene group, a propylene group, and An isopropylene group is mentioned. Among these, a methylene group and an ethylene group are preferable because of good polymerization activity.

In the general formula (3), R ⁴ is a monovalent alkyl group having 1 to 10 carbon atoms or a monovalent halogenated alkyl group having 1 to 10 carbon atoms. Examples of the monovalent alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, hexyl group, and cyclohexyl group. . Examples of the monovalent halogenated alkyl group having 1 to 10 carbon atoms include a fluoromethyl group, a chloromethyl group, a bromomethyl group, a difluoromethyl group, a dichloromethyl group, a difluoromethyl group, a trifluoromethyl group, a trichloromethyl group, Examples include 2,2,2-trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, perfluorobutyl group, and perfluoropentyl group. Among these, because of excellent solubility in polar solvents, as is R ^4, a methyl group and an ethyl group are preferred.

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

Examples of the cyclic olefin having an ester group include 2-acetoxybicyclo [2.2.1] hept-5-ene, 2-acetoxymethylbicyclo [2.2.1] hept-5-ene, and 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-propoxyl Nilbicyclo [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- Trifluoroethoxycarbonyl) bicyclo [2.2.1] hept-5-ene, 2-methoxycarbonyltricyclo [5.2.1.0 ^2,6 ] dec-8-ene, 2-ethoxycarbonyltricyclo [ 5.2.1.0 ^2,6 ] dec-8-ene, 2-propoxycarbonyltricyclo [5.2.1.0 ^2,6 ] dec-8-ene, 4-acetoxytetracyclo [6.2 .1.1 ^3, . 0 ^2,7 ] dodec-9-ene, 4-methoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-ethoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-propoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-butoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-methyl-4-methoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-methyl-4-ethoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-methyl-4-propoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-methyl-4-butoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-methyl-4- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene and the like.

Examples of the cyclic olefin having a cyano group include 4-cyanotetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-methyl-4-cyanotetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4,5-dicyanotetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 2-cyanobicyclo [2.2.1] hept-5-ene, 2-methyl-2-cyanobicyclo [2.2.1] hept-5-ene, 2 , 3-dicyanobicyclo [2.2.1] hept-5-ene, and the like.

Examples of the cyclic olefin having an acid anhydride group include, for example, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4,5-dicarboxylic anhydride, bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic anhydride, 2-carboxymethyl-2- Hydroxycarbonylbicyclo [2.2.1] hept-5-ene anhydride, and the like.

Examples of the cyclic olefin having a halogen atom include 2-chlorobicyclo [2.2.1] hept-5-ene, 2-chloromethylbicyclo [2.2.1] hept-5-ene, 2- (chlorophenyl). ) Bicyclo [2.2.1] hept-5-ene, 4-chlorotetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-methyl-4-chlorotetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene and the like.

  These monomers (b1) may be used alone or in combination of two or more.

Examples of the cyclic olefin monomer (b2) having no polar group include bicyclo [2.2.1] hept-2-ene (also referred to as “norbornene”), 5-ethyl-bicyclo [2.2.1]. Hept-2-ene, 5-butyl-bicyclo [2.2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene, 5-methylidene-bicyclo [2. 2.1] hept-2-ene, 5-vinyl-bicyclo [2.2.1] hept-2-ene, tricyclo [5.2.1.0 ^2,6 ] deca-3,8-diene (conventional name: dicyclopentadiene), tetracyclo [10.2.1.0 ^2,11. 0 ^4,9 ] pentadeca-4,6,8,13-tetraene, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene (also referred to as “tetracyclododecene”), 9-methyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methylidene-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethylidene-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-vinyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-propenyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, pentacyclo [9.2.1.1 ^3,9 . 0 ^2,10 . 0 ^4,8 ] pentadeca-5,12-diene, cyclobutene, cyclopentene, cyclopentadiene, cyclohexene, cycloheptene, cyclooctene, cyclooctadiene, indene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H -Indene, 9-phenyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7] dodeca-4-ene, tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] tetradeca-3,5,7,12-tetraene, pentacyclo [9.2.1.1 ^3,9 . 0 ^2,10 . 0 ^4,8 ] pentadeca-12-ene and the like.
These monomers (b2) may be used alone or in combination of two or more.

Specific examples of the monomer (b3) other than the cyclic olefin include ethylene; propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3- Ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, An α-olefin having 2 to 20 carbon atoms such as 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene; Non-conjugated dienes such as hexadiene, 1,5-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, and derivatives thereof Body; and the like. Among these, α-olefin is preferable.
These monomers (b3) may be used alone or in combination of two or more.

  Among these monomers (b1) to (b3), the cyclic olefin monomer (b1) having a polar group other than the protic polar group is preferable from the viewpoint that the effect of the present invention becomes more remarkable. A cyclic olefin having an N-substituted imide group is particularly preferred.

  The content ratio of the copolymerizable monomer (b) unit in the cyclic olefin polymer (A1) is preferably 10 to 90 mol%, more preferably 20 to 80, based on all monomer units. It is mol%, More preferably, it is 30-70 mol%. It is. If the content of the copolymerizable monomer (b) is too small, the cyclic olefin polymer (A1) may have insufficient solubility in a polar solvent. May be insufficient, or a dissolution residue may be generated during development.

In addition, in this invention, it is good also as a cyclic olefin polymer (A1) by introduce | transducing a protic polar group into a cyclic olefin polymer which does not have a protic polar group using a well-known modifier.
The polymer having no protic polar group is obtained by polymerizing at least one of the above-described monomers (b1) and (b2) and an optional combination of the monomer (b3) as necessary. be able to.

As the modifier for introducing a protic polar group, a compound having a protic polar group and a reactive carbon-carbon unsaturated bond in one molecule is usually used.
Specific examples of such compounds include acrylic acid, methacrylic acid, angelic acid, tiglic acid, oleic acid, elaidic acid, erucic acid, brassic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, atropaic acid. Unsaturated carboxylic acids such as acids and cinnamic acids; allyl alcohol, methyl vinyl methanol, crotyl alcohol, methallyl alcohol, 1-phenylethen-1-ol, 2-propen-1-ol, 3-butene-1- All, 3-buten-2-ol, 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-buten-2-ol, 2-methyl- Saturation of 3-buten-1-ol, 4-penten-1-ol, 4-methyl-4-penten-1-ol, 2-hexen-1-ol, etc. Alcohol; and the like.
The modification reaction of the polymer using these modifiers may be performed according to a conventional method, and is usually performed in the presence of a radical generator.

  The cyclic olefin polymer (A1) used in the present invention may be a ring-opening polymer obtained by ring-opening polymerization of the above-described monomer, or an addition polymer obtained by addition polymerization of the above-described monomer. Although it may be a polymer, it is preferably a ring-opening polymer from the viewpoint that the effect of the present invention becomes more remarkable.

  The ring-opening polymer comprises a ring-opening metathesis polymerization of a cyclic olefin monomer having a protic polar group (a) and a copolymerizable monomer (b) used as necessary in the presence of a metathesis reaction catalyst. Can be manufactured. As a manufacturing method, the method etc. which are described in [0039]-[0079] of international publication 2010/110323 can be used, for example.

  The acrylic resin (A2) used in the present invention is not particularly limited, but is selected from carboxylic acid having an acrylic group, carboxylic acid anhydride having an acrylic group, or an epoxy group-containing acrylate compound and an oxetane group-containing acrylate compound. A homopolymer or copolymer having at least one essential component is preferred.

Specific examples of the carboxylic acid having an acrylic group include (meth) acrylic acid [meaning acrylic acid and / or methacrylic acid. The same applies to methyl (meth) acrylate. ], Crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, glutaconic acid, phthalic acid mono- (2-((meth) acryloyloxy) ethyl), N- (carboxyphenyl) maleimide, N- (carboxyphenyl) ) (Meth) acrylamide and the like.
Specific examples of the carboxylic acid anhydride having an acrylic group include maleic anhydride and citraconic anhydride.
Specific examples of the epoxy group-containing acrylate compound include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, acrylate 3,4. -Epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, acrylic acid- Examples include 3,4-epoxycyclohexylmethyl and 3,4-epoxycyclohexylmethyl methacrylate.
Specific examples of the oxetane group-containing acrylate compound include (meth) acrylic acid (3-methyloxetane-3-yl) methyl, (meth) acrylic acid (3-ethyloxetane-3-yl) methyl, and (meth) acrylic acid. (3-methyloxetane-3-yl) ethyl, (meth) acrylic acid (3-ethyloxetane-3-yl) ethyl, (meth) acrylic acid (3-chloromethyloxetane-3-yl) methyl, (meth) Acrylic acid (oxetane-2-yl) methyl, (meth) acrylic acid (2-methyloxetane-2-yl) methyl, (meth) acrylic acid (2-ethyloxetane-2-yl) methyl, (1-methyl- 1-oxetanyl-2-phenyl) -3- (meth) acrylate, (1-methyl-1-oxetanyl) -2-trifluoromethyl-3- (me ) Acrylate, and (1-methyl-1-oxetanyl) -4-trifluoromethyl-2- (meth) acrylate.
Of these, (meth) acrylic acid, maleic anhydride, glycidyl (meth) acrylate, methacrylic acid-6,7-epoxyheptyl, and the like are preferable.

  The acrylic resin (A2) is composed of at least one selected from unsaturated carboxylic acid, unsaturated carboxylic acid anhydride and epoxy group-containing unsaturated compound, and other acrylate monomers or copolymerizable monomers other than acrylate And a copolymer thereof.

Other acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl ( (Meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, ethylhexyl (meth) acrylate, nonyl (meth) Acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meta Acrylate, alkyl (meth) acrylate such as isostearyl (meth) acrylate; hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, Hydroxyalkyl (meth) acrylates such as 3-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; phenoxyalkyls such as phenoxyethyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate ( (Meth) acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) Acrylate, alkoxyalkyl (meth) acrylate such as 2-methoxybutyl (meth) acrylate; polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, Polyalkylene glycol (meth) acrylates such as nonylphenoxypolyethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate Cyclohexyl (meth) acrylate, 2- Methylcyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, tricyclo [ 5.2.1.0 ^{2, 6]} decan-8-yl (meth) acrylate, tricyclo [5.2.1.0 ^{2, 6]-3-decene-8-yl} (meth) acrylate, tricyclo [5 2.1.0 ^{2, 6} ] -3-decene-9-yl (meth) acrylate, bornyl (meth) acrylate, cycloalkyl (meth) acrylate such as isobornyl (meth) acrylate; phenyl (meth) acrylate, naphthyl (Meth) acrylate, biphenyl (meth) acrylate, benzyl (meth) acrylate , Tetrahydrofurfuryl (meth) acrylate, 5-tetrahydrofurfuryloxycarbonylpentyl (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, 2- (2-vinyloxyethoxy) (meth) acrylate ) Ethyl, 2- [tricyclo [5.2.1.0 ^{2, 6} ] decan-8-yloxy] ethyl (meth) acrylate, 2- [tricyclo [5.2.1.0 ^{2, 6} ] -3- Decene-8-yloxy] ethyl (meth) acrylate, 2- [tricyclo [5.2.1.0 ^{2, 6} ] -3-decene-9-yloxy] ethyl (meth) acrylate, γ-butyrolactone (meth) acrylate , Maleimide, N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-cyclohexylmaleimi N-benzylmaleimide, N-phenylmaleimide, N- (2,6-diethylphenyl) maleimide, N- (4-acetylphenyl) maleimide, N- (4-hydroxyphenyl) maleimide, N- (4-acetoxyphenyl) ) Maleimide, N- (4-dimethylamino-3,5-dinitrophenyl) maleimide, N- (1-anilinonaphthyl-4) maleimide, N- [4- (2-benzoxazolyl) phenyl] maleimide, N- (9-acridinyl) maleimide and the like.
Among these, methyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, tricyclo [5.2.1.0 ^{2, 6} Decan-8-yl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide and the like are preferable.

The copolymerizable monomer other than the acrylate is not particularly limited as long as it is a compound copolymerizable with the carboxylic acid having an acrylic group, a carboxylic acid anhydride having an acrylic group, or an epoxy group-containing acrylate compound. , Vinyl benzyl methyl ether, vinyl glycidyl ether, styrene, α-methyl styrene, vinyl toluene, indene, vinyl naphthalene, vinyl biphenyl, chlorostyrene, bromostyrene, chloromethyl styrene, p-tert-butoxystyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-acetoxystyrene, p-carboxystyrene, 4-hydroxyphenyl vinyl ketone, acrylonitrile, methacrylonitrile, (meth) acrylamide, 1,2-epoxy-4-vinyl Examples include radically polymerizable compounds such as rucyclohexane, isobutene, norbornene, butadiene, and isoprene.
These compounds may be used alone or in combination of two or more.
The monomer polymerization method may be in accordance with a conventional method, for example, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method or the like is employed.

  The polyimide (A3) used by this invention can be obtained by heat-processing the polyimide precursor obtained by making tetracarboxylic anhydride and diamine react. Examples of the precursor for obtaining polyimide include polyamic acid, polyamic acid ester, polyisoimide, and polyamic acid sulfonamide.

  The polyimide (A3) used in the present invention is synthesized by a known method. That is, a tetracarboxylic dianhydride and a diamine are selectively combined, and these are combined with N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, hexamethylphosphorotriamide, It is synthesized by a known method such as reacting in a polar solvent such as γ-butyrolactone or cyclopentanone.

  When superposing | polymerizing using diamine excessively, a carboxylic acid anhydride can be made to react with the terminal amino group of the produced | generated polyimide (A3), and a terminal amino group can be protected. Moreover, when superposing | polymerizing using tetracarboxylic anhydride excessively, an amine compound can be made to react with the terminal acid anhydride group of the produced | generated polyimide (A3), and a terminal acid anhydride group can also be protected.

  Examples of such carboxylic anhydrides include phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic acid Examples of amine compounds include anhydrides, itaconic anhydride, tetrahydrophthalic anhydride and the like. Examples of amine compounds include aniline, 2-hydroxyaniline, 3-hydroxyaniline, 4-hydroxyaniline, 2-ethynylaniline, 3-ethynylaniline, 4- And ethynylaniline.

The cardo resin (A4) used in the present invention is a resin having a cardo structure, that is, a skeleton structure in which two cyclic structures are bonded to a quaternary carbon atom constituting the cyclic structure. A common cardo structure is a fluorene ring bonded to a benzene ring.
Specific examples of the skeleton structure in which two cyclic structures are bonded to a quaternary carbon atom constituting the cyclic structure include a fluorene skeleton, a bisphenol fluorene skeleton, a bisaminophenyl fluorene skeleton, a fluorene skeleton having an epoxy group, and an acrylic group. And a fluorene skeleton having the same.
The cardo resin (A4) used in the present invention is formed by polymerizing a skeleton having the cardo structure by a reaction between functional groups bonded thereto. The cardo resin (A4) has a structure in which a main chain and bulky side chains are connected by one element (cardo structure), and has a ring structure in a direction substantially perpendicular to the main chain.

（上記一般式（４）中、ｎは０〜１０の整数である。） As an example of the cardo structure, an example of a cardo structure having an epoxy glycidyl ether structure is shown in the following general formula (4).

(In the general formula (4), n is an integer of 0 to 10.)

Monomers having a cardo structure include, for example, bis (glycidyloxyphenyl) fluorene type epoxy resin; condensate of bisphenol fluorene type epoxy resin and acrylic acid; 9,9-bis (4-hydroxyphenyl) fluorene, Cardio structure-containing bisphenols such as 9-bis (4-hydroxy-3-methylphenyl) fluorene; 9,9-bis (cyanoalkyl) fluorenes such as 9,9-bis (cyanomethyl) fluorene; -9,9-bis (aminoalkyl) fluorenes such as bis (3-aminopropyl) fluorene;
The cardo resin (A4) is a polymer obtained by polymerizing a monomer having a cardo structure, but may be a copolymer with other copolymerizable monomers.
The polymerization method of the monomer may be according to a conventional method, and for example, a ring-opening polymerization method or an addition polymerization method is employed.

Although it does not specifically limit as polysiloxane (A5) used by this invention, Preferably the polymer obtained by mixing and making 1 type (s) or 2 or more types of the organosilane represented by following General formula (5) become. Can be mentioned.
_{^{(R 5) m -Si- (OR}} 6) 4-m (5)

In the general formula (5), ^{R 5} is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having from 6 to 15 carbon atoms, more ^{R 5} each They may be the same or different. These alkyl groups, alkenyl groups, and aryl groups may all have a substituent or may be an unsubstituted form having no substituent, and are selected according to the characteristics of the composition. it can. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, n-decyl group, trifluoromethyl group, 2,2 , 2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 3-glycidoxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3-aminopropyl group, 3-mercaptopropyl Group, 3-isocyanatopropyl group. Specific examples of the alkenyl group include a vinyl group, a 3-acryloxypropyl group, and a 3-methacryloxypropyl group. Specific examples of the aryl group include phenyl group, tolyl group, p-hydroxyphenyl group, 1- (p-hydroxyphenyl) ethyl group, 2- (p-hydroxyphenyl) ethyl group, 4-hydroxy-5- (p -Hydroxyphenylcarbonyloxy) pentyl group and naphthyl group.

In the general formula (5), R ⁶ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and a plurality of R ⁶ May be the same or different. In addition, both of these alkyl groups and acyl groups may have a substituent or may be an unsubstituted form having no substituent, and can be selected according to the characteristics of the composition. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Specific examples of the acyl group include an acetyl group. Specific examples of the aryl group include a phenyl group.

  Further, in the above general formula (5), m is an integer of 0 to 3, tetrafunctional silane when m = 0, trifunctional silane when m = 1, and bifunctional when m = 2. When the functional silane, m = 3, it becomes a monofunctional silane.

Specific examples of the organosilane represented by the general formula (5) include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, and tetraphenoxysilane; methyltrimethoxysilane, methyltriethoxysilane, Methyltriisopropoxysilane, methyltrin-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltrin-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n- Butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3 Methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 1- (p-hydroxyphenyl) ) Ethyltrimethoxysilane, 2- (p-hydroxyphenyl) ethyltrimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxy Silane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltri Trifunctional silanes such as toxisilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, di-n-butyldimethoxy And bifunctional silanes such as silane and diphenyldimethoxysilane; monofunctional silanes such as trimethylmethoxysilane and tri-n-butylethoxysilane.
Of these organosilanes, trifunctional silanes are preferably used from the viewpoint of crack resistance and hardness of the resulting resin film. These organosilanes may be used alone or in combination of two or more.

  The polysiloxane (A5) used in the present invention is obtained by hydrolysis and partial condensation of the above-mentioned organosilane. A general method can be used for hydrolysis and partial condensation. For example, a solvent, water, and a catalyst as necessary are added to the mixture, and the mixture is heated and stirred. During stirring, if necessary, hydrolysis by-products (alcohols such as methanol) and condensation by-products (water) may be distilled off by distillation.

The weight average molecular weight (Mw) of the binder resin (A) used in the present invention is usually 1,000 to 1,000,000, preferably 1,500 to 100,000, more preferably 2,000 to 10. , 000.
The molecular weight distribution of the binder resin (A) is usually 4 or less, preferably 3 or less, and more preferably 2.5 or less, as a weight average molecular weight / number average molecular weight (Mw / Mn) ratio.
The weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) of the binder resin (A) are values obtained as polystyrene equivalent values by gel permeation chromatography (GPC) using a solvent such as tetrahydrofuran as an eluent. It is.

(Radiation sensitive compound (B))
The radiation sensitive compound (B) is a compound capable of causing a chemical reaction by irradiation with radiation such as ultraviolet rays and electron beams. In the present invention, the radiation sensitive compound (B) is preferably one that can control the alkali solubility of the resin film formed from the radiation sensitive resin composition, and it is particularly preferable to use a photoacid generator.

  Examples of such a radiation-sensitive compound (B) include azide compounds such as acetophenone compounds, triarylsulfonium salts, and quinonediazide compounds, with azide compounds being preferred, and quinonediazide compounds being particularly preferred.

  As the quinonediazide compound, for example, an ester compound of a quinonediazidesulfonic acid halide and a compound having a phenolic hydroxyl group can be used. Specific examples of the quinone diazide sulfonic acid halide include 1,2-naphthoquinone diazide-5-sulfonic acid chloride, 1,2-naphthoquinone diazide-4-sulfonic acid chloride, 1,2-benzoquinone diazide-5-sulfonic acid chloride, and the like. Can be mentioned. Typical 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-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 hydroxyl group Examples thereof include oligomers obtained by copolymerizing one or more compounds and 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 radiation-sensitive compounds can be used alone or in combination of two or more.

  The content of the radiation sensitive compound (B) in the radiation sensitive resin composition of the present invention is preferably 20 to 100 parts by weight, more preferably 25 to 70 parts by weight with respect to 100 parts by weight of the binder resin (A). Parts, more preferably 30 to 50 parts by weight. By setting the content of the radiation sensitive compound (B) within this range, the exposure sensitivity of the resin film obtained using the radiation sensitive resin composition of the present invention, shape retention after baking, and transparency are further improved. Can be.

(Antioxidant (C))
In addition to the binder resin (A) and the radiation sensitive compound (B) described above, the radiation sensitive resin composition of the present invention includes an antioxidant (C) represented by the following general formula (1) (hereinafter simply referred to as “oxidation”). Inhibitor (C) ”).

In the general formula (1), R ¹ is a hydrogen atom or an alkyl group having 1 to 9 carbon atoms which may have a substituent, and preferably has a hydrogen atom or a substituent. It is a C4-C8 alkyl group. In the present invention, by using a combination of the binder resin (A) and the radiation sensitive compound (B) described above and the antioxidant (C), the radiation sensitive resin composition of the present invention is excellent in storage stability, In addition, the obtained resin film can have high exposure sensitivity and high transparency even after baking in an oxidizing atmosphere.

Among the antioxidants (C) used in the present invention, for example, those in which R ¹ is water or an elementary atom include, for example, pentaerythritol tetrakis (6) represented by the following formula (6) commercially available as a reagent. 2-mercaptoacetate) can be used as it is. In addition, R ¹ is an optionally substituted alkyl group having 1 to 9 carbon atoms, for example, pentaerythritol tetrakis (2 represented by the following formula (6) commercially available as a reagent: - the mercaptoacetate) as a starting material, the thiolate of pentaerythritol tetrakis (2-mercaptoacetate), halides of alkane corresponding to R ¹ (R ^{1 X; X} is by reacting a halogen atom) and synthesized be able to.

Further, the antioxidant (C) used in the present invention contains four R ¹ in one molecule, but all four R ¹ may be the same, or Each may be different. For example, when a thiolate of pentaerythritol tetrakis (2-mercaptoacetate) and an alkane halide corresponding to R ¹ are reacted to obtain an antioxidant (C), the starting material pentaerythritol tetrakis ( among the thiol group of the 2-mercaptoacetate), while for some is substituted with R ^1, without being substituted with R ^1, which may thiol group remains. In such a case, a part of R ¹ existing in one molecule is a corresponding alkyl group, and the rest is a hydrogen atom.

  The content of the antioxidant (C) in the radiation-sensitive resin composition of the present invention is preferably 0.01 to 50 parts by weight, more preferably 1 to 100 parts by weight with respect to 100 parts by weight of the binder resin (A). 30 parts by weight, more preferably 1 to 20 parts by weight. By making content of antioxidant (C) into this range, the storage stability of the radiation sensitive resin composition of this invention, the exposure sensitivity at the time of setting it as a resin film, and transparency can be improved more appropriately.

  In the present invention, an antioxidant other than the antioxidant (C) may be used in combination with the antioxidant (C), and is not particularly limited. The phenolic antioxidants, phosphorus antioxidants, amine antioxidants, lactone antioxidants, etc. that are used in these polymers can be used, and among these, phenolic antioxidants are preferred. .

A conventionally well-known thing can be used as a phenolic antioxidant, for example, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2 , 4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate and the like, and JP-A No. 1-168633. Acrylate compounds described in Japanese Patent Publication No. 2; 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, octadecyl-3- (3,5- Di-t-butyl-4-hydroxyphenyl) propionate, 2,2′-methylene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidene-bis (6-t − Butyl-m-cresol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), bis (3-cyclohexyl-2-hydroxy-5-methylphenyl) methane, 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 1 , 1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], Triethylene glycol bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], 1,3,5, -trimethyl-2, , 6, -Tris (3'5'-di-t-butyl-4-hydroxybenzyl) benzene, tocopherol and other alkyl-substituted phenolic compounds; 6- (4-hydroxy-3,5-di-t-butylanilino) -2,4-bis-octylthio-1,3,5-triazine, 6- (4-hydroxy-3,5-dimethylanilino) -2,4-bis-octylthio-1,3,5-triazine, 6 -(4-Hydroxy-3-methyl-5-t-butylanilino) -2,4-bis-octylthio-1,3,5-triazine, 2-octylthio-4,6-bis- (3,5-di- and a triazine group-containing phenolic compound such as t-butyl-4-oxyanilino) -1,3,5-triazine. Among these, alkyl-substituted phenol compounds are preferable, and hindered phenol compounds and semi-hindered phenol compounds are more preferable.
These antioxidants can be used alone or in combination of two or more.

  In the present invention, the total content in the case of using an antioxidant other than the antioxidant (C) together with the antioxidant (C) is preferably 100 parts by weight of the binder resin (A). It is 0.01-30 weight part, More preferably, it is 0.1-20 weight part, More preferably, it is 1-10 weight part. By making these total content into this range, the storage stability of the radiation-sensitive resin composition of the present invention, the exposure sensitivity and the transparency when used as a resin film can be more appropriately increased.

(Crosslinking agent (D))
Moreover, in addition to each component mentioned above, the radiation sensitive resin composition of this invention may contain the crosslinking agent (D). The crosslinking agent (D) used in the present invention is one that forms a crosslinked structure between crosslinking agent molecules by heating, or that reacts with the binder resin (A) to form a crosslinked structure between resin molecules. Includes compounds having two or more reactive groups. Examples of such a reactive group include an amino group, a carboxy group, a hydroxyl group, an epoxy group, and an isocyanate group, more preferably an amino group, an epoxy group, and an isocyanate group, and particularly preferably an amino group and an epoxy group. .

  Although the molecular weight of a crosslinking agent (D) is not specifically limited, Usually, it is 100-100,000, Preferably it is 300-50,000, More preferably, it is 500-10,000. The crosslinking agent (D) can be used alone or in combination of two or more, and in particular, exposure of the resin film obtained using the radiation-sensitive resin composition of the present invention by using two or more in combination. Sensitivity, shape retention after firing, and transparency can be further improved.

  Specific examples of the crosslinking agent (D) include aliphatic polyamines such as hexamethylenediamine; aromatic polyamines such as 4,4′-diaminodiphenyl ether and diaminodiphenylsulfone; 2,6-bis (4′-azidobenzal) Azides such as cyclohexanone and 4,4′-diazidodiphenylsulfone; polyamides such as nylon, polyhexamethylenediamineterephthalamide and polyhexamethyleneisophthalamide; N, N, N ′, N ′, N ″, Melamines which may have a methylol group such as N ″-(hexaalkoxyalkyl) melamine or an imino group (trade names “Cymel 303, Cymel 325, Cymel 370, Cymel 232, Cymel 235, Cymel 272, Cymel 212, My Coat 506 "{End Cymel series, Mycoat series, etc. made by Ndustries Co., Ltd.]; even if it has a methylol group or imino group such as N, N ′, N ″, N ′ ″-(tetraalkoxyalkyl) glycoluril, etc. Good glycolurils (trade name “Cymel 1170” {Cytech series manufactured by Cytec Industries, Inc.}); acrylate compounds such as ethylene glycol di (meth) acrylate; hexamethylene diisocyanate polyisocyanate, isophorone diisocyanate polyisocyanate Isocyanate compounds such as tolylene diisocyanate polyisocyanate, hydrogenated diphenylmethane diisocyanate; 1,4-di- (hydroxymethyl) cyclohexane, 1,4-di- (hydroxymethyl) norbornane; , 4-trihydroxycyclohexane; bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, polyphenol type epoxy resin, cyclic aliphatic epoxy resin, aliphatic glycidyl ether, epoxy acrylate heavy And epoxy compounds such as coalescence;

  Specific examples of the epoxy compound include a trifunctional epoxy compound having a dicyclopentadiene skeleton (trade name “XD-1000”, manufactured by Nippon Kayaku Co., Ltd.), 2,2-bis (hydroxymethyl) 1-butanol. 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct (15-functional alicyclic epoxy resin having a cyclohexane skeleton and a terminal epoxy group, trade name “EHPE3150”, manufactured by Daicel Chemical Industries, Ltd.), epoxidation 3-cyclohexene-1,2-dicarboxylate bis (3-cyclohexenylmethyl) modified ε-caprolactone (aliphatic cyclic trifunctional epoxy resin, trade name “Epolide GT301”, manufactured by Daicel Chemical Industries), epoxidized butane Tetracarboxylic acid tetrakis (3-cyclohexenylmethyl) modified ε-caprolactone (fat Aliphatic cyclic tetrafunctional epoxy resin, trade name “Epolide GT401” manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate (trade name “Celoxide 2021”) , “Celoxide 2021P” manufactured by Daicel Chemical Industries, Ltd.), 1,2: 8,9-diepoxy limonene (trade name “Celoxide 3000” manufactured by Daicel Chemical Industries, Ltd.), 2- (3,4-epoxycyclohexyl) ethyl Epoxy compounds having an alicyclic structure such as trimethoxysilane (trade name “Z-6043”, manufactured by Toray Dow Corning);

  Aromatic amine type polyfunctional epoxy compound (trade name “H-434”, manufactured by Tohto Kasei Kogyo Co., Ltd.), isocyanuric acid tris (2,3-epoxypropyl) (polyfunctional epoxy compound having triazine skeleton, trade name “TEPIC” , Nissan Chemical Industries, Ltd.), cresol novolac type polyfunctional epoxy compound (trade name “EOCN-1020”, manufactured by Nippon Kayaku Co., Ltd.), phenol novolac type polyfunctional epoxy compound (Epicoat 152, 154, manufactured by Japan Epoxy Resin Co., Ltd.) , Polyfunctional epoxy compound having a naphthalene skeleton (trade name “HP-4700”, manufactured by DIC Corporation), chain alkyl polyfunctional epoxy compound (trade name “SR-TMP”, manufactured by Sakamoto Pharmaceutical Co., Ltd.), polyfunctional Epoxy polybutadiene (trade name “Epolide PB3600”, manufactured by Daicel Chemical Industries), Resin glycidyl polyether compound (trade name “SR-GLG”, Sakamoto Yakuhin Kogyo Co., Ltd.), diglycerin polyglycidyl ether compound (trade name “SR-DGE”, Sakamoto Yakuhin Kogyo Co., Ltd., polyglycerin polyglycidyl ether) Epoxy having no alicyclic structure such as a compound (trade name “SR-4GL”, manufactured by Sakamoto Pharmaceutical Co., Ltd.), glycidoxypropyltrimethylsilane (trade name “Z-6040”, manufactured by Toray Dow Corning) A compound;

  The content of the crosslinking agent (D) in the radiation-sensitive resin composition of the present invention is not particularly limited, taking into consideration the degree of heat resistance required for the resin film obtained using the radiation-sensitive resin composition of the present invention. However, it is preferably 5 to 80 parts by weight, more preferably 20 to 75 parts by weight, and further preferably 25 to 70 parts by weight with respect to 100 parts by weight of the binder resin (A). If the crosslinking agent (D) is too much or too little, the heat resistance tends to decrease.

(Compound (E) having an acidic group or a thermal latent acidic group)
Moreover, in addition to each component mentioned above, the radiation sensitive resin composition of this invention may contain the compound (E) which has an acidic group or a heat | fever latent acidic group. The compound having an acidic group or a thermal latent acidic group is not particularly limited as long as it has an acidic group or a thermal latent acidic group that generates an acidic group by heating, but preferably an aliphatic compound, an aromatic compound, Heterocyclic compounds, more preferably aromatic compounds and heterocyclic compounds.
These compounds having an acidic group or a heat-latent acidic group can be used alone or in combination of two or more. By blending the compound (E) having an acidic group or a heat-latent acidic group, the shape retention after firing of the resin film obtained using the radiation-sensitive resin composition of the present invention can be further enhanced.

The number of acidic groups in the compound having an acidic group is not particularly limited, but those having two or more acidic groups are preferable. The acidic groups may be the same as or different from each other.
The acidic group may be an acidic functional group, and specific examples thereof include strong acidic groups such as sulfonic acid group and phosphoric acid group; weak acidic groups such as carboxy group, thiol group and carboxymethylenethio group; Can be mentioned. Among these, a carboxy group, a thiol group or a carboxymethylenethio group is preferable, and a carboxy group is particularly preferable. Among these acidic groups, those having an acid dissociation constant pKa in the range of 3.5 to 5.0 are preferred. When there are two or more acidic groups, it is preferable that the first dissociation constant pKa1 is an acid dissociation constant and the first dissociation constant pKa1 is in the above range. The pKa is determined according to pKa = −logKa by measuring the acid dissociation constant Ka = [H ₃ O ⁺ ] [B ⁻ ] / [BH] under dilute aqueous solution conditions. Here, BH represents an organic acid, and B ⁻ represents a conjugate base of the organic acid.
In addition, the measuring method of pKa can calculate hydrogen ion concentration, for example using a pH meter, and can calculate from the density | concentration of a relevant substance, and hydrogen ion concentration.

Moreover, the compound which has an acidic group may have substituents other than an acidic group.
As such substituents, in addition to hydrocarbon groups such as alkyl groups and aryl groups, halogen atoms; alkoxy groups, aryloxy groups, acyloxy groups, heterocyclic oxy groups; substituted with alkyl groups, aryl groups, or heterocyclic groups Polar groups having no proton such as amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group; alkylthio group, arylthio group, heterocyclic thio group; Examples thereof include a hydrocarbon group substituted with a polar group having no proton.

  Specific examples of the compound (F) having such an acidic group include methanoic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, glycolic acid, Glyceric acid, ethanedioic acid (also called “oxalic acid”), propanedioic acid (also called “malonic acid”), butanedioic acid (also called “succinic acid”), pentanedioic acid, hexanedioic acid ( Also referred to as “adipic acid”), 1,2-cyclohexanedicarboxylic acid, 2-oxopropanoic acid, 2-hydroxybutanedioic acid, 2-hydroxypropanetricarboxylic acid, mercaptosuccinic acid, dimercaptosuccinic acid, 2,3-dimercapto -1-propanol, 1,2,3-trimercaptopropane, 2,3,4-trimercapto-1-butanol, 2,4-dimercap 1,3-butanediol, 1,3,4-trimercapto-2-butanol, 3,4-dimercapto-1,2-butanediol, aliphatic compounds such as 1,5-dimercapto-3-Chiapentan;

  Benzoic acid, p-hydroxybenzenecarboxylic acid, o-hydroxybenzenecarboxylic acid, 2-naphthalenecarboxylic acid, methylbenzoic acid, dimethylbenzoic acid, trimethylbenzoic acid, 3-phenylpropanoic acid, dihydroxybenzoic acid, dimethoxybenzoic acid, benzene -1,2-dicarboxylic acid (also referred to as “phthalic acid”), benzene-1,3-dicarboxylic acid (also referred to as “isophthalic acid”), benzene-1,4-dicarboxylic acid (also referred to as “terephthalic acid”) ), Benzene-1,2,3-tricarboxylic acid, benzene-1,2,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, benzenehexacarboxylic acid, biphenyl-2,2′-dicarboxylic acid 2- (carboxymethyl) benzoic acid, 3- (carboxymethyl) benzoic acid, 4- (carboxymethyl) benzoic acid Benzoic acid, 2- (carboxycarbonyl) benzoic acid, 3- (carboxycarbonyl) benzoic acid, 4- (carboxycarbonyl) benzoic acid, 2-mercaptobenzoic acid, 4-mercaptobenzoic acid, diphenolic acid, 2-mercapto -6-naphthalenecarboxylic acid, 2-mercapto-7-naphthalenecarboxylic acid, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,4-naphthalenedithiol, 1, 5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1 , 2,3-Tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene, 1,3,5-tris (mercapto) Aromatic compounds such as ethyl) benzene;

  Nicotinic acid, isonicotinic acid, 2-furoic acid, pyrrole-2,3-dicarboxylic acid, pyrrole-2,4-dicarboxylic acid, pyrrole-2,5-dicarboxylic acid, pyrrole-3,4-dicarboxylic acid, imidazole Five-membered nitrogen atoms such as 2,4-dicarboxylic acid, imidazole-2,5-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, pyrazole-3,5-dicarboxylic acid Heterocyclic compounds; thiophene-2,3-dicarboxylic acid, thiophene-2,4-dicarboxylic acid, thiophene-2,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, thiazole-2,4-dicarboxylic acid, thiazole -2,5-dicarboxylic acid, thiazole-4,5-dicarboxylic acid, isothiazole-3,4-dicarboxylic acid, isothiazole -3,5-dicarboxylic acid, 1,2,4-thiadiazole-2,5-dicarboxylic acid, 1,3,4-thiadiazole-2,5-dicarboxylic acid, 3-amino-5-mercapto-1,2, 4-thiadiazole, 2-amino-5-mercapto-1,3,4-thiadiazole, 3,5-dimercapto-1,2,4-thiadiazole, 2,5-dimercapto-1,3,4-thiadiazole, 3- (5-mercapto-1,2,4-thiadiazol-3-ylsulfanyl) succinic acid, 2- (5-mercapto-1,3,4-thiadiazol-2-ylsulfanyl) succinic acid, (5-mercapto-1 , 2,4-thiadiazol-3-ylthio) acetic acid, (5-mercapto-1,3,4-thiadiazol-2-ylthio) acetic acid, 3- (5-mercapto-1,2,4) Thiadiazol-3-ylthio) propionic acid, 2- (5-mercapto-1,3,4-thiadiazol-2-ylthio) propionic acid, 3- (5-mercapto-1,2,4-thiadiazol-3-ylthio) Succinic acid, 2- (5-mercapto-1,3,4-thiadiazol-2-ylthio) succinic acid, 4- (3-mercapto-1,2,4-thiadiazol-5-yl) thiobutanesulfonic acid, 4 -5-membered heterocyclic compound containing a nitrogen atom and a sulfur atom such as (2-mercapto-1,3,4-thiadiazol-5-yl) thiobutanesulfonic acid;

Pyridine-2,3-dicarboxylic acid, pyridine-2,4-dicarboxylic acid, pyridine-2,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, pyridine-3,5 -Dicarboxylic acid, pyridazine-3,4-dicarboxylic acid, pyridazine-3,5-dicarboxylic acid, pyridazine-3,6-dicarboxylic acid, pyridazine-4,5-dicarboxylic acid, pyrimidine-2,4-dicarboxylic acid, pyrimidine -2,5-dicarboxylic acid, pyrimidine-4,5-dicarboxylic acid, pyrimidine-4,6-dicarboxylic acid, pyrazine-2,3-dicarboxylic acid, pyrazine-2,5-dicarboxylic acid, pyridine-2,6- Dicarboxylic acid, triazine-2,4-dicarboxylic acid, 2-diethylamino-4,6-dimercapto-s-triazine, 2-dipropyl Mino-4,6-dimercapto-s-triazine, 2-dibutylamino-4,6-dimercapto-s-triazine, 2-anilino-4,6-dimercapto-s-triazine, 2,4,6-trimercapto- 6-membered heterocyclic compounds containing a nitrogen atom such as s-triazine.
Among these, it is preferable that the number of acidic groups is two or more from the viewpoint that the adhesion of the obtained cured film can be further improved.

  The compound having a heat latent acidic group may be a group that generates an acidic functional group by heating. Specific examples thereof include a sulfonium base, a benzothiazolium base, an ammonium base, a phosphonium base, a block carboxylic acid group, and the like. Among these, a sulfonium base is preferable. For example, a phosphorus hexafluoride-based or antimony hexafluoride-based sulfonium base can be used. As such a sulfonium base, for example, Sun-Aid SI series (100L, 110L, 150, 180L, manufactured by Sanshin Chemical Industry Co., Ltd.) can be used.

  Moreover, as a specific example of the compound having a thermal latent acidic group among the compounds having an acidic group or a thermal latent acidic group (E), the acidic group of the compound having the acidic group is converted into a thermal latent acidic group. Compound. For example, 1,2,4-benzenetricarboxylic acid tris (1-propoxyethyl) obtained by converting a carboxy group of 1,2,4-benzenetricarboxylic acid into a block carboxylic acid group has a heat latent acidic group. It can be used as a compound.

  The content of the compound having an acidic group or thermal latent acidic group (E) in the radiation-sensitive resin composition of the present invention is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the binder resin (A). The range is more preferably 1 to 45 parts by weight, still more preferably 2 to 40 parts by weight, and still more preferably 3 to 30 parts by weight. By making the usage-amount of the compound (E) which has an acidic group or a heat | fever latent acidic group into the said range, the shape retainability after baking of the resin film obtained can be improved.

(Other ingredients)
Moreover, the radiation-sensitive resin composition of the present invention may further contain a solvent. The solvent is not particularly limited, and is known as a solvent for the resin composition, for example, acetone, methyl ethyl ketone, cyclopentanone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2- Linear ketones such as octanone, 3-octanone and 4-octanone; alcohols such as n-propyl alcohol, isopropyl alcohol, n-butyl alcohol and cyclohexanol; ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether and dioxane Alcohol alcohols such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propyl formate, butyl formate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate Esters such as methyl butyrate, 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 Propylene glycols such as ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether; diety such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether Glycols; 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; Examples include polar solvents such as dimethylacetamide, dimethylformamide, and N-methylacetamide. These solvents may be used alone or in combination of two or more. The content of the solvent is preferably in the range of 10 to 10,000 parts by weight, more preferably 50 to 5000 parts by weight, and still more preferably 100 to 1000 parts by weight with respect to 100 parts by weight of the binder resin (A). In addition, when making a resin composition contain a solvent, a solvent will be normally removed after cured film formation.

  Further, the radiation-sensitive resin composition of the present invention is a surfactant, a coupling agent or a derivative thereof, a sensitizer, a light stabilizer, an antifoaming agent, if desired, as long as the effect of the present invention is not inhibited. Other compounding agents such as pigments, dyes, and fillers; Among these, for example, those described in JP 2011-75609 A can be used as the coupling agent or derivative thereof, the sensitizer, and the light stabilizer.

(Other ingredients)
Moreover, the radiation-sensitive resin composition of the present invention may further contain a solvent. The solvent is not particularly limited, and is known as a solvent for the resin composition, for example, acetone, methyl ethyl ketone, cyclopentanone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2- Linear ketones such as octanone, 3-octanone and 4-octanone; alcohols such as n-propyl alcohol, isopropyl alcohol, n-butyl alcohol and cyclohexanol; ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether and dioxane Alcohol alcohols such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propyl formate, butyl formate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate Esters such as methyl butyrate, 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 Propylene glycols such as ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether; diety such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether Glycols; 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; Examples include polar solvents such as dimethylacetamide, dimethylformamide, and N-methylacetamide. These solvents may be used alone or in combination of two or more. The content of the solvent is preferably in the range of 10 to 10,000 parts by weight, more preferably 50 to 5000 parts by weight, and still more preferably 100 to 1000 parts by weight with respect to 100 parts by weight of the binder resin (A). In addition, when making a resin composition contain a solvent, a solvent will be normally removed after cured film formation.

  Further, the radiation-sensitive resin composition of the present invention is a surfactant, a coupling agent or a derivative thereof, a sensitizer, a light stabilizer, an antifoaming agent, if desired, as long as the effect of the present invention is not inhibited. Other compounding agents such as pigments, dyes, and fillers; Among these, for example, those described in JP 2011-75609 A can be used as the coupling agent or derivative thereof, the sensitizer, and the light stabilizer.

  The surfactant is used for the purpose of preventing striations (after the streaks). Examples of the surfactant include silicone surfactants, fluorine surfactants, polyoxyalkylene surfactants, methacrylic acid copolymer surfactants, and acrylic acid copolymer surfactants. it can.

  Examples of the silicone surfactant include “SH28PA”, “SH29PA”, “SH30PA”, “ST80PA”, “ST83PA”, “ST86PA”, “SF8416”, “SH203”, “SH230”, “SF8419”, “SF8422”, “FS1265”, “SH510”, “SH550”, “SH710”, “SH6040”, “SH8400”, “SF8410”, “SH8700”, “SF8427” (above, manufactured by Toray Dow Corning), Trade names “KP-321”, “KP-323”, “KP-324”, “KP-340”, “KP-341” (manufactured by Shin-Etsu Chemical Co., Ltd.), trade names “TSF400”, “TSF401” , “TSF410”, “TSF4440”, “TSF4445”, “TSF4450” “TSF4446”, “TSF4452”, “TSF4460” (manufactured by Momentive Performance Materials Japan GK), trade names “BYK300”, “BYK301”, “BYK302”, “BYK306”, “BYK307”, “BYK310” ”,“ BYK315 ”,“ BYK320 ”,“ BYK322 ”,“ BYK323 ”,“ BYK331 ”,“ BYK333 ”,“ BYK370 ”“ BYK375 ”,“ BYK377 ”,“ BYK378 ”(above, manufactured by BYK Japan) Can be mentioned.

Examples of the fluorosurfactant include Fluorinert “FC-430”, “FC-431” (manufactured by Sumitomo 3M), Surflon “S-141”, “S-145”, “S-381”, “S-393” (manufactured by Asahi Glass Co., Ltd.), EFtop (registered trademark) “EF301”, “EF303”, “EF351”, “EF352” (manufactured by Gemco), MegaFuck (registered trademark) “F171” ”,“ F172 ”,“ F173 ”,“ R40 ”(manufactured by DIC) and the like.
Examples of the polyoxyalkylene surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, and the like. And polyethylene glycol dilaurate, polyethylene glycol distearate polyoxyethylene dialkyl esters, and the like.
These surfactants can be used alone or in combination of two or more.

  The content of the surfactant in the radiation-sensitive resin composition of the present invention is preferably 0.001 to 1 part by weight, more preferably 0.01 to 0 parts per 100 parts by weight of the binder resin (A). .1 part by weight. When the content of the surfactant is in the above range, the effect of preventing striation (after the application stripe) can be further enhanced.

The preparation method of the radiation sensitive resin composition of this invention is not specifically limited, What is necessary is just to mix each component which comprises a radiation sensitive resin composition by a well-known method.
The mixing method is not particularly limited, but it is preferable to mix a solution or dispersion obtained by dissolving or dispersing each component constituting the radiation-sensitive resin composition in a solvent. Thereby, a radiation sensitive resin composition is obtained with the form of a solution or a dispersion liquid.

  The method for dissolving or dispersing each component constituting the radiation-sensitive resin composition may be in accordance with 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.

(Electronic parts)
Next, the electronic component of the present invention will be described. The electronic component of the present invention has a resin film made of the above-described radiation-sensitive resin composition of the present invention.

  Examples of the electronic component of the present invention include an electronic component having a configuration in which a semiconductor element is mounted on a substrate. Specifically, an active matrix substrate, an organic EL element substrate, an integrated circuit element substrate, and a solid-state imaging An active matrix substrate and an organic EL element substrate are preferable from the viewpoint that the effect of improving the characteristics by forming the resin film made of the radiation-sensitive resin composition of the present invention described above is particularly remarkable.

  The active matrix substrate as an example of the electronic component of the present invention is not particularly limited, and switching elements such as thin film transistors (TFTs) are arranged in a matrix on the substrate, and a gate for driving the switching elements. Examples include a structure in which a gate signal line for supplying a signal and a source signal line for supplying a display signal to the switching element are provided so as to cross each other. As a thin film transistor as an example of a switching element, a structure in which a gate electrode, a gate insulating layer, a semiconductor layer, a source electrode, and a drain electrode are provided over a substrate is exemplified.

  Furthermore, the organic EL element substrate as an example of the electronic component of the present invention includes, for example, an anode, a hole injection transport layer, an organic light emitting layer as a semiconductor layer, an electron injection layer, and a cathode on the substrate. And a structure having a light-emitting body portion and a pixel separation film for separating the light-emitting body portion.

  For example, when the electronic component of the present invention is an active matrix substrate, the above-described resin film made of the radiation-sensitive resin composition of the present invention includes a protective film and a planarizing film formed on the surface of the active matrix substrate, It can be a gate insulating film formed in contact with a semiconductor layer (for example, an amorphous silicon layer) of a thin film transistor constituting an active matrix substrate. Or when the electronic component of this invention is an organic EL element substrate, it can be set as the sealing film formed in the surface of an organic EL element substrate.

  In the electronic component of the present invention, the method for forming the resin film is not particularly limited, and for example, a coating method, a film lamination method, or the like can be used.

  The application method is, for example, a method in which a radiation-sensitive resin composition is applied and then dried by heating to remove the solvent. As a method for applying the radiation-sensitive resin composition, for example, various methods such as a spray method, a spin coating method, a roll coating method, a die coating method, a doctor blade method, a spin coating method, a bar coating method, and a screen printing method are adopted. can do. The heating and drying conditions vary depending on the type and blending ratio of each component, but are usually 30 to 150 ° C., preferably 60 to 120 ° C., usually 0.5 to 90 minutes, preferably 1 to 60 minutes, and more. Preferably it may be performed in 1 to 30 minutes.

  In the film lamination method, the radiation-sensitive resin composition is applied onto a B-stage film-forming substrate such as a resin film or a metal film, and then the solvent is removed by heat drying to obtain a B-stage film. This is a method of laminating films. The heating and drying conditions can be appropriately selected according to the type and mixing ratio of each component, but the heating temperature is usually 30 to 150 ° C., and the heating time is usually 0.5 to 90 minutes. . Film lamination can be performed using a pressure laminator, a press, a vacuum laminator, a vacuum press, a roll laminator or the like.

  The thickness of the resin film is not particularly limited, and may be set as appropriate according to the use. However, the resin film is a protective film or planarizing film for an active matrix substrate, or a sealing film for an organic EL element substrate. In this case, the thickness of the resin film is preferably 0.1 to 100 μm, more preferably 0.5 to 50 μm, and still more preferably 0.5 to 30 μm.

  Next, the resin film thus formed is patterned in a predetermined pattern. As a method for patterning the resin film, for example, the radiation sensitive resin composition of the present invention is used to form a resin film before patterning, and the resin film before patterning is irradiated with actinic radiation to form a latent image pattern And then exposing the pattern to a resin film having a latent image pattern by bringing a developer into contact therewith.

As the actinic radiation, it is possible to activate the radiation-sensitive compound (B) contained in the radiation-sensitive resin composition and change the alkali solubility of the radiation-sensitive resin composition containing the radiation-sensitive compound (B). There is no particular limitation. Specifically, ultraviolet rays, ultraviolet rays having a single wavelength such as g-line or i-line, light rays such as KrF excimer laser light and ArF excimer laser light; particle beams such as electron beams; As a method for selectively irradiating these actinic radiations in a pattern to form a latent image pattern, a conventional method may be followed. A method of irradiating a light beam such as a laser beam or an ArF excimer laser beam through a desired mask pattern, a method of drawing with a particle beam such as an electron beam, or the like can be used. When light is used as the active radiation, it may be single wavelength light or mixed wavelength light. Irradiation conditions may be appropriately selected depending on the active radiation to be used, for example, when using a light beam of wavelength 200 to 450 nm, the amount of irradiation is usually 10~1,000mJ / cm ^2, preferably 50 to 500 mJ / It is a range of cm ² and is determined according to irradiation time and illuminance. After irradiation with actinic radiation in this manner, the resin film is heat-treated at a temperature of about 60 to 130 ° C. for about 1 to 2 minutes as necessary.

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

As an aqueous medium of the alkaline aqueous solution, water; water-soluble organic solvents such as methanol and ethanol can be used. The alkaline aqueous solution may have a surfactant added in an appropriate amount.
As a method of bringing the developer into contact with the resin film having the latent image pattern, for example, a paddle method, a spray method, a dipping method, or the like is used. The development is usually appropriately selected in the range of 0 to 100 ° C, preferably 5 to 55 ° C, more preferably 10 to 30 ° C, and usually 30 to 180 seconds.

The resin film on which the target pattern is formed in this manner can be rinsed with a rinsing liquid in order to remove the development residue, if necessary. After the rinse treatment, the remaining rinse liquid is removed with compressed air or compressed nitrogen.
Furthermore, in order to deactivate the radiation-sensitive compound (B) contained in the radiation-sensitive resin composition, the entire surface of the electronic component can be irradiated with actinic radiation as necessary. For irradiation with actinic radiation, the method exemplified in the formation of the latent image pattern can be used. The resin film may be heated simultaneously with irradiation or after irradiation. Examples of the heating method include a method of heating an electronic component in a hot plate or an oven. The temperature is usually in the range of 100 to 300 ° C, preferably 120 to 200 ° C.

  Moreover, when the radiation sensitive resin composition of this invention contains a crosslinking agent (D), the resin film formed in this way can perform a crosslinking reaction after patterning. Such crosslinking may be appropriately selected according to the type of the crosslinking agent (D) contained in the radiation-sensitive resin composition, 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 according to the area and thickness of the resin film, the equipment used, and the like. For example, when using a hot plate, the oven is usually used for 5 to 60 minutes. When used, it is usually in the range of 30 to 90 minutes. Heating may be performed in an inert gas atmosphere as necessary. Any inert gas may be used as long as it does not contain oxygen and does not oxidize the resin film. Examples thereof include nitrogen, argon, helium, neon, xenon, and krypton. Among these, nitrogen and argon are preferable, and nitrogen is particularly preferable. In particular, an inert gas having an oxygen content of 0.1% by volume or less, preferably 0.01% by volume or less, particularly nitrogen is suitable. These inert gases can be used alone or in combination of two or more.

In this way, an electronic component having a patterned resin film can be manufactured.
In addition, when the electronic component of the present invention is an active matrix substrate or an organic EL element substrate, after forming the resin film patterned in this way, another component (for example, an ITO electrode, In order to bake and harden the alignment film or the like, baking is performed in an oxidizing atmosphere such as the air. The firing temperature at this time is usually 150 to 350 ° C, preferably 180 to 300 ° C, more preferably 200 to 250 ° C. In this case, the patterned resin film obtained using the radiation-sensitive resin composition of the present invention is also fired in an oxidizing atmosphere. However, on the other hand, since the resin film formed in this way is obtained using the radiation-sensitive resin composition of the present invention described above, high transparency is obtained even after baking in an oxidizing atmosphere. Therefore, it is suitable for various electronic component applications such as an active matrix substrate and an organic EL element substrate. In addition to this, since the resin film obtained using the radiation-sensitive resin composition of the present invention has high exposure sensitivity, it is possible to reduce the radiation dose during production, thereby producing Can be improved. Furthermore, since the radiation-sensitive resin composition of the present invention used for forming such a resin film is excellent in storage stability, productivity can be improved also in this respect. .

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. “Part” in each example is based on weight unless otherwise specified.
In addition, the definition and evaluation method of each characteristic are as follows.

<Storage stability>
The radiation sensitive resin composition is put in a glass ampoule and sealed, placed in a thermostatic bath at −20 ° C. and allowed to stand for 7 days, and then the state of the radiation sensitive resin composition after standing is visually observed. The storage stability was evaluated on the basis of
A: No precipitation of components in the resin composition is observed.
C: Precipitation of components in the resin composition was observed.

<Exposure sensitivity>
A radiation-sensitive resin composition is applied onto a glass substrate (Corning, product name Corning 1737) by spin coating, and is heated and dried (prebaked) at 90 ° C. for 2 minutes using a hot plate. A 5 μm resin film was formed. Then, to pattern the resin film, the contact hole pattern of 5μm using a formable mask, by varying the exposure amount from 50 mJ / cm ² to 500 mJ / cm ² per 50 mJ / cm ^2, the exposure step Went. Next, a resin having contact hole patterns with different exposure amounts is obtained by developing with a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds and rinsing with ultrapure water for 30 seconds. A laminate composed of a film and a glass substrate was obtained.
And the contact hole formation part of the obtained laminated body was observed using the optical microscope, and the length of the longest part of the contact hole pattern of the resin film of the part exposed by each exposure amount was measured, respectively. Then, an approximate curve is created from the relationship between each exposure amount and the length of the longest part of the contact hole pattern of the resin film formed at the corresponding exposure amount, and the exposure amount when the contact hole pattern becomes 5 μm is calculated. The amount of exposure was calculated as exposure sensitivity and evaluated according to the following criteria. The lower the exposure when the contact hole pattern is 5 μm, the more preferable it is because the contact hole can be formed with low energy or in a short time.
A: exposure amount when the contact hole pattern is 5μm is, 200 mJ / cm ² less B: the exposure amount when the contact hole pattern is 5μm is, 5 mJ / cm ² or more, 300 mJ / cm ² less than C: contact hole The exposure when the pattern is 5 μm is 300 mJ / cm ² or more

<Heat resistant transparency>
A radiation-sensitive resin composition is applied onto a glass substrate (Corning, product name Corning 1737) by spin coating, and dried by heating (pre-baking) at 90 ° C. for 2 minutes using a hot plate. A 5 μm resin film was formed. Next, this resin film was immersed in a 0.4 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds, then washed with ultrapure water for 30 seconds, and then the light intensity at 365 nm. Was irradiated in the air for 300 seconds with a UV of 50 mJ / cm ² . Then, the resin film irradiated with ultraviolet rays is subjected to middle baking in an N ₂ atmosphere at 110 ° C. for 11 minutes using an oven, and then post baking is performed in an N ₂ atmosphere at 230 ° C. for 60 minutes. Thus, a test sample made of a glass substrate on which a resin film was formed was obtained. The test sample thus obtained was baked in an oxidizing atmosphere heated at 230 ° C. for 60 minutes in the air using an oven, and also at 230 ° C. for 60 minutes in the air. Baking was performed in a heated oxidizing atmosphere. And the transmittance | permeability of the sample which performed the baking in oxidizing atmosphere was measured with the wavelength of 400 nm to 700 nm using the spectrophotometer V-560 (made by JASCO Corporation). The light transmittance of the resin film was calculated as a conversion value when a glass substrate without a resin film was used as a blank and the thickness of the resin film was 2 μm. And based on the obtained light transmittance, transparency was evaluated on the following reference | standard.
A: Light transmittance is 90% or more B: Light transmittance is 80% or more and less than 90% C: Light transmittance is less than 80%

<< Synthesis Example 1 >>
<Preparation of Cyclic Olefin Polymer (A-1)>
40 mol% N-phenyl-bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide (NBPI), and 4-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodeca-9-ene (TCDC) 60 parts by mole monomer mixture 100 parts, 1,5-hexadiene 2.0 parts, (1,3-dimesitylimidazoline-2-ylidene) ( Tricyclohexylphosphine) benzylidene ruthenium dichloride (synthesized by the method described in Org. Lett., Vol. 1, page 953, 1999), and 200 parts of diethylene glycol ethyl methyl ether made of nitrogen-substituted glass The polymerization reaction liquid was obtained by charging into a pressure-resistant reactor and making it react at 80 degreeC for 4 hours, stirring.

  And the obtained polymerization reaction liquid was put into an autoclave, and it stirred at 150 degreeC and the hydrogen pressure of 4 MPa for 5 hours, and performed the hydrogenation reaction, and obtained the polymer solution containing a cyclic olefin polymer (A-1). . The polymerization conversion rate of the obtained cyclic olefin polymer (A-1) was 99.7%, polystyrene-equivalent weight average molecular weight was 7,150, number average molecular weight was 4,690, molecular weight distribution was 1.52, and hydrogenation rate. Was 99.7%. Moreover, the solid content concentration of the polymer solution of the obtained cyclic olefin polymer (A-1) was 34.4% by weight.

Example 1
As binder resin (A), 291 parts of polymer solution of cyclic olefin polymer (A-1) obtained in Synthesis Example 1 (100 parts as cyclic olefin polymer (A-1)), radiation sensitive compound (B) 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.5 mol) 40 parts of antioxidant, as antioxidant (C), 16 parts of antioxidant (C-1) (compound having R ¹ = Sec-butyl group in the above general formula (1)), crosslinking agent (D ), Epoxidized butanetetracarboxylic acid tetrakis (3-cyclohexenylmethyl) modified ε-caprolactone (aliphatic cyclic tetrafunctional epoxy resin, trade name “Epolide GT401”, dicelization 45 parts from Gaku Kogyo Co., Ltd., and 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate (trade name “Celoxide 2021P”, manufactured by Daicel Chemical Industries, Ltd.) 5 as the crosslinking agent (D) parts, compounds having an acidic group or a thermal latent acid group as (E), PF ₆ ^- sulfonium salt (trade name "San-Aid SI-110L", available from Sanshin chemical Industry Co., Ltd.) 4 parts, 7 parts of phthalic acid, the cup As a ring agent, 5 parts of (3-glycidyloxypropyl) trimethoxysilane (trade name “SH6040”, manufactured by Toray Dow Corning), silicone surfactant (trade name “KP-341”, manufactured by Shin-Etsu Chemical Co., Ltd.) ) 0.03 part and 100 parts of ethylene glycol dimethyl ether as a solvent were mixed and dissolved, and then the polytate having a pore diameter of 0.45 μm A radiation-sensitive resin composition was prepared by filtration through a rafluoroethylene filter.

  And each evaluation of storage stability, exposure sensitivity, and heat-resistant transparency was performed using the radiation sensitive resin composition obtained above. The results are shown in Table 1.

Example 2
As antioxidant (C), instead of 16 parts of antioxidant (C-1) (compound which is R ¹ = Sec-butyl group in the above general formula (1)), antioxidant (C-2) (A compound having R ¹ = 2-ethylhexyl group in the above general formula (1)) Except for using 16 parts, a radiation-sensitive resin composition was obtained in the same manner as in Example 1, and each evaluation was performed in the same manner. It was. The results are shown in Table 1.

Example 3
As antioxidant (C), instead of 16 parts of antioxidant (C-1) (compound in which R ¹ = Sec-butyl group in the general formula (1)), antioxidant (C-3) (A compound having R ¹ = n-octyl group in the above general formula (1)) Except for using 16 parts, a radiation-sensitive resin composition was obtained in the same manner as in Example 1, and each evaluation was performed in the same manner. It was. The results are shown in Table 1.

Example 4
As antioxidant (C), instead of 16 parts of antioxidant (C-1) (compound in which R ¹ = Sec-butyl group in the above general formula (1)), antioxidant (C-4) (A compound having R ¹ = n-hexyl group in the general formula (1)) Except for using 16 parts, a radiation-sensitive resin composition was obtained in the same manner as in Example 1, and each evaluation was performed in the same manner. It was. The results are shown in Table 1.

Example 5
(In the general formula (1), R 1 ⁼ n-hexyl, Compound) antioxidant (C-4) except for changing the amount of the 10 parts of the 16 parts, the same procedure as in Example 4 A radiation-sensitive resin composition was obtained and each evaluation was performed in the same manner. The results are shown in Table 1.

Example 6
The blending amount of the antioxidant (C-3) (the compound having R ¹ = n-octyl group in the above general formula (1)) is changed from 16 parts to 5 parts, and other than the antioxidant (C) 3,9-bis [2- {3- (3-tertiarybutyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8 as an antioxidant , 10-tetraoxaspiro [5,5] undecane (for example, trade name “ADK STAB AO-80”, manufactured by ADEKA, semi-hindered phenol antioxidant) Similarly, the radiation sensitive resin composition was obtained and each evaluation was performed similarly. The results are shown in Table 1.

Example 7
(In the general formula (1), R 1 ⁼ n-octyl group, Compound) antioxidant (C-3) except for changing the amount of 10 parts 5 parts, the same procedure as in Example 6 A radiation-sensitive resin composition was obtained, and each evaluation was performed in the same manner. The results are shown in Table 1.

Example 8
The blending amount of the antioxidant (C-4) (compound having R ¹ = n-hexyl group in the above general formula (1)) is changed from 16 parts to 5 parts, and other than the antioxidant (C) 3,9-bis [2- {3- (3-tertiarybutyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8 as an antioxidant , 10-tetraoxaspiro [5,5] undecane (trade name “Adeka Stab AO-80”, manufactured by ADEKA) was further added in the same manner as in Example 4 to obtain a radiation-sensitive resin composition. Each evaluation was performed in the same manner. The results are shown in Table 1.

Example 9
(In the general formula (1), R 1 ⁼ n-hexyl, Compound) antioxidant (C-4) except for changing the amount of 10 parts 5 parts, the same procedure as in Example 8 A radiation-sensitive resin composition was obtained and each evaluation was performed in the same manner. The results are shown in Table 1.

Example 10
As an antioxidant other than the antioxidant (C), 3,9-bis [2- {3- (3-tertiarybutyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl ] -2,4,8,10-tetraoxaspiro [5,5] undecane instead of 6 parts 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl A radiation-sensitive resin composition was obtained in the same manner as in Example 8 except that 6 parts of -4-hydroxybenzyl) benzene (trade name “Irganox 1330”, manufactured by BASF) was used, and each evaluation was performed in the same manner. The results are shown in Table 1.

Example 11
As an antioxidant other than the antioxidant (C), 3,9-bis [2- {3- (3-tertiarybutyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl ] Instead of 6 parts of -2,4,8,10-tetraoxaspiro [5,5] undecane, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] ( A radiation-sensitive resin composition was obtained in the same manner as in Example 6 except that 6 parts of trade name “Irganox 1010” (manufactured by BASF) was used, and each evaluation was performed in the same manner. The results are shown in Table 1.

<< Comparative Example 1 >>
Antioxidant (C-1) as the antioxidant (C) (a compound having R ¹ = Sec-butyl group in the general formula (1)) instead of 16 parts 3,9-bis [2- {3- (3-tertiarybutyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane (product) A radiation-sensitive resin composition was obtained in the same manner as in Example 1 except that 16 parts of the name “ADK STAB AO-80” (manufactured by ADEKA) were used, and each evaluation was performed in the same manner. The results are shown in Table 1.

<< Comparative Example 2 >>
3,9-bis [2- {3- (3-tertiarybutyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] The amount of undecane was changed from 16 parts to 6 parts, and antioxidant (C′-5) (a compound in which R ^{1 in the} above general formula (1) is a dodecyl group) 10 parts Except for further blending, a radiation-sensitive resin composition was obtained in the same manner as in Comparative Example 1, and each evaluation was performed in the same manner. The results are shown in Table 1.

<< Comparative Example 3 >>
Sensitive in the same manner as in Comparative Example 2, except that the amount of the antioxidant (C′-5) (the compound in which R ^{1 in the} above general formula (1) is a dodecyl group) was changed from 10 parts to 5 parts. A radiation resin composition was obtained and each evaluation was performed in the same manner. The results are shown in Table 1.

<< Comparative Example 4 >>
Antioxidant (C-1) as an antioxidant (C) (a compound in which R ¹ = Sec-butyl group in the general formula (1)) instead of 16 parts 1,3,5-trimethyl- Except that 10 parts of 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene (trade name “Irganox 1330”, manufactured by BASF) was used, the same procedure as in Example 1 was performed. A radiation-sensitive resin composition was obtained, and each evaluation was performed in the same manner. The results are shown in Table 1.

<< Comparative Example 5 >>
Antioxidant (C-1) as the antioxidant (C) (a compound having R ¹ = Sec-butyl group in the general formula (1)) instead of 16 parts pentaerythritol tetrakis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name “Irganox 1010”, manufactured by BASF) 16 parts were used in the same manner as in Example 1 to obtain a radiation-sensitive resin composition. In the same manner, each evaluation was performed. The results are shown in Table 1.

<< Comparative Example 6 >>
Radiation sensitive resin composition as in Comparative Example 5, except that the amount of pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] was changed from 16 parts to 6 parts. A product was obtained and evaluated in the same manner. The results are shown in Table 1.

<< Comparative Example 7 >>
Radiation-sensitive resin composition as in Comparative Example 5 except that the amount of pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] was changed from 16 parts to 2 parts. A product was obtained and evaluated in the same manner. The results are shown in Table 1.

  As shown in Table 1, the radiation-sensitive resin composition comprising the binder resin (A), the radiation-sensitive compound (B), and the antioxidant (C) represented by the general formula (1) is storage stable. In addition, the resin film obtained using the radiation-sensitive resin composition has high exposure sensitivity and excellent heat-resistant transparency (transparency after firing in an oxidizing atmosphere). (Examples 1-11).

On the other hand, when only the antioxidant other than the antioxidant (C) is used instead of the antioxidant (C) represented by the general formula (1), the resulting resin film is inferior in exposure sensitivity. In particular, when the amount of the antioxidant other than the antioxidant (C) was increased to 16 parts, the exposure sensitivity was too low to obtain a sample having a contact hole pattern of 5 μm ( Comparative Examples 1, 4-6). In addition, when the blending amount of the antioxidant other than the antioxidant (C) is reduced to 2 parts, the exposure sensitivity of the resulting resin film is somewhat improved, but heat resistant transparency (after firing in an oxidizing atmosphere) (Transparency) was reduced (Comparative Example 7).
In addition, instead of the antioxidant (C) represented by the general formula (1), when a compound having the same structure as the general formula (1) but having too many carbon atoms in R ¹ is used. The radiation-sensitive resin composition obtained was inferior in storage stability (Comparative Examples 2 and 3).

Claims (5)

A radiation-sensitive resin composition comprising a binder resin (A), a radiation-sensitive compound (B), and an antioxidant (C) represented by the following general formula (1).

(In the general formula (1), R ¹ is a hydrogen atom or an alkyl group having 1 to 9 carbon atoms which may have a substituent.)   The radiation sensitive resin composition of Claim 1 which further contains a crosslinking agent (D).   The radiation sensitive resin composition of Claim 1 or 2 which further contains the compound (E) which has an acidic group or a heat | fever latent acidic group.   An electronic component provided with the resin film which consists of a radiation sensitive resin composition in any one of Claims 1-3.   The electronic component according to claim 4, wherein the electronic component is manufactured through a step of baking in an oxidizing atmosphere after forming a resin film made of the radiation-sensitive resin composition, patterning the resin film.