KR102217197B1 - Radiation-sensitive resin composition and electronic component - Google Patents

Abstract

Binder resin (A), radiation-sensitive compound (B), crosslinking agent (C), sulfur-free semi-hindered phenolic antioxidant and/or sulfur-free less hindered phenolic antioxidant (D), sulfur-containing phenolic oxidation It provides a radiation-sensitive resin composition containing an inhibitor (E). Advantageous Effects of Invention According to the present invention, it is possible to provide a radiation-sensitive resin composition capable of providing a resin film having high exposure sensitivity, excellent shape retention after firing, and having high transparency even after firing in an oxidizing atmosphere.

Description

Radiation-sensitive resin composition and electronic component TECHNICAL FIELD {RADIATION-SENSITIVE RESIN COMPOSITION AND ELECTRONIC COMPONENT}

The present invention relates to an electronic component having a radiation-sensitive resin composition and a resin film made of the radiation-sensitive resin composition, and more particularly, it has high exposure sensitivity, excellent shape retention after firing, and high even after firing in an oxidizing atmosphere. It relates to a radiation-sensitive resin composition capable of providing a resin film having transparency, 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, and electronic components such as black matrix have a protective film for preventing their deterioration or damage, and for flattening the element surface or wiring. Various resin films are formed as a planarization film, an electric insulating film for maintaining electric insulation, and the like. In addition, in the organic EL element, a resin film as a pixel separation film is formed in order to separate the light-emitting body portion, and in elements such as a display element for a thin film transistor type liquid crystal or an integrated circuit element, in order to insulate between wirings arranged in a layered form. A resin film as an interlayer insulating film is formed.

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

In order to meet these needs, for example, Patent Document 1 discloses a radiation-sensitive resin composition containing a cyclic olefin polymer, a crosslinking agent, a radiation-sensitive compound, a phenolic aging inhibitor, and a non-phenolic aging inhibitor. . However, according to the radiation-sensitive resin composition described in Patent Document 1, a resin film having high transparency can be obtained even after firing in an oxidizing atmosphere, but the obtained resin film has a low exposure sensitivity to radiation, and therefore, the viewpoint of improving productivity. In, improvement was desired.

Japanese Unexamined Patent Publication No. 2005-292278

The present invention is provided with a radiation-sensitive resin composition capable of providing a resin film having high exposure sensitivity, excellent shape retention after firing, and having high transparency even after firing in an oxidizing atmosphere, and a resin film made of such a radiation-sensitive resin composition. It is an object of the present invention to provide electronic components.

As a result of intensive research in order to achieve the above object, the inventors of the present invention have shown that, along with a binder resin, a radiation-sensitive compound, and a crosslinking agent, two specific antioxidants, specifically, a sulfur-free semi-hindered phenolic antioxidant and/ Alternatively, it has been found that the above object can be achieved by blending a sulfur-free, less hindered phenolic antioxidant and a sulfur-containing phenolic antioxidant in combination to achieve the present invention.

That is, according to the present invention,

[1] Binder resin (A), radiation-sensitive compound (B), crosslinking agent (C), sulfur-free semi-hindered phenolic antioxidant and/or sulfur-free, less hindered phenolic antioxidant (D), containing sulfur A radiation-sensitive resin composition containing a phenolic antioxidant (E),

[2] The radiation-sensitive resin composition according to [1], further containing a compound (F) having an acidic group or a thermally latent acidic group,

[3] the sulfur-containing phenolic antioxidant (E) is a hindered phenolic antioxidant containing a sulfur atom, a semi-hindered phenolic antioxidant containing a sulfur atom, and a less hindered phenolic containing a sulfur atom The radiation-sensitive resin composition according to [1] or [2], which is at least one type selected from antioxidants,

[4] The content of the sulfur-free semi-hindered phenolic antioxidant and/or the sulfur-free less hindered phenolic antioxidant (D) is 0.1 to 20 parts by weight based on 100 parts by weight of the binder resin (A) And the radiation-sensitive resin composition according to any one of [1] to [3], wherein the content of the sulfur-containing phenolic antioxidant (E) is 0.1 to 15 parts by weight with respect to 100 parts by weight of the binder resin (A),

[5] The radiation-sensitive resin composition according to any one of [1] to [4], wherein the radiation-sensitive compound (B) is an azide compound,

[6] An electronic component provided with a resin film made of the radiation-sensitive resin composition according to any one of [1] to [5], and

[7] The electronic component according to [6], which is manufactured through a step of forming a resin film made of the radiation-sensitive resin composition, patterning the resin film, and firing in an oxidizing atmosphere.

Is provided.

According to the present invention, a radiation-sensitive resin composition capable of providing a resin film having high exposure sensitivity, excellent shape retention after firing, and having high transparency even after firing in an oxidizing atmosphere, and a resin film comprising the radiation-sensitive resin composition are provided. Electronic components can be provided.

The radiation-sensitive resin composition of the present invention includes a binder resin (A), a radiation-sensitive compound (B), a crosslinking agent (C), a sulfur-free semi-hindered phenolic antioxidant and/or a sulfur-free non-hindered phenolic antioxidant ( It contains D) and a sulfur-containing phenolic antioxidant (E).

(Binder resin (A))

The binder resin (A) used in the present invention is not particularly limited, but a cyclic olefin polymer (A1) having a protic polar group, an acrylic resin (A2), a cardo resin (A3), a polysiloxane (A4), or a polyimide It is preferable that it is (A5), and a cyclic olefin polymer (A1) which has a protic polar group is especially preferable among these. These binder resins (A) may be used individually, respectively, or may use 2 or more types together.

As the cyclic olefin polymer (A1) having a protic polar group (hereinafter, simply referred to as ``cyclic olefin polymer (A1)''), a polymer of one or two or more cyclic olefin monomers, or one or two or more cyclic olefins A copolymer of a monomer and a monomer copolymerizable therewith may be mentioned, but in the present invention, a cyclic olefin monomer (a) having at least a protic polar group is used as a monomer for forming a cyclic olefin polymer (A1). It is desirable to do.

Here, the protic polar group refers to a group including an atom in which a hydrogen atom is directly bonded to an atom belonging to Group 15 or 16 of the periodic table. Among the atoms belonging to Group 15 or 16 of the periodic table, atoms belonging to the first or second period of Group 15 or 16 of the periodic table are preferred, more preferably an oxygen atom, a nitrogen atom, or a sulfur atom, particularly preferred It is an oxygen atom.

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

As a specific example of the cyclic olefin monomer (a) having a protic polar group (hereinafter, appropriately referred to as "monomer (a)"), 2-hydroxycarbonylbicyclo[2.2.1]hepto-5-ene , 2-methyl-2-hydroxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-carboxymethyl-2-hydroxycarbonylbicyclo[2.2.1]hepto-5-ene, 2- Hydroxycarbonyl-2-methoxycarbonylmethylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-2-ethoxycarbonylmethylbicyclo[2.2.1]hepto-5- N, 2-hydroxycarbonyl-2-propoxycarbonylmethylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-2-butoxycarbonylmethylbicyclo[2.2.1] Hepto-5-ene, 2-hydroxycarbonyl-2-pentyloxycarbonylmethylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-2-hexyloxycarbonylmethylbicyclo [2.2.1]Hepto-5-ene, 2-hydroxycarbonyl-2-cyclohexyloxycarbonylmethylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-2-phenoxy Cycarbonylmethylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-2-naphthyloxycarbonylmethylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycar Bornyl-2-biphenyloxycarbonylmethylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-2-benzyloxycarbonylmethylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-2-hydroxyethoxycarbonylmethylbicyclo[2.2.1]hepto-5-ene, 2,3-dihydroxycarbonylbicyclo[2.2.1]hepto-5-ene , 2-hydroxycarbonyl-3-methoxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-3-ethoxycarbonylbicyclo[2.2.1]hepto-5 -Ene, 2-hydroxycarbonyl-3-propoxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-3-butoxycarbonylbicyclo[2.2.1]hepto -5-ene, 2-hydroxycarbonyl-3-pentyloxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-3-hexyloxycarbonylbicyclo[2.2.1 ]Hepto-5-ene, 2-hydroxycarbonyl-3-cyclohexyloxycarbonylbicyclo[2.2. 1]Hepto-5-ene, 2-hydroxycarbonyl-3-phenoxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-3-naphthyloxycarbonylbicyclo[ 2.2.1]Hepto-5-ene, 2-hydroxycarbonyl-3-biphenyloxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-3-benzyloxycarbo Nylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-3-hydroxyethoxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-3- Hydroxycarbonylmethylbicyclo[2.2.1]hepto-5-ene, 3-methyl-2-hydroxycarbonylbicyclo[2.2.1]hepto-5-ene, 3-hydroxymethyl-2-hydro Roxycarbonylbicyclo[2.2.1]hepto-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 ]dodeca-9-ene, 4-methyl-4-hydroxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodeca-9-ene, 4,5-dihydroxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodeca-9-ene, 4-carboxymethyl-4-hydroxycarbonyltetracyclo[6.2.1.1 ^{3, 6} .0 ^2,7 ]dodeca-9-ene, N-(hydroxycarbonylmethyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(hydroxycar Bornylethyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(hydroxycarbonylpentyl)bicyclo[2.2.1]hepto-5-ene-2,3- Dicarboximide, N-(dihydroxycarbonylethyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(dihydroxycarbonylpropyl)bicyclo[2.2. 1]Hepto-5-ene-2,3-dicarboximide, N-(hydroxycarbonylphenethyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-( 2-(4-hydroxyphenyl)-1-(hydroxycarbonyl)ethyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(hydroxycarbonylphenyl) Cyclic oleate containing carboxyl groups such as bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide Pin; 2-(4-hydroxyphenyl)bicyclo[2.2.1]hepto-5-ene, 2-methyl-2-(4-hydroxyphenyl)bicyclo[2.2.1]hepto-5-ene, 4- (4-hydroxyphenyl)tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodeca-9-ene, 4-methyl-4-(4-hydroxyphenyl)tetracyclo[6.2.1.1 ^{3, 6} .0 ^2,7 ]dodeca-9-ene, 2-hydroxybicyclo[2.2.1] hepto-5-ene, 2-hydroxymethylbicyclo[2.2.1] hepto-5-ene, 2 -Hydroxyethylbicyclo[2.2.1]hepto-5-ene, 2-methyl-2-hydroxymethylbicyclo[2.2.1]hepto-5-ene, 2,3-dihydroxymethylbicyclo[ 2.2.1]Hepto-5-ene, 2-(hydroxyethoxycarbonyl)bicyclo[2.2.1]hepto-5-ene, 2-methyl-2-(hydroxyethoxycarbonyl)bicyclo[ 2.2.1]Hepto-5-ene, 2-(1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl)bicyclo[2.2.1]hepto-5-ene, 2 -(2-hydroxy-2-trifluoromethyl-3,3,3-trifluoropropyl)bicyclo[2.2.1]hepto-5-ene, 3-hydroxytricyclo[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} ]Dodeca-9-ene, 4-hydroxymethyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]Dodeca-9-ene, 4,5-dihydroxymethyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodeca-9-ene, 4-(hydroxyethoxycarbonyl)tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodeca-9-ene, 4- Methyl-4-(hydroxyethoxycarbonyl)tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodeca-9-ene, N-(hydroxyethyl)bicyclo[2.2.1]hepto- And hydroxyl group-containing cyclic olefins such as 5-ene-2,3-dicarboximide and N-(hydroxyphenyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide. have. Among these, a carboxyl group-containing cyclic olefin is preferable from the viewpoint of increasing the adhesion of the resulting resin film, and 4-hydroxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodeca-9-ene is It is particularly preferred. These monomers (a) may be used individually, respectively, and may be used in combination of 2 or more types.

The content ratio of the unit of the monomer (a) in the cyclic olefin polymer (A1) is preferably 10 to 90 mol% with respect to all monomer units. If the content ratio of the unit of the monomer (a) is too small, when the radiation-sensitive compound is added to the resin composition of the present invention, the radiation-sensitive property may become insufficient, or a dissolution residue may occur during development. If it is too large, there is a concern that the solubility of the cyclic olefin polymer (A1) in a polar solvent may become insufficient.

Further, the cyclic olefin polymer (A1) used in the present invention may be a copolymer obtained by copolymerizing a cyclic olefin monomer (a) having a protic polar group and a monomer (b) copolymerizable therewith. As such a copolymerizable monomer, a cyclic olefin monomer having a polar group other than a protic polar group (b1), a cyclic olefin monomer having no polar group (b2), and a monomer other than a cyclic olefin (b3) (hereinafter, appropriately , "Monomer (b1)", "monomer (b2)", and "monomer (b3)") are mentioned.

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

As the cyclic olefin having an N-substituted imide group, a monomer represented by the following formula (1) or a monomer represented by the following formula (2) is exemplified.

[Formula 1]

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

[Formula 2]

(In the formula (2), R ² represents a C 1 to C 3 divalent alkylene group, R ³ represents a C 1 to C 10 monovalent alkyl group or a C 1 to C 10 monovalent halogenated alkyl group.)

In the formula (1), R ¹ is an alkyl group or aryl group having 1 to 16 carbon atoms, and specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n- Hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group and linear alkyl groups such as n-hexadecyl group; Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, norbornyl group, bornyl group, isobornyl group , Cyclic alkyl groups such as decahydronaphthyl group, tricyclodecanyl group, and adamantyl group; 2-propyl group, 2-butyl group, 2-methyl-1-propyl group, 2-methyl-2-propyl group, 1-methylbutyl group, 2-methylbutyl group, 1-methylpentyl group, 1-ethylbutyl And branched alkyl groups such as a group, 2-methylhexyl group, 2-ethylhexyl group, 4-methylheptyl group, 1-methylnonyl group, 1-methyltridecyl group, and 1-methyltetradecyl group. Moreover, a benzyl group etc. are mentioned as a specific example of the aryl group. Among these, from the viewpoint of more excellent heat resistance and solubility in a polar solvent, an alkyl group and an aryl group having 6 to 14 carbon atoms are preferable, and an alkyl group and an aryl group having 6 to 10 carbon atoms are more preferable. When carbon number is 4 or less, solubility in polar solvent is inferior, when carbon number is 17 or more, heat resistance is poor, and when the resin film is patterned, there is a problem that it is melted by heat and the pattern is lost.

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

On the other hand, in the formula (2), R ² is a C 1 to C 3 divalent alkylene group, and examples of the C 1 to C 3 divalent alkylene group include a methylene group, an ethylene group, a propylene group, and an isopropylene group. have. Among these, since the polymerization activity is good, a methylene group and an ethylene group are preferable.

Further, in the above formula (2), R ³ is a C 1 to C 10 monovalent alkyl group or a C 1 to C 10 monovalent halogenated alkyl group. 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, for example, fluoromethyl group, chloromethyl group, bromomethyl group, difluoromethyl group, dichloromethyl group, difluoromethyl group, trifluoromethyl group, trichloromethyl group, 2 , 2,2-trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, perfluorobutyl group, perfluoropentyl group, and the like. Among these, since the solubility in a polar solvent is excellent, a methyl group or an ethyl group is preferable as R ³ .

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

As a cyclic olefin having an ester group, for example, 2-acetoxybicyclo[2.2.1]hepto-5-ene, 2-acetoxymethylbicyclo[2.2.1]hepto-5-ene, 2- Methoxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-ethoxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-propoxycarbonylbicyclo[2.2.1]hepto -5-ene, 2-butoxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-cyclohexyloxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-methyl-2- Methoxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-methyl-2-ethoxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-methyl-2-propoxycarbo Nylbicyclo[2.2.1]hepto-5-ene, 2-methyl-2-butoxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-methyl-2-cyclohexyloxycarbonylbicyclo[ 2.2.1]Hepto-5-ene, 2-(2,2,2-trifluoroethoxycarbonyl)bicyclo[2.2.1]hepto-5-ene, 2-methyl-2-(2,2 ,2-trifluoroethoxycarbonyl)bicyclo[2.2.1]hepto-5-ene, 2-methoxycarbonyltricyclo[5.2.1.0 ^2,6 ]deca-8-ene, 2-ethoxy Carbonyltricyclo[5.2.1.0 ^2,6 ]deca-8-ene, 2-propoxycarbonyltricyclo[5.2.1.0 ^2,6 ]deca-8-ene, 4-acetoxytetracyclo[6.2.1.1] ^3,6 .0 ^2,7 ]dodeca-9-ene, 4-methoxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodeca-9-ene, 4-ethoxycarbonyl Tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodeca-9-ene, 4-propoxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodeca-9-ene, 4-butoxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodeca-9-ene, 4-methyl-4-methoxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^{2 ,7} ]dodeca-9-ene, 4-methyl-4-ethoxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodeca-9-ene, 4-methyl-4-propoxy Carbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodeca-9-ene, 4-methyl-4-butoxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodeca-9-ene, 4-(2,2,2-trifluoroethoxycarbonyl)tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodeca-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.

As a cyclic olefin having a cyano group, for example, 4-cyanotetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodeca-9-ene, 4-methyl-4-cyanotetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ]dodeca-9-ene, 4,5-dicyanotetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodeca-9-ene, 2- Cyanobicyclo[2.2.1]hepto-5-ene, 2-methyl-2-cyanobicyclo[2.2.1]hepto-5-ene, 2,3-dicyanobicyclo[2.2.1]hepto-5 -Yen, etc.

As a cyclic olefin having an acid anhydride group, for example, tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodeca-9-ene-4,5-dicarboxylic anhydride, bicyclo[2.2 .1]hepto-5-ene-2,3-dicarboxylic anhydride, 2-carboxymethyl-2-hydroxycarbonylbicyclo[2.2.1]hepto-5-ene-anhydride, and the like.

As a cyclic olefin having a halogen atom, for example, 2-chlorobicyclo[2.2.1]hepto-5-ene, 2-chloromethylbicyclo[2.2.1]hepto-5-ene, 2-( Chlorophenyl)bicyclo[2.2.1]hepto-5-ene, 4-chlorotetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodeca-9-ene, 4-methyl-4-chlorotetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ]Dodeca-9-en, etc.

These monomers (b1) may be used individually, respectively, and may be used in combination of 2 or more types.

As the cyclic olefin monomer (b2) having no polar group, bicyclo[2.2.1]hepto-2-ene (also referred to as norbornene"), 5-ethyl-bicyclo[2.2.1]hepto-2-ene , 5-butyl-bicyclo[2.2.1]hepto-2-ene, 5-ethylidene-bicyclo[2.2.1]hepto-2-ene, 5-methylidene-bicyclo[2.2.1]hepto- 2-ene, 5-vinyl-bicyclo[2.2.1]hepto-2-ene, tricyclo[5.2.1.0 ^2,6 ]deca-3,8-diene (common 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 ]dodeca-4-ene (“tetra Cyclododecene"), 9-methyl-tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodeca-4-ene, 9-ethyl-tetracyclo[6.2.1.1 ^3,6 .0 ^{2 ,7} ]dodeca-4-ene, 9-methylidene-tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodeca-4-ene, 9-ethylidene-tetracyclo[6.2.1.1 ^{3, 6} .0 ^2,7 ]dodeca-4-ene, 9-vinyl-tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodeca-4-ene, 9-propenyl-tetracyclo[6.2. 1.1 ^3,6 .0 ^2,7 ]dodeca-4-ene, pentacyclo[9.2.1.1 ^3,9 .0 ^2,10 .0 ^4,8 ] ^pentadeca -5,12-diene, cyclobutene, cyclo Pentene, 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 individually, respectively, and may be used in combination of 2 or more types.

As a specific example of the monomer (b3) other than a cyclic olefin, 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, 3-ethyl-1-hexene, 1-octene, 1-decene, 1- Α-olefins having 2 to 20 carbon atoms such as dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; Non-conjugated dienes such as 1,4-hexadiene, 1,5-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, and 1,7-octadiene, and these And derivatives of. Among these, α-olefins are preferable. These monomers (b3) may be used individually, respectively, and may be used in combination of 2 or more types.

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

The content ratio of the unit of the copolymerizable monomer (b) in the cyclic olefin polymer (A1) is preferably 10 to 90 mol% with respect to all monomer units. If the content ratio of the unit of the copolymerizable monomer (b) is too small, the solubility of the cyclic olefin polymer (A1) in a polar solvent may be insufficient, and if too large, the radiation-sensitive compound is added to the resin composition of the present invention. When added, there is a risk that radiation-sensitive properties may become insufficient, or a dissolution residue may occur during development.

In addition, in the present invention, a cyclic olefin polymer (A1) may be obtained by introducing a protic polar group into a cyclic olefin polymer having no protic polar group using a known modifier. A polymer having no protic polar group can be obtained by polymerization by arbitrarily combining at least one of the above-described monomers (b1) and (b2) and a monomer (b3) as necessary.

In addition, 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 monomers, or may be an addition polymer obtained by addition polymerization of the above-described monomers. From the viewpoint of becoming remarkable, it is preferably a ring-opening polymer.

The ring-opening polymer can be produced by ring-opening metathesis polymerization of a cyclic olefin monomer (a) having a protic polar group and a copolymerizable monomer (b) used as necessary in the presence of a metathesis reaction catalyst. As the manufacturing method, for example, a method described in International Publication No. 2010/110323 [0039] to [0079] can be used. On the other hand, the addition polymer includes a cyclic olefin monomer (a) having a protic polar group and a copolymerizable monomer (b) used as needed, a known addition polymerization catalyst, for example, a titanium, zirconium or vanadium compound and an organoaluminum compound. It can be obtained by polymerization using a catalyst consisting of.

In addition, in the case where the cyclic olefin polymer (A1) used in the present invention is a ring-opening polymer, it is preferable to further perform a hydrogenation reaction to obtain a hydrogenated product in which a carbon-carbon double bond contained in the main chain is hydrogenated. Do. In the case where the cyclic olefin polymer (A1) is a hydrogenated product, the ratio of hydrogenated carbon-carbon double bonds (hydrogenation rate) is usually 50% or more, and from the viewpoint of heat resistance, it is preferably 70% or more, and 90 It is more preferable that it is 95% or more, and it is still more preferable that it is 95% or more.

In addition, the acrylic resin (A2) used in the present invention is not particularly limited, but is selected from a carboxylic acid having an acrylic group, a carboxylic anhydride having an acrylic group, or an epoxy group-containing acrylate compound and an oxetane group-containing acrylate compound. Homopolymers or copolymers having at least one essential component are preferred.

As a specific example of the carboxylic acid which has an acrylic group, (meth)acrylic acid [the meaning of acrylic acid and/or methacrylic acid. Hereinafter, methyl (meth)acrylate, etc. are also the same], 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, etc. are mentioned. Maleic anhydride, citraconic anhydride, etc. are mentioned as a specific example of the carboxylic anhydride which has an acrylic group.

Specific examples of the epoxy group-containing acrylate compound include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, and glycidyl α-n-butyl acrylate. , Acrylic acid-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-3,4-epoxycyclohexylmethyl, methacrylic acid-3,4-epoxycyclohexylmethyl, etc. are mentioned.

As specific examples of the oxetane group-containing acrylate compound, (meth)acrylic acid (3-methyloxetan-3-yl)methyl, (meth)acrylic acid (3-ethyloxetan-3-yl)methyl, (meth) Acrylic acid (3-methyloxetan-3-yl) ethyl, (meth) acrylic acid (3-ethyloxetan-3-yl) ethyl, (meth) acrylic acid (3-chloromethyloxetan-3-yl) methyl, ( Meth) acrylic acid (oxetan-2-yl) methyl, (meth) acrylic acid (2-methyloxetan-2-yl) methyl, (meth) acrylic acid (2-ethyloxetan-2-yl) methyl, (1- Methyl-1-oxetanyl-2-phenyl)-3-(meth)acrylate, (1-methyl-1-oxetanyl)-2-trifluoromethyl-3-(meth)acrylate, and ( 1-methyl-1-oxetanyl)-4-trifluoromethyl-2-(meth)acrylate, etc. are mentioned. Among these, (meth)acrylic acid, maleic anhydride, glycidyl (meth)acrylate, methacrylic acid-6,7-epoxyheptyl, and the like are preferable.

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

Other acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and 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)acrylic Alkyl (meth)acrylates, such as a rate, lauryl (meth)acrylate, stearyl (meth)acrylate, and isostearyl (meth)acrylate; Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth) Hydroxyalkyl (meth)acrylates such as acrylate and 4-hydroxybutyl (meth)acrylate; Phenoxyalkyl (meth)acrylates such as phenoxyethyl (meth)acrylate and 2-hydroxy-3-phenoxypropyl (meth)acrylate; 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-propoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-methoxybutyl ( Alkoxyalkyl (meth)acrylates such as meth)acrylate; Polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, Polyalkylene glycols such as polypropylene glycol mono (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, ethoxy polypropylene glycol (meth) acrylate, and nonylphenoxy polypropylene glycol (meth) acrylate ( 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 ]decane-8-yl(meth)acrylate, tricyclo[5.2.1.0 ^{2, 6} ]-3-decen-8-yl(meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]-3-decen-9-yl(meth)acrylate, bornyl(meth)acrylate, isobor Cycloalkyl (meth)acrylates such as nil (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)ethyl (meth)acrylate, 2-[tricyclo[5.2.1.0 ^2,6 ]decane-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-butyl Maleimide, N-cyclohexylmaleimide, 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, etc. are mentioned. 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} ]decane-8-yl(meth)acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, and the like are preferred.

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 anhydride having an acrylic group, or an acrylate compound containing an epoxy group. For example, vinylbenzyl methyl ether, Vinyl glycidyl ether, styrene, α-methylstyrene, vinyltoluene, indene, vinylnaphthalene, vinylbiphenyl, chlorostyrene, bromostyrene, chloromethylstyrene, p-tert-butoxystyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-acetoxystyrene, p-carboxystyrene, 4-hydroxyphenylvinylketone, acrylonitrile, methacrylonitrile, (meth)acrylamide, 1,2-epoxy- And radical polymerizable compounds such as 4-vinylcyclohexane, isobutene, norbornene, butadiene, and isoprene. These compounds may be used individually, respectively, and may be used in combination of 2 or more types. The polymerization method of the monomer may be performed according to a conventional method, and for example, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method, and the like are employed.

The cardo resin (A3) used in the present invention is a resin having a cardo structure, that is, a skeletal structure in which two cyclic structures are bonded to a quaternary carbon atom constituting a cyclic structure. The general cardo structure is a benzene ring bonded to a fluorene ring.

Specific examples of a skeletal structure in which two cyclic structures are bonded to a quaternary carbon atom constituting a cyclic structure include a fluorene skeleton, a bisphenol fluorene skeleton, a bisaminophenylfluorene skeleton, a fluorene skeleton having an epoxy group, And a fluorene skeleton having an acrylic group.

The cardo resin (A3) used in the present invention is formed by polymerization by a reaction or the like between the functional groups bonded thereto by the skeleton having the cardo structure. Cardo resin (A3) has a structure (cardo structure) in which a main chain and a bulk side chain are connected by one element, and has a cyclic structure in a direction substantially perpendicular to the main chain.

As an example of the cardo structure, an example of the cardo structure having an epoxy glycidyl ether structure is shown in the following formula (3).

[Formula 3]

(In said formula (3), n is an integer of 0-10.)

The monomer having a cardo structure is, for example, bis(glycidyloxyphenyl)fluorene type epoxy resin; Condensation product of bisphenol fluorene type epoxy resin and acrylic acid; Cardo structure-containing bisphenols, such as 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-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 9,9-bis(3-aminopropyl)fluorene, etc. are mentioned.

Cardo resin (A3) 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 performed according to a conventional method, and for example, a ring-opening polymerization method or an addition polymerization method or the like is employed.

Although it does not specifically limit as the polysiloxane (A4) used by this invention, Preferably, the polymer obtained by mixing and reacting 1 type or 2 or more types of organosilane represented by following formula (4) is mentioned.

(R ⁴ ) _m -Si-(OR ⁵ ) _4-m (4)

In the formula (4), R ⁴ 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 6 to 15 carbon atoms, and a plurality of R ⁴ may be the same or different, respectively. . In addition, these alkyl groups, alkenyl groups, and aryl groups may all have a substituent, or may be an unsubstituted body not having a substituent, and may be selected according to the characteristics of the composition. 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 and a 3-isocyanate propyl group. As a specific example of an alkenyl group, a vinyl group, a 3-acryloxypropyl group, and a 3-methacryloxypropyl group are mentioned. 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 are mentioned.

In addition, in the formula (4), R ⁵ 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 ⁵ may be the same or different. You can do it. In addition, all of these alkyl groups and acyl groups may have a substituent or may be an unsubstituted body not having a substituent, and may be selected according to the characteristics of the composition. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, and n-butyl group. An acetyl group is mentioned as a specific example of an acyl group. A phenyl group is mentioned as a specific example of the aryl group.

In the formula (4), m is an integer of 0 to 3, in the case of m = 0, a tetrafunctional silane, in the case of m = 1, a trifunctional silane, and in the case of m = 2, a bifunctional silane. In the case of m = 3, it is a monofunctional silane.

Specific examples of the organosilane represented by the above formula (4) 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-hexyltriethoxy Silane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane Silane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 1-(p-hydroxyphenyl)ethyltrimethoxysilane, 2-(p-hydroxyphenyl)ethyltri Methoxysilane, 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, 3,3,3 -Trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl) Trifunctional silanes such as ethyl trimethoxysilane and 3-mercaptopropyl trimethoxysilane; Difunctional silanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, din-butyldimethoxysilane, and diphenyldimethoxysilane; And monofunctional silanes such as trimethylmethoxysilane and trin-butylethoxysilane.

Among these organosilanes, trifunctional silanes are preferably used from the viewpoint of crack resistance and hardness of the obtained resin film. These organosilanes may be used alone or in combination of two or more.

The polysiloxane (A4) used in the present invention is obtained by hydrolyzing and partially condensing the organosilane described above. General methods can be used for hydrolysis and partial condensation. For example, a solvent, water, and, if necessary, a catalyst are added to the mixture, followed by heating and stirring. During stirring, if necessary, hydrolysis by-products (alcohol such as methanol) and condensation by-products (water) may be distilled off by distillation.

The polyimide (A5) used in the present invention can be obtained by heat-treating a polyimide precursor obtained by reacting a tetracarboxylic anhydride and a diamine. As a precursor for obtaining a polyimide, polyamic acid, polyamic acid ester, polyisoimide, polyamic acid sulfonamide, etc. are mentioned.

The polyimide (A5) used in the present invention is synthesized by a known method. That is, tetracarboxylic dianhydride and diamine are selectively combined, and these are N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, hexamethylphos It is synthesized by a known method, such as reacting in a polar solvent such as porotriamide, γ-butyrolactone, and cyclopentanone.

When the diamine is excessively used for polymerization, a carboxylic anhydride can be reacted with the terminal amino group of the produced polyimide (A5) to protect the terminal amino group. Further, when polymerization is performed using an excess of tetracarboxylic acid anhydride, an amine compound may be reacted with the terminal acid anhydride group of the produced polyimide (A5) to protect the terminal acid anhydride group.

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

The weight average molecular weight (Mw) of the binder resin (A) used in the present invention is usually in the range of 1,000 to 1,000,000, preferably 1,500 to 100,000, and more preferably 2,000 to 10,000.

In addition, the molecular weight distribution of the binder resin (A) is a weight average molecular weight/number average molecular weight (Mw/Mn) ratio, and is usually 4 or less, preferably 3 or less, and more preferably 2.5 or less.

The weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the binder resin (A) are determined as polystyrene conversion values by gel permeation chromatography (GPC) using a solvent such as tetrahydrofuran as an eluent. Losing value.

(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 or electron beams. In the present invention, the radiation-sensitive compound (B) is preferably capable of controlling the alkali solubility of the resin film formed from the resin composition, and particularly, it is preferable to use a photoacid generator.

Examples of the radiation-sensitive compound (B) include an azide compound such as an acetophenone compound, a triarylsulfonium salt, and a quinone diazide compound, but preferably an azide compound, particularly preferably a quinone It is a diazide compound.

As the quinone diazide compound, for example, an ester compound of a quinone diazide sulfonic 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, etc. are mentioned. Representative examples of the compound having a phenolic hydroxyl group include 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane, 4,4'-[1-[4-[ 1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol, and the like. Compounds having phenolic hydroxyl groups other than these include 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, and 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, furnace Oligomers of rock resins, oligomers obtained by copolymerizing a compound having one or more phenolic hydroxyl groups with dicyclopentadiene, and the like.

In addition, as a photoacid generator, in addition to a quinone diazide compound, an onium salt, a halogenated organic compound, an α,α'-bis(sulfonyl)diazomethane compound, and an α-carbonyl-α'-sulfonyldiazomethane Known compounds, such as a system compound, a sulfone compound, an organic acid ester compound, an organic acid amide compound, and an organic acid imide compound, can be used.

Each of 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 10 to 100 parts by weight, more preferably 15 to 70 parts by weight, based on 100 parts by weight of the binder resin (A). , More preferably 20 to 50 parts by weight. By setting the content of the radiation-sensitive compound (B) to this range, exposure sensitivity, shape retention after firing, and transparency of the resin film obtained by using the radiation-sensitive resin composition of the present invention can be made more favorable.

(Crosslinking agent (C))

The crosslinking agent (C) used in the present invention is to form a crosslinked structure between the crosslinking agent molecules by heating, or to form a crosslinked structure between the resin molecules by reacting with the binder resin (A). And compounds having a group. Examples of such a reactive group include an amino group, a carboxyl group, a hydroxyl group, an epoxy group, and an isocyanate group, more preferably an amino group, an epoxy group, and an isocyanate group, and an amino group and an epoxy group are particularly preferable.

The molecular weight of the crosslinking agent (C) is not particularly limited, but is usually 100 to 100,000, preferably 300 to 50,000, and more preferably 500 to 10,000. The crosslinking agent (C) can be used alone or in combination of two or more, and in particular, by using two or more kinds in combination, exposure sensitivity of the resin film obtained using the radiation-sensitive resin composition of the present invention, shape retention after firing, And transparency can be made better.

As a specific example of a crosslinking agent (C), Aliphatic polyamines, such as hexamethylenediamine; Aromatic polyamines such as 4,4'-diaminodiphenyl ether and diaminodiphenylsulfone; Azides, such as 2,6-bis(4'-azidebenzal)cyclohexanone and 4,4'-diazide diphenyl sulfone; Polyamides such as nylon, polyhexamethylenediamine terephthalamide, and polyhexamethylene isophthalamide; Melamines which may have methylol groups such as N,N,N',N',N",N"-(hexaalkoxyalkyl) melamine, imino groups, etc. (brand names "Cymel 303, Cymel 325, Cymel 370 , Cymel 232, Cymel 235, Cymel 272, Cymel 212, Mycoat 506" (above, Cytech Industries, Inc. make) and other Cymel series, Mycoat series); Glycourils which may have methylol groups such as N,N',N",N"'-(tetraalkoxyalkyl)glycoluril, imino groups, etc. (trade name "Cymel 1170" {above, manufactured by Cytech Industries Co., Ltd.} Cymel series such as); Acrylate compounds such as ethylene glycol di(meth)acrylate; Isocyanate compounds, such as hexamethylene diisocyanate type polyisocyanate, isophorone diisocyanate type polyisocyanate, tolylene diisocyanate type polyisocyanate, and hydrogenated diphenylmethane diisocyanate; 1,4-di-(hydroxymethyl)cyclohexane, 1,4-di-(hydroxymethyl)norbornane; 1,3,4-trihydroxycyclohexane; Bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolac type epoxy resin, polyphenol type epoxy resin, cyclic aliphatic epoxy resin, aliphatic glycidyl ether, epoxy acrylate polymer, etc. Epoxy compounds are mentioned.

As a specific example of the epoxy compound, a trifunctional epoxy compound having dicyclopentadiene as a skeleton (trade name "XD-1000", manufactured by Nippon Explosives Co., Ltd.), 1 of 2,2-bis(hydroxymethyl)1-butanol ,2-epoxy-4-(2-oxylanyl)cyclohexane adduct (15 functional alicyclic epoxy resin having a cyclohexane skeleton and terminal epoxy group, brand name ``EHPE3150'', manufactured by Daicel Chemical Industries, Ltd.), epoxidation 3 -Cyclohexene-1,2-dicarboxylic acid bis(3-cyclohexenylmethyl) formula ε-caprolactone (aliphatic cyclic trifunctional epoxy resin, brand name "Epolide GT301", manufactured by Daicel Chemical Industries, Ltd.) , Epoxidized butanetetracarboxylic acid tetrakis (3-cyclohexenylmethyl) formula ε-caprolactone (aliphatic cyclic tetrafunctional epoxy resin, brand name ``Epolide GT401'', manufactured by Daicel Chemical Industries, Ltd.), 3, 4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate (trade names "Celoxide 2021", "Celoxide 2021P", manufactured by Daicel Chemical Industries, Ltd.), 1,2:8,9-D Epoxylimonene (brand name "Celloxide 3000", manufactured by Daicel Chemical Industries, Ltd.), 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (brand name "Z-6043", manufactured by Toray Dow Corning), etc. Epoxy compounds having an alicyclic structure;

Aromatic amine type polyfunctional epoxy compound (trade name "H-434", manufactured by Toto Chemical Industries, Ltd.), isocyanurate tris (2,3-epoxypropyl) (polyfunctional epoxy compound having a triazine skeleton, brand name "TEPIC", Nissan Chemical Co., Ltd.), cresol novolac-type polyfunctional epoxy compound (trade name ``EOCN-1020'', manufactured by Nippon Explosives Co., Ltd.), phenol novolak-type polyfunctional epoxy compound (Epicoat 152, 154, Japan Epoxy Resin Co., Ltd.), Polyfunctional epoxy compound having a naphthalene skeleton (trade name EXA-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 ``E Polyde PB3600", Daicel Chemical Industries, Ltd.), glycerin glycidyl polyether compound (trade name "SR-GLG", Sakamoto Pharmaceutical Co., Ltd. product), diglycerin polyglycidyl ether compound (trade name "SR-DGE" , Manufactured by Sakamoto Pharmaceutical Co., Ltd., polyglycerin polyglycidyl ether compound (brand name ``SR-4GL'', manufactured by Sakamoto Pharmaceutical Co., Ltd.), glycidoxypropyltrimethylsilane (brand name ``Z-6040'', manufactured by Toray Dow Corning) Epoxy compounds which do not have an alicyclic structure, such as), are mentioned.

The content of the crosslinking agent (C) in the radiation-sensitive resin composition of the present invention is not particularly limited, and may be arbitrarily set in consideration of the degree of heat resistance required for the resin film obtained by using the radiation-sensitive resin composition of the present invention. , With respect to 100 parts by weight of the binder resin (A), it is usually 5 to 80 parts by weight, preferably 20 to 75 parts by weight, and more preferably 25 to 70 parts by weight. Even if there are too many crosslinking agents (C), there exists a tendency for at least heat resistance to fall too much.

(Sulfur-free semi-hindered phenolic antioxidant and/or sulfur-free less-hindered phenolic antioxidant (D))

In addition, the radiation-sensitive resin composition of the present invention, in addition to the above-described binder resin (A), radiation-sensitive compound (B), and crosslinking agent (C), does not contain a sulfur-free semi-hindered phenolic antioxidant and/or does not contain sulfur. It contains the less hindered phenol type antioxidant (D).

The sulfur-free semi-hindered phenolic antioxidant is a semi-hindered phenolic antioxidant that does not substantially contain sulfur atoms, i.e., has a phenolic structure, does not contain a sulfur atom substantially, and has a phenolic structure. One of the ortho positions of the constituting OH group (phenolic hydroxyl group) is a bulk group (eg, t-butyl group), and the other is a methyl group.

In addition, the sulfur-free less hindered phenolic antioxidant is a less hindered phenolic antioxidant that does not substantially contain a sulfur atom, that is, has a phenolic structure, does not substantially contain a sulfur atom, and One of the ortho positions of the OH group (phenolic hydroxyl group) constituting the structure is a bulk group (eg, t-butyl group), and the other is an antioxidant in which hydrogen. In addition, in this invention, "sulfur-free" means that a sulfur atom is not contained substantially, and even if it contains as long as it is about the amount of impurities, there is no problem.

As a specific example of the sulfur-free semi-hindered phenol-based antioxidant, for example, 3,9-bis[2-{3-(3-tertiary butyl-4-hydroxy-5-methylphenyl)propionyloxy }-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane (for example, the brand name "Adecastab AO-80", manufactured by ADEKA), ethylenebis (Oxyethylene)bis[3-(5-tert-butyl-hydroxy-m-tolyl)propionate] (for example, the brand name "Irganox 245", manufactured by BASF), triethylene glycolbis[3 -(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] (For example, a brand name "Adecastab AO-70", manufactured by ADEKA), etc. are mentioned.

In addition, as a specific example of the sulfur-free less hindered phenol-based antioxidant, for example, 1,1,3-tris-(2-methyl-4-hydroxy-5-tertiarybutylphenyl)butane (Example For example, the brand name "adecastab AO-30", manufactured by ADEKA), 4,4'-butylidenebis(6-t-butyl-3-methylphenol) (for example, the brand name "adecastab AO" -40", manufactured by ADEKA), 4,4'-thiobis(6-t-butyl-3-methylphenol) (e.g., brand name "Smilizer WX-R", manufactured by Sumitomo Chemical), etc. have.

These sulfur-free semi-hindered phenolic antioxidants and sulfur-free less-hindered phenolic antioxidants may be used alone or in combination of two or more.

The content of the sulfur-free semi-hindered phenolic antioxidant and/or sulfur-free less hindered phenolic antioxidant (D) in the radiation-sensitive resin composition of the present invention is based on 100 parts by weight of the binder resin (A). , Preferably it is 0.1 to 20 parts by weight, more preferably 1 to 15 parts by weight, and still more preferably 2 to 10 parts by weight. Exposure sensitivity of a resin film obtained by using the radiation-sensitive resin composition of the present invention by making the content of the crosslinking agent sulfur-free semi-hindered phenolic antioxidant and/or sulfur-free non-hindered phenolic antioxidant (D) within this range , Shape retention after firing, and transparency can be made more favorable.

(Sulfur-containing phenolic antioxidant (E))

In addition, the radiation-sensitive resin composition of the present invention includes the above-described binder resin (A), radiation-sensitive compound (B) and crosslinking agent (C), and a sulfur-free semi-hindered phenolic antioxidant and/or sulfur-free. In addition to the less hindered phenolic antioxidant (D), a sulfur-containing phenolic antioxidant (E) is contained.

The sulfur-containing phenolic antioxidant (E) is a phenolic antioxidant containing a sulfur atom. As a specific example of the sulfur-containing phenolic antioxidant (E), 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4, 4'-thiobis(6-t-butyl-3-methylphenol), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino )-1,3,5-triazine, 2,4-bis[(octylthio)methyl]-ortho-cresol, 4,6-bis[(dodecylthio)methyl]-ortho-cresol, phosphorous acid tris(2 ,4-di-t-butylphenyl) and the like.

The sulfur-containing phenolic antioxidants may be used alone or in combination of two or more. Among these, a hindered phenolic antioxidant containing a sulfur atom, containing a sulfur atom, from the viewpoint of the high effect of improving the exposure sensitivity, shape retention after firing, and transparency of the resin film obtained by using the radiation-sensitive resin composition of the present invention. The semi-hindered phenol type antioxidant and the less hindered phenol type antioxidant containing a sulfur atom are preferable.

The content of the sulfur-containing phenolic antioxidant (E) in the radiation-sensitive resin composition of the present invention is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 10 parts by weight based on 100 parts by weight of the binder resin (A). It is a weight part, More preferably, it is 1-5 weight part. By setting the content of the sulfur-containing phenolic antioxidant (E) in this range, exposure sensitivity, shape retention after firing, and transparency of the resin film obtained using the radiation-sensitive resin composition of the present invention can be made more favorable.

(Compound (F) having an acidic group or a thermally latent acidic group)

Moreover, the radiation-sensitive resin composition of this invention may contain the compound (F) which has an acidic group or a heat latent acidic group in addition to each component mentioned above. The compound having an acidic group or a thermally latent acidic group may have an acidic group or a thermally latent acidic group that generates an acidic group by heating, and is not particularly limited, but is preferably an aliphatic compound, an aromatic compound, or a heterocyclic compound. Preferably, they are an aromatic compound and a heterocyclic compound. These compounds having an acidic group or a thermally latent acidic group may be used alone or in combination of two or more. By blending the compound (F) having an acidic group or a thermally latent acidic group, it is possible to further improve the shape retention of the resin film obtained by using the radiation-sensitive resin composition of the present invention after firing.

The number of acidic groups in the compound having an acidic group is not particularly limited, but it is preferable to have two or more acidic groups. The acidic groups may be the same or different from each other.

As an acidic group, what is necessary is just to be an acidic functional group, As a specific example, Strong acidic groups, such as a sulfonic acid group and a phosphoric acid group; Weakly acidic groups, such as a carboxyl group, a thiol group, and a carboxymethylenethio group, are mentioned. Among these, a carboxyl group, a thiol group, or a carboxymethylenethio group is preferable, and a carboxyl group is particularly preferable. Moreover, among these acidic groups, it is preferable that the acid dissociation constant pKa is in the range of 3.5 or more and 5.0 or less. In addition, when there are two or more acidic groups, the first dissociation constant pKa1 is used as the acid dissociation constant, and the first dissociation constant pKa1 is preferably in the above range. In addition, pKa is determined according to pKa = -logKa by measuring the acid dissociation constant Ka = [H ₃ O ⁺ ][B ^- ]/[BH] under the condition of a dilute aqueous solution. Here, BH represents an organic acid, and B ^- represents a conjugated base of an organic acid. In addition, the measurement method of pKa can measure the hydrogen ion concentration using, for example, a pH meter, and calculate it from the concentration of the substance and the hydrogen ion concentration.

Moreover, the compound which has an acidic group may have a substituent other than an acidic group.

Examples of such a substituent include hydrocarbon groups such as an alkyl group and an aryl group, as well as a halogen atom; Alkoxy group, aryloxy group, acyloxy group, heterocyclic oxy group; An amino group, an acylamino group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, or an aryloxycarbonylamino group substituted with an alkyl group, aryl group, or heterocyclic group; And a polar group having no proton, such as an alkylthio group, an arylthio group, and a heterocyclic thio group, and a hydrocarbon group substituted with a polar group having no proton.

Specific examples of the compound (F) having such an acidic group include methanic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, glycolic acid, and glyceric acid. , Ethanoic acid (also called “oxalic acid”), propanoic acid (also called “malonic acid”), butanedioic acid (also called “succinic acid”), pentanedioic acid, hexanoic acid (also called “adipic acid”), 1,2 -Cyclohexanedicarboxylic acid, 2-oxopropanoic acid, 2-hydroxybutane diacid, 2-hydroxypropanetricarboxylic acid, mercaptosuccinic acid, dimercaptosuccinic acid, 2,3-dimercapto-1- Propanol, 1,2,3-trimercaptopropane, 2,3,4-trimercapto-1-butanol, 2,4-dimercapto-1,3-butanediol, 1,3,4-trimercapto Aliphatic compounds such as 2-butanol, 3,4-dimercapto-1,2-butanediol, and 1,5-dimercapto-3-thiapentane;

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 (" 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, 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)benzene, 1,3,5-tris(mercaptomethyl)benzene, 1,2,3-tris(mercaptoethyl) ) Aromatic compounds such as benzene, 1,2,4-tris(mercaptoethyl)benzene, and 1,3,5-tris(mercaptoethyl)benzene;

Nicotinic acid, isonicotinic acid, 2-proic acid, pyrrole-2,3-dicarboxylic acid, pyrrole-2,4-dicarboxylic acid, pyrrole-2,5-dicarboxylic acid, pyrrole-3,4-dicar Carboxylic acid, imidazole-2,4-dicarboxylic acid, imidazole-2,5-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, pyrazole-3,4-dicarboxyl 5-membered heterocyclic compounds containing nitrogen atoms such as acid and pyrazole-3,5-dicarboxylic acid; 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-(2-mer 5-membered heterocyclic compounds containing a nitrogen atom and a sulfur atom, such as capto-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-dicarboxyl 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-dipropylamino-4,6-dimercapto-s-triazine, 2-dibutylamino Nitrogen atoms such as -4,6-dimercapto-s-triazine, 2-anilino-4,6-dimercapto-s-triazine, and 2,4,6-trimercapto-s-triazine The 6-membered heterocyclic compound containing is mentioned.

Among these, it is preferable that the number of acidic groups is 2 or more from a viewpoint that adhesiveness of the obtained cured film can be improved more.

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

The content of the compound having an acidic group or a thermally latent acidic group (F) in the radiation-sensitive resin composition of the present invention is preferably 0.1 to 50 parts by weight, more preferably based on 100 parts by weight of the binder resin (A). Preferably, it is in the range of 1 to 45 parts by weight, more preferably 2 to 40 parts by weight, particularly preferably 3 to 30 parts by weight. By setting the amount of the compound (F) having an acidic group or a thermally latent acidic group to the above range, it is possible to appropriately increase the shape retention of the obtained resin film after firing.

(Other formulations)

The radiation-sensitive resin composition of the present invention may further contain a solvent. The solvent is not particularly limited, and known as a solvent for the resin composition, such as acetone, methyl ethyl ketone, cyclopentanone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone , Linear ketones such as 4-heptanone, 2-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 ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Esters such as propyl formate, butyl formate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl lactate, and ethyl lactate; Cellosolve esters, such as a cellosolve acetate, a methyl cellosolve acetate, an ethyl cellosolve acetate, a propyl cellosolve acetate, and a butyl cellosolve acetate; Propylene glycols such as propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monobutyl ether; Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether; saturated γ-lactones such as γ-butyrolactone, γ-valerolactone, γ-caprolactone, and γ-caprylolactone; Halogenated hydrocarbons such as trichloroethylene; Aromatic hydrocarbons such as toluene and xylene; And 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 in the range of preferably 10 to 10000 parts by weight, more preferably 50 to 5000 parts by weight, still more preferably 100 to 1000 parts by weight, based on 100 parts by weight of the binder resin (A). In addition, when the resin composition contains a solvent, the solvent is usually removed after the resin film is formed.

In addition, the radiation-sensitive resin composition of the present invention, if desired, as long as the effect of the present invention is not impaired, a surfactant, a coupling agent or a derivative thereof, a sensitizer, a light stabilizer, an antifoaming agent, a pigment, a dye, a filler, etc. It may contain other compounding agents and the like. Among these, for example, a coupling agent or a derivative thereof, a sensitizer, and a light stabilizer may be those described in JP2011-75609A.

Surfactants are used for the purpose of preventing striation (marking of coating streaks) and improving developability. Examples of the surfactant include silicone surfactants, fluorine surfactants, polyoxyalkylene surfactants, methacrylic acid copolymer surfactants, and acrylic acid copolymer surfactants.

As a silicone surfactant, for example, "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) , Brand names "KP-321", "KP-323", "KP-324", "KP-340", "KP-341" (above, manufactured by Shin-Etsu Chemical Industries, Ltd.), brand names "TSF400", "TSF401", ``TSF410'', ``TSF4440'', ``TSF4445'', ``TSF4450'', ``TSF4446'', ``TSF4452'', ``TSF4460'' (above, manufactured by Momentive Performance Materials Japan joint company), brand name ``BYK300'', "BYK301", "BYK302", "BYK306", "BYK307", "BYK310", "BYK315", "BYK320", "BYK322", "BYK323", "BYK331", "BYK333", "BYK370" "BYK375" , "BYK377", "BYK378" (above, manufactured by Big Chemistry Japan), and the like.

As a fluorine-based surfactant, for example, fluorine nut "FC-430", "FC-431" (above, manufactured by Sumitomo 3M), Suflon "S-141", "S-145", "S- 381'', ``S-393'' (above, manufactured by Asahi Glass Co., Ltd.), FTOP (registered trademark) ``EF301'', ``EF303'', ``EF351'', ``EF352'' (above, manufactured by Gemco Corporation), MegaPak (registered) Trademark) "F171", "F172", "F173", "R-30" (above, manufactured by DIC Corporation), etc. are mentioned.

Examples of polyoxyalkylene surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, and polyoxyethylene nonylphenyl ether. Oxyethylene alkyl ethers, polyethylene glycol dilaurate, polyethylene glycol distearate polyoxyethylene dialkyl esters, etc. are mentioned.

These surfactants may 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 0.05 to 5 parts by weight, more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the binder resin (A). When the content of the surfactant is in the above range, the effect of preventing striation (applied streaks) can be further enhanced.

The method for preparing the radiation-sensitive resin composition of the present invention is not particularly limited, and each component constituting the radiation-sensitive resin composition may be mixed by a 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, the radiation-sensitive resin composition is obtained in the form of a solution or dispersion.

A method of dissolving or dispersing each component constituting the radiation-sensitive resin composition in a solvent may be performed according to 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, three rolls, or the like can be used. Further, after dissolving or dispersing each component in a solvent, it may be filtered using, for example, a filter having a pore diameter 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 radiation-sensitive resin composition of the present invention described above.

Examples of the electronic component of the present invention include those having a configuration in which a semiconductor element is mounted on a substrate, and specifically, an active matrix substrate, an organic EL element substrate, an integrated circuit element substrate, and a solid state An imaging device substrate or the like may be mentioned, and an active matrix substrate and an organic EL device substrate are preferred from the viewpoint of particularly remarkable effect of improving properties by forming the resin film made of the radiation-sensitive resin composition of the present invention described above.

The active matrix substrate as an example of the electronic component of the present invention is not particularly limited, but a switching element such as a thin film transistor (TFT) is disposed on the substrate in a matrix form, and a gate signal for driving the switching element is provided. A configuration in which a gate signal line to be supplied and a source signal line for supplying a display signal to the switching element are formed to cross each other is exemplified. In addition, as a thin film transistor as an example of a switching element, a structure including a gate electrode, a gate insulating layer, a semiconductor layer, a source electrode, and a drain electrode on a substrate, etc. are exemplified.

In addition, as an organic EL element substrate as an example of the electronic component of the present invention, for example, on the substrate, a light-emitting body portion composed of an anode, a hole injection transport layer, an organic light-emitting layer as a semiconductor layer, an electron injection layer, and a cathode, and the like, , And having a configuration having a pixel separation film for separating the light-emitting body portion are exemplified.

For example, when the electronic component of the present invention is an active matrix substrate, the resin film made of the radiation-sensitive resin composition of the present invention described above constitutes a protective film, a planarization film, and an active matrix substrate formed on the surface of the active matrix substrate. A gate insulating film formed by contacting a semiconductor layer (for example, an amorphous silicon layer) of a thin film transistor can be used. Alternatively, when the electronic component of the present invention is an organic EL element substrate, it can be used as a sealing film formed on the surface of the organic EL element substrate.

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

The coating method is, for example, a method of applying a radiation-sensitive resin composition, followed by heating and drying to remove a solvent. As a method of applying the radiation-sensitive resin composition, various methods such as a spray method, a spin coat method, a roll coat method, a die coat method, a doctor blade method, a rotation coating method, a bar coating method, and a screen printing method are used. Can be adopted. The heating and drying conditions are different depending on the type and blending ratio of each component, but usually at 30 to 150°C, preferably at 60 to 120°C, usually 0.5 to 90 minutes, preferably 1 to 60 minutes, more Preferably, it may be carried out for 1 to 30 minutes.

In the film lamination method, after applying the radiation-sensitive resin composition onto a substrate for forming a B stage film such as a resin film or a metal film, the solvent is removed by heat drying to obtain a B stage film, and then this B stage film is This is how to stack. The heating and drying conditions can be appropriately selected depending on the kind 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 press machine such as a pressure laminator, a press, a vacuum laminator, a vacuum press, and a roll laminator.

The thickness of the resin film is not particularly limited and may be appropriately set according to the application. When the resin film is a protective film for an active matrix substrate, a planarization film, or a sealing film for an organic EL element substrate, the thickness of the resin film is preferably Is 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 of patterning the resin film, for example, using the radiation-sensitive resin composition of the present invention, the resin film before patterning is formed, the resin film before patterning is irradiated with actinic radiation to form a latent image pattern, and then And a method of making the pattern visible by contacting a developer with a resin film having a latent image pattern.

The actinic radiation is not particularly limited as long as it can 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). Specifically, ultraviolet rays, single-wavelength ultraviolet rays such as g-rays and i-rays, rays such as KrF excimer laser light, and ArF excimer laser light; Particle beams such as electron beams can be used. As a method of forming a latent image pattern by selectively irradiating these active radiation in a pattern, a conventional method may be used, for example, ultraviolet rays, g-line, i-line, KrF excimer laser light by a reduction projection exposure apparatus or the like. , A method of irradiating light rays such as ArF excimer laser light through a desired mask pattern, or a method of drawing with particle beams such as electron beams, etc. can be used. When a light beam is used as the actinic radiation, it may be a single wavelength light or a mixed wavelength light. The irradiation conditions are appropriately selected depending on the active radiation to be used. For example, when a light beam having a wavelength of 200 to 450 nm is used, the irradiation amount is usually 10 to 1,000 mJ/cm 2, preferably 50 to 500 mJ/cm 2 It is a range and is determined according to the irradiation time and illuminance. After irradiating the active radiation in this way, the resin film is heat treated at a temperature of about 60 to 130°C for about 1 to 2 minutes, if necessary.

Next, the latent image pattern formed on the resin film before patterning is developed and made visible. As a 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; Secondary amines such as diethylamine and di-n-propylamine; Tertiary amines such as triethylamine and methyldiethylamine; Quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide and choline; Alcohol amines such as dimethylethanolamine and triethanolamine; Pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]undeca-7-ene, 1,5-diazabicyclo[4.3.0]nona-5-ene, N-methylpyrrolidone, etc. And cyclic amines. Each of these alkaline compounds can be used alone or in combination of two or more.

As an aqueous medium of an alkaline aqueous solution, water; Water-soluble organic solvents such as methanol and ethanol can be used. The alkaline aqueous solution may be obtained by adding an appropriate amount of a surfactant or the like.

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

In this way, the resin film on which the target pattern is formed can be rinsed with a rinse solution in order to remove the development residue, if necessary. After the rinsing treatment, the remaining rinse liquid is removed with compressed air or compressed nitrogen.

Further, if necessary, in order to deactivate the radiation-sensitive compound (B) contained in the radiation-sensitive resin composition, the entire surface of the electronic component may be irradiated with active radiation. For irradiation of active radiation, the method exemplified for formation of the latent image pattern can be used. You may heat the resin film simultaneously with irradiation or after irradiation. As a heating method, a method of heating an electronic component in a hot plate or an oven is mentioned, for example. The temperature is usually in the range of 100 to 300°C, preferably 120 to 200°C.

After patterning the resin film formed in this way, a crosslinking reaction can be performed. Such crosslinking may be performed by appropriately selecting a method according to the type of crosslinking agent (C) 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 depending on the area or thickness of the resin film, the equipment used, etc. For example, when using a hot plate, usually 5 to 60 minutes, the oven In the case of using, it is usually in the range of 30 to 90 minutes. Heating may be performed in an inert gas atmosphere as necessary. As an inert gas, what is necessary is just what does not contain oxygen and does not oxidize a resin film, For example, nitrogen, argon, helium, neon, xenon, krypton, etc. are mentioned. 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 preferable. These inert gases may be used alone or in combination of two or more.

In this way, an electronic component provided with 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 a patterned resin film in this way, additional components (for example, ITO electrodes, alignment films, etc.) In order to perform baking solidification, baking is performed in an oxidizing atmosphere such as in the air. The firing temperature at this time is usually 150 to 350°C, preferably 180 to 300°C, and more preferably 200 to 250°C. In addition, at this time, the patterned resin film obtained by using the radiation-sensitive resin composition of the present invention is similarly fired in an oxidizing atmosphere. However, on the other hand, since the resin film thus formed is obtained using the radiation-sensitive resin composition of the present invention described above, high transparency can be realized even after firing in an oxidizing atmosphere as described above, and therefore, the active matrix It is suitable for use in various electronic components such as substrates and organic EL element substrates. Further, in addition to this, since the resin film obtained by using the radiation-sensitive resin composition of the present invention has high exposure sensitivity, the amount of radiation irradiated during production can be reduced, thereby improving productivity. Furthermore, since the resin film obtained by using the radiation-sensitive resin composition of the present invention is excellent in shape retention after firing, a fine pattern can be formed with high precision, and thereby it can also contribute to miniaturization and high performance of electronic components.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. "Parts" in each example are based on weight unless otherwise noted.

In addition, the definition and evaluation method of each characteristic are as follows.

<Exposure sensitivity>

On a glass substrate (Corning, product name Corning 1737), a radiation-sensitive resin composition was applied by a spin coating method, and then heat-dried (prebaked) at 90° C. for 2 minutes using a hot plate, and a resin having a film thickness of 3 μm A film was formed. Next, in order to pattern the resin film, an exposure step was performed by changing the exposure amount every 50 mJ/cm 2 from 100 mJ/cm 2 to 250 mJ/cm 2 using a mask capable of forming a 5 μm contact hole pattern. Subsequently, development treatment was performed at 25° C. for 120 seconds using a 0.4% by weight aqueous solution of tetramethylammonium hydroxide, followed by rinsing with ultrapure water for 30 seconds, thereby comprising a resin film having a contact hole pattern having a different exposure amount and a glass substrate. A laminate was obtained.

And the contact hole formation part of the obtained laminated body was observed using an 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, the exposure amount when the contact hole pattern becomes 5 μm is calculated, and the exposure amount is determined by exposure sensitivity. It was calculated as. The lower the exposure amount when the contact hole pattern becomes 5 µm, the more preferable it is because the contact hole can be formed with lower energy or in a short time.

＜Heat resistance and transparency＞

On a glass substrate (Corning, product name Corning 1737), a radiation-sensitive resin composition was applied by a spin coating method, and then heat-dried (prebaked) at 90° C. for 2 minutes using a hot plate, and a resin having a film thickness of 3 μm A film was formed. Next, the resin film was immersed for 120 seconds at 25°C using a 0.4% by weight aqueous solution of tetramethylammonium hydroxide, and then washed with ultrapure water for 30 seconds, followed by light in 365 nm. Ultraviolet rays having an intensity of 5 mW/cm 2 were irradiated in air for 300 seconds. And the resin film irradiated with ultraviolet rays is subjected to middle bake by heating at 110°C for 10 minutes using a hot plate, and then post-baking by heating at 230°C for 60 minutes in an N ₂ atmosphere using an oven By performing, a test sample made of a glass substrate with a resin film was obtained. And the thus obtained test sample was further baked in an oxidizing atmosphere heated at 230° C. for 60 minutes in the air using an oven. Then, the transmittance of the sample baked in an oxidizing atmosphere was measured at a wavelength of 400 nm to 700 nm using a spectrophotometer V-560 (manufactured by Nihon Spectrophotometer). In addition, the light transmittance of the resin film was calculated as a converted value when the glass substrate to which the resin film was not attached was used as a blank and the thickness of the resin film was set to 2 µm. And based on the obtained light transmittance, transparency was evaluated based on the following criteria.

A: Light transmittance is 85% or more

B: Light transmittance is 80% or more and less than 85%

C: Light transmittance is 75% or more and less than 80%

D: Light transmittance is less than 75%

<Shape retention after firing>

On a glass substrate (Corning, product name Corning 1737), a radiation-sensitive resin composition was applied by a spin coating method, and then heat-dried (prebaked) at 90° C. for 2 minutes using a hot plate, and a resin having a film thickness of 3 μm A film was formed. Next, the resin film was irradiated with ultraviolet rays having a light intensity of 5 mW/cm 2 at 365 nm through a mask having a hole pattern of 3 µm × 3 µm, and the calculated exposure sensitivity as exposure sensitivity in air. I did. Subsequently, after immersion treatment at 25°C for 120 seconds using a 0.4% by weight aqueous solution of tetramethylammonium hydroxide, washing was performed with ultrapure water for 30 seconds, and then the light intensity at 365 nm was 5 mW/cm 2 Phosphorous ultraviolet rays were irradiated in the air for 300 seconds. Then, the resin film irradiated with ultraviolet rays was subjected to middle bake by heating at 110°C for 10 minutes using a hot plate, and then post-baking by heating at 230°C for 60 minutes in an N ₂ atmosphere to contact A test sample made of a glass substrate provided with a resin film in which holes were formed was obtained. And for the test sample thus obtained, the contact hole was observed with an optical microscope, and the hole shape after firing was evaluated according to the following criteria.

A: The angle of the rising portion of the contact hole from the substrate is 60° or more, and no round portion is observed in the shape of the upper end portion of the contact hole.

B: The angle of the rising portion of the contact hole from the substrate is 60° or more, but the upper end portion of the contact hole is rounded.

C: The angle of the rising part of the contact hole from the substrate is 50° or more and less than 60°

D: The angle of the rising portion of the contact hole from the substrate is less than 50°

<< Synthesis Example 1 >>

<Preparation of cyclic olefin polymer (A1a) having a protic polar group>

N-phenylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide (NBPI) 40 mol%, and 4-hydroxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^{2, 7} ] Dodeca-9-ene (TCDC) 100 parts of the monomer mixture consisting of 60 mol%, 2.8 parts of 1,5-hexadiene, (1,3-dimesitylimidazoline-2-ylidene) (tricyclo Hexylphosphine) benzylidene ruthenium dichloride (Org. Lett., Volume 1, page 953, synthesized by the method described in 1999) 0.02 parts, and 200 parts of diethylene glycol ethylmethyl ether, nitrogen-substituted glass pressure-resistant reactor And reacted at 80° C. for 4 hours while stirring to obtain a polymerization reaction solution.

And the obtained polymerization reaction liquid was put into an autoclave, and it stirred for 5 hours at 150 degreeC and hydrogen pressure of 4 MPa, and hydrogenation reaction was performed, and the polymer solution containing the cyclic olefin polymer (A1a) was obtained. The polymerization conversion ratio of the obtained cyclic olefin polymer (A1a) was 99.8%, the weight average molecular weight in terms of polystyrene was 5,098, the number average molecular weight was 3,227, the molecular weight distribution was 1.58, and the hydrogenation rate was 99.9%. In addition, the solid content concentration of the polymer solution of the obtained cyclic olefin polymer (A1a) was 34.4% by weight.

<< Synthesis Example 2 >>

<Preparation of cyclic olefin polymer (A1b) having a protic polar group>

In place of 40 mol% of N-phenylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(2-ethylhexyl)-bicyclo[2.2.1]hepto-5-ene Polymerization and hydrogenation were carried out in the same manner as in Synthesis Example 1, except that 40 mol% of -2,3-dicarboxyimide (NEHI) was used, and the amount of 1,5-hexadiene was changed from 2.8 parts to 2.0 parts. Thus, a polymer solution containing a cyclic olefin polymer (A1b) was obtained. The polymerization conversion ratio of the obtained cyclic olefin polymer (A1b) was 99.7%, the weight average molecular weight in terms of polystyrene was 7,150, the number average molecular weight was 4,690, the molecular weight distribution was 1.52, and the hydrogenation rate was 99.7%.

<< Synthesis Example 3 >>

<Preparation of acrylic resin (A2)>

Into a flask equipped with a cooling tube and a stirrer, 7 parts of 2,2'-azobis-(2,4-dimethylvaleronitrile) and 200 parts of diethylene glycol ethylmethyl ether were injected. Subsequently, 16 parts of methacrylic acid, 16 parts of tricyclo[5.2.1.0 ^2,6 ]decane-8-yl methacrylate, 20 parts of 2-methylcyclohexyl acrylate, 40 parts of glycidyl methacrylate, styrene After 10 parts and 3 parts of α-methylstyrene dimer were injected and replaced with nitrogen, stirring was slowly started. Subsequently, the temperature of the solution was raised to 70° C., and the polymer solution containing the acrylic resin (A2) was obtained by holding this temperature for 4 hours. The polystyrene conversion weight average molecular weight (Mw) of acrylic resin (A2) was 8,000, and molecular weight distribution (Mw/Mn) was 2.3. Moreover, the solid content concentration of the obtained acrylic resin (A2) solution was 34.4 weight%.

<< Synthesis Example 4 >>

<Preparation of cardo resin (A3)>

Equivalent reactants of bisphenol fluorene-type epoxy resin and acrylic acid in a four-neck flask equipped with a reflux condenser (solid content concentration 50%, solid content equivalent acid value 1.28 mgKOH/g, epoxy equivalent weight 21,300. Synnittetsu Chemical Co., Ltd. product name “ASF-” 400" solution), 198.53 parts of 50% propylene glycol monomethyl ether acetate solution, 39.54 parts of benzophenonetetracarboxylic dianhydride, 8.13 parts of succinic anhydride, 48.12 parts of propylene glycol monomethyl ether acetate, and 0.45 parts of triphenylphosphine were injected. Then, the mixture was stirred for 1 hour under heating at 120 to 125°C, further heated and stirred at 75 to 80°C for 6 hours, then 8.6 parts of glycidyl methacrylate was added, and further at 80°C for 8 hours. It stirred for time and obtained Cardo resin (A3).

<< Synthesis Example 5 >>

<Preparation of polysiloxane (A4)>

74.91 parts of methyltrimethoxysilane, 69.41 parts of phenyltrimethoxysilane, and 150.36 parts of diacetone alcohol were poured into a three-necked flask, and 0.338 parts of phosphoric acid (0.2% by weight based on the injected monomer) was added to 55.8 parts of water while stirring at room temperature. The dissolved aqueous phosphoric acid solution was added over 10 minutes. After that, the flask was immersed in an oil bath at 70°C and stirred for 1 hour, and then the oil bath was heated to 115°C over 30 minutes. One hour after the start of temperature increase, the inner temperature of the solution reached 100°C, and thereafter, the solution was heated and stirred for 2 hours (in the meantime, the inner temperature was from 100 to 110°C). A total of 115 parts of methanol and water were distilled off as by-products. To the diacetone alcohol solution of the obtained polysiloxane, diacetone alcohol was added so that the solid content concentration was 34.4% to obtain a polysiloxane (A4) solution.

<< Example 1 >>

As a binder resin (A), 291 parts of a polymer solution of the cyclic olefin polymer (A1a) obtained in Synthesis Example 1 (100 parts as a cyclic olefin polymer (A1a)), as a radiation-sensitive compound (B), 1,1,3 -Condensation product of tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.5 mol) (B1) 40 Part, as crosslinking agent (C), epoxidized butanetetracarboxylic acid tetrakis (3-cyclohexenylmethyl) formula ε-caprolactone (aliphatic cyclic tetrafunctional epoxy resin, brand name ``Epolyd GT401'', Daicel Chemical Ind.) 40 parts, 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate (trade name ``Celoxide 2021P'', manufactured by Daicel Chemical Industries) as crosslinking agent (C) ) 10 parts, as a sulfur-free semi-hindered phenolic antioxidant and/or a sulfur-free less-hindered phenolic antioxidant (D), 3,9-bis[2-{3-(3-tertiarybutyl- 4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane (trade name "adecastab AO-80" , Manufactured by ADEKA) 6 parts, as a sulfur-containing phenolic antioxidant (E), 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propio carbonate (trade name "Irganox 1035", BASF Corporation) 2 parts, an acid group or a compound (F) having a thermal latent acid, PF ₆ ^- based sulfonium salt (trade name "Sun Aid SI-110L", Sanshin chemical Ind. ) 4 parts, phthalic acid 7 parts, as a coupling agent, (3-glycidyloxypropyl) trimethoxysilane (trade name "SH6040", manufactured by Toray Dow Corning) 5 parts, and as a solvent, ethylene glycol dimethyl ether After 750 parts were mixed and dissolved, it was filtered through a filter made of polytetrafluoroethylene having a pore diameter of 0.45 µm to prepare a radiation-sensitive resin composition.

And each evaluation of exposure sensitivity, heat resistance transparency, and shape-retaining property after baking was performed using the radiation-sensitive resin composition obtained above. Table 1 shows the results.

<< Examples 2 to 42 >>

When preparing a radiation-sensitive resin composition, except having used each compound shown in Tables 1-3 in the compounding amount shown in Tables 1-3, it carried out similarly to Example 1, and prepared the radiation-sensitive resin composition, and the same Evaluation was conducted. The results are shown in Tables 1 to 3.

In addition, in Tables 1-3, each compound is as follows.

-The "cyclic olefin polymer (A1b)" is a cyclic olefin polymer (A1b) obtained in Synthesis Example 2.

-"Acrylic resin (A2)" is an acrylic resin (A2) obtained in Synthesis Example 3.

-"Cardo resin (A3)" is a cardo resin (A3) obtained in Synthesis Example 4.

-"Polysiloxane (A4)" is a polysiloxane (A4) obtained in Synthesis Example 5.

``Radiation-sensitive compound (B2)'' is 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane (1 mol) and 1,2-naphthoquinonediazide- It is a condensate (radiation-sensitive compound (B)) of 5-sulfonic acid chloride (2 mol).

-"Crosslinking agent (Cymel 370)" is a methylol group type methylated melamine resin (brand name "Cymel 370", manufactured by Cytech Industries, a crosslinking agent (C)).

``Sulfur-free, non-hindered phenolic antioxidant (adecastab AO-40)'' is 4,4'-butylidenebis(6-t-butyl-3-methylphenol) (trade name ``adecastab AO -40", manufactured by ADEKA).

· “Sulfur-free hindered phenolic antioxidant (Irganox 1010)” is pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (trade name “Irganox 1010", manufactured by BASF).

``Sulfur-containing phenolic antioxidant (Smilizer WX-R)'' is 4,4'-thiobis(6-t-butyl-3-methylphenol) (trade name ``Smilizer WX-R'', manufactured by Sumitomo Chemical) to be.

-"Non-phenolic anti-aging agent (Smilizer TPL-R)" is dilauryl-3,3'-thiodipropionate (trade name "Smilizer TPL-R", manufactured by Sumitomo Chemical Co., Ltd.).

-"Non-phenolic anti-aging agent (Irgafos 168)" is phosphorous acid tris (2,4-di-t-butylphenyl) (trade name "Irgafos 168", manufactured by BASF).

Is based sulfonium salt (trade name "Sun Aid SI-150L", manufactured Sanshin Chemical Co., ^Ltd.), "SbF ₆ ^- based sulfonium salt (SI-150L)" is SbF _6.

Is based sulfonium salt (trade name "Sun Aid SI-100L", manufactured Sanshin Chemical Co., ^Ltd.), "SbF ₆ ^- based sulfonium salt (SI-100L)" is SbF _6.

<<Comparative Examples 1 to 7>>

When preparing a radiation-sensitive resin composition, except having used each compound shown in Table 3 in the compounding amount shown in Table 3, it carried out similarly to Example 1, and prepared the radiation-sensitive resin composition, and evaluated similarly. Table 3 shows the results.

As shown in Tables 1 to 3, binder resin (A), radiation-sensitive compound (B), crosslinking agent (C), sulfur-free semi-hindered phenolic antioxidant and/or sulfur-free non-hindered phenolic oxidation The resin film obtained by using the radiation-sensitive resin composition containing the inhibitor (D) and the sulfur-containing phenolic antioxidant (E) has high exposure sensitivity, heat resistance and transparency (transparency after firing in an oxidizing atmosphere), and shape after firing It was excellent in retainability (Examples 1-42).

On the other hand, when the sulfur-containing phenolic antioxidant (E) was not blended, or when a non-phenolic antioxidant was used instead, the resulting resin film was inferior in heat resistance and transparency (transparency after firing in an oxidizing atmosphere). (Comparative Examples 1, 5, 6).

In addition, when a sulfur-free semi-hindered phenolic antioxidant and/or a sulfur-free less-hindered phenolic antioxidant (D) is not blended, or when a sulfur-free hindered phenolic antioxidant is used instead The resin film obtained was inferior to exposure sensitivity (Comparative Examples 2-4).

In addition, when the crosslinking agent (C) was not blended, the obtained resin film was inferior in heat resistance and transparency (transparency after firing in an oxidizing atmosphere) and shape retention after firing (Comparative Example 7).

Claims (7)

Binder resin (A), radiation-sensitive compound (B), crosslinking agent (C), sulfur-free semi-hindered phenolic antioxidant and/or sulfur-free less hindered phenolic antioxidant (D), sulfur-containing phenolic oxidation It contains an inhibitor (E), and a compound having a thermally latent acidic group,
The radiation-sensitive resin composition wherein the content of the sulfur-containing phenolic antioxidant (E) is 1 to 15 parts by weight based on 100 parts by weight of the binder resin (A). The method of claim 1,
A radiation-sensitive resin composition further containing a compound having an acidic group. The method according to claim 1 or 2,
In the above sulfur-containing phenolic antioxidant (E) is a hindered phenolic antioxidant containing a sulfur atom, a semi-hindered phenolic antioxidant containing a sulfur atom, and a less hindered phenolic antioxidant containing a sulfur atom At least one radiation-sensitive resin composition selected. The method according to claim 1 or 2,
A radiation-sensitive resin composition in which the content of the sulfur-free semi-hindered phenolic antioxidant and/or sulfur-free less hindered phenolic antioxidant (D) with respect to 100 parts by weight of the binder resin (A) is 0.1 to 20 parts by weight . The method according to claim 1 or 2,
The radiation-sensitive resin composition in which the radiation-sensitive compound (B) is an azide compound. An electronic component comprising a resin film made of the radiation-sensitive resin composition according to claim 1 or 2. The method of claim 6,
An electronic component manufactured through a step of forming a resin film made of the radiation-sensitive resin composition, patterning the resin film, and firing in an oxidizing atmosphere.