JP6844115B2 - Radiation-sensitive resin composition and electronic components - Google Patents

Description

The present invention relates to a radiation-sensitive resin composition and an electronic component including a resin film composed of the radiation-sensitive resin composition. More specifically, the present invention has a good appearance, high adhesion to a metal layer, chemical resistance and development. The present invention relates to a radiation-sensitive resin composition capable of providing a resin film having excellent properties, and an electronic component including a resin film made of the radiation-sensitive resin composition.

For electronic components such as various display elements such as organic EL elements and liquid crystal display elements, integrated circuit elements, solid-state imaging elements, color filters, and black matrices, surface protective films and element surfaces to prevent deterioration and damage are flattened. Various resin films are used as a flattening film for forming, an electrically insulating film for maintaining electrical insulation, an insulating film used for a rewiring layer (Re-Distribution Layer: RDL) formed on a surface protective film, and the like. It is provided.

Conventionally, thermosetting resin materials such as epoxy resin and polyimide have been widely used as resin materials for forming these resin films. In recent years, as the density of wiring and devices has increased, it has been required to develop new resin materials having excellent electrical properties such as low dielectric properties, adhesion to metals, and developability. There is.

In order to meet these requirements, for example, Patent Document 1 describes a polymer containing a polar group that reacts with an epoxy group, and a polyfunctional epoxy having an alicyclic structure in the main chain structure and having three or more epoxy groups. A cross-linking agent containing a compound and a radiation-sensitive composition containing a radiation-sensitive compound are disclosed. However, according to the radiation-sensitive resin composition described in Patent Document 1, although a resin film having excellent electrical characteristics and developability can be formed, the obtained resin film does not necessarily have sufficient adhesion to a metal layer such as copper. However, there is a problem that it cannot be used as an application requiring such characteristics, for example, as an insulating film application for a rewiring layer formed on a surface protective film.

International Publication No. 2005/09600

The present invention is a radiation-sensitive resin composition capable of providing a resin film having a good appearance without clouding, high adhesion to a metal layer, and excellent chemical resistance and developability, and such a radiation-sensitive resin composition. An object of the present invention is to provide an electronic component provided with a resin film made of a radiation-sensitive resin composition.

As a result of diligent research to achieve the above object, the present inventors, together with a binder resin and a radiation-sensitive compound, an epoxy-based cross-linking agent having a softening point of 30 ° C. or lower and a tetrafunctional or lower, and bisphenol. We have found that the above object can be achieved by blending with a type novolak resin, and have completed the present invention.

That is, according to the present invention.
[1] Contains a binder resin (A), a radiation-sensitive compound (B), an epoxy-based cross-linking agent (C) having a softening point of 30 ° C. or lower and a tetrafunctional or lower, and a bisphenol-type novolak resin (D). Radiation-sensitive resin composition,
[2] The radiation-sensitive resin composition according to the above [1], wherein the binder resin (A) is a cyclic olefin polymer containing a carboxyl group.
[3] The radiation-sensitive resin composition according to the above [1] or [2], wherein the bisphenol type novolak resin (D) has a weight average molecular weight of 500 to 2,000.
[4] The above-mentioned [1] to [3], wherein the content of the bisphenol type novolak resin (D) is 5 to 70 parts by weight with respect to 100 parts by weight of the binder resin (A). Radiation-sensitive resin composition, as well as
[5] An electronic component comprising a resin film comprising the radiation-sensitive resin composition according to any one of [1] to [4] above.
Is provided.

According to the present invention, a radiation-sensitive resin composition capable of providing a resin film having a good appearance without clouding, high adhesion to a metal layer, and excellent chemical resistance and developability, and a radiation-sensitive resin composition thereof. It is possible to provide an electronic component including a resin film made of a resin composition.

The radiation-sensitive resin composition of the present invention comprises a binder resin (A), a radiation-sensitive compound (B), an epoxy-based cross-linking agent (C) having a softening point of 30 ° C. or lower and a tetrafunctional or lower, and a bisphenol type. It contains novolak resin (D).

(Binder resin (A))
The binder resin (A) used in the present invention is not particularly limited, but is a cyclic olefin polymer (A1) having a protonic polar group, an acrylic resin (A2), a polyimide (A3), a cardo resin (A4) or a polysiloxane. (A5) is preferable, and among these, the cyclic olefin polymer (A1) having a protonic polar group is particularly preferable.
These binder resins (A) may be used alone or in combination of two or more.

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

Here, the protic polar group refers to a group containing an atom in which a hydrogen atom is directly bonded to an atom belonging to Group 15 or Group 16 of the periodic table. Among the atoms belonging to the 15th or 16th group of the periodic table, the atoms belonging to the 1st or 2nd period of the 15th or 16th period of the periodic table are preferable, and more preferably oxygen atom, nitrogen atom or sulfur. It is an atom, particularly preferably an oxygen atom.

Specific examples of such a protonic polar group include a polar group having an oxygen atom such as a hydroxyl group, a carboxy group (hydroxycarbonyl group), a sulfonic acid group, and a phosphoric acid group; a primary amino group and a secondary amino group. , A polar group having a nitrogen atom such as a primary amide group and a secondary amide group (imide group); a polar group having a sulfur atom such as a thiol group; and the like. Among these, those having an oxygen atom are preferable, and a carboxy group is more preferable. That is, in the present invention, among the cyclic olefin polymers (A1) having a protonic polar group, the cyclic olefin polymer having a carboxy group is particularly preferable.
In the present invention, the number of protonic polar groups bonded to the cyclic olefin polymer having a protonic polar group is not particularly limited, and different types of protonic polar groups may be contained.

Specific examples of the cyclic olefin monomer (a) having a protonic polar group (hereinafter, appropriately referred to as “monomer (a)”) include 2-hydroxycarbonylbicyclo [2.2.1] hept-. 5-ene, 2-methyl-2-hydroxycarbonylbicyclo [2.2.1] hept-5-ene, 2-carboxymethyl-2-hydroxycarbonylbicyclo [2.2.1] hept-5-ene, 2 -Hydroxycarbonyl-2-methoxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-ethoxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxy Carbonyl-2-propoxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-butoxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl- 2-Pentyloxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-hexyloxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl- 2-cyclohexyloxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-phenoxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2 -Naphthyloxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-biphenyloxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2 -Benzyloxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-hydroxyethoxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2,3-dihydroxycarbonyl Bicyclo [2.2.1] Hept-5-ene, 2-Hydroxycarbonyl-3-methoxycarbonyl Bicyclo [2.2.1] Hept-5-ene, 2-Hydroxycarbonyl-3-ethoxycarbonyl Bicyclo [2. 2.1] Hept-5-ene, 2-hydroxycarbonyl-3-propoxycarbonylbicyclo [2.2.1] Hept-5-ene, 2-hydroxycarbonyl-3-butoxycarbonylbicyclo [2.2.1] Hept-5-ene, 2-hydroxycarbonyl-3-pentyloxycarbonylbi Cyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3-hexyloxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3-cyclohexyloxycarbonylbicyclo [2.2.1] 2.2.1] Hept-5-ene, 2-hydroxycarbonyl-3-phenoxycarbonylbicyclo [2.2.1] Hept-5-ene, 2-hydroxycarbonyl-3-naphthyloxycarbonylbicyclo [2.2] .1] Hept-5-ene, 2-hydroxycarbonyl-3-biphenyloxycarbonylbicyclo [2.2.1] Hept-5-ene, 2-hydroxycarbonyl-3-benzyloxycarbonylbicyclo [2.2.1] ] Hept-5-ene, 2-hydroxycarbonyl-3-hydroxyethoxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3-hydroxycarbonylmethylbicyclo [2.2.1] hept -5-ene, 3-methyl-2-hydroxycarbonylbicyclo [2.2.1] hept-5-ene, 3-hydroxymethyl-2-hydroxycarbonylbicyclo [2.2.1] hept-5-ene, 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] Hept-5-ene-2,3-dicarboxyimide, N- (hydroxycarbonylethyl) bicyclo [2] .2.1] Hept-5-en-2,3-dicarboxyimide, N- (hydroxycarbonylpentyl) bicyclo [2.2.1] Hept-5-en-2,3-dicarboxyimide, N- (Dihydroxycarbonylethyl) bicyclo [2.2.1] hept-5-en-2,3-dicarboxyimide, N- (dihydroxycarbonylpropyl) bicyclo [2.2.1] hept-5-en-2, 3-Dicarboxyimide, N- (hydroxycarbonylphenyl) bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide, N- (2- (4-hydroxyphenyl) -1-( Hydroxycarbonyl) ethyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (hydroxycarbonylphenyl) bicyclo [2.2.1] hept-5-en-2, Carbonyl group-containing cyclic olefins such as 3-dicarboxyimide; 2- (4-hydroxyphenyl) bicyclo [2.2.1] hept-5-ene, 2-methyl-2- (4-hydroxyphenyl) bicyclo [2] .2.1] Hept-5-ene, 4- (4-hydroxyphenyl) tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] 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-hydroxyethyl Bicyclo [2.2.1] hepto-5-ene, 2-methyl-2-hydroxymethylbicyclo [2.2.1] hepto-5-ene, 2,3-dihydroxymethylbicyclo [2.2.1] Hept-5-ene, 2- (hydroxyethoxycarbonyl) bicyclo [2.2.1] hepto-5-ene, 2-methyl-2- (hydroxyethoxycarbonyl) bicyclo [2.2.1] hepto-5- En, 2- (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) bicyclo [2.2.1] hepto-5-ene, 2- (2-hydroxy-2-trifluoro) Methyl-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] Hept-5-ene-2,3-dicarboxyimide, N- (hydroxyphenyl) bicyclo [2.2] .1] Examples thereof include hydroxyl group-containing cyclic olefins such as hept-5-ene-2,3-dicarboxyimide. Among these, from the viewpoint of the adhesiveness of the resulting resin film is high, is preferably a carboxyl group-containing cycloolefin, 4-hydroxycarbonyl tetracyclo [6.2.1.1 ^{3, 6.} 0 ^2,7 ] Dodeca-9-ene is particularly preferable. These monomers (a) may be used individually or in combination of two or more.

The content ratio of the unit of the monomer (a) in the cyclic olefin polymer (A1) is preferably 10 to 90 mol%, preferably 20 to 80 mol%, more preferably 20 to 80 mol% with respect to all the monomer units. Is 30-70 mol%. If the content ratio of the unit of the monomer (a) is too small, the radiation sensitivity may be insufficient or a dissolution residue may be generated during development. If the content ratio is too large, the cyclic olefin polymer (A1) may be generated. May be insufficiently soluble in polar solvents.

Further, the cyclic olefin polymer (A1) used in the present invention is obtained by copolymerizing a cyclic olefin monomer (a) having a protonic polar group and a monomer (b) copolymerizable therewith. It may be a copolymer to be used. Examples of such a copolymerizable monomer include a cyclic olefin monomer (b1) having a polar group other than a protonic polar group, a cyclic olefin monomer (b2) having no polar group, and a cyclic olefin. (B3) (hereinafter, appropriately referred to as "monomer (b1)", "monomer (b2)", and "monomer (b3)").

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

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

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

(In the above general 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.)

(In the above general formula (2), R ² is a divalent alkylene group ^{having 1 to 3} carbon atoms, R 3 is a monovalent alkyl group having 1 to 10 carbon atoms, or a monovalent group having 1 to 10 carbon atoms. Represents an alkyl halide group of.)

In the above general formula (1), R ¹ is an alkyl group or an aryl group having 1 to 16 carbon atoms, and specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group and an n-butyl group. n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, Linear alkyl groups such as n-pentadecyl group and n-hexadecyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group. Cyclic alkyl groups such as group, norbornyl group, bornyl group, isobornyl group, decahydronaphthyl group, tricyclodecanyl group, 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 group, 2-methylhexyl group, 2-ethylhexyl group, 4-methylheptyl group, 1-methylnonyl group , 1-Methyltridecyl group, branched alkyl group such as 1-methyltetradecyl group; and the like. Further, specific examples of the aryl group include a benzyl group and the like. Among these, an alkyl group and an aryl group having 6 to 14 carbon atoms are preferable, and an alkyl group and an aryl group having 6 to 10 carbon atoms are more preferable because they are excellent in heat resistance and solubility in a polar solvent. When the number of carbon atoms is 4 or less, the solubility in a polar solvent is inferior, when the number of carbon atoms is 17 or more, the heat resistance is inferior, and when the resin film is patterned, it is melted by heat and the pattern disappears. There is a problem.

Specific examples of the monomer represented by the above general formula (1) include bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide and N-phenyl-bicyclo [2.2]. .1] Hept-5-en-2,3-dicarboxyimide, N-methylbicyclo [2.2.1] Hept-5-en-2,3-dicarboxyimide, N-ethylbicyclo [2.2] .1] Hept-5-en-2,3-dicarboxyimide, N-propylbicyclo [2.2.1] Hept-5-en-2,3-dicarboxyimide, N-butylbicyclo [2.2] .1] Hept-5-en-2,3-dicarboxyimide, N-cyclohexylbicyclo [2.2.1] Hept-5-en-2,3-dicarboxyimide, N-adamantylbicyclo [2.2] .1] Hept-5-en-2,3-dicarboxyimide, N- (1-methylbutyl) -bicyclo [2.2.1] Hept-5-en-2,3-dicarboxyimide, N-( 2-Methylbutyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (1-methylpentyl) -bicyclo [2.2.1] hept-5-ene- 2,3-Dicarboxyimide, N- (2-methylpentyl) -bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide, N- (1-ethylbutyl) -bicyclo [2 .2.1] Hept-5-en-2,3-dicarboxyimide, N- (2-ethylbutyl) -bicyclo [2.2.1] Hept-5-en-2,3-dicarboxyimide, N -(1-Methylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (2-methylhexyl) -bicyclo [2.2.1] hept-5 -En-2,3-dicarboxyimide, N- (3-methylhexyl) -bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide, N- (1-butylpentyl) -Vicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (2-butylpentyl) -bicyclo [2.2.1] hept-5-ene-2,3- Dicarboxyimide, N- (1-methylheptyl) -bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide, N- (2-methylheptyl) -bicyclo [2.2. 1] Hept-5-en-2,3-dicarboxyimide, N- (3-methylheptyl) -bicyclo [2.2.1] Hept-5-en-2,3- Dicarboxyimide, N- (4-methylheptyl) -bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide, N- (1-ethylhexyl) -bicyclo [2.2.1] ] Hept-5-en-2,3-dicarboxyimide, N- (2-ethylhexyl) -bicyclo [2.2.1] Hept-5-en-2,3-dicarboxyimide, N- (3-) Ethylhexyl) -bicyclo [2.2.1] hept-5-en-2,3-dicarboxyimide, N- (1-propylpentyl) -bicyclo [2.2.1] hept-5-en-2, 3-Dicarboxyimide, N- (2-propylpentyl) -bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide, N- (1-methyloctyl) -bicyclo [2. 2.1] Hept-5-en-2,3-dicarboxyimide, N- (2-methyloctyl) -bicyclo [2.2.1] Hept-5-en-2,3-dicarboxyimide, N -(3-Methyloctyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (4-methyloctyl) -bicyclo [2.2.1] hept-5 -En-2,3-dicarboxyimide, N- (1-ethylheptyl) -bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide, N- (2-ethylheptyl) -Bicyclo [2.2.1] Hept-5-en-2,3-dicarboxyimide, N- (3-ethylheptyl) -Bicyclo [2.2.1] Hept-5-en-2,3- Dicarboxyimide, N- (4-ethylheptyl) -bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide, N- (1-propylhexyl) -bicyclo [2.2. 1] Hept-5-en-2,3-dicarboxyimide, N- (2-propylhexyl) -bicyclo [2.2.1] Hept-5-en-2,3-dicarboxyimide, N-( 3-propylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (1-methylnonyl) -bicyclo [2.2.1] hept-5-ene- 2,3-Dicarboxyimide, N- (2-methylnonyl) -bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide, N- (3-methylnonyl) -bicyclo [2. 2.1] Hept-5-ene-2,3-dicarboxyimide, N- (4-methylnonyl) -bicyclo [2.2.1] Hept- 5-en-2,3-dicarboxyimide, N- (5-methylnonyl) -bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide, N- (1-ethyloctyl) -Vicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (2-ethyloctyl) -bicyclo [2.2.1] hept-5-en-2,3- Dicarboxyimide, N- (3-ethyloctyl) -bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide, N- (4-ethyloctyl) -bicyclo [2.2. 1] Hept-5-en-2,3-dicarboxyimide, N- (1-methyldecyl) -bicyclo [2.2.1] Hept-5-en-2,3-dicarboxyimide, N- (1) -Methyldodecyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (1-methylundecyl) -bicyclo [2.2.1] hept-5-ene -2,3-dicarboxyimide, N- (1-methyldodecyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (1-methyltridecyl)- Bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (1-methyltetradecyl) -bicyclo [2.2.1] hept-5-ene-2,3- Dicarboxyimide, N- (1-methylpentadecyl) -bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide, N-phenyl-tetracyclo [6.2.1.1 ^{3 , 6} . 0 ^2,7 ] Dodeca-9-ene-4,5-dicarboxyimide, N- (2,4-dimethoxyphenyl) -tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodeca-9-en-4,5-dicarboxyimide and the like can be mentioned. In addition, each of these may be used individually or may be used in combination of 2 or more types.

On the other hand, in the above general formula (2), R ² is a divalent alkylene group having 1 to 3 carbon atoms, and the divalent alkylene group having 1 to 3 carbon atoms includes a methylene group, an ethylene group, a propylene group and the like. Isopropylene group is mentioned. Among these, a methylene group and an ethylene group are preferable because the polymerization activity is good.

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

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

Examples of the cyclic olefin having an ester group include 2-acetoxybicyclo [2.2.1] hept-5-ene, 2-acetoxymethylbicyclo [2.2.1] hept-5-ene, and 2-methoxycarbonyl. Bicyclo [2.2.1] hept-5-ene, 2-ethoxycarbonylbicyclo [2.2.1] hept-5-ene, 2-propoxycarbonylbicyclo [2.2.1] hept-5-ene, 2-Butoxycarbonylbicyclo [2.2.1] hept-5-ene, 2-cyclohexyloxycarbonylbicyclo [2.2.1] hept-5-ene, 2-methyl-2-methoxycarbonylbicyclo [2.2] .1] Hept-5-ene, 2-methyl-2-ethoxycarbonylbicyclo [2.2.1] Hept-5-ene, 2-methyl-2-propoxycarbonylbicyclo [2.2.1] Hept-5 -En, 2-methyl-2-butoxycarbonylbicyclo [2.2.1] hept-5-ene, 2-methyl-2-cyclohexyloxycarbonylbicyclo [2.2.1] hept-5-ene, 2-en (2,2,2-trifluoroethoxycarbonyl) bicyclo [2.2.1] hept-5-ene, 2-methyl-2- (2,2,2-trifluoroethoxycarbonyl) bicyclo [2.2. 1] Hept-5-ene, 2-methoxycarbonyltricyclo [5.2.1.0 ^2,6 ] Deca-8-ene, 2-ethoxycarbonyltricyclo [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-ethoxycarbonyltetracyclo [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-propoxycarbonyltetracyclo [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-en and the like can be mentioned.

Examples of the cyclic olefin having a cyano group include 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] hept-5-ene, 2-methyl-2-cyanobicyclo [2.2.1] hept-5-ene, 2 , 3-Dicyanobicyclo [2.2.1] hept-5-ene, and the like.

Examples of the cyclic olefin having an acid anhydride group include tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodeca-9-ene-4,5-dicarboxylic acid anhydride, Bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxylic acid anhydride, 2-carboxymethyl-2- Hydroxycarbonylbicyclo [2.2.1] hept-5-ene anhydride, etc. may be mentioned.

Examples of the cyclic olefin having a halogen atom include 2-chlorobicyclo [2.2.1] hept-5-ene, 2-chloromethylbicyclo [2.2.1] hept-5-ene, and 2- (chlorophenyl). ) Bicyclo [2.2.1] hept-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 and the like can be mentioned.

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

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

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

Among these monomers (b1) to (b3), the cyclic olefin monomer (b1) having a polar group other than the protonic polar group is preferable from the viewpoint that the effect of the present invention becomes more remarkable. Cyclic olefins with N-substituted imide groups 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%, more preferably 20 to 80, based on the total monomer units. It is in mol%, more preferably 30-70 mol%. If the content of the unit of the copolymerizable monomer (b) is too small, the solubility of the cyclic olefin polymer (A1) in the polar solvent may be insufficient, and if it is too large, it is radiation-sensitive. May become insufficient or a dissolution residue may be generated during development.

In addition, in this invention, a cyclic olefin polymer (A1) may be obtained by introducing a protonic polar group into a cyclic olefin polymer having no protonic polar group by using a known modifier.
The polymer having no protonic polar group is obtained by polymerizing at least one of the above-mentioned monomers (b1) and (b2) and, if necessary, the monomer (b3) in an arbitrary combination. be able to.

As the modifier for introducing a protonic polar group, a compound having a protonic polar group and a reactive carbon-carbon unsaturated bond in one molecule is usually used.
Specific examples of such compounds include acrylic acid, methacrylic acid, angelic acid, tigric acid, oleic acid, ellaic acid, erucic acid, brassic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and atropa. Unsaturated carboxylic acids such as acids and silicic acids; allyl alcohol, methyl vinyl methanol, crotyl alcohol, metallic alcohol, 1-phenylethen-1-ol, 2-propen-1-ol, 3-butene-1- All, 3-butene-2-ol, 3-methyl-3-butene-1-ol, 3-methyl-2-butene-1-ol, 2-methyl-3-butene-2-ol, 2-methyl- Unsaturated alcohols such as 3-butene-1-ol, 4-penten-1-ol, 4-methyl-4-penten-1-ol, 2-hexene-1-ol; and the like.
The modification reaction of the polymer using these modifiers may be carried out according to a conventional method, and is usually carried out in the presence of a radical generator.

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

The ring-opening polymer is a ring-opening metathesis polymerization of a cyclic olefin monomer (a) having a protonic polar group and a copolymerizable monomer (b) used as needed in the presence of a metathesis reaction catalyst. Can be manufactured by As the manufacturing method, for example, the methods described in [0039] to [0079] of International Publication No. 2010/11323 can be used.

When the cyclic olefin polymer (A1) used in the present invention is a ring-opening polymer, a hydrogenation reaction is further carried out to hydrogenate the carbon-carbon double bond contained in the main chain. It is preferable to use a product. When 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 70% from the viewpoint of heat resistance. The above is preferable, 90% or more is more preferable, and 95% or more is further preferable.

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 acid anhydride having an acrylic group, or an epoxy group-containing acrylate compound and an oxetane group-containing acrylate compound. A homopolymer or copolymer containing at least one as an essential component is preferable.

Specific examples of the carboxylic acid having an acrylic group include (meth) acrylic acid [meaning acrylic acid and / or methacrylic acid. The same applies to methyl (meth) acrylate and the like. ], Crotonic acid, Mailenic acid, Fumaric acid, Citraconic acid, Mesaconic acid, Glutaconic acid, Mono-phthalate (2-((meth) acrylamide) ethyl), N- (carboxyphenyl) maleimide, N- (carboxyphenyl) ) (Meta) acrylamide and the like.
Specific examples of the carboxylic acid anhydride having an acrylic group include maleic anhydride, citraconic acid anhydride and the like.
Specific examples of the epoxy group-containing acrylate compound include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, -3,4 acrylate. -Epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, acrylic acid- Examples thereof include 3,4-epoxycyclohexylmethyl and methacrylic acid-3,4-epoxycyclohexylmethyl.
Specific examples of the oxetane group-containing acrylate compound include (meth) oxalic acid (3-methyloxetane-3-yl) methyl, (meth) oxalic acid (3-ethyloxetane-3-yl) methyl, and (meth) acrylic acid. (3-Methyloxetane-3-yl) ethyl, (meth) acrylate (3-ethyloxetane-3-yl) ethyl, (meth) acrylate (3-chloromethyloxetane-3-yl) methyl, (meth) Acrylate (oxetane-2-yl) methyl, (meth) acrylate (2-methyloxetane-2-yl) methyl, (meth) acrylate (2-ethyloxetane-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)- Examples thereof include 4-trifluoromethyl-2- (meth) acrylate.
Of these, (meth) acrylic acid, maleic anhydride, glycidyl (meth) acrylic acid, -6,7-epoxyheptyl methacrylate and the like are preferable.

The acrylic resin (A2) is a copolymerizable monomer other than an acrylate-based monomer or an acrylate with at least one selected from unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides and unsaturated compounds containing an epoxy group. It may be a copolymer with.

Other acrylate-based monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl ( Meta) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, ethylhexyl (meth) acrylate, nonyl (meth) Alkyl (meth) such as acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isostearyl (meth) acrylate. Acrylate; hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl ( Hydroxyalkyl (meth) acrylates such as meta) acrylates; phenoxyethyl (meth) acrylates, phenoxyalkyl (meth) acrylates such as 2-hydroxy-3-phenoxypropyl (meth) acrylates; 2-methoxyethyl (meth) acrylates, 2 Alkoxyalkyl (meth) acrylates such as −ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-methoxybutyl (meth) acrylate; polyethylene glycol mono (meth) acrylate. , Ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxy Polyalkylene glycol (meth) acrylates such as polypropylene glycol (meth) acrylates and nonylphenoxy polypropylene glycol (meth) acrylates; cyclohexyl (meth) acrylates, 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-decene-8-yl (meth) acrylate, tricyclo [5 2.1.0 ^{2, 6} ] -3-decene-9-cycloalkyl (meth) acrylates such as yl (meth) acrylates, bornyl (meth) acrylates and isobornyl (meth) acrylates; phenyl (meth) acrylates and naphthyls. (Meta) acrylate, biphenyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 5-tetrahydrofurfuryloxycarbonylpentyl (meth) acrylate, vinyl (meth) acrylate, (meth) acrylic acid Allyl, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, 2- [tricyclo [5.2.1.0 ^{2, 6} ] decan-8-yloxy] ethyl (meth) acrylate, 2- [tricyclo [5.2.1.0 ^{2, 6} ] -3-decene-8-yloxy] ethyl (meth) acrylate, 2- [tricyclo [5.2.1.0 ^{2, 6} ] -3-decene-9- Iloxy] ethyl (meth) acrylate, γ-butyrolactone (meth) acrylate, maleimide, N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, 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, Examples thereof include 5-dinitrophenyl) maleimide, N- (1-anilinononaphthyl-4) maleimide, N- [4- (2-benzoxazolyl) phenyl] maleimide, N- (9-acrydinyl) maleimide and the like. ..
Among these, methyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, tricyclo [5.2.1.0 ^{2, 6} ] Decane-8-yl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide and the like are preferable.

The copolymerizable monomer other than acrylate is not particularly limited as long as it is a compound copolymerizable with the above-mentioned carboxylic acid having an acrylic group, carboxylic acid anhydride having an acrylic group, or an epoxy group-containing acrylate compound. , Vinyl benzyl methyl ether, vinyl glycidyl ether, styrene, α-methyl styrene, vinyl toluene, inden, vinyl naphthalene, vinyl biphenyl, 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-4-vinylcyclohexane, isobutene, Examples thereof include radically polymerizable compounds such as norbornene, butadiene, and isoprene.
These compounds may be used alone or in combination of two or more.
The polymerization method of the above-mentioned monomer may follow a conventional method, and for example, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method and the like are adopted.

The polyimide (A3) used in the present invention can be obtained by heat-treating a polyimide precursor obtained by reacting a tetracarboxylic dianhydride with a diamine. Examples of the precursor for obtaining polyimide include polyamic acid, polyamic acid ester, polyisoimide, and polyamic acid sulfonamide.

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

When polymerization is carried out using an excess of diamine, the terminal amino group of the produced polyimide (A3) can be reacted with a carboxylic acid anhydride to protect the terminal amino group. Further, when the tetracarboxylic dian anhydride is excessively used for polymerization, the amine compound can be reacted with the terminal acid anhydride group of the produced polyimide (A3) to protect the terminal acid anhydride group.

Examples of such carboxylic acid anhydrides are phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydride phthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic acid. Anhydride, itaconic anhydride, tetrahydrophthalic anhydride and the like can be used as examples of amine compounds, such as aniline, 2-hydroxyaniline, 3-hydroxyaniline, 4-hydroxyaniline, 2-ethynylaniline, 3-ethynylaniline and 4-. Ethynylaniline and the like can be mentioned.

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

（上記一般式（３）中、ｍは０〜１０の整数である。） As an example of the cardo structure, an example of the cardo structure having an acrylate structure is shown in the following general formula (3).

(In the above general formula (3), m is an integer from 0 to 10.)

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

The polysiloxane (A5) used in the present invention is not particularly limited, but a polymer obtained by mixing and reacting one or more of organosilanes represented by the following general formula (4) is preferable. Can be mentioned.
(R ⁴ ) _p- Si- (OR ⁵ ) _4-p (4)

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

Further, in the general formula (4), ^{R 5} is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an acyl group, or an aryl group having from 6 to 15 carbon atoms having 1 to 6 carbon atoms, more ^{R 5} May be the same or different. Both the alkyl group and the acyl group may have a substituent or may be a non-substituted product having no substituent, and can be selected according to the characteristics of the composition. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl group. Specific examples of the acyl group include an acetyl group. Specific examples of the aryl group include a phenyl group.

Further, in the above general formula (4), p is an integer of 0 to 3, a tetrafunctional silane when p = 0, a trifunctional silane when p = 1, and a bifunctional silane when p = 2. When the sex silane is p = 3, it becomes a monofunctional silane.

Specific examples of the organosilane represented by the above general formula (4) include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, and tetraphenoxysilane; methyltrimethoxysilane, methyltriethoxysilane, and the like. Methyltriisopropoxysilane, methyltrin-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltrin-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n- Butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxy Silane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 1- (p-hydroxyphenyl) ethyltrimethoxysilane , 2- (p-Hydroxyphenyl) ethyltrimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, 3,3 , 3-Trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane , Trifunctional silanes such as 3-mercaptopropyltrimethoxysilane; bifunctional silanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, din-butyldimethoxysilane, diphenyldimethoxysilane; trimethylmethoxysilane, Monofunctional silanes such as tri-n-butylethoxysilane; can be mentioned.
Of 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 above-mentioned organosilane. Common methods can be used for hydrolysis and partial condensation. For example, a solvent, water and, if necessary, a catalyst are added to the mixture, and the mixture is heated and stirred. During stirring, hydrolyzed by-products (alcohol such as methanol) and condensed by-products (water) may be distilled off, if necessary.

The weight average molecular weight (Mw) of the binder resin (A) used in the present invention is usually 1,000 to 1,000,000, preferably 1,500 to 100,000, more preferably 2,000 to 30. It is in the range of 000.
The molecular weight distribution of the binder resin (A) is usually 4 or less, preferably 3 or less, and more preferably 2.5 or less in terms of weight average molecular weight / number average molecular weight (Mw / Mn) ratio.
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the binder resin (A) are values obtained as polystyrene-equivalent values by gel permeation chromatography (GPC) using a solvent such as tetrahydrofuran as an eluent. Is.

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

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

As the quinone diazide compound, for example, an ester compound of a quinone diazido sulfonic acid halide and a compound having a phenolic hydroxyl group can be used. Specific examples of the quinonediazide sulfonic acid halide include 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-benzoquinonediazide-5-sulfonic acid chloride and the like. Can be mentioned. Typical examples of compounds having a phenolic hydroxyl group are 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 can be mentioned. Examples of compounds having a phenolic hydroxyl group other than these include 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2-bis (4-hydroxyphenyl) propane, and tris (4-). Hydroxyphenyl) methane, 1,1,1-tris (4-hydroxy-3-methylphenyl) ethane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, novolak resin oligomers, phenolic hydroxyl groups Examples thereof include an oligomer obtained by copolymerizing one or more compounds with dicyclopentadiene.

Examples of the photoacid generator include quinone diazide compounds, onium salts, halogenated organic compounds, α, α'-bis (sulfonyl) diazomethane compounds, α-carbonyl-α'-sulfonyl diazomethane compounds, and sulfone compounds. Known compounds such as an organic acid ester compound, an organic acid amide compound, and an organic acid imide compound can be used.
These radiation-sensitive compounds can be used alone or in combination of two or more.

The content of the radiation-sensitive compound (B) in the radiation-sensitive resin composition of the present invention is preferably 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). Parts, more preferably 25 to 50 parts by weight. By setting the content of the radiation-sensitive compound (B) in this range, the adhesion, developability and low hygroscopicity of the resin film obtained by using the radiation-sensitive resin composition of the present invention to the metal layer are further improved. Can be.

(Epoxy-based cross-linking agent (C))
In addition to the binder resin (A) and the radiation-sensitive compound (B) described above, the radiation-sensitive resin composition of the present invention has an epoxy-based cross-linking agent (C) having a softening point of 30 ° C. or lower and tetrafunctional or lower. ) Is contained.

The epoxy-based cross-linking agent (C) is not particularly limited as long as it has a softening point of 30 ° C. or lower and tetrafunctional or lower, and such epoxy-based cross-linking agents will be described later and bisphenol-type novolak. When a resin film is formed by using the radiation-sensitive resin composition of the present invention by blending with the resin (D), the obtained resin film has a good appearance without becoming cloudy and adheres to the metal layer. It has high properties and can be excellent in chemical resistance and developability.

If an epoxy compound having a softening point of more than 30 ° C. is used, the effects of improving adhesion to the metal layer, chemical resistance and developability cannot be obtained. The softening point of the epoxy-based cross-linking agent (C) is preferably 25 ° C. or lower. That is, the epoxy-based cross-linking agent (C) is preferably liquid at room temperature (25 ° C.). The lower limit of the softening point of the epoxy-based cross-linking agent (C) is not particularly limited, and the softening point is not particularly limited as long as it is liquid at room temperature (25 ° C.). Further, when a pentafunctional or higher functional epoxy compound is used, the obtained resin film becomes inferior in metal adhesion. Therefore, the epoxy-based cross-linking agent (C) used in the present invention may be tetrafunctional or less, but preferably has a functional group number in the range of 2 to 4. The softening point of the epoxy-based cross-linking agent (C) can be measured according to, for example, JIS K 2207.

Further, the epoxy-based cross-linking agent (C) used in the present invention has an epoxy equivalent of 450 or less because the adhesion, chemical resistance and developability of the obtained resin film to the metal layer can be further improved. Is preferable, and more preferably 420 or less. The lower limit of the epoxy equivalent is not particularly limited, but is preferably 80 or more. The epoxy equivalent of the epoxy-based cross-linking agent (C) can be measured, for example, according to JIS K 7236 “How to determine the epoxy equivalent of an epoxy resin”.

Specific examples of the epoxy-based cross-linking agent (C) used in the present invention include, for example, epoxidized 3-cyclohexene-1,2-dicarboxylic acid bis (3-cyclohexenylmethyl) -modified ε-caprolactone (aliphatic cyclic trifunctional). Sexual epoxy resin, trade name "Epolide GT301", manufactured by Daicel Chemical Industries, Ltd.), epoxidized butane tetracarboxylic acid tetrakis (3-cyclohexenylmethyl) modified ε-caprolactone (aliphatic cyclic tetrafunctional epoxy resin, trade name) "Epolide GT401", manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-Epoxycyclohexenylmethyl-3', 4'-epoxycyclohexene carboxylate (trade names "Celoxide 2021", "Celoxide 2021P", manufactured by Daicel Chemical Industry Co., Ltd.) , 1,2: 8,9-diepoxy limonene (trade name "Ceroxide 3000", manufactured by Daicel Chemical Industries, Ltd.), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (trade name "Z-6043"), Toray Dow Corning Co., Ltd.) and other epoxy compounds with an alicyclic structure;

Bisphenol A type epoxy compound (trade name "jER 825", "jER 827", "jER 828", "jER YL980", manufactured by Mitsubishi Chemical Co., Ltd., trade name "EPICLON 840", "EPICLON 850", manufactured by DIC), Bisphenol F type epoxy compound (trade name "jER 806", "jER 807", "jER YL983U", manufactured by Mitsubishi Chemical Co., Ltd., trade name "EPICLON 830", "EPICLON 835", manufactured by DIC), hydrogenated bisphenol A type Epoxy compounds (trade name "jER YX8000", "jER YX8034" manufactured by Mitsubishi Chemical Co., Ltd., product name "ST-3000" manufactured by Nippon Steel & Sumitomo Metal Corporation, product name "Rica Resin HBE-100" manufactured by Shin Nihon Rika Co., Ltd., product name "Epolite 4000" Kyoei Kagaku Co., Ltd.), Long-chain bisphenol A type epoxy resin (trade names "EXA-4816", "EXA-4850-150", "EXA-4850-1000" manufactured by DIC), EO modified bisphenol A type epoxy compound (Product name "Adecaredin EP-4000L", "Adecaredin EP-4010L", manufactured by ADEKA), phenol novolac type polyfunctional epoxy compound (trade name "jER 152", manufactured by Mitsubishi Chemical Co., Ltd.), 1,6-bis (2) , 3-Epoxy Propane-1-yloxy) A polyfunctional epoxy compound having a naphthalene skeleton such as naphthalene (trade name "HP-4032D", manufactured by DIC), dicyclopentadiene dimethanol diglycidyl ether (trade name "Adecaredin EP-"). 4000L "," Adecaledin EP-4088L ", manufactured by ADEKA), glycidylamine type epoxy resin (trade name" product name "jER630", manufactured by Mitsubishi Chemical Corporation, product names "TETRAD-C", "TETRAD-X", Mitsubishi Gas Chemical Co., Ltd.), Chain Alkyl Polyfunctional Epoxy Compound (trade name "SR-TMP", manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.), Polyfunctional Epoxy Polybutadiene (trade name "Epolide PB3600", manufactured by Daicel Chemical Industry Co., Ltd.), Glycerin Glycidyl polyether compound (trade name "SR-GLG", manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.), diglycerin polyglycidyl ether compound (trade name "SR-DGE", manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., polyglycerin polyglycidyl ether compound (trade name) "SR-4GL", manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., γ-glycidoxypropyltrimethylsilane (trade name "Z6040", Toray Doukonin) Epoxy compounds that do not have an alicyclic structure, such as (manufactured by G); can be mentioned.

The content of the epoxy-based cross-linking agent (C) in the radiation-sensitive resin composition of the present invention is preferably 5 to 80 parts by weight, more preferably 10 to 75 parts by weight, based on 100 parts by weight of the binder resin (A). , More preferably 15 to 70 parts by weight. Even if the amount of the epoxy-based cross-linking agent (C) is too large or too small, the effect of adding the epoxy-based cross-linking agent (C), that is, the obtained resin film has a good appearance without becoming cloudy, and has adhesion and resistance to the metal layer. There is a risk that it will be difficult to obtain the effect that the chemical properties and developability can be improved.

(Bisphenol type novolak resin (D))
The radiation-sensitive resin composition of the present invention contains a bisphenol-type novolak resin (D) in addition to the binder resin (A), the radiation-sensitive compound (B), and the epoxy-based cross-linking agent (C) described above. As described above, in the present invention, when a resin film is formed using the radiation-sensitive resin composition of the present invention by blending the bisphenol type novolak resin (D) together with the epoxy-based cross-linking agent (C). The obtained resin film can be made to have a good appearance without becoming cloudy, have high adhesion to a metal layer, and have excellent chemical resistance and developability. In particular, in the present invention, the bisphenol type novolak resin (D) acts as a curing agent by reacting with the epoxy-based cross-linking agent (C) in the radiation-sensitive resin composition. The resin film to be obtained has excellent chemical resistance and can improve adhesion to the metal layer, and has two hydroxyl groups. Due to the action of the bisphenol structure, the epoxy-based cross-linking agent (C) Since the resin film is also excellent in alkali solubility even after the reaction with the above, the obtained resin film can be made excellent in developability.

（上記一般式（５）中、Ｒ^６、Ｒ^７は、それぞれ独立に水素原子又はメチル基を表し、Ｒ^８、Ｒ^９はそれぞれ独立に水素原子又はグリシジル基を表す。また、上記一般式（６）中、Ｒ^１０、Ｒ^１１は、それぞれ独立に水素原子又はメチル基を表し、Ｒ^１２、Ｒ^１３はそれぞれ独立に水素原子又はグリシジル基を表す。） The bisphenol type novolak resin (D) is produced by condensing bisphenol with aldehydes such as formaldehyde, acetaldehyde, and glyoxal. Further, as the bisphenol type novolak resin (D), a part of the phenolic hydroxyl group may be substituted with a glycidyl group. Examples of the bisphenol type novolak resin (D) include compounds having a unit represented by the following general formula (5) and / or the following general formula (6).

(In the above general formula (5), R ⁶ and R ⁷ independently represent a hydrogen atom or a methyl group, and R ⁸ and R ⁹ independently represent a hydrogen atom or a glycidyl group, respectively. 6) Among them, R ¹⁰ and R ¹¹ independently represent a hydrogen atom or a methyl group, and R ¹² and R ¹³ independently represent a hydrogen atom or a glycidyl group, respectively.)

The bisphenol type novolak resin (D) used in the present invention preferably has a weight average molecular weight (Mw) of 500 to 3,000, more preferably 600 to 2,000, and 700 to 1,500. More preferred. When the weight average molecular weight (Mw) is in the above range, the effect of addition thereof, that is, the appearance of the obtained resin film is improved without becoming cloudy, and the adhesion to the metal layer, chemical resistance and development are improved. The effect that the sex can be improved can be further enhanced. The weight average molecular weight (Mw) of the bisphenol type novolak resin (D) is a value obtained as a polystyrene-equivalent value by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent.

The content of the bisphenol type novolak resin (D) in the radiation-sensitive resin composition of the present invention is preferably 5 to 70 parts by weight, more preferably 10 to 60 parts by weight, based on 100 parts by weight of the binder resin (A). , More preferably 15 to 50 parts by weight. By setting the content of the bisphenol type novolak resin (D) in the above range, the effect of adding the bisphenol type novolak resin (D), that is, the appearance of the obtained resin film is improved without becoming cloudy, and the adhesion to the metal layer is improved. The effect that the chemical resistance and the developability can be improved can be further enhanced.

(Other compounding agents)
Further, the radiation-sensitive resin composition of the present invention may further contain a solvent. The solvent is not particularly limited and is known as a solvent for the resin composition, for example, acetone, methyl ethyl ketone, cyclopentanone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-. Linear ketones such as octanone, 3-octanone and 4-octanone; alcohols such as n-propyl alcohol, isopropyl alcohol, n-butyl alcohol and cyclohexanol; ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether and dioxane Classes: Alcohol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propyl formate, butyl formate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl lactate, ethyl lactate, etc. Esters; Cellosolve esters such as cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate; propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol. Propropylene glycols such as 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; γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-capryro Saturated γ-lactones such as lactone; halogenated hydrocarbons such as trichloroethylene; aromatic hydrocarbons such as toluene and xylene; polar solvents such as dimethylacetamide, dimethylformamide and N-methylacetamide can be mentioned. These solvents may be used alone or in combination of two or more. The content of the solvent is preferably in the range of 10 to 10000 parts by weight, more preferably 50 to 5000 parts by weight, and further preferably 100 to 1000 parts by weight with respect to 100 parts by weight of the binder resin (A). When the radiation-sensitive resin composition contains a solvent, the solvent is usually removed after the cured film is formed.

Further, the radiation-sensitive resin composition of the present invention may further contain a silane coupling agent. By blending a silane coupling agent, the adhesion of the resin film formed from the radiation-sensitive resin composition of the present invention to the metal layer can be further improved.

The silane coupling agent is not particularly limited, and examples thereof include those having a reactive functional group such as an amino group, a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group.

Specific examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and N-phenyl-3-amino. Propyltrimethoxysilane, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-gly Examples thereof include sidoxylpropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane and the like. .. These silane coupling agents (F) can be used alone or in combination of two or more. Among these, γ-glycidoxypropyltrimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane are preferable from the viewpoint of high adhesion to the substrate.

The content of the silane coupling agent in the radiation-sensitive resin composition of the present invention is preferably 0.01 to 100 parts by weight, more preferably 0.1 to 50 parts by weight, based on 100 parts by weight of the binder resin (A). Parts, more preferably 0.5 to 20 parts by weight. By setting the content of the silane coupling agent in the above range, the effect of adding the silane coupling agent can be further enhanced.

Further, the radiation-sensitive resin composition of the present invention is a compound having an acidic group or a thermopotential acidic group, a surfactant, a sensitizer, and a photostabilizer, if desired, as long as the effects of the present invention are not impaired. , Other compounding agents such as antifoaming agents, pigments, dyes, fillers; etc. may be contained. Among these, for example, as the compound having an acidic group or a thermopotential acidic group, those described in JP-A-2014-29766 can be used, and surfactants, sensitizers and light stabilizers can be used. Can be used as described in JP-A-2011-75609.

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 a 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 a dispersion.

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

(Electronic components)
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. Examples thereof include an active matrix substrate, an organic EL element substrate, an integrated circuit element substrate, and a solid-state imaging. The resin film made of the radiation-sensitive resin composition of the present invention includes element substrates and the like, and is used for resin film applications in which adhesion to a metal layer is required among such electronic components, particularly such electronic components. It can be suitably used as an insulating film for a rewiring layer used for a rewiring layer (Re-Distribution Layer: RDL) formed on a surface protective film of a constituent element. In particular, since the resin film made of the radiation-sensitive resin composition of the present invention has excellent adhesion to the metal layer, it has excellent adhesion to copper constituting the rewiring layer, and the radiation-sensitive resin composition of the present invention. Since the resin film made of a material is also excellent in developability, it is possible to appropriately form a resin film according to the pattern of the rewiring layer. Furthermore, since the resin film made of the radiation-sensitive resin composition of the present invention is also excellent in low hygroscopicity, the reliability of the obtained electronic component can be further improved.

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

The coating method is, for example, a method in which the radiation-sensitive resin composition is coated and then heat-dried to remove the solvent. Various methods for applying the radiation-sensitive resin composition include, for example, a spray method, a spin coating method, a roll coating method, a die coating method, a doctor blade method, a rotary coating method, a bar coating method, a screen printing method, and an inkjet method. The method can be adopted. The heating and drying conditions vary depending on the type and blending ratio of each component, but are usually 30 to 150 ° C., preferably 60 to 120 ° C., usually 0.5 to 90 minutes, preferably 1 to 60 minutes, and more. It may be preferably carried out in 1 to 30 minutes.

In the film laminating method, the radiation-sensitive resin composition is applied onto a base material for forming a B-stage film such as a resin film or a metal film, and then the solvent is removed by heating and drying to obtain a B-stage film, and then this B-stage is obtained. This is a method of laminating films. The heating and drying conditions can be appropriately selected according to the type and blending 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. .. The film laminating can be performed using a crimping machine such as a pressure laminator, a press, a vacuum laminator, a vacuum press, or a roll laminator.

The thickness of the resin film is not particularly limited, but is preferably 0.1 to 100 μm, more preferably 0.5 to 50 μm, and even more preferably 0.5 to 30 μm.

Next, the resin film thus formed is patterned in a predetermined pattern. As a method for patterning the resin film, for example, the radiation-sensitive resin composition of the present invention is used to form a resin film before patterning, and the resin film before patterning is irradiated with active radiation to perform a latent image pattern. Then, a method of making the pattern manifest by bringing the developing solution into contact with the resin film having the latent image pattern can be mentioned.

The active radiation may be one that 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). There is no particular limitation. Specifically, ultraviolet rays, ultraviolet rays having a single wavelength such as g-rays and i-rays, light rays such as KrF excimer laser light and ArF excimer laser light; particle beams such as electron beams; and the like can be used. As a method of selectively irradiating these active radiations in a pattern to form a latent image pattern, a conventional method may be followed. For example, an ultraviolet ray, a g-ray, an i-ray, or a KrF excimer may be used by a reduced projection exposure device or the like. A method of irradiating a light beam such as a laser beam or an ArF excimer laser beam through a desired mask pattern, a method of drawing with a particle beam such as an electron beam, or the like can be used. When light rays are used as the active radiation, it may be single wavelength light or mixed wavelength light. The irradiation conditions are appropriately selected according to the active radiation to be used. For example, when light rays having a wavelength of 200 to 450 nm are used, the irradiation amount is usually 10 to 5,000 mJ / cm ² , preferably 50 to 1, It is in the range of 500 mJ / cm ² , 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 manifest. As the developing solution, 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; aqueous ammonia; primary amines such as ethylamine and n-propylamine; diethylamine. , Secondary amines such as di-n-propylamine; Tertiary amines such as triethylamine and methyldiethylamine; Tertiary 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] undec-7-ene, 1,5-diazabicyclo [4.3.0] nona-5 Cyclic amines such as -ene and N-methylpyrrolidone; and the like. These alkaline compounds can be used alone or in combination of two or more.

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

The resin film on which the desired pattern is formed in this way can be rinsed with a rinsing solution, if necessary, in order to remove the development residue. After the rinsing treatment, the remaining rinsing liquid is removed with compressed air or compressed nitrogen.
Further, if necessary, the entire surface of the electronic component can be irradiated with active radiation in order to inactivate the radiation-sensitive compound (B) contained in the radiation-sensitive resin composition. For the irradiation of active radiation, the method exemplified for the formation of the latent image pattern can be used. The resin film may be heated at the same time as or after the irradiation. Examples of the heating method include a method of heating an electronic component in a hot plate or an oven. The temperature is usually in the range of 80-300 ° C, preferably 100-200 ° C.

Next, the resin film thus formed is patterned and then subjected to a cross-linking reaction. Such cross-linking may be appropriately selected depending on the type of the epoxy-based cross-linking agent (C) contained in the radiation-sensitive resin composition, but is usually carried out by heating. The heating method can be performed using, for example, a hot plate, an oven, or the like. The heating temperature is usually 180 to 250 ° C., and the heating time is appropriately selected depending on the area and thickness of the resin film, the equipment used, etc. For example, when using a hot plate, the oven is usually operated for 5 to 60 minutes. When used, it is usually in the range of 30-90 minutes. Heating may be performed in an inert gas atmosphere, if necessary. The inert gas may be any gas that does not contain oxygen and does not oxidize the resin film, and examples thereof include nitrogen, argon, helium, neon, xenon, and krypton. Among these, nitrogen and argon are preferable, and nitrogen is particularly preferable. In particular, an inert gas having an oxygen content of 0.1% by volume or less, preferably 0.01% by volume or less, particularly nitrogen is preferable. These inert gases can be used alone or in combination of two or more.
In this way, an electronic component having a patterned resin film can be manufactured.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. Unless otherwise specified, "parts" in each example are based on weight.
The definition and evaluation method of each characteristic are as follows.

<Appearance of coating film>
The radiation-sensitive resin compositions prepared in each Example and each Comparative Example were evaluated by observing the appearance of the coating film when applied on a substrate with an optical microscope and using the following criteria. If the appearance of the coating film is good, it can be evaluated that the adhesion between the coating film and the underlying substrate is uniform. On the other hand, if the appearance of the coating film is inferior, not only the coating method but also spin coating or the like can be evaluated. Even when the resin film is formed by another method, it can be evaluated that a resin film capable of evaluating various characteristics cannot be obtained.
◯: The phenomenon as illustrated in the evaluation “x” below was not confirmed, and the appearance of the coating film was good.
X: The appearance of the coating film was impaired, such as the coating film becoming cloudy white, leaving bubble marks on the coating film, leaving radial streaks on the coating film, and the film thickness was not uniform.

<Adhesion to copper>
Using a sputtering device, the radiation-sensitive resin composition prepared in each Example and each Comparative Example was spin-coated on a silicon wafer formed of copper having a film thickness of 100 nm on a titanium film having a thickness of 50 nm, and then hot. A resin film was formed by prebaking at 120 ° C. for 2 minutes using a plate. Then, by heating in nitrogen at 230 ° C. for 1 hour, a silicon wafer with a resin film on which a resin film having a thickness of 3 μm was formed was obtained. Then, using the obtained silicon wafer with a resin film, the adhesion of the formed resin film to copper was evaluated by the surface-interface cutting method (SAICAS method) described below.

Specifically, a 1 mm wide notch is made in the resin film portion of the wafer with the resin film obtained above with a cutter, and the wafer with the resin film with the notch is used as an adhesion measuring device by Daipla Wintes. Using a Psycus DN-20 type, using a single crystal diamond cutting edge (1.0 mm width, rake angle 20 ° clearance angle 10 °), horizontal speed 0.2 μm / sec, vertical speed 0.02 μm / sec. When the sample was cut and the cutting edge was cut to the interface between the resin film and the surface of the soda glass, the parallel force FH [N] was measured by moving the cutting edge parallel to the substrate at a vertical speed of 0 μm / sec. Then, the peel strength P is obtained from the obtained parallel force FH [N] and the width w [m] of the cutting edge from the formula of "P [N / m] = FH [N] / w [m]". The obtained peel strength P was evaluated as a value of the adhesion of the resin film to copper according to the following criteria. It can be evaluated that the larger the value of the peel strength P, the better the adhesion of the resin film to copper.
◯: Peeling strength P is 100 N / m or more Δ: Peeling strength P is 100 N / m or more and less than 70 N / m ×: Peeling strength P is less than 70 N / m

<Chemical resistance>
The resin compositions prepared in each Example and each Comparative Example were spin-coated on a silicon wafer, dried by heating at 120 ° C. for 2 minutes using a hot plate, and then heated and dried at 230 ° C. for 1 minute in a nitrogen atmosphere. A sample for evaluation was obtained by forming a resin film by curing under the conditions. Then, the obtained evaluation sample was immersed in tetrahydrofuran at 25 ° C. for 30 minutes, and the rate of change in the thickness of the resin film before and after the immersion was measured to evaluate the chemical resistance. The rate of change in the thickness of the resin film before and after immersion is as follows: "Rate of change in thickness of resin film before and after immersion (%) = (| Thickness of resin film after immersion-Thickness of resin film before immersion | / Before immersion" The thickness of the resin film) × 100 ”was calculated. The chemical resistance was evaluated according to the following criteria.
◯: The rate of change in the thickness of the resin film before and after immersion is less than 1% Δ: The rate of change in the thickness of the resin film before and after immersion is 1% or more and less than 3% ×: The rate of change in the thickness of the resin film before and after immersion is 3 %that's all

<Developability>
The radiation-sensitive resin compositions prepared in each Example and each Comparative Example were spin-coated on a silicon wafer and then heat-dried at 120 ° C. for 2 minutes using a hot plate to form a resin film having a thickness of 3 μm. .. Next, exposure was performed at ^{400 mJ / cm 2} using a high-pressure mercury lamp that emits light having wavelengths of g-line (436 nm), h-line (405 nm), and i-line (365 nm). Then, the exposed sample is immersed in a 2.38% tetramethylammonium hydroxide aqueous solution (alkali developer) at 23 ° C. for 3 minutes, and then rinsed with ultrapure water for 30 seconds to show the surface condition of the developed sample. Was visually observed, and the developability was evaluated according to the following criteria. It can be judged that the resin film insoluble or does not swell is excellent in developability as a positive type resin film.
◯: The resin film was completely dissolved.
X: The resin film was not dissolved at all or was swollen.

<< Synthesis example 1 >>
<Preparation of cyclic olefin polymer (A-1)>
N-Phenyl-bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide (NBPI) 40 mol%, and 4-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 .. 0 ^2,7 ] 100 parts of a monomer mixture consisting of 60 mol% of dodeca-9-ene (TCDC), 2.0 parts of 1,5-hexadiene, (1,3-dimesityl imidazoline-2-ylidene) ( Tricyclohexylphosphine) Made of glass with 0.02 parts of benzylidene lutenium dichloride (synthesized by the method described in Org. Lett., Vol. 1, p. 953, 1999) and 200 parts of diethylene glycol ethyl methyl ether substituted with nitrogen. The mixture was charged in a pressure-resistant reactor and reacted at 80 ° C. for 4 hours with stirring to obtain a polymerization reaction solution.

Then, the obtained polymerization reaction solution was placed in an autoclave and stirred at 150 ° C. and a hydrogen pressure of 4 MPa for 5 hours to carry out a hydrogenation reaction to obtain a polymer solution containing a cyclic olefin polymer (A-1). .. The obtained cyclic olefin polymer (A-1) has a polymerization conversion rate of 99.7%, a polystyrene-equivalent weight average molecular weight of 7,150, a number average molecular weight of 4,690, a molecular weight distribution of 1.52, and a hydrogenation rate. Was 99.7%. Moreover, the solid content concentration of the polymer solution of the obtained cyclic olefin polymer (A-1) was 34.4% by weight.

<< Example 1 >>
As the binder resin (A), 291 parts of the polymer solution of the cyclic olefin polymer (A-1) obtained in Synthesis Example 1 (100 parts as the cyclic olefin polymer (A-1)), the radiation-sensitive compound (B). As, 4,4'-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride 35 parts (condensate with (2.5 mol)), as an epoxy-based cross-linking agent (C), epoxidized butane tetracarboxylic acid tetrakis (3-cyclohexenylmethyl) -modified ε-caprolactone (trade name "Epolide GT401", Daisel Made by Kagaku Kogyo Co., Ltd., aliphatic cyclic tetrafunctional epoxy resin, epoxy equivalent: 220, liquid at room temperature) 30 parts, as bisphenol type novolak resin (D), bisphenol A type novolak resin (trade name "PAPS-BPAN", Made by Asahi Organic Materials Industry Co., Ltd., Weight average molecular weight (Mw): 940, Number average molecular weight (Mn): 670, Molecular weight distribution (Mw / Mn): 1.4, Softening point: 124 ° C.) 20 parts, and as a solvent , 160 parts of diethylene glycol ethyl methyl ether were mixed and dissolved, and then filtered through a filter made of polytetrafluoroethylene having a pore size of 0.45 μm to prepare a radiation-sensitive resin composition.

Then, using the radiation-sensitive resin composition obtained above, each measurement / evaluation of the appearance of the coating film, the adhesion to copper, the chemical resistance, and the developability was performed. The results are shown in Table 1.

<< Example 2 >>
The radiation-sensitive resin composition was prepared in the same manner as in Example 1 except that the blending amount of the bisphenol A type novolak resin (trade name "PAPS-BPAN", manufactured by Asahi Organic Materials Industry Co., Ltd.) was changed from 20 parts to 60 parts. It was prepared and measured and evaluated in the same manner. The results are shown in Table 1.

<< Example 3 >>
Replacing 30 parts of epoxidized butane tetracarboxylic acid tetrakis (3-cyclohexenylmethyl) -modified ε-caprolactone (trade name "Epolide GT401", manufactured by Daicel Chemical Industries, Ltd.), bisphenol F type epoxy compound (trade name "jER YL983U") , Mitsubishi Chemical Co., Ltd., bifunctional epoxy compound, epoxy equivalent: 170, softening point: liquid at room temperature) 23 parts, bisphenol A type novolak resin (trade name "PAPS-BPAN", Asahi Organic Materials Industry Co., Ltd.) The epoxy resin composition was prepared in the same manner as in Example 1 except that the blending amount of (manufactured) was changed from 20 parts to 40 parts, and the measurement and evaluation were carried out in the same manner. The results are shown in Table 1.

<< Comparative Example 1 >>
A radiation-sensitive resin composition was prepared in the same manner as in Example 1 except that the bisphenol A type novolak resin (trade name "PAPS-BPAN", manufactured by Asahi Organic Materials Industry Co., Ltd.) was not blended, and measured in the same manner. Evaluation was performed. The results are shown in Table 1.

<< Comparative Example 2 >>
Bisphenol A type novolak resin (trade name "PAPS-BPAN", manufactured by Asahi Organic Materials Industry Co., Ltd.) Instead of 40 parts, phenol novolac resin (trade name "EPR5010G", manufactured by Asahi Organic Materials Industry Co., Ltd., weight average molecular weight (Mw)) : 9500) A radiation-sensitive resin composition was prepared in the same manner as in Example 3 except that 60 parts were used, and measurement and evaluation were carried out in the same manner. The results are shown in Table 1.

<< Comparative Example 3 >>
Biphenyl aralkyl resin (trade name "MEH-7851-4H", manufactured by Meiwa Kasei Co., Ltd.) instead of 20 parts of bisphenol A type novolak resin (trade name "PAPS-BPAN", manufactured by Asahi Organic Materials Industry Co., Ltd.) Mw): 9900) A radiation-sensitive resin composition was prepared in the same manner as in Example 1 except that 60 parts were used, and the measurement and evaluation were carried out in the same manner. The results are shown in Table 1.

<< Comparative Example 4 >>
Replacing 30 parts of epoxidized butane tetracarboxylic acid tetrakis (3-cyclohexenylmethyl) -modified ε-caprolactone (trade name "Epolide GT401", manufactured by Daicel Chemical Industries, Ltd.), glycidyl ether type epoxy compound (trade name "Epiclon HP7200HH") , DIC, polyfunctional epoxy compound, epoxy equivalent: 280, softening point: 92 ° C) 38 parts, bisphenol A type novolak resin (trade name "PAPS-BPAN", manufactured by Asahi Organic Materials Industry Co., Ltd.) A radiation-sensitive resin composition was prepared in the same manner as in Example 1 except that the blending amount of the above was changed from 20 parts to 40 parts, and the measurement and evaluation were carried out in the same manner. The results are shown in Table 1.

As shown in Table 1, a binder resin (A), a radiation-sensitive compound (B), an epoxy-based cross-linking agent (C) having a softening point of 30 ° C. or lower and a tetrafunctional or lower, and a bisphenol-type novolak resin ( The resin film obtained by using the radiation-sensitive resin composition containing D) has a good appearance when formed into a coating film, and is excellent in adhesion to a metal layer (copper), chemical resistance, and developability. There were (Examples 1 to 3). From this result, the resin film obtained by using the radiation-sensitive resin composition of the present invention is used for applications requiring high adhesion to a metal layer, specifically, a surface protective film for an element constituting an electronic component. It can be said that it is particularly suitable for resin film applications for the rewiring layer formed on the top.

On the other hand, when the bisphenol type novolak resin (D) was not blended, the obtained resin film was inferior in adhesion to the metal layer (copper) and chemical resistance (Comparative Example 1).
When a high molecular weight phenol novolac resin is used instead of the bisphenol type novolak resin (D), the mixing of each component is insufficient in the radiation-sensitive resin composition, and therefore, the coating film becomes cloudy. It occurred (poor appearance), and a resin film capable of evaluating various characteristics could not be obtained (Comparative Example 2).
Further, when a biphenyl aralkyl resin is used instead of the bisphenol type novolac resin (D), the obtained resin film is inferior in adhesion to the metal layer (copper), and further, it does not show alkali solubility and is developed. It was inferior in sex (Comparative Example 3).
Further, when an epoxy compound having a softening point of more than 30 ° C. is used instead of the epoxy-based cross-linking agent (C) having a softening point of 30 ° C. or less and tetrafunctional or less, a resin film obtained is obtained. Was inferior in adhesion to the metal layer (copper) and chemical resistance, and was inferior in developability because it did not show alkali solubility (Comparative Example 4).

Claims (3)

It contains a binder resin (A), a radiation-sensitive compound (B), an epoxy-based cross-linking agent (C) having a softening point of 30 ° C. or lower and a tetrafunctional or lower, and a bisphenol-type novolak resin (D) .
The binder resin (A) is a cyclic olefin polymer containing a carboxyl group, and the binder resin (A) is a cyclic olefin polymer.
The content of the bisphenol type novolak resin (D) is, relative to the binder resin (A) 100 parts by weight of 15 to 50 parts by weight der Ru radiation-sensitive resin composition. The radiation-sensitive resin composition according to claim 1 , wherein the bisphenol type novolak resin (D) has a weight average molecular weight of 500 to 2,000. An electronic component comprising a resin film comprising the radiation-sensitive resin composition according to claim 1 or 2.