JPWO2012133617A1 - Resin composition and semiconductor element substrate - Google Patents

Abstract

  A resin composition comprising a binder resin (A), a silane-modified resin (B), and a compound (C) having an acidic group or a heat-latent acidic group, the silane-modified resin (B), The ratio with the compound (C) having an acidic group or a thermal latent acidic group is, by weight ratio, “silane-modified resin (B) / compound having an acidic group or thermal latent acidic group (C)” = 0.5 The resin composition is characterized by being ˜20.

Description

  The present invention relates to a resin composition and a semiconductor element substrate provided with a resin film made of the resin composition. More specifically, the present invention has excellent storage stability and is excellent in pattern formability and transparency by development. The present invention relates to a resin composition capable of providing a resin film and a semiconductor element substrate including a resin film made of the resin composition.

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

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

  In order to meet these requirements, for example, Patent Document 1 discloses a resin (A), a crosslinking agent (B) having an epoxy group, a triazine ring structure or a glycoluril structure, and an imino group, a methylol group and an alkoxy group. A radiation-sensitive resin composition containing a crosslinking agent (C) having at least one functional group selected from the group consisting of butyl groups and a radiation-sensitive compound (D) is disclosed. However, the resin film obtained by using the resin composition described in Patent Document 1 has a pattern formation property by development, in particular, development adhesion (development pattern in the case where the development pattern width is narrowed and the definition is increased). Adhesion) is not always sufficient, and therefore, improvement of pattern formation by development has been desired.

JP 2010-224533 A

  An object of this invention is to provide the resin composition which has the outstanding storage stability and can provide the resin film excellent in pattern formation property and transparency. Another object of the present invention is to provide a semiconductor element substrate having a resin film made of such a resin composition.

  As a result of diligent research to achieve the above object, the present inventors have obtained a resin composition comprising a binder resin and a silane-modified resin and a compound having an acidic group or a thermal latent acidic group in a predetermined ratio. The present inventors have found that the above object can be achieved by a product, and have completed the present invention.

  That is, according to the present invention, a resin composition comprising a binder resin (A), a silane-modified resin (B), and a compound (C) having an acidic group or a thermal latent acidic group, the silane The ratio of the modified resin (B) and the compound (C) having the acidic group or the thermal latent acidic group is expressed by a weight ratio of “silane modified resin (B) / compound having an acidic group or thermal latent acidic group”. (C) ”= 0.5 to 20 is provided.

Preferably, the silane-modified resin (B) is a chemical compound of at least one polymer material selected from polyester, polyamide, polyimide, polyamic acid, epoxy resin, acrylic resin, urethane resin, and phenol resin, and a silicon compound. It is a compound formed by binding.
Preferably, the silicon compound is a silicon compound represented by the following formula and / or a partial hydrolysis condensate of the silicon compound represented by the following formula.
_{^{(R 8) r -Si- (OR}} 9) 4-r
(In the above formula, r is an integer of 0 to 3, and R ⁸ is an alkyl group having 1 to 10 carbon atoms which may have a functional group directly bonded to a carbon atom, or an aryl having 6 to 20 carbon atoms. Or an unsaturated aliphatic group having 2 to 10 carbon atoms, and when R ⁸ is plural, the plural R ⁸ may be the same or different from each other, and R ⁹ is hydrogen. An alkyl group having 1 to 10 carbon atoms which may have an atom or a functional group directly bonded to a carbon atom, and when R ⁹ is plural, the plural R ⁹ are the same, May be different.)
Preferably, the content ratio of the silane-modified resin (B) is 1 to 100 parts by weight with respect to 100 parts by weight of the binder resin (A).
Preferably, the binder resin (A) is a cyclic olefin polymer having a protic polar group or an acrylic resin.
Preferably, the resin composition of the present invention further contains a radiation sensitive compound (D).
Preferably, the resin composition of the present invention further contains a crosslinking agent (E).

  Moreover, according to this invention, a semiconductor element substrate provided with the resin film which consists of one of the said resin compositions is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition which has the outstanding storage stability and can give the resin film excellent in the pattern formation property and transparency by image development, and a resin film consisting of such a resin composition A semiconductor element substrate can be provided.

  The resin composition of the present invention contains a binder resin (A), a silane-modified resin (B), and a compound (C) having an acidic group or a heat-latent acidic group, the silane-modified resin (B), and an acidic group Or the ratio with the compound (C) which has a thermal latent acidic group is a weight ratio, "silane modified resin (B) / compound (C) which has an acidic group or thermal latent acidic group" = 0.5-20 It is in the range.

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

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

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

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

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

  The content ratio of the monomer (a) unit in the cyclic olefin polymer (A1) is preferably 10 to 90 mol% with respect to the total monomer units. When the content ratio of the monomer (a) unit is too small, the radiation sensitivity becomes insufficient when a radiation sensitive compound is added to the resin composition of the present invention, or a dissolution residue is generated during development. If the amount is too large, the solubility of the cyclic olefin polymer (A1) in the polar solvent may be insufficient.

  In addition, the more preferable range of the content rate of the unit of a monomer (a) changes with kinds of resin film comprised by the resin composition of this invention. Specifically, when the resin film is a resin film that is patterned by photolithography, such as a protective film of an active matrix substrate or a sealing film of an organic EL element substrate, a monomer ( The content ratio of the unit a) is more preferably 40 to 70 mol%, and particularly preferably 50 to 60 mol%. On the other hand, when the resin film is a resin film that is not patterned by photolithography, such as a gate insulating film of an active matrix substrate or a pixel isolation film of an organic EL element substrate, the monomer (a) The content ratio of the unit is more preferably 20 to 80 mol%, and particularly preferably 30 to 70 mol%.

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

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

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

（上記式（２）中、Ｒ^２は炭素数１〜３のアルキレン基、Ｒ^３は、炭素数１〜１０のアルキル基または炭素数１〜１０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 formula (1) or a monomer represented by the following formula (2).

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

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

In the above formula (1), R ¹ is an alkyl group having ¹ to 16 carbon atoms or an aryl group. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, n -Pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n -Linear alkyl groups such as 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 , Norbornyl group, bornyl group, isobornyl group, decahydronaphthyl group, tricyclodecanyl group, adamantyl group, etc. Alkyl group; 2-propyl group, 2-butyl group, 2-methyl-1-propyl group, 2-methyl-2-propyl group, 1-methylbutyl group, 2-methylbutyl group, 1-methylpentyl group, 1-ethylbutyl Groups, branched alkyl groups such as 2-methylhexyl group, 2-ethylhexyl group, 4-methylheptyl group, 1-methylnonyl group, 1-methyltridecyl group, 1-methyltetradecyl group, and the like. Specific examples of the aryl group include a benzyl group. Among these, since it is excellent in heat resistance and solubility in a polar solvent, 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. If the number of carbons in these groups is too small, the solubility in polar solvents may be poor. If the number of carbons is too large, the heat resistance will be poor, and if the resin film is patterned, it will melt by heat and disappear. There is a risk of it.

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

On the other hand, in the above formula (2), R ² is an alkylene group having 1 to 3 carbon atoms, and examples of the alkylene group having 1 to 3 carbon atoms include a methylene group, an ethylene group, a propylene group, and an isopropylene group. Among these, a methylene group and an ethylene group are preferable because of good polymerization activity.

In the above formula (2), R ³ is an alkyl group having 1 to 10 carbon atoms or a halogenated alkyl group having 1 to 10 carbon atoms. Examples of the 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 halogenated alkyl group having 1 to 10 carbon atoms include a fluoromethyl group, a chloromethyl group, a bromomethyl group, a difluoromethyl group, a dichloromethyl group, a difluoromethyl group, a trifluoromethyl group, a trichloromethyl group, and 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 above formulas (1) and (2) can be obtained, for example, by an amidation reaction between a corresponding amine and 5-norbornene-2,3-dicarboxylic acid anhydride. The obtained monomer can be efficiently isolated by separating and purifying the reaction solution of the amidation reaction by a known method.

Examples of the cyclic olefin having an ester group include 2-acetoxybicyclo [2.2.1] hept-5-ene, 2-acetoxymethylbicyclo [2.2.1] hept-5-ene, and 2-methoxycarbonyl. Bicyclo [2.2.1] hept-5-ene, 2-ethoxycarbonylbicyclo [2.2.1] hept-5-ene, 2-propoxycarbonylbicyclo [2.2.1] hept-5-ene, 2-butoxycarbonylbicyclo [2.2.1] hept-5-ene, 2-cyclohexyloxycarbonylbicyclo [2.2.1] hept-5-ene, 2-methyl-2-methoxycarbonylbicyclo [2.2 .1] Hept-5-ene, 2-methyl-2-ethoxycarbonylbicyclo [2.2.1] hept-5-ene, 2-methyl-2-propoxyl Nilbicyclo [2.2.1] hept-5-ene, 2-methyl-2-butoxycarbonylbicyclo [2.2.1] hept-5-ene, 2-methyl-2-cyclohexyloxycarbonylbicyclo [2.2 .1] Hept-5-ene, 2- (2,2,2-trifluoroethoxycarbonyl) bicyclo [2.2.1] hept-5-ene, 2-methyl-2- (2,2,2- Trifluoroethoxycarbonyl) bicyclo [2.2.1] hept-5-ene, 2-methoxycarbonyltricyclo [5.2.1.0 ^2,6 ] dec-8-ene, 2-ethoxycarbonyltricyclo [ 5.2.1.0 ^2,6 ] dec-8-ene, 2-propoxycarbonyltricyclo [5.2.1.0 ^2,6 ] dec-8-ene, 4-acetoxytetracyclo [6.2 .1.1 ^3, . 0 ^2,7 ] dodec-9-ene, 4-methoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-ethoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-propoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-butoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-methyl-4-methoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-methyl-4-ethoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-methyl-4-propoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-methyl-4-butoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-methyl-4- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene and the like.

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

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

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

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

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

Specific examples of the monomer (b3) other than the cyclic olefin include ethylene; propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3- Ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 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-eicocene; -Non-conjugated dienes such as hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, and derivatives thereof; Among these, an α-olefin, particularly ethylene is preferable.
These monomers (b3) may be used alone or in combination of two or more.

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

  The content ratio of the copolymerizable monomer (b) unit in the cyclic olefin polymer (A1) is preferably 10 to 90 mol% with respect to the total monomer units. If the content ratio of the copolymerizable monomer (b) is too small, the solubility of the cyclic olefin polymer (A1) in the polar solvent may be insufficient. When a radiation sensitive compound is added to the resin composition, the radiation sensitivity may be insufficient, or a dissolution residue may be generated during development.

  In addition, the more preferable range of the content rate of the unit of the monomer (b) which can be copolymerized changes with kinds of resin film comprised by the resin composition of this invention. Specifically, when the resin film is a resin film that is patterned by photolithography, such as a protective film of an active matrix substrate or a sealing film of an organic EL element substrate, copolymerization is possible. As for the content rate of the unit of a monomer (b), it is more preferable that it is 30-60 mol%, and it is especially preferable that it is 40-50 mol%. On the other hand, if the resin film is a resin film that is not patterned by photolithography, such as a gate insulating film of an active matrix substrate or a pixel isolation film of an organic EL element substrate, a copolymerizable single quantity As for the content rate of the unit of a body (b), it is more preferable that it is 20-80 mol%, and it is especially preferable that it is 30-70 mol%.

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

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

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

  The ring-opening polymer comprises a ring-opening metathesis polymerization of a cyclic olefin monomer having a protic polar group (a) and a copolymerizable monomer (b) used as necessary in the presence of a metathesis reaction catalyst. Can be manufactured.

  The metathesis reaction catalyst may be any catalyst as long as it is a group 3-11 transition metal compound of the periodic table and performs ring-opening metathesis polymerization of the cyclic olefin monomer (a) having a protic polar group. For example, as a metathesis reaction catalyst, one described in Olefin Metathesis and Metathesis Polymerization (KJ Ivinand JC Mol, Academic Press, San Diego 1997) can be used.

  As a metathesis reaction catalyst, a periodic table group 3-11 transition metal carbene complex catalyst is mentioned, for example. Among these, use of a ruthenium carbene complex catalyst is preferable.

  Examples of the periodic table Group 3-11 transition metal-carbene complex catalyst include a tungsten alkylidene complex catalyst, a molybdenum alkylidene complex catalyst, a rhenium alkylidene complex catalyst, and a ruthenium carbene complex catalyst.

Specific examples of the tungsten alkylidene complex ^{_{catalysts, W (N-2,6-Pr}} i 2 C 6 H 3) (CHBu t) (OBu t) 2, W (N-2,6-Pr i 2 C 6 H ^{_{3) (CHBu t) (OCMe}} 2 CF 3) 2, W (N-2,6-Pr i 2 C 6 H 3) (CHBu t) (OCMe (CF 3) 2) 2, W (N-2, ^{_{6-Pr i 2 C 6 H}} 3) (CHCMe 2 Ph) (OBu t) 2 W (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OCMe 2 CF 3) 2, W ^{_{(N-2,6-Pr i 2}} C 6 H 3) (CHCMe 2 Ph) (OCMe (CF 3) 2) 2 and the like.

Specific examples of molybdenum alkylidene complex _{^{catalyst, Mo (N-2,6-Pr}} i 2 C 6 H 3) (CHBu t) (OBu t) 2, Mo (N-2,6-Pr i 2 C 6 H _{^{3) (CHBu t) (OCMe}} 2 CF 3) 2, Mo (N-2,6-Pr i 2 C 6 H 3) (CHBu t) (OCMe (CF 3) 2) 2, Mo (N-2, _{^{6-Pr i 2 C 6 H}} 3) (CHCMe 2 Ph) (OBu t) 2 Mo (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OCMe 2 CF 3) 2, Mo _{^{(N-2,6-Pr i 2}} C 6 H 3) (CHCMe 2 Ph) (OCMe (CF 3) 2) 2, Mo (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph ) (BIPHEN), Mo (N -2,6-Pr i 2 _{6 H 3) (CHCMe 2 Ph} ) (BINO) (THF) , and the like.

Specific examples of rhenium alkylidene complex ^{catalyst, Re (CBu t) (CHBu} t) (O-2,6-Pr i 2 C 6 H 3) 2, Re (CBu t) (CHBu t) (O-2- _{^{Bu t C 6 H 4) 2}} , Re (CBu t) (CHBu t) (OCMe 2 CF 3) 2, Re (CBu t) (CHBu t) (OCMe (CF 3) 2) 2, Re (CBu t) (CHBu ^t ) (O-2,6-Me ₂ C ₆ H ₃ ) _{2 and the} like.

In the above formula, the Pr ⁱ isopropyl group, a Bu ^t is tert- butyl group, Me is a a methyl group, Ph refers to a phenyl group, BIPHEN is 5,5 ', 6,6'-tetramethyl-3, 3′-di-tert-butyl-1,1′-biphenyl-2,2′-dioxy group, BINO represents 1,1′-dinaphthyl-2,2′-dioxy group, and THF represents tetrahydrofuran. .

  Further, specific examples of the ruthenium carbene complex catalyst include compounds represented by the following formula (3) or (4).

In the above formulas (3) and (4), ═CR ⁴ R ⁵ and ═C═CR ⁴ R ⁵ are carbene compounds containing a carbene carbon at the reaction center. R ⁴ and R ⁵ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom, an alkoxy group, an aryl Oxy group, acyloxy group, amino group, acylamino group, diacylamino group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, phosphino group, silyl group, these carbene compounds may or may not contain heteroatoms May be. L ¹ represents a hetero atom-containing carbene compound, and L ² represents any neutral electron donating compound.

Here, the hetero atom-containing carbene compound refers to a compound containing a carbene carbon and a hetero atom. Both L ¹ and L ² or L ¹ is a heteroatom-containing carbene compound, and a ruthenium metal atom is directly bonded to the carbene carbon contained therein, and a group containing a heteroatom is bonded.

L ³ and L ⁴ each independently represent an arbitrary anionic ligand. Also, two, three, four, five or six of R ⁴ , R ⁵ , L ¹ , L ² , L ³ and L ⁴ are bonded to each other to form a multidentate chelating ligand. May be. Specific examples of heteroatoms include N, O, P, S, As, and Se atoms. Among these, from the viewpoint of obtaining a stable carbene compound, N, O, P, S atoms and the like are preferable, and N atom is particularly preferable.

In the above formulas (3) and (4), the anionic (anionic) ligands L ³ and L ⁴ are ligands having a negative charge when separated from the central metal, for example, fluorine atoms Halogen atoms such as chlorine atom, bromine atom and iodine atom; hydrocarbon groups containing oxygen such as diketonate group, alkoxy group, aryloxy group and carboxyl group; fat substituted with halogen atoms such as cyclopentadienyl chloride Examples thereof include a cyclic hydrocarbon group. Among these, a halogen atom is preferable and a chlorine atom is more preferable.

When L ² is a neutral electron donating compound other than a heteroatom-containing carbene compound, L ² may be any ligand as long as it has a neutral charge when separated from the central metal. Specific examples thereof include carbonyls, amines, pyridines, ethers, nitriles, esters, phosphines, thioethers, aromatic compounds, olefins, isocyanides, thiocyanates, and the like. Among these, phosphines and pyridines are preferable, and trialkylphosphine is more preferable. Further, when R ⁴ and L ² or R ⁵ and L ² are bonded to each other to form a bidentate chelating ligand, pyridines and ethers are preferable.

  Examples of the ruthenium complex catalyst represented by the above formula (3) include benzylidene (1,3-dimesitymylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesitylmimidazole). Lysine-2-ylidene) (3-methyl-2-buten-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, ((2- (1-methylethoxy) phenyl) methylene) (1,3-dimesitylimidazo Lysine-2-ylidene) ruthenium dichloride, benzylidene (1,3-dimesityrimimidazolidine-2-ylidene) bis (3-bromopyridine) ruthenium dichloride (3- (2-pyridinyl) propylidene) (1,3-di Mesitylimidazolidine-2-ylidene) ruthenium dichloride, benzili (1,3-dimesityl-octahydrobenzimidazol-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (3-phenylindene-1-ylidene) (1,3-dimesityl-4-imidazoline-2-ylidene) (Tricyclohexylphosphine) ruthenium dichloride, (2-thienylmethylene) (1,3-dimesityl-4-imidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (2-thienylmethylene) (1,3-dimesityl- 4,5-dimethyl-4-imidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (2-thienylmethylene) (1,3,4-triphenyl-4,5-dihydro-1H-1,2, 4-triazole-5-ylide ) (Tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-4-imidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-2,3-dihydrobenzimidazole-2) -Ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene) (tricyclohexylphosphine) ruthenium dichloride, Benzylidene (4,5-dichloro-1,3-dimesityl-4-imidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (4,5-dibromo-1,3-dimesityl-4- Imidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (3-phenylindene-1-ylidene) (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (3- Phenylindene-1-ylidene) (1,3-dimesitylimidazolidin-2-ylidene) bis (pyridine) ruthenium dichloride, ((2- (1-acetylethoxy) phenyl) methylene) (1,3-dimesi Tyrimidazolidine-2-ylidene) ruthenium dichloride, (phenylthiomethylene) (1,3-dimesityrylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (phenylthiomethylene) (1,3-dimesityl) -4-Imidazoline- -Ylidene) (tricyclohexylphosphine) ruthenium dichloride, (ethylthiomethylene) (1,3-dimesityl-4-imidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, ((1-aza-2-oxocyclopentyl) Methylene) (1,3-dimesityl-4-imidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, ((carbazol-9-yl) methylene) (1,3-dimesityl-4-imidazoline-2-ylidene) (Tricyclohexylphosphine) ruthenium dichloride, ((2- (1-methylethoxy) -5- (N, N-dimethylaminosulfonyl) phenyl) methylene) (1,3-dimesitylimidazolidin-2-ylidene) ruthenium Dichloride, (2- (1-methylethoxy) -5- (trifluoroacetoamino) phenyl) methylene) (1,3-bis (2,6-diisopropylphenyl) imidazolidin-2-ylidene) ruthenium dichloride, benzylidene [1, 3-di (1-phenylethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) ruthenium dichloride, (1,3-diisopropylhexahydropyrimidin-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium A ruthenium carbene complex in which a heteroatom-containing carbene compound such as dichloride, benzylidene (1,3-dimesitylhexahydropyrimidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride and a neutral electron donating compound are bonded; Two heteroatom-containing carbene compounds such as benzylidenebis (1,3-dicyclohexyl-4-imidazoline-2-ylidene) ruthenium dichloride and benzylidenebis (1,3-diisopropyl-4-imidazoline-2-ylidene) ruthenium dichloride were bonded. Ruthenium carbene complex; and the like.

  Examples of the ruthenium carbene complex catalyst represented by the above formula (4) include (phenylvinylidene) (1,3-dimesityrylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (t-butylvinylidene). ) (1,3-diisopropyl-4-imidazoline-2-ylidene) (tricyclopentylphosphine) ruthenium dichloride, bis (1,3-dicyclohexyl-4-imidazoline-2-ylidene) phenylvinylidene ruthenium dichloride, and the like.

  The amount of the metathesis reaction catalyst used is the molar ratio of monomer to catalyst, catalyst: monomer = 1: 100 to 1: 2,000,000, preferably 1: 500 to 1: 1,000,000, More preferably, it is 1: 1,000-1: 500,000. If the amount of catalyst is too large, it may be difficult to remove the catalyst, and if it is too small, sufficient polymerization activity may not be obtained.

  Ring-opening polymerization using a metathesis reaction catalyst can be performed in a solvent or without a solvent. When the hydrogenation reaction is carried out as it is without isolating the produced polymer after completion of the polymerization reaction, the polymerization is preferably carried out in a solvent.

  The solvent is not particularly limited as long as it dissolves the produced polymer and does not inhibit the polymerization reaction. Examples of the solvent used include aliphatic hydrocarbons such as n-pentane, n-hexane, and n-heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, and bicyclo Alicyclic hydrocarbons such as heptane, tricyclodecane, hexahydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; nitrogen-containing compounds such as nitromethane, nitrobenzene, acetonitrile, propionitrile and benzonitrile Hydrocarbons; ethers such as diethyl ether, tetrahydrofuran, dioxane, etc .; acetone, ethyl methyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc. Ketones; methyl acetate, ethyl acetate, ethyl propionate, methyl benzoate, chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, halogenated hydrocarbons such as chlorobenzene; and the like. Among these, the use of aromatic hydrocarbons, alicyclic hydrocarbons, ethers, ketones or esters is preferable.

  The concentration of the monomer mixture in the solvent is preferably 1 to 50% by weight, more preferably 2 to 45% by weight, and still more preferably 5 to 40% by weight. If the concentration of the monomer mixture is less than 1% by weight, the productivity of the polymer may be deteriorated. If it exceeds 50% by weight, the viscosity after polymerization may be too high, and subsequent hydrogenation and the like may be difficult. is there.

  The metathesis reaction catalyst may be dissolved in a solvent and added to the reaction system, or may be added as it is without being dissolved. Examples of the solvent for preparing the catalyst solution include the same solvents as those used for the polymerization reaction.

  In the polymerization reaction, a molecular weight modifier can be added to the reaction system in order to adjust the molecular weight of the polymer. Examples of molecular weight modifiers include α-olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene; α, ω- such as 1,4-pentadiene, 1,5-hexadiene and 1,6-heptadiene. Diolefins; Styrenes such as styrene, vinyltoluene and divinylbenzene; Ethers such as ethyl vinyl ether, isobutyl vinyl ether and allyl glycidyl ether; Halogen containing vinyl compounds such as allyl chloride; Oxygen containing vinyl such as allyl acetate, allyl alcohol and glycidyl methacrylate Compound; Nitrogen-containing vinyl compounds such as acrylonitrile and acrylamide can be used. A polymer having a desired molecular weight is obtained by using 0.05 to 50 mol% of a molecular weight modifier with respect to the monomer mixture containing the cyclic olefin monomer (a) having a protic polar group. Can do.

  The polymerization temperature is not particularly limited, but is usually −100 ° C. to + 200 ° C., preferably −50 ° C. to + 180 ° C., more preferably −30 ° C. to + 160 ° C., and further preferably 0 ° C. to + 140 ° C. The polymerization time is usually from 1 minute to 100 hours, and can be appropriately adjusted according to the progress of the reaction.

  On the other hand, the addition polymer comprises a cyclic olefin monomer having a protic polar group (a) and a copolymerizable monomer (b) used as required by a known addition polymerization catalyst such as titanium, It can be obtained by polymerization using a catalyst comprising a zirconium or vanadium compound and an organoaluminum compound. These polymerization catalysts can be used alone or in combination of two or more. The amount of the polymerization catalyst is a molar ratio of the metal compound to the monomer in the polymerization catalyst and is usually in the range of 1: 100 to 1: 2,000,000.

  Further, when the cyclic olefin polymer (A1) used in the present invention is a ring-opening polymer, a hydrogenation reaction is further performed, and hydrogenation in which carbon-carbon double bonds contained in the main chain are hydrogenated is performed. 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. Preferably, it is 90% or more, more preferably 95% or more.

Hydrogenation ratio of the hydrogenated product may, for example, carbon in the ^{1 H-NMR} spectrum of the ring-opening polymer - a peak intensity derived from the carbon-carbon double bond, carbon in the ^{1 H-NMR} spectrum of the hydrogenated product - carbon double It can obtain | require by comparing with the peak intensity derived from coupling | bonding.

  The hydrogenation reaction can be performed, for example, by converting a carbon-carbon double bond in the main chain of the ring-opening polymer into a saturated single bond using hydrogen gas in the presence of a hydrogenation catalyst.

  The hydrogenation catalyst to be used is not particularly limited, such as a homogeneous catalyst and a heterogeneous catalyst, and those generally used for hydrogenation of olefin compounds can be used as appropriate.

  Examples of homogeneous catalysts include transitions such as cobalt acetate and triethylaluminum, nickel acetylacetonate and triisobutylaluminum, a combination of titanocene dichloride and n-butyllithium, zirconocene dichloride and sec-butyllithium, tetrabutoxytitanate and dimethylmagnesium, etc. Ziegler catalyst comprising a combination of a metal compound and an alkali metal compound; ruthenium carbene complex catalyst, chlorotris (triphenylphosphine) rhodium described in the above-mentioned ring-opening metathesis reaction catalyst, JP-A-7-2929, JP-A-7- 149823, JP-A-11-109460, JP-A-11-158256, JP-A-11-193323, JP-A-11-109460, etc. Noble metal complex catalyst consisting iodonium compounds; and the like.

  Examples of the heterogeneous catalyst include a hydrogenation catalyst in which a metal such as nickel, palladium, platinum, rhodium, and ruthenium is supported on a carrier such as carbon, silica, diatomaceous earth, alumina, and titanium oxide. More specifically, for example, nickel / silica, nickel / diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina and the like can be used. These hydrogenation catalysts can be used alone or in combination of two or more.

  Among these, rhodium, ruthenium, and the like from the point that the carbon-carbon double bond in the polymer can be selectively hydrogenated without causing side reactions such as modification of the functional group contained in the ring-opening polymer. The use of a noble metal complex catalyst and a palladium supported catalyst such as palladium / carbon is preferred, and the use of a ruthenium carbene complex catalyst or a palladium supported catalyst is more preferred.

  The ruthenium carbene complex catalyst described above can be used as a ring-opening metathesis reaction catalyst and a hydrogenation catalyst. In this case, the ring-opening metathesis reaction and the hydrogenation reaction can be performed continuously.

  When a ring-opening metathesis reaction and a hydrogenation reaction are continuously performed using a ruthenium carbene complex catalyst, a vinyl compound such as ethyl vinyl ether or a catalyst modifier such as an α-olefin is added to activate the catalyst. Then, a method of starting the hydrogenation reaction is preferably employed. Furthermore, it is also preferable to employ a method of improving the activity by adding a base such as triethylamine or N, N-dimethylacetamide.

  The hydrogenation reaction is usually performed in an organic solvent. As an organic solvent, it can select suitably by the solubility of the hydride to produce | generate, The organic solvent similar to the said polymerization solvent can be used. Therefore, after the polymerization reaction, the hydrogenation catalyst can be added to the reaction solution or the filtrate obtained by filtering the metathesis reaction catalyst from the reaction solution without replacing the solvent.

  The conditions for the hydrogenation reaction may be appropriately selected according to the type of hydrogenation catalyst used. The amount of the hydrogenation catalyst used is usually 0.01 to 50 parts by weight, preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the ring-opening polymer. . The reaction temperature is generally −10 ° C. to + 250 ° C., preferably 0 ° C. to + 240 ° C., more preferably 20 ° C. to + 230 ° C. At a temperature lower than this range, the reaction rate becomes slow. Conversely, at a high temperature, a side reaction tends to occur. The pressure of hydrogen is usually 0.01 to 10.0 MPa, preferably 0.05 to 8.0 MPa, more preferably 0.1 to 6.0 MPa.

  The time for the hydrogenation reaction is appropriately selected in order to control the hydrogenation rate. The reaction time is usually in the range of 0.1 to 50 hours, and 50% or more, preferably 70% or more, more preferably 90% or more, most preferably, of the carbon-carbon double bonds of the main chain in the polymer. 95% or more can be hydrogenated.

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

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

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

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

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

The cardo resin (A3) used in the present invention is a resin having a cardo structure, that is, a skeleton structure in which two cyclic structures are bonded to a quaternary carbon atom constituting the cyclic structure. A common cardo structure is a fluorene ring bonded to a benzene ring.
Specific examples of the skeleton structure in which two cyclic structures are bonded to a quaternary carbon atom constituting the cyclic structure include a fluorene skeleton, a bisphenol fluorene skeleton, a bisaminophenyl fluorene skeleton, a fluorene skeleton having an epoxy group, and an acrylic group. And a fluorene skeleton having the same.
The cardo resin (A3) used in the present invention is formed by polymerizing a skeleton having the cardo structure by a reaction between functional groups bonded thereto. The cardo resin (A3) has a structure (cardo structure) in which the main chain and bulky side chains are connected by one element, and has a ring structure in a direction substantially perpendicular to the main chain.

（上記式（５）中、ｎは０〜１０の整数である。）As an example of the cardo structure, an example of a cardo structure in which an acryloyl group is bonded as a functional group is shown in the following formula (5).

(In said formula (5), n is an integer of 0-10.)

Monomers having a cardo structure include, for example, bis (glycidyloxyphenyl) fluorene type epoxy resin; condensate of bisphenol fluorene type epoxy resin and acrylic acid; 9,9-bis (4-hydroxyphenyl) fluorene, Cardio structure-containing bisphenols such as 9-bis (4-hydroxy-3-methylphenyl) fluorene; 9,9-bis (cyanoalkyl) fluorenes such as 9,9-bis (cyanomethyl) fluorene; -9,9-bis (aminoalkyl) fluorenes such as bis (3-aminopropyl) fluorene;
The cardo resin (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 selected according to the type of polymerizable functional group possessed by the monomer. For example, a ring-opening polymerization method or an addition polymerization method is employed.

Although it does not specifically limit as polysiloxane (A4) used by this invention, Preferably the polymer obtained by mixing and making 1 type, or 2 or more types of the organosilane represented by following formula (6) mention is mentioned. It is done.
_{^{(R 6) m -Si- (OR}} 7) 4-m (6)

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

In the above formula (6), R ⁷ 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 ⁷ are Each may be the same or different. In addition, both of these alkyl groups and acyl groups may have a substituent or may be an unsubstituted form having no substituent, and can be selected according to the characteristics of the composition. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Specific examples of the acyl group include an acetyl group. Specific examples of the aryl group include a phenyl group.

  Further, in the above formula (6), m is an integer of 0 to 3. When m = 0, tetrafunctional silane, when m = 1, trifunctional silane, when m = 2, bifunctional. When silane, m = 3, it is a monofunctional silane.

Specific examples of the organosilane represented by the above formula (6) include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, and tetraphenoxysilane; methyltrimethoxysilane, methyltriethoxysilane, methyl Triisopropoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltrin-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyl Trimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methyl Acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 1- (p-hydroxyphenyl) ) Ethyltrimethoxysilane, 2- (p-hydroxyphenyl) ethyltrimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxy Silane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimeth Trifunctional silanes such as silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, di-n-butyldimethoxy And bifunctional silanes such as silane and diphenyldimethoxysilane; monofunctional silanes such as trimethylmethoxysilane and tri-n-butylethoxysilane.
Of these organosilanes, trifunctional silanes are preferably used from the viewpoint of crack resistance and hardness of the resulting resin film. These organosilanes may be used alone or in combination of two or more.

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

The polyimide (A5) used by this invention can be obtained by heat-processing the polyimide precursor obtained by making tetracarboxylic dianhydride and diamine react. Examples of the precursor for obtaining polyimide include polyamic acid, polyamic acid ester, polyisoimide, and polyamic acid sulfonamide.
Specific examples of the acid dianhydride that can be used as a raw material for obtaining the polyimide (A5) include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2 , 3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride Anhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3- Dicarboxyphenyl) propane dianhydride, 2,2-bis [3-[(3,4-dicarboxybenzoyl) amino] -4-hydroxyphenyl] hexafluoropropane dianhydride, 1,1-bis (3 4-dicarboxyphenyl ) Ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) Methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2 , 2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride and other aromatic tetracarboxylic dianhydrides, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2 , 3 And the like 4-tetracarboxylic acid dianhydride aliphatic cyclopentane tetracarboxylic dianhydride. These acid dianhydrides can be used alone or in combination of two or more.

  Specific examples of the diamine that can be used as a raw material for obtaining the polyimide (A5) include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'- Diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 1,4-bis (4-aminophenoxy) Benzene, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4- Aminophenoxy) biphenyl, {4- (4-aminophenoxy) phenyl} ether, 1,4-bis (4-aminophenoxy) benzene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-diethyl-4 , 4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2 ', 3,3'-tetramethyl- 4,4′-diaminobiphenyl, 3,3 ′, 4,4′-tetramethyl-4,4′-diaminobiphenyl, 2,2′-di (trifluoromethyl) -4,4′-diaminobiphenyl; or Compounds in which the aromatic ring of these compounds is substituted with an alkyl group or a halogen atom; aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, bis [(3-aminopropyl) di Tylsilyl] ether; 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,6-diamino-1,3-benzenedicarboxylic acid, 2,5-diamino-1, 4-benzenedicarboxylic acid, bis (4-amino-3-carboxyphenyl) ether, bis (4-amino-3,5-dicarboxyphenyl) ether, bis (4-amino-3-carboxyphenyl) sulfone, bis ( 4-amino-3,5-dicarboxyphenyl) sulfone, 4,4′-diamino-3,3′-dicarboxybiphenyl, 4,4′-diamino-3,3′-dicarboxy-5,5′- Dimethylbiphenyl, 4,4′-diamino-3,3′-dicarboxy-5,5′-dimethoxybiphenyl, 1,4-bis (4-amino-3-carboxypheno) Xy) benzene, 1,3-bis (4-amino-3-carboxyphenoxy) benzene, bis [4- (4-amino-3-carboxyphenoxy) phenyl] sulfone, bis [4- (4-amino-3-) Diamine compounds having a carboxyl group such as carboxyphenoxy) phenyl] propane, 2,2-bis [4- (4-amino-3-carboxyphenoxy) phenyl] hexafluoropropane; 2,4-diaminophenol, 3,5- Diaminophenol, 2,5-diaminophenol, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, bis (3-amino-4-hydroxyphenyl) ether, bis (4-amino-3-hydroxyphenyl) ether, Bis (4-amino-3,5-dihydroxyphenyl) ether, bis ( -Amino-4-hydroxyphenyl) methane, bis (4-amino-3-hydroxyphenyl) methane, bis (4-amino-3,5-dihydroxyphenyl) methane, bis (3-amino-4-hydroxyphenyl) sulfone Bis (4-amino-3-hydroxyphenyl) sulfone, bis (4-amino-3,5-dihydroxyphenyl) sulfone, bis (2-hydroxy-5-aminoanilide) isophthalate, 2- (4-aminobenzoyl) Amino) -4-aminophenol, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 2,2- Bis (4-amino-3,5-dihydroxyphenyl) hexafluoropropane, 4,4′- Diamino-3,3′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxy-5,5′-dimethylbiphenyl, 4,4′-diamino-3,3′-dihydroxy-5,5 ′ -Dimethoxybiphenyl, 1,4-bis (3-amino-4-hydroxyphenoxy) benzene, 1,3-bis (3-amino-4-hydroxyphenoxy) benzene, 1,4-bis (4-amino-3- Hydroxyphenoxy) benzene, 1,3-bis (4-amino-3-hydroxyphenoxy) benzene, bis [4- (3-amino-4-hydroxyphenoxy) phenyl] sulfone, bis [4- (3-amino-4) -Hydroxyphenoxy) phenyl] propane, 2,2-bis [4- (3-amino-4-hydroxyphenoxy) phenyl] hexafluoropropyl Bread, 2,2-bis [N- (2-hydroxy-5-aminophenyl) benzamido-4-yl] hexafluoropropane, 2,2-bis [3-[(3-aminobenzoyl) amino] -4- Diamine compounds having a phenolic hydroxy group such as hydroxyphenyl] hexafluoropropane, 2,2-bis [3-[(4-aminobenzoyl) amino] -4-hydroxyphenyl] hexafluoropropane; 1,3-diamino- 4-mercaptobenzene, 1,3-diamino-5-mercaptobenzene, 1,4-diamino-2-mercaptobenzene, bis (4-amino-3-mercaptophenyl) ether, 2,2-bis (3-amino- Diamine compounds having a thiophenol group such as 4-mercaptophenyl) hexafluoropropane; 1,3 Diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-5-sulfonic acid, 1,4-diaminobenzene-2-sulfonic acid, bis (4-aminobenzene-3-sulfonic acid) ether, 4,4 ′ -Diaminobiphenyl) 3,3'-disulfonic acid, diamine compounds having a sulfonic acid group such as 4,4'-diamino-3,3'-dimethylbiphenyl-6,6'-disulfonic acid; and the like. These diamines can be used alone or in combination of two or more.

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

  When superposing | polymerizing using diamine excessively, a carboxylic anhydride can be made to react with the terminal amino group of the produced | generated polyimide (A5), and a terminal amino group can be protected. Moreover, when superposing | polymerizing using tetracarboxylic anhydride excessively, an amine compound can be made to react with the terminal acid anhydride group of the produced | generated polyimide (A5), and a terminal acid anhydride group can also be protected.

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

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

(Silane modified resin (B))
The silane-modified resin (B) used in the present invention has a resin part and a silane compound part in a state where they are chemically bonded to each other.

  Although it does not specifically limit as a material which comprises the resin part of a silane modified resin (B), The polymeric material which has a functional group which can be couple | bonded chemically with a silane compound part is preferable. Such a polymer material is not particularly limited, and examples thereof include polyester, polyamide, polyimide, polyamic acid, epoxy resin, acrylic resin, urethane resin, and phenol resin. Among these, polyamic acid, epoxy resin, acrylic resin, and phenol resin are preferable from the viewpoint that the effect of the present invention becomes more remarkable. The functional group that can be bonded to the silane compound part is not particularly limited, and examples thereof include a hydroxyl group, an amino group, a thiol group, a carboxylic acid group, an acid anhydride group, an epoxy group, an amide group, and an imide group. From the viewpoint of reactivity with the silane compound, a hydroxyl group, a carboxylic acid group or an acid anhydride group is preferred.

Although it does not specifically limit as a silicon compound which comprises the silane compound part of a silane modified resin (B), For example, the silicon compound represented by following formula (7) and / or the silicon compound represented by following formula (7) In view of the fact that the effects of the present invention become more prominent, the following formula (7) can be obtained by partial hydrolysis of the silicon compound represented by formula (7). The silicon compound represented by 8) is preferred.
_{^{(R 8) r -Si- (OR}} 9) 4-r (7)

In said formula (7), r is an integer of 0-3. R ⁸ is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an unsaturated aliphatic group having 2 to 10 carbon atoms, which may have a functional group directly bonded to a carbon atom. There, when R ⁸ is plural, a plurality of R ⁸ may be different from one another respectively the same. Also, R ⁹ is a hydrogen atom or a directly bonded to an alkyl group having 1 to 10 carbon atoms which may have a functional group to a carbon atom, when R ⁹ is plural, a plurality of R ⁹ May be the same or different. Further, examples of the functional group directly constituting R ⁸ and R ⁹ and bonded to a carbon atom include a hydroxyl group, an epoxy group, a halogen group, a mercapto group, a carboxyl group, and a methacryloxy group.
In the above formula (8), p is 0 or 1. q is an integer of 2 to 10.

Specific examples of the alkyl group having 1 to 10 carbon atoms that may have a functional group directly bonded to a carbon atom constituting R ⁸ and R ⁹ include a methyl group, an ethyl group, an n-propyl group, i -Propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, i-pentyl group, sec-pentyl group, n-hexyl group, i-hexyl group, sec -Hexyl, cyclopentyl, cyclohexyl, cycloheptyl, 3-chloropropyl, 3-glycidoxypropyl, epoxypropyl, 3-methacryloxypropyl, 3-mercaptopropyl, 3,3,3 -A trifluoropropyl group etc. are mentioned.
Specific examples of the aryl group having 6 to 20 carbon atoms which may have a functional group directly bonded to a carbon atom constituting R ⁸ include a phenyl group, a toluyl group, a p-hydroxyphenyl group, 1- ( Examples include p-hydroxyphenyl) ethyl group, 2- (p-hydroxyphenyl) ethyl group, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyl group, naphthyl group and the like.
Specific examples of the unsaturated aliphatic group having 1 to 10 carbon atoms that may have a functional group directly bonded to a carbon atom constituting R ⁸ include a vinyl group, a 3-acryloxypropyl group, Examples include a 3-methacryloxypropyl group.

  Specific examples of such silicon compounds include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetra i-propoxysilane, tetrabutoxysilane, tetra i-butoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, n -Propyltrimethoxysilane, i-propyltrimethoxysilane, 3-chloropropyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane, i- Propyltriethoxysilane, 3-chloropropyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, methyltri-i-propoxysilane, ethyltri-i-propoxysilane, n-propyl Pyrtri i-propoxy silane, i-propyl tri i-propoxy silane, 3-chloropropyl tri i-propoxy silane, vinyl tri i-propoxy silane, phenyl tri i-propoxy silane, methyl tributoxy silane, ethyl tributoxy silane, n- Propyltributoxysilane, i-propyltributoxysilane, 3-chloropropyltributoxysilane, vinyltributoxysilane, phenyltributoxysilane, 3,3,3-trifluorotrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, Methyltriglycidoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3,4-epoxycyclohexyltrimethoxysilane, 3,3,3-trifluoro Triethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3,4-epoxycyclohexyltriethoxysilane, 3,3,3-trifluorotrii -Propoxysilane, 3-methacryloxypropyltri-i-propoxysilane, 3-glycidoxypropyltri-i-propoxysilane, 3-mercaptopropyltri-i-propoxysilane, 3,4-epoxycyclohexyltri-i-propoxysilane, 3, , 3,3-trifluorotributoxysilane, 3-methacryloxypropyltributoxysilane, 3-glycidoxypropyltributoxysilane, 3-mercaptopropyltributoxysilane, 3,4-epoxycyclohexyl Ributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane and the like can be mentioned, and these are preferably used as a partial hydrolysis condensate. These can be used alone or in combination of two or more.

  Further, when the silane compound part is a partial hydrolysis condensate of a silicon compound, the partial condensate obtained by partial hydrolysis of the above-described silicon compound may be used as it is, or the obtained part A part of the condensate may be substituted by causing a dealcoholization reaction using an alcohol having a functional group such as an epoxy group, a halogen group, a mercapto group, a carboxyl group, or a methacryloxy group. . A partial hydrolysis condensate having such a functional group can be easily obtained by substituting the partial condensate obtained by partial hydrolysis of the above-described silicon compound with an alcohol having such a functional group. Can do.

  The method of chemically bonding the resin part and the silane compound part to obtain the silane-modified resin (B) is not particularly limited. For example, a polymer material having a hydroxyl group in the resin part is used, and the silane compound part is obtained. A method of chemically bonding the resin part and the silane compound part by subjecting the alkoxyl group to a dealcoholization reaction is mentioned. Alternatively, a polymer material having a carboxylic acid group or an acid anhydride group is used for the resin part, a compound having a glycidyloxy group is used for the silane compound part, and these are subjected to an addition reaction, or the oxirane ring is opened. And a method of causing a ring-opening esterification reaction. Further, after the resin part and the silane compound part are chemically bonded, the resin part can be polymerized to polymerize the resin part. In this case, a low molecular organic material is used as a material to be chemically bonded to the silane compound portion, and after the low molecular organic material and the silane compound portion are chemically bonded, the low molecular organic material is polymerized. Thus, a method of increasing the molecular weight can also be adopted.

  For example, among the above methods, according to the dealcoholization reaction, the material constituting the resin part and the material constituting the silane compound part are charged, heated, and the transesterification reaction is performed while distilling off the generated alcohol. Thus, a silane-modified resin (B) can be obtained. The reaction temperature is usually 70 to 150 ° C., preferably 80 to 130 ° C., and the total reaction time is usually 2 to 15 hours. If the reaction temperature is too low, the alcohol cannot be distilled off efficiently, and if the reaction temperature is too high, curing condensation of the material constituting the silane compound part may be initiated.

  In the above dealcoholization reaction, a conventionally known ester-hydroxyl ester exchange catalyst can be used for promoting the reaction. Examples of the transesterification catalyst include organic acids such as acetic acid, p-toluenesulfonic acid, benzoic acid, and propionic acid, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, and cobalt. And metals such as germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium and manganese, oxides thereof, organic acid salts, halides and alkoxides. Of these, metal organic acid salts and organic acids are preferably used, and organic tin and organic acid tin are particularly preferable. Specifically, acetic acid, tin octylate, and dibutyltin dilaurate are preferable.

  Further, the dealcoholization reaction can be carried out in an organic solvent or without a solvent. The organic solvent is not particularly limited as long as it is a material constituting the resin part and an organic solvent that dissolves the material constituting the silane compound part. For example, dimethylformamide, dimethylacetamide, methyl ethyl ketone, cyclohexanone, diethylene glycol methyl ethyl ether It is preferable to use an aprotic polar solvent having a boiling point of 75 ° C. or higher.

  Alternatively, among the methods described above, according to the ring-opening esterification reaction, the material constituting the resin part and the material constituting the silane compound part are charged and heated to cause the ring-opening esterification reaction. A silane-modified resin (B) can be obtained. The reaction temperature is usually 40 to 130 ° C., preferably 70 to 110 ° C., and the total reaction time is usually 1 to 7 hours. If the reaction temperature is too low, the reaction time becomes long. If the reaction temperature is too high, curing condensation of the material constituting the silane compound part may be started.

  In the ring-opening esterification reaction, a catalyst for promoting the reaction can be used. Examples of the catalyst include three compounds such as 1,8-diaza-bicyclo [5.4.0] -7-undecene, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol. Secondary amines; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, benzimidazole; tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, Organic phosphines such as phenylphosphine; tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholine Tetraphenyl boron salts such as La phenyl borate, and the like.

  Further, the ring-opening esterification reaction is preferably performed in the presence of an organic solvent. The organic solvent is not particularly limited as long as it is an organic solvent that dissolves the material constituting the resin part and the material constituting the silane compound part. For example, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, cyclohexanone and the like can be used.

  The ratio of the resin part and the silane compound part of the silane-modified resin (B) used in the present invention is a weight ratio of “resin part: silane compound part”, preferably 1:50 to 50: 1, more preferably. 1:10 to 10: 1. By making the ratio of the resin part and the silane compound part within the above range, the effect of the present invention becomes more remarkable, which is preferable.

  The content of the silane-modified resin (B) in the resin composition of the present invention may be determined in relation to the content of the compound (C) having an acidic group or a thermal latent acidic group, which will be described later. (A) Preferably it is 1-100 weight part with respect to 100 weight part, More preferably, it is 2-50 weight part, More preferably, it is 5-40 weight part. If the content of the silane-modified resin (B) is too small, the pattern formability by development is lowered, and in particular, when the development pattern width is narrowed, the adhesion of the development pattern may be lowered. On the other hand, if it is too much, there is a possibility that the pattern formability by development, particularly the hole shape at the time of firing, is deteriorated.

(Compound (C) having an acidic group or a thermal latent acidic group)
The compound (C) having an acidic group or a heat-latent acidic group used in the present invention is not particularly limited as long as it has an acid group or a heat-latent acidic group that generates an acidic group by heating. Group compounds, aromatic compounds and heterocyclic compounds, more preferably aromatic compounds and heterocyclic compounds.
These compounds (C) having an acidic group or a heat-latent acidic group can be used alone or in combination of two or more.

The number of acidic groups and thermal latent acidic groups of the compound (C) having an acidic group or thermal latent acidic group is not particularly limited, but it has two or more acidic groups and / or thermal latent acidic groups in total. Those are preferred. The acidic groups may be the same as or different from each other.
The acidic group may be any acidic functional group, and specific examples thereof include strongly acidic groups such as sulfonic acid group and phosphoric acid group; weak acidic groups such as carboxy group, thiol group and carboxymethylenethio group; Can be mentioned. Among these, a carboxy group, a thiol group, or a carboxymethylenethio group is preferable, and a carboxy group is particularly preferable. Among these acidic groups, those having an acid dissociation constant pKa in the range of 3.5 to 5.0 are preferred. When there are two or more acidic groups, it is preferable that the first dissociation constant pKa1 is an acid dissociation constant and the first dissociation constant pKa1 is in the above range. The pKa is determined according to pKa = −logKa by measuring the acid dissociation constant Ka = [H ₃ O ⁺ ] [B ⁻ ] / [BH] under dilute aqueous solution conditions. Here, BH represents an organic acid, and B ⁻ represents a conjugate base of the organic acid.
In addition, the measuring method of pKa can calculate hydrogen ion concentration, for example using a pH meter, and can calculate from the density | concentration of a relevant substance, and hydrogen ion concentration.
The heat-latent acidic group may be any group that generates an acidic functional group upon heating. Specific examples thereof include a sulfonium base, a benzothiazolium base, an ammonium base, a phosphonium base, a block carboxylic acid group, and the like. Is mentioned. Among these, a block carboxylic acid group is preferable. The carboxy group blocking agent used to obtain the blocked carboxylic acid group is not particularly limited, but is preferably a vinyl ether compound.

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

  Among the compounds (C) having such an acidic group or thermal latent acidic group, specific examples of the compound having an acidic group include methanoic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, butanoic acid, and pentanoic acid. , Hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, glycolic acid, glyceric acid, ethanedioic acid (also referred to as “oxalic acid”), propanedioic acid (also referred to as “malonic acid”), butane diacid. Acid (also referred to as “succinic acid”), pentanedioic acid, hexanedioic acid (also referred to as “adipic acid”), 1,2-cyclohexanedicarboxylic acid, 2-oxopropanoic acid, 2-hydroxybutanedioic acid, 2 -Hydroxypropanetricarboxylic acid, mercaptosuccinic acid, dimercaptosuccinic acid, 2,3-dimercapto-1-propanol, 1,2,3-trimercaptopropa 2,3,4-trimercapto-1-butanol, 2,4-dimercapto-1,3-butanediol, 1,3,4-trimercapto-2-butanol, 3,4-dimercapto-1,2- Aliphatic compounds such as 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 (also referred to as “terephthalic acid”) ), Benzene-1,2,3-tricarboxylic acid, benzene-1,2,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, benzenehexacarboxylic acid, biphenyl-2,2′-dicarboxylic acid 2- (carboxymethyl) benzoic acid, 3- (carboxymethyl) benzoic acid, 4- (carboxymethyl) benzoic acid Benzoic acid, 2- (carboxycarbonyl) benzoic acid, 3- (carboxycarbonyl) benzoic acid, 4- (carboxycarbonyl) benzoic acid, 2-mercaptobenzoic acid, 4-mercaptobenzoic acid, diphenolic acid, 2-mercapto -6-naphthalenecarboxylic acid, 2-mercapto-7-naphthalenecarboxylic acid, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,4-naphthalenedithiol, 1, 5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1 , 2,3-Tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene, 1,3,5-tris (mercapto) Aromatic compounds such as ethyl) benzene;

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

Pyridine-2,3-dicarboxylic acid, pyridine-2,4-dicarboxylic acid, pyridine-2,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, pyridine-3,5 -Dicarboxylic acid, pyridazine-3,4-dicarboxylic acid, pyridazine-3,5-dicarboxylic acid, pyridazine-3,6-dicarboxylic acid, pyridazine-4,5-dicarboxylic acid, pyrimidine-2,4-dicarboxylic acid, pyrimidine -2,5-dicarboxylic acid, pyrimidine-4,5-dicarboxylic acid, pyrimidine-4,6-dicarboxylic acid, pyrazine-2,3-dicarboxylic acid, pyrazine-2,5-dicarboxylic acid, pyridine-2,6- Dicarboxylic acid, triazine-2,4-dicarboxylic acid, 2-diethylamino-4,6-dimercapto-s-triazine, 2-dipropyl Mino-4,6-dimercapto-s-triazine, 2-dibutylamino-4,6-dimercapto-s-triazine, 2-anilino-4,6-dimercapto-s-triazine, 2,4,6-trimercapto- 6-membered heterocyclic compounds containing a nitrogen atom such as s-triazine.
Among these, the number of acidic groups in the compound having an acidic group is preferably 2 or more, and particularly preferably 3 from the viewpoint that the adhesion of the resulting resin film can be further improved.

  In addition, as a specific example of the compound having a thermal latent acidic group among the compounds (C) having an acidic group or a thermal latent acidic group, the acidic group of the compound having the acidic group is converted into a thermal latent acidic group. Compound. For example, 1,2,4-benzenetricarboxylic acid tris (1-propoxyethyl) obtained by converting a carboxy group of 1,2,4-benzenetricarboxylic acid into a block carboxylic acid group has a heat latent acidic group. It can be used as a compound. From the viewpoint that the adhesiveness of the resulting resin film can be further improved, the number of heat-latent acidic groups in the compound having a heat-latent acidic group is preferably 2 or more, and particularly preferably 3.

  In the resin composition of the present invention, the ratio of the silane-modified resin (B) to the compound (C) having an acidic group or a thermal latent acidic group is “silane modified resin (B) / acidic group or thermal latent. The weight ratio of the compound (C) having an acidic group is 0.5 to 20, preferably 0.7 to 18, and more preferably 1 to 15. In the present invention, the resin composition is blended with the silane-modified resin (B) and the compound (C) having an acidic group or a heat-latent acidic group, and the ratio is within the above range. The resulting resin film can be made excellent in pattern formability and transparency while making the product excellent in storage stability. If the content ratio of the silane-modified resin (B) is too small, the pattern forming property is lowered, and in particular, a residue at the time of development is easily generated, or the storage stability of the resin composition is lowered. On the other hand, when the content ratio of the compound (C) having an acidic group or a heat-latent acidic group is too small, there is a possibility that the pattern forming property, particularly the hole shape at the time of firing, is deteriorated.

  Moreover, what is necessary is just to determine content of the compound (C) which has an acidic group or a heat | fever latent acidic group in the resin composition of this invention by relationship with a silane modified resin (B) as mentioned above, but a binder. Preferably it is 0.05-200 weight part with respect to resin (A), More preferably, it is 0.1-75 weight part, More preferably, it is 0.3-40 weight part. If the content of the compound (C) having an acidic group or a heat-latent acidic group is too small, the pattern forming property is lowered. In particular, when the pattern width is narrowed, the adhesion of the pattern and the hole shape at the time of firing are reduced. May get worse. On the other hand, if the content of the compound (C) having an acidic group or a heat-latent acidic group is too large, the pattern forming property is lowered, and in particular, a residue at the time of pattern formation tends to be generated. Storage stability will decrease.

(Radiation sensitive compound (D))
The resin composition of the present invention further comprises a radiation-sensitive compound (D) in addition to the binder resin (A), the silane-modified resin (B), and the compound (C) having an acidic group or a heat-latent acidic group. It may be contained. The radiation sensitive compound (D) 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 (D) is preferably one that can control the alkali solubility of the resin film formed from the resin composition, and it is particularly preferable to use a photoacid generator.

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

  As the quinonediazide compound, for example, an ester compound of a quinonediazidesulfonic acid halide and a compound having a phenolic hydroxyl group can be used. Specific examples of the quinone diazide sulfonic acid halide include 1,2-naphthoquinone diazide-5-sulfonic acid chloride, 1,2-naphthoquinone diazide-4-sulfonic acid chloride, 1,2-benzoquinone diazide-5-sulfonic acid chloride, and the like. Can be mentioned. Typical examples of the compound having a phenolic hydroxyl group include 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 ′-[1- [4- [1. -[4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and the like. Other compounds having a phenolic hydroxyl group include 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2-bis (4-hydroxyphenyl) propane, tris (4- Hydroxyphenyl) methane, 1,1,1-tris (4-hydroxy-3-methylphenyl) ethane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, novolac resin oligomer, phenolic hydroxyl group Examples thereof include oligomers obtained by copolymerizing one or more compounds and dicyclopentadiene.

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

  The content of the radiation sensitive compound (D) in the resin composition of the present invention is preferably 10 to 100 parts by weight, more preferably 15 to 70 parts by weight, and still more preferably 100 parts by weight of the binder resin (A). Is in the range of 20-50 parts by weight. If the content of the radiation sensitive compound (D) is within this range, when patterning the resin film made of the resin composition, the difference in solubility in the developer between the radiation irradiated part and the radiation non-irradiated part becomes large, The radiation sensitivity is also high, and it is preferable because patterning by development is easy.

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

  Although the molecular weight of a crosslinking agent (E) is not specifically limited, Usually, it is 100-100,000, Preferably it is 300-50,000, More preferably, it is 500-10,000. A crosslinking agent can be used individually or in combination of 2 types or more, respectively.

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

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

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

  The content of the crosslinking agent (E) in the resin composition of the present invention is not particularly limited, and is arbitrarily set in consideration of the degree of heat resistance required for the resin film obtained using the resin composition of the present invention. However, the amount is usually 5 to 80 parts by weight, preferably 7 to 75 parts by weight, and more preferably 10 to 70 parts by weight with respect to 100 parts by weight of the binder resin (A). If the crosslinking agent (E) is too much or too little, the heat resistance tends to decrease.

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

  In addition, the resin composition of the present invention is a surfactant, an acidic compound, a coupling agent or a derivative thereof, a sensitizer, a latent acid generator, an oxidation, if desired, as long as the effects of the present invention are not inhibited. It may contain other compounding agents such as an inhibitor, a light stabilizer, an antifoaming agent, a pigment, a dye, and a filler;

  The surfactant is used for the purpose of preventing striation (after application stripes) and improving developability. Specific examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and the like. Polyoxyethylene aryl ethers; Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Fluorine surfactants; Silicone surfactants; Methacrylic acid copolymer System surfactants; acrylic acid copolymer system surfactants; and the like.

  The coupling agent or derivative thereof has an effect of further improving the adhesion between the resin film made of the resin composition and each layer including the semiconductor layer constituting the semiconductor element substrate. As the coupling agent or derivative thereof, a compound having one atom selected from a silicon atom, a titanium atom, an aluminum atom, and a zirconium atom and having a hydrocarbyloxy group or a hydroxy group bonded to the atom can be used.

As a coupling agent or a derivative thereof, for example,
Tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane,
Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n- Butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, n-decyltrimethoxysilane, p-styryl Trimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyl Nyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-amino Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyl Limethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyl Triethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-ethyl (trimethoxysilylpropoxymethyl) oxetane, 3-ethyl (triethoxysilylpropoxymethyl) Kisetan, 3-triethoxysilyl-N-(1,3-dimethyl - butylidene) propylamine, trialkoxysilanes such as bis (triethoxysilylpropyl) tetrasulfide,
Dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxy Silane, di-n-butyldimethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyl Dimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, Diphenyldie Xysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropylmethyldiethoxysilane In addition to dialkoxysilanes such as N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane,
Silicon atom-containing compounds such as methyltriacetyloxysilane and dimethyldiacetyloxysilane;

(Tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy) titanium, titanium-i-propoxyoctylene glycolate, di-i-propoxybis (acetylacetonato) titanium, propanedi Oxytitanium bis (ethylacetoacetate), tri-n-butoxytitanium monostearate, di-i-propoxytitanium distearate, titanium stearate, di-i-propoxytitanium diisostearate, (2-n-butoxycarbonyl Titanium atom-containing compounds such as benzoyloxy) tributoxytitanium, di-n-butoxy bis (triethanolaminato) titanium, as well as the preneact series (manufactured by Ajinomoto Fine Techno Co., Ltd.);
Aluminum atom-containing compounds such as (acetoalkoxyaluminum diisopropylate);
(Tetranormal propoxyzirconium, tetranormalbutoxyzirconium, zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, zirconium butoxyacetylacetonate bis (ethylacetoacetate), zirconium dibutoxybis (ethylacetoacetate), zirconium tetraacetyl Zirconium atom-containing compounds such as acetonate and zirconium tributoxy systemate).

  Specific examples of the sensitizer include 2H-pyrido- (3,2-b) -1,4-oxazin-3 (4H) -ones, 10H-pyrido- (3,2-b) -1,4. -Benzothiazines, urazoles, hydantoins, barbituric acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxans, maleimides and the like.

  As the antioxidant, there can be used phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, lactone antioxidants and the like used in ordinary polymers. For example, as phenols, 2,6-di-t-butyl-4-methylphenol, p-methoxyphenol, styrenated phenol, n-octadecyl-3- (3 ′, 5′-di-t-butyl-4 '-Hydroxyphenyl) propionate, 2,2'-methylene-bis (4-methyl-6-t-butylphenol), 2-t-butyl-6- (3'-t-butyl-5'-methyl-2' -Hydroxybenzyl) -4-methylphenyl acrylate, 4,4'-butylidene-bis- (3-methyl-6-tert-butylphenol), 4,4'-thio-bis (3-methyl-6-tert-butylphenol) ), Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], alkylated bisphenols, etc. Can. Examples of the phosphorus-based antioxidant include triphenyl phosphite and tris (nonylphenyl) phosphite. Examples of the sulfur-based antioxidant include dilauryl thiodipropionate.

  Examples of light stabilizers include ultraviolet absorbers such as benzophenone-based, salicylic acid ester-based, benzotriazole-based, cyanoacrylate-based, and metal complex-based salts, hindered amine-based (HALS), and the like that capture radicals generated by light. Either is acceptable. Among these, HALS is a compound having a piperidine structure and is preferable because it is less colored with respect to the resin composition and has good stability. Specific compounds include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl 1,2,3,4 -Butanetetracarboxylate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate and the like.

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

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

  The solid content concentration of the resin composition of the present invention is usually 1 to 70% by weight, preferably 5 to 60% by weight, and more preferably 10 to 50% by weight. If the solid content concentration is within this range, dissolution stability, coating properties, film thickness uniformity of the formed resin film, flatness, and the like can be highly balanced.

(Semiconductor element substrate)
Next, the semiconductor element substrate of the present invention will be described. The semiconductor element substrate of the present invention has a resin film made of the above-described resin composition of the present invention.

  The semiconductor element substrate of the present invention is not particularly limited as long as it has a configuration in which a semiconductor element is mounted on the substrate, but is not limited to an active matrix substrate, an organic EL element substrate, an integrated circuit element substrate, and a solid-state imaging element. An active matrix substrate and an organic EL element substrate are preferable from the viewpoint that the effect of improving the characteristics by forming the resin film made of the resin composition of the present invention described above is particularly remarkable.

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

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

  The resin film constituting the semiconductor element substrate of the present invention is made of the resin composition described above, and is formed in contact with the surface of the semiconductor element mounted on the semiconductor element substrate or the semiconductor layer included in the semiconductor element. The resin film is preferably not particularly limited, but when the semiconductor element substrate of the present invention is an active matrix substrate or an organic EL element substrate, it can be configured as follows. That is, for example, when the semiconductor element substrate of the present invention is an active matrix substrate, the above-described resin film made of the resin composition of the present invention is a protective film or active matrix formed on the surface of the active matrix substrate. A gate insulating film formed in contact with a semiconductor layer (for example, an amorphous silicon layer) of a thin film transistor that forms a substrate can be used. Alternatively, when the semiconductor element substrate of the present invention is an organic EL element substrate, a sealing film formed on the surface of the organic EL element substrate or a light emitter part (usually an anode, A pixel separation film for separating a hole injection transport layer, an organic light emitting layer as a semiconductor layer, an electron injection layer, and a cathode).

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

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

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

  The thickness of the resin film is not particularly limited and may be appropriately set depending on the application. However, when the resin film is a protective film for an active matrix substrate or a sealing film for an organic EL element substrate. The thickness of the resin film is preferably 0.1 to 100 μm, more preferably 0.5 to 50 μm, and still more preferably 0.5 to 30 μm.

  Moreover, when the resin composition of this invention contains a crosslinking agent (E), a crosslinking reaction can be performed about the resin film formed by the above-mentioned coating method or film lamination method. Such crosslinking may be appropriately selected depending on the type of the crosslinking agent (E), but is usually performed by heating. The heating method can be performed using, for example, a hot plate or an oven. The heating temperature is usually 180 to 250 ° C., and the heating time is appropriately selected according to the area and thickness of the resin film, the equipment used, and the like. For example, when using a hot plate, the oven is usually used for 5 to 60 minutes. When used, it is usually in the range of 30 to 90 minutes. Heating may be performed in an inert gas atmosphere as necessary. Any inert gas may be used as long as it does not contain oxygen and does not oxidize the resin film. Examples thereof include nitrogen, argon, helium, neon, xenon, and krypton. Among these, nitrogen and argon are preferable, and nitrogen is particularly preferable. In particular, an inert gas having an oxygen content of 0.1% by volume or less, preferably 0.01% by volume or less, particularly nitrogen is suitable. These inert gases can be used alone or in combination of two or more.

  In addition, if the resin film made of the resin composition described above is formed in a predetermined pattern, such as a protective film for an active matrix substrate or a sealing film for an organic EL element substrate, it is patterned. Also good. As a method for patterning a resin film, for example, a resin composition is made to contain a radiation sensitive compound (D), and a resin film before patterning is formed using the resin composition containing the radiation sensitive compound (D). In addition, there is a method in which a latent image pattern is formed by irradiating the resin film before patterning with actinic radiation, and then the developer is brought into contact with the resin film having the latent image pattern, thereby revealing the pattern.

The actinic radiation is not particularly limited as long as it can activate the radiation-sensitive compound (D) contained in the resin composition and change the alkali solubility of the resin composition containing the radiation-sensitive compound (D). Specifically, ultraviolet rays, ultraviolet rays having a single wavelength such as g-line or i-line, light rays such as KrF excimer laser light and ArF excimer laser light; particle beams such as electron beams; As a method for selectively irradiating these actinic radiations in a pattern to form a latent image pattern, a conventional method may be used. For example, ultraviolet, g-line, i-line, KrF excimer is used by a reduction projection exposure apparatus 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 is used as the active radiation, it may be single wavelength light or mixed wavelength light. Irradiation conditions may be appropriately selected depending on the active radiation to be used, for example, when using a light beam of wavelength 200 to 450 nm, the amount of irradiation is usually 10~1,000mJ / cm ^2, preferably 50 to 500 mJ / It is a range of cm ² and is determined according to irradiation time and illuminance. After irradiation with actinic radiation in this manner, the resin film is heat-treated at a temperature of about 60 to 130 ° C. for about 1 to 2 minutes as necessary.

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

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

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

  In the present invention, the resin film can be subjected to a crosslinking reaction after being patterned. Crosslinking may be performed according to the method described above.

  The resin composition of the present invention is obtained by blending the binder resin (A) with the silane-modified resin (B) and the compound (C) having an acidic group or a thermal latent acidic group at a specific ratio. Therefore, the resin composition of the present invention is excellent in storage stability, and the resin film obtained using the resin composition of the present invention is excellent in pattern formability and transparency by development. According to the present invention, by applying such a resin film to a semiconductor element substrate, the resin film included in the semiconductor element substrate can be patterned with high accuracy. A semiconductor element substrate capable of improving performance can be provided. Moreover, since the resin film obtained using the resin composition of this invention is excellent in transparency, it can be used suitably for the use as which transparency is requested | required.

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

<Polymerization conversion>
After completion of the polymerization reaction, the residual amount of the monomer in the reaction solution was measured using gas chromatography and calculated from the value.

<Hydrogen addition rate>
^{From the 1} H-NMR spectrum, the number of moles of carbon-carbon double bonds hydrogenated was determined as a ratio to the number of moles of carbon-carbon double bonds before hydrogenation. Based on the pre-hydrogenation ratio, the ratio of carbon-carbon double bonds that were hydrogenated was determined as mol%.

<Weight average molecular weight / number average molecular weight>
The molecular weight in terms of polystyrene was calculated using gel permeation chromatography (abbreviation GPC, manufactured by Tosoh Corporation, using a combination of three types of columns: “HLC-8020”, TSKgel SuperH2000, TSKgel SuperH4000, and TSKgel SuperH5000). Tetrahydrofuran was used as the developing solvent.

<Development adhesion>
The resin composition was spin coated on a silicon wafer and then pre-baked at 100 ° C. for 2 minutes using a hot plate to form a 2.5 μm thick resin film. Next, in order to pattern the resin film, there are 10 strip-like slits (corresponding to spaces) that can transmit light in parallel, and the width between adjacent slits (corresponding to lines) is the same as the slit width. Through a mask (that is, a mask capable of forming a line-and-space pattern with the same width), ultraviolet light having a light intensity at 365 nm of 5 mW / cm ² was irradiated for a desired time. In addition, as the mask, a total of eight types of slit widths and widths between adjacent slits were used: 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 10 μm, 25 μm, and 50 μm, respectively.

  Next, a 0.4 wt% tetramethylammonium hydroxide aqueous solution was used as a developing solution, and after a development process by a paddle method at 23 ° C. for 120 seconds, rinsing with ultrapure water was performed for 30 seconds. The paddle method is a method in which a developer is placed on a resin film. As described above, a resin film having a pattern (line and space pattern) in which a mask is transferred onto a glass substrate (that is, line width and space width of 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 10 μm, 25 μm, and 50 μm). Eight types of resin films) were prepared. In this example, since a resin film is produced using a positive-type resin composition having radiation sensitivity, in the resin film, the portion corresponding to the slit portion of the mask corresponds to the portion where the resin film is removed, This is called a space portion, and a portion between adjacent slits of the mask corresponds to a portion where the resin film remains, and this is called a line portion. And the glass substrate in which the resin film which has such a pattern was formed was made into the adhesiveness measurement sample, and the adhesiveness was evaluated with the following method.

That is, the adhesion was evaluated by observing the adhesion measurement sample obtained above using an optical microscope. Specifically, first, the presence or absence of a line part peeled off from the substrate was confirmed. If there is no peeled line part, it can be said that the adhesiveness is high. When there was a peeled line portion, the maximum width of the line portion was confirmed, and evaluation was performed according to the following criteria. The line portion is more easily peeled off from the substrate as the width is smaller. Accordingly, it can be said that the smaller the maximum width of the line portion peeled from the substrate is, the higher the adhesion is.
○: The peeled line portion does not exist. Or, even if the peeled line part exists, the maximum line width of the peeled line part is 3 μm or less. Δ: The maximum line width of the peeled line part is 4 to 5 μm.
X: The maximum line width of the peeled line part is 10 μm or more.

<Residue during development>
The radiation sensitive resin composition was spin coated on a silicon wafer and then pre-baked at 100 ° C. for 2 minutes using a hot plate to form a 2.5 μm thick resin film. Next, the resin film was irradiated with ultraviolet rays having a light intensity at 365 nm of 5 mW / cm ² in the air for 60 seconds through a mask having a hole pattern of 8 μm × 8 μm. Next, development processing was performed at 23 ° C. for 120 seconds using a 0.4 wt% tetramethylammonium hydroxide aqueous solution, followed by rinsing with ultrapure water for 30 seconds to form a contact hole pattern.
And about the resin film which has the pattern of the contact hole obtained in this way, the presence or absence of the melt | dissolution residue in a contact hole was confirmed using the scanning electron microscope (SEM), and the following references | standards evaluated. It is preferable that no dissolution residue is observed because the pattern forming property by development is excellent.
○: No development residue was observed.
X: Development residue was observed.

<Hall state during firing>
The resin film having the contact hole pattern obtained in the same manner as the evaluation of the residue at the time of development described above was irradiated with ultraviolet rays having a light intensity at 365 nm of 5 mW / cm ² in the air for 100 seconds. And the cross section of the obtained pattern was observed with the electron microscope, the lower end width of the pattern was measured, and this was made into "the lower end width a of the pattern before post-baking". Next, the resin film having the obtained pattern was post-baked at 230 ° C. for 1 hour using an oven, and the resulting post-baked resin film was observed with a cross section of the pattern with an electron microscope. While evaluating the shape of the upper end, the lower end width of the pattern was measured, and this was defined as “the lower end width b of the post-baked pattern”. And the ratio (b / a) of the lower end width b of the pattern after post-baking to the lower end width a of the pattern before post-baking was calculated | required, and the following reference | standard evaluated.
○: b / a was 0.8 or more.
Δ: b / a was 0.5 or more and less than 0.8.
X: b / a was less than 0.5, or the shape of the contact hole was distorted.

<Transparency>
A resin composition is spin-coated on a glass substrate (Corning 1737 (product name)) and then pre-baked at 100 ° C. for 2 minutes using a hot plate to give a resin film having a thickness of 2.5 μm. Formed. Next, the resin film was immersed in a 0.4 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 120 seconds, washed with ultrapure water for 30 seconds, and then the light intensity at 365 nm. There ultraviolet is 5 mW / cm ^2, 100 seconds, was irradiated in air. And about the resin film irradiated with the ultraviolet-ray, the test sample which consists of a glass substrate in which the resin film was formed was obtained by performing the post-baking heated for 60 minutes at 230 degreeC using oven. And about the obtained test sample, the transmittance | permeability in wavelength 400nm is measured using a spectrophotometer (the JASCO Corporation make, "ultraviolet visible spectrophotometer V-560 (product name)", and resin The transparency of the film was evaluated according to the following criteria: The transmittance of the resin film is calculated as a conversion value when a glass substrate without a resin film is used as a blank and the resin film thickness is 2 μm. Sought by.
○: Light transmittance is 90% or more Δ: Light transmittance is 80% or more and less than 90% ×: Light transmittance is less than 80%

<Storage stability>
After preparing the resin composition, it was allowed to stand for 7 days in an environment of 23 ° C. and 50% humidity. Thereafter, the resin film having a contact hole pattern obtained in the same manner as the evaluation of the development residue was applied at 365 nm. Ultraviolet rays having a light intensity of 5 mW / cm ² were irradiated in the air for 100 seconds. And the cross section of the obtained pattern was observed with the electron microscope, the lower end width of the pattern was measured, and this was made into "the lower end width a 'of the pattern before post-baking of the resin composition after being left for 7 days." Then, the ratio of the lower end width a ′ of the pattern before post-baking of the resin composition after standing for 7 days to the lower end width a of the pattern before post-baking obtained by the evaluation of the hole state during firing described above (a ′ / a) was determined and evaluated according to the following criteria.
A: a ′ / a was 0.95 or more and 1.05 or less.
X: a ′ / a was less than 0.95 or more than 1.05.

<< Synthesis Example 1 >>
<Preparation of Cyclic Olefin Polymer (A-1)>
N- (2-ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide 40 mol% and 4-hydroxycarbonyltetracyclo [6.2.1.13 ^{, 6} . 100 parts of a monomer mixture consisting of 60 mol% of 0 ^2,7 ] dodec-9-ene, 2 parts of 1,5-hexadiene, (1,3-dimesityrylimidazoline-2-ylidene) (tricyclohexylphosphine) benzylidene 0.02 part of ruthenium dichloride (synthesized by the method described in Org. Lett., Vol. 1, page 953, 1999) and 200 parts of diethylene glycol ethyl methyl ether were charged into a nitrogen pressure-substituted glass pressure-resistant reactor. The mixture was reacted for 4 hours at 80 ° C. with stirring to obtain a polymerization reaction solution.

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

<< Synthesis Example 2 >>
<Preparation of acrylic polymer (A-2)>
A flask equipped with a condenser and a stirrer was charged with 7 parts of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 200 parts of diethylene glycol ethyl methyl ether. Subsequently, 16 parts of methacrylic acid, 16 parts of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 20 parts of 2-methylcyclohexyl acrylate, 40 parts of glycidyl methacrylate, 10 parts of styrene and α-methyl After 3 parts of styrene dimer was charged and purged with nitrogen, stirring was started gently. Next, the temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4 hours to obtain a polymer solution containing the acrylic polymer (A-2). The acrylic polymer (A-2) had a polystyrene equivalent weight average molecular weight (Mw) of 8,000 and a molecular weight distribution (Mw / Mn) of 2.3. Moreover, solid content concentration of the obtained acrylic polymer (A-2) solution was 34.4 weight%.

<< Synthesis Example 3 >>
<Preparation of poly (methyltrimethoxysilane)>
A flask equipped with a stirrer, a reflux condenser, and a thermometer was charged with 136 parts of methyltrimethoxysilane and 32 parts of methanol. Next, an aqueous solution obtained by dissolving 0.1 part of concentrated hydrochloric acid in 13.5 parts of ion-exchanged water (0.75 molar equivalent with respect to methyltrimethoxysilane) was added dropwise over 5 minutes while stirring at room temperature. The reaction was continued for 4 hours. Then, after the reaction for 4 hours, the reflux condenser was replaced with a fractionation tube, followed by distilling off low-boiling components at a temperature of 80 ° C. and normal pressure for 30 minutes. Di (methyltrimethoxysilane) was obtained by performing distillation until it became. When the obtained poly (methyltrimethoxysilane) was analyzed by gel permeation chromatography (GPC), the obtained poly (methyltrimethoxysilane) had a weight average molecular weight of 490 (polystyrene conversion).

<< Synthesis Example 4 >>
<Preparation of silane-modified epoxy resin (B-1) solution>
800.0 parts of bisphenol A type epoxy resin (epoxy equivalent 480 g / eq) and 960.0 parts of diethylene glycol dimethyl ether were added to a reactor equipped with a stirrer, a condenser, and a thermometer, and dissolved at 80 ° C. Then, 605.0 parts of poly (methyltrimethoxysilane) obtained in Synthesis Example 3 and 2.3 parts of dibutyltin laurate as a catalyst were added, and a demethanol reaction was performed at 80 ° C. for 5 hours. A silane-modified epoxy resin (B-1) solution was obtained. The obtained silane-modified epoxy resin has an active ingredient (after curing) of 50% by weight, a silica-equivalent weight / bisphenol-type epoxy resin weight (weight ratio) of 0.51, and an epoxy equivalent of 1400 g / eq. Met. Moreover, it was confirmed by ¹ H-NMR that 87 mol% of the methoxy group of the partial condensate component of poly (methyltrimethoxysilane) was retained.

<< Synthesis Example 5 >>
<Preparation of silane-modified phenol resin (B-2)>
In a reaction apparatus equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas introduction tube, 800 parts of a novolac type phenol resin (manufactured by Arakawa Chemical Industry Co., Ltd., trade name Tamanoru 759), the poly ( 590.3 parts of methyltrimethoxysilane) was added and melt mixed at 100 ° C. Here, 3 parts of dibutyltin dilaurate as a catalyst was added and subjected to a demethanol reaction at 110 ° C. for 7 hours, and 80 parts of methanol was distilled off to obtain a silane-modified phenol resin (B-2). .

<< Synthesis Example 6 >>
<Production of epoxy group-containing methoxysilane partial condensate>
1400 parts of glycidol and 9140 parts of poly (methyltrimethoxysilane) obtained in Synthesis Example 3 were charged into a reaction apparatus equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas introduction tube while stirring under a nitrogen stream. After raising the temperature to 90 ° C., 2.2 parts of dibutyltin dilaurate was added and reacted. During the reaction, methanol produced using a water separator was distilled off, and the reaction was cooled when the amount reached about 630 parts. The time required for cooling after raising the temperature was 6 hours. Next, about 30 parts of methanol remaining in the system was removed under reduced pressure at 13 kPa for about 10 minutes to obtain an epoxy group-containing alkoxysilane partial condensate.

<< Synthesis Example 7 >>
<Preparation of silane-modified polyamic acid (B-3)>
After adding 112 parts of 4,4′-diaminodiphenyl ether and 1170 parts of N-methylpyrrolidone to a 2 L three-necked flask equipped with a stirrer, a condenser, a thermometer, and a nitrogen gas introduction tube, and mixing well at room temperature, 60 While cooling to below ℃, 118 parts of pyromellitic dianhydride was added and stirred for 30 minutes to synthesize polyamic acid. The resulting polyamic acid had a polyimide-converted solid residue of 15% by weight. Next, 500 parts of N-methylpyrrolidone was added, the temperature was raised to 80 ° C., 40.2 parts of the epoxy group-containing alkoxysilane partial condensate obtained in Synthesis Example 6, and 0.24 part of 2-methylimidazole as a catalyst. And reacted at 80 ° C. for 4 hours. And after the reaction for 4 hours, it cooled to room temperature and obtained the silane modified polyamic acid (B-3) of 12 weight% of hardening residues.

<< Synthesis Example 8 >>
<Production of glycidyl ether group-containing tetramethoxysilane partial condensate>
A reactor equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas inlet tube was used. The average number of Si in the mixture was 4, and the number average molecular weight was 480) 8,957.9 parts, and the temperature was raised to 90 ° C. with stirring in a nitrogen stream. Added and reacted. During the reaction, methanol produced using a water separator was distilled off, and the reaction was cooled when the amount reached about 550 parts. It took 5 hours to cool after raising the temperature. Next, about 68 parts of methanol remaining in the system was removed under reduced pressure at 13 kPa for about 10 minutes to obtain a glycidyl ether group-containing tetramethoxysilane partial condensate.

<< Synthesis Example 9 >>
<Manufacture of silane-modified acrylic resin (B-4)>
A reactor equipped with a stirrer, a cooling pipe, a thermometer and a gas introduction pipe was charged with 1461 parts of diethylene glycol dimethyl ether, heated to 100 ° C. under a nitrogen stream, and then 417 parts of butyl methacrylate and 83.3 parts of hydroxyethyl acrylate. 25 parts of mixed monomer and ditertiary butyl peroxide were added dropwise over 1 hour, and further mixed monomer consisting of 250 parts of methyl methacrylate and 83.3 parts of methacrylic acid and 10 parts of ditertiary butyl peroxide were each 1 hour. And then reacted at 120 ° C. for 3 hours to obtain a carboxyl group-containing acrylic polymer solution having a solid content of 37% by weight. The number average molecular weight of the obtained carboxyl group-containing acrylic polymer was 50,000, and the acid value (per solid content) was 65 mgKOH / g.

  Then, 700 parts of the carboxyl group-containing acrylic polymer solution prepared by the above method, 152 parts of the glycidyl ether group-containing tetramethoxysilane partial condensate obtained in Synthesis Example 8 and 30 parts of methanol were charged into a similar reactor, and nitrogen was added. By reacting at 80 ° C. for 6 hours under an air stream, a silane-modified acrylic resin (B-4) having a cured residue of 38.3 wt% was obtained.

Example 1
<Preparation of resin composition>
As the binder resin (A), 291 parts of the cyclic olefin polymer (A-1) solution obtained in Synthesis Example 1 (100 parts as the cyclic olefin polymer (A-1)) and 359 parts of diethylene glycol ethyl methyl ether as the solvent As the silane-modified resin (B), 20 parts of the silane-modified epoxy resin (B-1) solution obtained in Synthesis Example 4 (10 parts as the silane-modified epoxy resin (B-1)), acidic group or thermal latent acidity As the compound (C) having a group, 3 parts of 1,2,4-benzenetricarboxylic acid, and as the radiation-sensitive compound (D), 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3 -30 parts of a condensate of phenylpropane (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2 mol), and as crosslinking agent (E), 3, - epoxycyclohexenylmethyl 3 ', 4'-epoxy cyclohexene carboxylate 30 parts were mixed and dissolved, was filtered through a polytetrafluoroethylene filter with a pore size of 0.45μm resin composition was prepared.

  And each evaluation of image development adhesiveness, the residue at the time of image development, the hole state at the time of baking, transparency, and storage stability was performed using the resin composition obtained above. The results are shown in Table 1.

Example 2
Resin composition in the same manner as in Example 1 except that the amount of 1,2,4-benzenetricarboxylic acid as the compound (C) having an acidic group or a thermal latent acidic group was changed from 3 parts to 10 parts. Things were obtained and evaluated in the same manner. The results are shown in Table 1.

Example 3
While changing the compounding quantity of the silane modified epoxy resin (B-1) solution as a silane modified resin (B) from 20 parts to 60 parts (30 parts as a silane modified epoxy resin (B-1)), an acidic group or heat A resin composition was obtained in the same manner as in Example 1 except that the amount of 1,2,4-benzenetricarboxylic acid as the compound (C) having a latent acidic group was changed from 3 parts to 2 parts. The same evaluation was performed. The results are shown in Table 1.

Example 4
As the crosslinking agent (E), N, N, N ′, N ′, N ″, N ″-(hexa) instead of 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate A resin composition was obtained and evaluated in the same manner as in Example 1 except that 10 parts of a methoxymethyl) melamine-based crosslinking agent was used. The results are shown in Table 1.

Example 5
Implemented except that 5 parts of tris (2,3-epoxypropyl) isocyanurate was used in place of 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate as the crosslinking agent (E) In the same manner as in Example 1, a resin composition was obtained and evaluated in the same manner. The results are shown in Table 1.

Example 6
As in Example 5, except that 10 parts of the silane-modified phenol resin (B-2) obtained in Synthesis Example 5 was used as the silane-modified resin (B) instead of the silane-modified epoxy resin (B-1). Thus, a resin composition was obtained and evaluated in the same manner. The results are shown in Table 1.

Example 7
As in Example 6, except that 20 parts of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane was used as the crosslinking agent (E) instead of tris (2,3-epoxypropyl) isocyanurate. Thus, a resin composition was obtained and evaluated in the same manner. The results are shown in Table 1.

Example 8
As the compound (C) having an acidic group or a thermal latent acidic group, propylene glycol monomethyl ether of 1,2,4-benzenetricarboxylic acid tris (1-propoxyethyl) instead of 1,2,4-benzenetricarboxylic acid A resin composition was obtained in the same manner as in Example 7 except that 5 parts of an acetate solution (3 parts as 1,2,4-benzenetricarboxylic acid tris (1-propoxyethyl)) was used, and evaluation was similarly performed. Went. The results are shown in Table 1.

Example 9
As the silane-modified resin (B), instead of the silane-modified epoxy resin (B-1) solution, 83 parts of the silane-modified polyamic acid (B-3) solution obtained in Synthesis Example 7 (silane-modified polyamic acid (B-3)) ) Was used in the same manner as in Example 1 except that 10 parts) were used, and evaluation was performed in the same manner. The results are shown in Table 1.

Example 10
As the silane-modified resin (B), instead of the silane-modified epoxy resin (B-1) solution, 26 parts of the silane-modified acrylic resin (B-4) solution obtained in Synthesis Example 9 (silane-modified acrylic resin (B-4) ) Was used in the same manner as in Example 1 except that 10 parts) were used, and evaluation was performed in the same manner. The results are shown in Table 1.

Example 11
As binder resin (A), 291 parts of acrylic polymer (A-2) solution obtained in Synthesis Example 2 (100 parts as acrylic polymer (A-2)), 359 parts of diethylene glycol ethyl methyl ether as solvent, silane As the modified resin (B), 20 parts of the silane-modified epoxy resin (B-1) solution obtained in Synthesis Example 4 (10 parts as the silane-modified epoxy resin (B-1)), an acidic group or a heat latent acidic group As a compound (C), 5 parts of 1,2,4-benzenetricarboxylic acid tris (1-propoxyethyl) in propylene glycol monomethyl ether acetate solution (1,2,4-benzenetricarboxylic acid tris (1-propoxyethyl)) 3 parts), 1,1,3-tris (2,5-dimethyl-4-hydroxyphene) as the radiation-sensitive compound (D) 30) part of a condensate of 3-phenylpropane (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2 mol) and 2- (3,4) as the crosslinking agent (E) -Epoxycyclohexyl) After mixing and dissolving 10 parts of ethyltrimethoxysilane, the mixture was filtered through a polytetrafluoroethylene filter having a pore diameter of 0.45 µm to prepare a resin composition. The obtained resin composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 12
As in Example 11, except that 10 parts of the silane-modified phenol resin (B-2) obtained in Synthesis Example 5 was used as the silane-modified resin (B) instead of the silane-modified epoxy resin (B-1). Thus, a resin composition was obtained and evaluated in the same manner. The results are shown in Table 1.

<< Comparative Example 1 >>
A resin composition was obtained in the same manner as in Example 1 except that 1,2,4-benzenetricarboxylic acid as the compound (C) having an acidic group or a thermal latent acidic group was not blended. Evaluation was performed. The results are shown in Table 1.

<< Comparative Example 2 >>
Except having changed the compounding quantity of 1,2,4-benzenetricarboxylic acid as a compound (C) which has an acidic group or a thermal latent acidic group from 3 parts to 0.3 parts, it is the same as that of Example 1, A resin composition was obtained and evaluated in the same manner. The results are shown in Table 1.

<< Comparative Example 3 >>
Resin composition in the same manner as in Example 1 except that the compounding amount of 1,2,4-benzenetricarboxylic acid as the compound (C) having an acidic group or a thermal latent acidic group was changed from 3 parts to 30 parts. Things were obtained and evaluated in the same manner. The results are shown in Table 1.

<< Comparative Example 4 >>
A resin composition was obtained and evaluated in the same manner as in Example 1 except that the silane-modified epoxy resin (B-1) solution as the silane-modified resin (B) was not blended. The results are shown in Table 1.

<< Comparative Example 5 >>
Example except that the acrylic polymer (A-2) as the binder resin (A) is not blended and the blending amount of the silane-modified phenol resin (B-2) as the silane-modified resin (B) is 100 parts. In the same manner as in No. 12, a resin composition was obtained and evaluated in the same manner. The results are shown in Table 1.

  As shown in Table 1, a resin composition obtained by blending a binder resin (A) with a silane-modified resin (B) and a compound (C) having an acidic group or a heat-latent acidic group in a specific ratio is The resin film obtained by using the resin composition was excellent in storage stability, and was excellent in pattern formation by development and had high transparency (Examples 1 to 12).

On the other hand, when the compound (C) having an acidic group or a thermal latent acidic group is not blended, or the weight ratio of “silane-modified resin (B) / compound having an acidic group or thermal latent acidic group (C)” However, when it was too high as 33.3, the resin film obtained was inferior in the development adhesion and the hole state during firing (Comparative Examples 1 and 2).
When the weight ratio of “silane-modified resin (B) / compound having acidic group or thermal latent acidic group (C)” is too low at 0.3, the resulting resin composition is inferior in storage stability. Further, when a resin film was used, a development residue was generated (Comparative Example 3).
Further, when the silane-modified resin (B) was not blended, the development adhesion was poor, and the development pattern adhesion when the development pattern width was narrowed was insufficient (Comparative Example 4).
Furthermore, when the binder resin (A) is not blended, the resulting resin composition is inferior in storage stability. Further, when it is formed as a resin film, the development residue, the hole state during firing, and the transparency (Comparative Example 5).

Claims (8)

  A resin composition comprising a binder resin (A), a silane-modified resin (B), and a compound (C) having an acidic group or a heat-latent acidic group, the silane-modified resin (B), The ratio with the compound (C) having an acidic group or a thermal latent acidic group is, by weight ratio, “silane-modified resin (B) / compound having an acidic group or thermal latent acidic group (C)” = 0.5 A resin composition characterized by being ~ 20.   The silane-modified resin (B) chemically bonds at least one polymer material selected from polyester, polyamide, polyimide, polyamic acid, epoxy resin, acrylic resin, urethane resin, and phenol resin, and a silicon compound. The resin composition according to claim 1, wherein the resin composition is a compound formed by: The resin composition according to claim 2, wherein the silicon compound is a silicon compound represented by the following formula and / or a partial hydrolysis-condensation product of the silicon compound represented by the following formula.
_{^{(R 8) r -Si- (OR}} 9) 4-r
(In the above formula, r is an integer of 0 to 3, and R ⁸ is an alkyl group having 1 to 10 carbon atoms which may have a functional group directly bonded to a carbon atom, or an aryl having 6 to 20 carbon atoms. Or an unsaturated aliphatic group having 2 to 10 carbon atoms, and when R ⁸ is plural, the plural R ⁸ may be the same or different from each other, and R ⁹ is hydrogen. An alkyl group having 1 to 10 carbon atoms which may have an atom or a functional group directly bonded to a carbon atom, and when R ⁹ is plural, the plural R ⁹ are the same, May be different.)   4. The resin composition according to claim 1, wherein a content ratio of the silane-modified resin (B) is 1 to 100 parts by weight with respect to 100 parts by weight of the binder resin (A). object.   The resin composition according to any one of claims 1 to 4, wherein the binder resin (A) is a cyclic olefin polymer having a protic polar group or an acrylic resin.   The resin composition according to any one of claims 1 to 5, further comprising a radiation sensitive compound (D).   The resin composition according to any one of claims 1 to 6, further comprising a crosslinking agent (E).   A semiconductor element substrate provided with the resin film which consists of a resin composition in any one of Claims 1-7.