JP5640864B2 - Negative photosensitive resin composition and electronic component - Google Patents

Description

  The present invention relates to a negative photosensitive resin composition, and a resin film and an electronic component obtained by using this negative photosensitive resin composition. More specifically, the present invention relates to pattern formation by development, transparency, and heat resistance. The present invention relates to a negative photosensitive resin composition that can provide a resin film that is excellent in resistance and outgas generation is suppressed, and a resin film and an electronic component that are obtained using the negative photosensitive 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 acrylic resins and epoxy resins have been widely used as resin materials for forming these resin films. In recent years, along with the increase in the density of wiring and devices, these resin materials can be finely patterned in addition to electrical characteristics such as low dielectric properties, and further, device reliability such as low outgassing properties can be achieved. Development of a resin material with excellent properties is required.

  In order to meet these requirements, for example, Patent Document 1 discloses a photopolymerizable acrylate oligomer, a bifunctional or higher polyfunctional photopolymerizable acrylate monomer, a photopolymerizable compound having an ethylenically unsaturated double bond and a carboxyl group. , A photosensitive resin composition containing an aminosilane-modified epoxy resin, a photopolymerization initiator, and an organic solvent is disclosed. However, the photosensitive resin composition described in Patent Document 1 is insufficient in reducing the amount of outgas, and is therefore used for applications that require particularly low outgassing properties such as organic light emitting diodes (OLEDs) and liquid crystal display panels. In such a case, there is a problem that the lifetime is shortened.

  Moreover, in the resin film for constituting the various electronic components described above, the pattern shape can be maintained without being melted or deformed before and after the heating process when the resin film is used as a pattern (maintaining the heat resistant shape). Sex) is required. On the other hand, in order to improve these heat-resistant shape retention and heat-resistant transparency, for example, Patent Document 2 has a resin such as a cyclic olefin resin, a crosslinking agent having an epoxy group, a triazine ring structure or a glycoluril structure. And a radiation sensitive resin composition comprising a crosslinking agent having at least one functional group selected from the group consisting of an imino group, a methylol group, and an alkoxybutyl group, and a radiation sensitive compound such as a photoacid generator Things are disclosed.

  However, in the radiation-sensitive resin composition described in Patent Document 2, actinic radiation is applied to the entire surface of the substrate having the patterned resin film in order to deactivate heat resistance, in particular, a photoacid generator as a radiation-sensitive compound. In the case of not passing through the step of irradiating, the heat-resistant transparency (high transparency even after heating) was not always sufficient.

JP-A-5-295080 JP 2010-224533 A

  An object of the present invention is to provide a negative photosensitive resin composition that can provide a resin film that is excellent in pattern formation by development, transparency, and heat resistance, and that suppresses outgassing. . Another object of the present invention is to provide a resin film obtained using such a negative photosensitive resin composition, and an electronic component including the resin film.

  As a result of diligent research to achieve the above object, the present inventors include a cyclic olefin resin having a protic polar group, an unsaturated group-containing compound, a silane-modified organic-inorganic hybrid compound, and a radical-generating photopolymerization initiator. The present inventors have found that the above object can be achieved by the resin composition thus formed, and have completed the present invention.

That is, according to the present invention, a cyclic olefin polymer having a protic polar group (A), an unsaturated group-containing compound (B), a silane-modified organic-inorganic hybrid compound (C), and a radical-generating photopolymerization initiator ( Ri Na contain D), the silane modified organic-inorganic hybrid compound (C) is an organic portion and an inorganic portion, has these in a state of being chemically bonded to each other, and the inorganic part those containing silicon atoms, the organic portion, the negative photosensitive resin composition Ru der polymeric material having an inorganic portion and chemically bondable functional groups are provided.

Preferably, the unsaturated group-containing compound (B) is a (meth) acrylic acid ester.
Preferably, the radical generating photopolymerization initiator (D) is a compound having sensitivity to light having a wavelength of 400 nm or less, and the content of the radical generating photopolymerization initiator (D) is the protonic polarity. It is 1-30 weight part with respect to 100 weight part of cyclic olefin polymer (A) which has group.

Moreover, according to this invention, the resin film obtained using one of the said negative photosensitive resin compositions is provided.
Furthermore, according to this invention, an electronic component provided with the said resin film is provided.

  According to the present invention, a negative photosensitive resin composition capable of providing a resin film that is excellent in pattern formation by development, transparency, and heat resistance, and that can suppress outgassing, such a negative type. A resin film obtained using the photosensitive resin composition and an electronic component including such a resin film can be provided. In particular, according to the negative photosensitive resin composition of the present invention, after forming a resin film obtained by using this, the entire surface of the resin film is irradiated with actinic radiation in order to deactivate the photopolymerization initiator. Even when the process is not performed, the obtained resin film can be excellent in heat-resistant transparency (high transparency even after heating).

  The negative photosensitive resin composition of the present invention includes a cyclic olefin polymer (A) having a protic polar group, an unsaturated group-containing compound (B), a silane-modified organic-inorganic hybrid compound (C), and radical generating light. It is a negative photosensitive resin composition containing a polymerization initiator (D).

(Cyclic olefin polymer having a protic polar group (A))
The cyclic olefin polymer (A) having a protic polar group used in the present invention (hereinafter simply referred to as “cyclic olefin polymer (A)”) has a cyclic structure of a cyclic olefin monomer unit in the main chain. A homopolymer or copolymer of a cyclic olefin monomer having an (alicyclic ring or aromatic ring) and having a protic polar group.

  As such a cyclic olefin polymer (A), a polymer of one or two or more cyclic olefin monomers, or one or two or more cyclic olefin monomers and a monomer copolymerizable therewith In the present invention, the cyclic olefin monomer (a) having at least a protic polar group is used as the monomer for forming the cyclic olefin polymer (A). Is preferred.

  Here, the protic polar group means 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, and 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 units of the monomer (a) in the cyclic olefin polymer (A) is preferably 10 to 90 mol%, more preferably 15 to 80 mol%, further based on the total monomer units. Preferably it is 20-70 mol%. If the content ratio of the monomer (a) unit is too small, the heat resistance may be insufficient. On the other hand, if it is too large, the cyclic olefin polymer (A) is insufficiently soluble in the polar solvent. There is a risk of becoming.

  The cyclic olefin polymer (A) 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２価のアルキレン基、Ｒ^３は、炭素数１〜１０の１価のアルキル基、または、炭素数１〜１０の１価のハロゲン化アルキル基を表す。） Examples of the cyclic olefin having an N-substituted imide group include a monomer represented by the following 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 is a divalent alkylene group having 1 to ³ carbon atoms, R ³ is a monovalent alkyl group having 1 to 10 carbon atoms, or a monovalent alkyl group having 1 to 10 carbon atoms. Represents a halogenated alkyl group.)

In the above formula (1), R ¹ is an alkyl group having ¹ to 16 carbon atoms or an aryl group, and 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 Cyclic such as 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. When the carbon number is 4 or less, the solubility in a polar solvent is poor, when the carbon number is 17 or more, the heat resistance is poor, and when the resin film is patterned, the pattern is lost by melting with heat. There is a problem.

Specific examples of the monomer represented by the 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 Boxyimide, 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-dicarboxy Imido, 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 a divalent alkylene group having 1 to 3 carbon atoms. Examples of the divalent alkylene group having 1 to 3 carbon atoms include a methylene group, an ethylene group, a propylene group, A propylene group is mentioned. Among these, a methylene group and an ethylene group are preferable because of good polymerization activity.

In the above formula (2), R ³ is a monovalent alkyl group having 1 to 10 carbon atoms or a monovalent halogenated alkyl group having 1 to 10 carbon atoms. Examples of the monovalent alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, hexyl group, and cyclohexyl group. . Examples of the monovalent halogenated alkyl group having 1 to 10 carbon atoms include a fluoromethyl group, a chloromethyl group, a bromomethyl group, a difluoromethyl group, a dichloromethyl group, a difluoromethyl group, a trifluoromethyl group, a trichloromethyl group, Examples include 2,2,2-trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, perfluorobutyl group, and perfluoropentyl group. Among these, because of excellent solubility in polar solvents, as 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, An α-olefin having 2 to 20 carbon atoms such as 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene; -Non-conjugated dienes such as hexadiene, 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 (A) is preferably 10 to 90 mol%, more preferably 15 to 80, based on all monomer units. It is mol%, More preferably, it is 20-70 mol%. If the content ratio of the copolymerizable monomer (b) is too small, the solubility of the cyclic olefin polymer (A) in the polar solvent may be insufficient. May be insufficient.

In addition, in this invention, it is good also as a cyclic olefin polymer (A) 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 weight average molecular weight of the cyclic olefin polymer (A) used in the present invention can be arbitrarily selected depending on the production purpose of the polymer, but is usually 1,000 to 1,000,000, preferably 1,500 to 500,000, more preferably 2,000 to 50,000. The weight average molecular weight (Mw) of the cyclic olefin polymer (A) is a value determined as a polystyrene equivalent value by gel permeation chromatography (GPC).

  The cyclic olefin polymer (A) used in the present invention may be a ring-opening polymer obtained by ring-opening polymerization of the above-mentioned monomer, or an addition polymer obtained by addition polymerization of the above-mentioned 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, benzyl Den (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-Ilidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazole-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 2-Ilidene) (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-dimesitylimidazolidine-2-ylidene) Ruthenium dichloride, ((2- (1-methylethoxy) -5- (trifluoroacetamino) 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 carbene complex in which hetero atom-containing carbene compound such as ruthenium dichloride and benzylidene (1,3-dimesitylhexahydropyrimidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride and neutral electron donating compound are combined 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 are combined. Ruthenium carbene complexes; 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) to be used as necessary, by using 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 (A) used in the present invention is a ring-opening polymer, a hydrogenation reaction is further performed, and hydrogenation in which a carbon-carbon double bond contained in the main chain is hydrogenated is performed. It is preferable to use a product. When the cyclic olefin polymer (A) 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 a coupling | bonding.

  The hydrogenation reaction can be performed, for example, by converting a carbon-carbon double bond in the main chain of the ring-opened 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.

(Unsaturated group-containing compound (B))
The unsaturated group-containing compound (B) used in the present invention is not particularly limited as long as it is a compound containing a carbon-carbon unsaturated bond, but (meth) acrylic acid [meaning acrylic acid and / or methacrylic acid] . The same applies hereinafter. ], (Meth) acrylic acid esters, aromatic vinyl compounds, vinyl ester compounds, vinyl ether compounds, vinyl ketone compounds, epoxy group-containing vinyl compounds, and the like. Among these, (meth) acrylic acid esters are preferable from the viewpoint that the effects of the present invention can be made more remarkable.

  Specific examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-isocyanate. Natoethyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, (3-methyl-3-oxetanyl) methyl acrylate, ethylene glycol dimethacrylate, Diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tricyclodecane dimethanol di (meth) acrylate, neopentyl glycol dimethacrylate, 1,6-hexanedi Examples include all di (meth) acrylate, pentaerythritol triacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, ethoxylated isocyanuric acid triacrylate, ethoxylated glycerin triacrylate, and the like.

  Examples of aromatic vinyl compounds include styrene, α-methyl styrene, vinyl toluene, 2,4-dimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, crotylbenzene, and vinyl naphthalene. Can be mentioned.

  Examples of the vinyl ester compound include vinyl acetate, vinyl butyrate, vinyl propionate, vinyl caproate, divinyl adipate, vinyl benzoate and the like.

  Examples of vinyl ether compounds include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, 1,4-butanediol divinyl ether, diethylene glycol divinyl ether, cyclohexane dimethanol divinyl ether, and the like.

  Examples of the vinyl ketone compound include vinyl methyl ketone, vinyl ethyl ketone, and vinyl phenyl ketone.

  Examples of the epoxy group-containing vinyl compound include 1,2-epoxy-5-hexene, 1,2-epoxy-7-octene, 1,2-epoxy-9-decene, and 8-hydroxy-6,7-epoxy-1-. Examples include octene.

  These unsaturated group-containing compounds (B) can be used alone or in combination of two or more.

  The content of the unsaturated group-containing compound (B) in the negative photosensitive resin composition of the present invention is preferably 1 to 200 parts by weight, more preferably 100 parts by weight of the cyclic olefin polymer (A). Is 10 to 180 parts by weight, more preferably 20 to 150 parts by weight. If the content of the unsaturated group-containing compound (B) is too small, the film formability may be lowered. On the other hand, if the content is too large, a residue may be generated during development.

(Silane-modified organic-inorganic hybrid compound (C))
The silane-modified organic-inorganic hybrid compound (C) used in the present invention has an organic part and an inorganic part in a state in which they are chemically bonded to each other, and contains a silicon atom in the inorganic part.

  Although it does not specifically limit as a material which comprises the organic part of a silane modified organic inorganic hybrid compound (C), The polymeric material which has a functional group which can be couple | bonded chemically with an inorganic 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 capable of binding to the inorganic part is not particularly limited, and examples thereof include a hydroxyl group, amino group, thiol group, carboxylic acid group, acid anhydride group, epoxy group, amide group, and imide group. From the viewpoint of reactivity with the inorganic part, a hydroxyl group, a carboxylic acid group or an acid anhydride group is preferred.

Although it does not specifically limit as a material which comprises the inorganic part of a silane modified organic inorganic hybrid compound (C), For example, it represents with the organosilicon compound represented by following formula (5), and / or following formula (5). The partial hydrolysis condensate of an organosilicon compound is mentioned, The partial hydrolysis condensate represented by following formula (6) is especially preferable from the point that the effect of this invention becomes still more remarkable.
_{^{(R 6) r -Si- (OR}} 7) 4-r (5)

In said formula (5), r is an integer of 0-3. R ⁶ 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. , when R ⁶ is plural, plural R ⁶ may be different even in respectively the same. R ⁷ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a functional group directly bonded to a carbon atom, and when R ⁷ is plural, a plurality of R ⁷ May be the same or different. In addition, examples of the functional group directly constituting a carbon atom constituting R ⁶ and R ⁷ include a hydroxyl group, an epoxy group, a halogen group, a mercapto group, a carboxyl group, and a methacryloxy group.
In the above formula (6), p is 0 or 1. q is an integer of 2 to 10, and R ⁶ and R ⁷ are the same as in the above formula (5).

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 ⁶ and R ⁷ 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 ⁶ 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 ⁶ include a vinyl group, a 3-acryloxypropyl group, Examples include a 3-methacryloxypropyl group.

  Specific examples of such organosilicon 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 Propyltri-i-propoxysilane, i-propyltri-i-propoxysilane, 3-chloropropyltri-i-propoxysilane, vinyltri-i-propoxysilane, phenyltri-i-propoxysilane, methyltributoxysilane, ethyltributoxysilane, 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-trif Orotriethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3,4-epoxycyclohexyltriethoxysilane, 3,3,3-trifluorotri i-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 Examples include rutoriboxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane, which are preferably used as a partial hydrolysis condensate. These can be used alone or in combination of two or more.

  When the inorganic part is a partial hydrolysis condensate, the partial condensate obtained by partial hydrolysis of the organosilicon compound described above may be used as it is, or the obtained partial condensate may be used as it is. You may use what substituted a part by performing a dealcoholization reaction using the alcohol which has functional groups, such as an epoxy group, a halogen group, a mercapto group, a carboxyl group, or a methacryloxy group. By replacing the partial condensate obtained by partial hydrolysis of the organosilicon compound described above with an alcohol having such a functional group, a partial hydrolysis condensate having such a functional group can be easily obtained. be able to.

  The method of chemically bonding the organic part and the inorganic part to obtain the silane-modified organic-inorganic hybrid compound (C) is not particularly limited. For example, a polymer material having a hydroxyl group in the organic part is used, and the inorganic part is inorganic. A method of chemically bonding an organic part and an inorganic part by subjecting a part alkoxyl group to a dealcoholization reaction is mentioned. Alternatively, a polymer material having a carboxylic acid group or an acid anhydride group is used in the organic part, a compound having a glycidyloxy group is used in the inorganic part, and these are subjected to an addition reaction, or the oxirane ring is opened, Examples thereof include a method for causing a ring-opening esterification reaction. In addition, the organic part can be polymerized by chemically bonding the organic part and the inorganic part and then polymerizing the organic part. In this case, a low molecular organic material is used as a material to be chemically bonded to the inorganic part. After the low molecular organic material and the inorganic part are chemically bonded, the low molecular organic material is polymerized. Alternatively, a method for increasing the molecular weight can also be employed.

  For example, among the above methods, according to the dealcoholization reaction, the material constituting the organic part and the material constituting the inorganic part are charged, heated, and the ester exchange reaction is performed while distilling off the generated alcohol. A silane-modified organic-inorganic hybrid compound (C) 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 inorganic part may be started.

  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 that constitutes the organic part and an organic solvent that dissolves the material that constitutes the inorganic 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 above methods, according to the ring-opening esterification reaction, by charging the material constituting the organic part and the material constituting the inorganic part and heating, by causing the ring-opening esterification reaction, A silane-modified organic-inorganic hybrid compound (C) 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, and if the reaction temperature is too high, curing condensation of the material constituting the inorganic 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, and the organic solvent is not particularly limited as long as it is an organic solvent that dissolves a material constituting the organic part and a material constituting the inorganic part. For example, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, cyclohexanone, etc. can be used.

  The ratio of the organic part to the inorganic part of the silane-modified organic-inorganic hybrid compound (C) used in the present invention is preferably a weight ratio of “organic part: inorganic part”, preferably 1:50 to 50: 1, more preferably. Is 1:10 to 10: 1. By setting the ratio of the organic part to the inorganic part in the above range, the effect of the present invention becomes more remarkable, which is preferable.

  The content of the silane-modified organic-inorganic hybrid compound (C) in the negative photosensitive resin composition of the present invention is preferably 1 to 100 parts by weight, more preferably 2 to 50 parts by weight, still more preferably 5 to 40 parts by weight. Part. If the content of the silane-modified organic-inorganic hybrid compound (C) is too small, the pattern formability by development is lowered, and particularly 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.

(Radical generation type photopolymerization initiator (D))
The radical-generating photopolymerization initiator (D) used in the present invention is not particularly limited as long as it is a compound that generates a radical by irradiating light and causes a chemical reaction. Preferably, it is 400 nm or less. It is preferably a compound that has sensitivity to light of a wavelength and generates a radical and causes a chemical reaction when irradiated with light having a wavelength of 400 nm or less, specifically, radiation such as ultraviolet rays or electron beams.

Specific examples of the radical generating photopolymerization initiator (D) include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone, α-amino- Acetophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2- Methylpropiophenone, p-tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethyl ketal, benzylmethoxyethyl Cetal, benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberon, methyleneanthrone, 4-azidobenzylacetophenone, 2,6-bis ( p-azidobenzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione -2- (o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o Benzoyl) oxime, Michler's ketone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone , Naphthalenesulfonyl chloride, quinolinesulfonyl chloride, n-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, N, N-octamethylenebisacridine, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (manufactured by BASF, Irgacure 379EG), 1,7-bis (9 -Acridyl) -heptane (ADEKA) N1717), 1,2-octanedione, 1- [4- (phenylthio)-, 2- (o-benzoyloxime)] (manufactured by BASF, OXE-01), ethanone, 1- [9-ethyl- 6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime) (manufactured by BASF, OXE-02), carbon tetrachloride, tribromophenylsulfone, benzoin peroxide, Examples thereof include a combination of a photoreductive dye such as eosin or methylene blue and a reducing agent such as ascorbic acid or triethanolamine.
Among these, N, N-octamethylenebisacridine, and ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime) ) Is preferred. These radical generating photopolymerization initiators (D) can be used alone or in combination of two or more.

  The content of the radical-generating photopolymerization initiator (D) in the negative photosensitive resin composition of the present invention is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the cyclic olefin polymer (A), More preferably, it is 3 to 20 parts by weight. If the content of the radical generating photopolymerization initiator (D) is too small, the film formability may be lowered. On the other hand, if it is too much, a residue is generated during development or the heat-resistant transparency is lowered. There is a fear.

(Other ingredients)
The negative photosensitive resin composition of the present invention may further contain a solvent. The solvent is not particularly limited, and known solvents for various resin materials such as 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 ethers 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, ethyl lactate; cellosolv 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 Propylene glycols such as monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether; die such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether Lenglycols; saturated γ-lactones such as γ-butyrolactone, γ-valerolactone, γ-caprolactone, 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 10000 parts by weight, more preferably 50 to 5000 parts by weight, and further preferably 100 to 1000 parts by weight with respect to 100 parts by weight of the cyclic olefin polymer (A). In addition, when a negative photosensitive resin composition is made to contain a solvent, a solvent will usually be removed after resin film formation.

Moreover, the negative photosensitive resin composition of the present invention may further contain a compound having an acidic group. The compound having an acidic group is not particularly limited as long as it has an acidic group, but is preferably an aliphatic compound, an aromatic compound, or a heterocyclic compound, and more preferably an aromatic compound or a heterocyclic compound. .
These compounds having an acidic group can be used alone or in combination of two or more. The acidic group may be heat latent.

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

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

  Specific examples of the compound having such an acidic group include methanoic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, butanoic acid, 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”), butanedioic acid (also referred to as “succinic acid”), pentanedioic acid, hexane Diacid (also referred to as “adipic acid”), 1,2-cyclohexanedicarboxylic acid, 2-oxopropanoic acid, 2-hydroxybutanedioic acid, 2-hydroxypropanetricarboxylic acid, mercaptosuccinic acid, dimercaptosuccinic acid, 2, 3-dimercapto-1-propanol, 1,2,3-trimercaptopropane, 2,3,4-trimercapto-1-butanol, 2 Aliphatic groups such as 4-dimercapto-1,3-butanediol, 1,3,4-trimercapto-2-butanol, 3,4-dimercapto-1,2-butanediol, 1,5-dimercapto-3-thiapentane Compound;

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

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

Pyridine-2,3-dicarboxylic acid, pyridine-2,4-dicarboxylic acid, pyridine-2,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, pyridine-3,5 -Dicarboxylic acid, pyridazine-3,4-dicarboxylic acid, pyridazine-3,5-dicarboxylic acid, pyridazine-3,6-dicarboxylic acid, pyridazine-4,5-dicarboxylic acid, pyrimidine-2,4-dicarboxylic acid, pyrimidine -2,5-dicarboxylic acid, pyrimidine-4,5-dicarboxylic acid, pyrimidine-4,6-dicarboxylic acid, pyrazine-2,3-dicarboxylic acid, pyrazine-2,5-dicarboxylic acid, pyridine-2,6- Dicarboxylic acid, triazine-2,4-dicarboxylic acid, 2-diethylamino-4,6-dimercapto-s-triazine, 2-dipropyl Mino-4,6-dimercapto-s-triazine, 2-dibutylamino-4,6-dimercapto-s-triazine, 2-anilino-4,6-dimercapto-s-triazine, 2,4,6-trimercapto- 6-membered heterocyclic compounds containing a nitrogen atom such as s-triazine.
Among these, the number of acidic groups 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 the present invention, a latent acid generator can be used as the compound having an acidic group because the same effect as described above can be obtained. Examples of the latent acid generator include sulfonium salts, benzothiazolium salts, ammonium salts, phosphonium salts, and block carboxylic acids, which are cationic polymerization catalysts that generate an acid by heating. Among these, block carboxylic acid is preferable.

  In addition, the content of the compound having an acidic group in the negative photosensitive resin composition of the present invention is preferably 0.1 to 50 parts by weight, more preferably 1 to 50 parts by weight with respect to the cyclic olefin polymer (A). The range is 45 parts by weight, more preferably 2 to 40 parts by weight, and still more preferably 3 to 30 parts by weight. By making the usage-amount of the compound which has an acidic group into the said range, a resin composition can be made excellent in liquid stability.

  Moreover, the negative photosensitive resin composition of this invention may contain the crosslinking agent further. The crosslinking agent used in the present invention is one that forms a crosslinked structure between crosslinking agent molecules by heating, or one that reacts with the cyclic olefin polymer (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 further preferably an amino group and an epoxy group. An epoxy compound having an epoxy group is particularly preferable. Moreover, as an epoxy group, a terminal epoxy group and an alicyclic epoxy group are preferable, and an alicyclic epoxy group is more preferable.

  Although the molecular weight of a crosslinking agent 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 include aliphatic polyamines such as hexamethylenediamine; aromatic polyamines such as 4,4′-diaminodiphenyl ether and diaminodiphenylsulfone; 2,6-bis (4′-azidobenzal) cyclohexanone, 4 , 4′-diazidodiphenylsulfone and other azides; nylon, polyhexamethylenediamine terephthalamide, polyhexamethyleneisophthalamide and other polyamides; N, N, N ′, N ′, N ″, N ″ Melamines which may have a methylol group such as-(hexaalkoxyalkyl) melamine or an imino group (trade names "Cymel 303, Cymel 325, Cymel 370, Cymel 232, Cymel 235, Cymel 272, Cymel 212, Myel Coat 506 "{End, Cytec Indah Cymel series, Mycoat series, etc. manufactured by Torys Co., Ltd.]; N, N ′, N ″, N ′ ″-(tetraalkoxyalkyl) glycoluril and other methylol groups and imino groups 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 and hydrogenated diphenylmethane diisocyanate; 1,4-di- (hydroxymethyl) cyclohexane, 1,4-di- (hydroxymethyl) norbornane; 1,3,4 Trihydroxycyclohexane; bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, polyphenol type epoxy resin, cyclic aliphatic epoxy resin, aliphatic glycidyl ether, epoxy acrylate polymer, etc. And epoxy compounds.

  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 An epoxy compound having an alicyclic structure such as an aliphatic cyclic tetrafunctional epoxy resin, trade name “Epolide GT401”, manufactured by Daicel Chemical Industries, Ltd .;

  Aromatic amine type polyfunctional epoxy compound (trade name “H-434”, manufactured by Tohto Kasei Kogyo Co., 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., multifunctional epoxy polybutadiene (trade name" Epolide PB3600 ", manufactured by Daicel Chemical Industries), glycerin glycidyl polyether compound (trade name" SR-GLG ", Sakamoto Pharmaceutical Co., Ltd.) Diglycerin polyglycidyl ether compound (product) An epoxy compound having no alicyclic structure such as “SR-DGE”, Sakamoto Pharmaceutical Co., Ltd., polyglycerin polyglycidyl ether compound (trade name “SR-4GL”, Sakamoto Pharmaceutical Co., Ltd.); Can do.

  Among epoxy compounds, polyfunctional epoxy compounds having two or more epoxy groups are preferred, and the resin film obtained using the negative photosensitive resin composition of the present invention can be made excellent in heat-resistant shape retention. A polyfunctional epoxy compound having an alicyclic structure and having 3 or more epoxy groups is particularly preferable.

  The content of the crosslinking agent in the negative photosensitive resin composition of the present invention is not particularly limited, taking into consideration the degree of heat resistance required for the resin film obtained using the negative photosensitive resin composition of the present invention. However, it is usually 5 to 80 parts by weight, preferably 20 to 75 parts by weight, more preferably 25 to 70 parts by weight with respect to 100 parts by weight of the cyclic olefin polymer (A). . If the amount of the crosslinking agent is too much or too little, the heat resistance tends to decrease.

  In addition, the negative photosensitive resin composition of the present invention is a surfactant, an acidic compound, a coupling agent or a derivative thereof, a sensitizer, a latent acid, if desired, as long as the effects of the present invention are not inhibited. Other compounding agents such as a generator, an antioxidant, 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.

  A coupling agent or a derivative thereof has an effect of further improving the adhesion between a resin film made of a negative photosensitive resin composition and each layer including a semiconductor layer constituting a 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 negative photosensitive 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 negative photosensitive resin composition of this invention is not specifically limited, What is necessary is just to mix each component which comprises a negative photosensitive 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 negative photosensitive resin composition in a solvent. Thereby, a negative photosensitive resin composition is obtained with the form of a solution or a dispersion liquid.

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

  The solid concentration of the negative photosensitive 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.

  Further, the content ratio of Na, Mg, Al, K, Ca, Cr, Mn, Fe and Ni in the negative photosensitive resin composition of the present invention is preferably a weight ratio with respect to the entire negative photosensitive resin composition. Is less than 500 ppb, more preferably less than 200 ppb, particularly preferably less than 100 ppb.

(Resin film)
The resin film of the present invention can be obtained using the above-described negative photosensitive resin composition of the present invention. As the resin film of the present invention, those obtained by forming the above-described negative photosensitive resin composition of the present invention on a substrate are preferable.

  For example, a printed wiring board, a silicon wafer substrate, a glass substrate, a plastic substrate, or the like can be used as the substrate. In addition, a glass substrate, a plastic substrate or the like used in the display field in which a thin transistor type liquid crystal display element, a color filter, a black matrix, or the like is formed is also preferably used.

  The method for forming the resin film is not particularly limited, and for example, a method such as a coating method or a film lamination method can be used.

  The application method is, for example, a method in which a negative photosensitive resin composition is applied and then dried by heating to remove the solvent. Examples of the method for applying the negative photosensitive resin composition include 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. Can be adopted. The heating and drying conditions vary depending on the type and blending ratio of each component, but are usually 30 to 150 ° C., preferably 60 to 120 ° C., usually 0.5 to 90 minutes, preferably 1 to 60 minutes, and more. Preferably it may be performed in 1 to 30 minutes.

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

  The thickness of the resin film is not particularly limited and may be set as appropriate according to the application. The resin film is, for example, a protective film for an active matrix substrate or a sealing film for an organic EL element substrate. In some cases, 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 negative photosensitive resin composition of this invention contains a crosslinking agent, 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 according to the type of the crosslinking agent, 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, the resin film formed using the negative photosensitive 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. In some cases, it may be patterned. As a method for patterning the resin film, for example, a resin film before patterning is formed, and the resin film before patterning is irradiated with actinic radiation to cause the radical-generating photopolymerization initiator (D) to act. And a method in which a latent image pattern is formed, and then the pattern is made visible by bringing a developer into contact with the resin film having the latent image pattern.

As the active radiation, the radical-generating photopolymerization initiator (D) contained in the negative photosensitive resin composition is activated to change the alkali solubility of the resin composition containing the radical-generating photopolymerization initiator (D). Although it will not specifically limit if it can be made, The light of a wavelength of 400 nm or less is preferable. 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, the amount of irradiation is usually 10~1,000mJ / cm ^2, preferably in the range from 50 to 500 mJ / cm ^2, irradiation time and intensity It depends on. 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 way can be rinsed with a rinsing liquid as necessary in order to remove development residues. After the rinse treatment, the remaining rinse liquid is removed with compressed air or compressed nitrogen.

  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.

(Electronic parts)
The electronic component of the present invention includes the above-described resin film of the present invention. Although it does not specifically limit as an electronic component of this invention, Various semiconductor devices are mentioned, Specifically, an active matrix board | substrate, an organic EL element board | substrate, an integrated circuit element board | substrate, a solid-state image sensor board | substrate etc. are mentioned.

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

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

  When the electronic component of the present invention is a semiconductor device, the resin film constituting the electronic component of the present invention is a resin film formed in contact with a semiconductor element surface or a semiconductor layer included in the semiconductor element. Preferably there is. In particular, when the electronic component 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 electronic component of the present invention is an active matrix substrate, the above-described resin film of the present invention is a protective film formed on the surface of the active matrix substrate or a thin film transistor constituting the active matrix substrate. A gate insulating film formed in contact with a semiconductor layer (for example, an amorphous silicon layer) can be used. Alternatively, when the electronic component 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 positive electrode) included in the organic EL element substrate. 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.

  The negative photosensitive resin composition of the present invention includes a cyclic olefin polymer (A) having a protic polar group, an unsaturated group-containing compound (B), a silane-modified organic-inorganic hybrid compound (C), and radical generating light. Since the polymerization initiator (D) is contained, the resin film obtained using the negative photosensitive resin composition of the present invention is excellent in pattern formation by development, transparency, and heat resistance, And generation | occurrence | production of outgas is suppressed. In particular, the negative photosensitive resin composition of the present invention is formed on the entire surface of the resin film in order to deactivate the photopolymerization initiator after forming a resin film obtained by using this and patterning as necessary. Even if it does not pass through the process of irradiating actinic radiation, the obtained resin film can be made excellent in heat-resistant transparency (high transparency even after heating). Therefore, according to the present invention, in order to inactivate the photopolymerization initiator, the step of irradiating actinic radiation can be omitted, and thus the resulting resin film can be subjected to pattern formation by development, transparency, The manufacturing process can be simplified while being excellent in heat resistance and low outgassing properties. And the resin film obtained using such a negative photosensitive resin composition of this invention can be used suitably as various electronic components, especially an active matrix board | substrate and an organic EL element board | substrate.

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

<Development residual film>
The negative photosensitive resin composition was applied onto a silicon wafer using a spin coater and then pre-baked at 100 ° C. for 2 minutes using a hot plate to prepare a 2.5 μm film. In addition, the film thickness (F1) of the produced film was measured using an optical microscope (Dainippon Screen Mfg. Co., Ltd., Lambda Ace VM-1200). Next, an ultraviolet ray having a light intensity at 365 nm of 5 mW / cm ² was irradiated for a desired time to perform an exposure process. Thereafter, a 2.38 wt% tetramethylammonium hydroxide aqueous solution was used for development treatment at 23 ° C. for 60 seconds to obtain a resin film formed on the silicon wafer. Thereafter, the film thickness (F2) of the film after the development treatment was measured using an optical film thickness meter. Then, from the film thickness before development processing (F1) and the film thickness after development processing (F2), the development residual film after the development processing according to “development residual film ratio (%) = (F2 / F1) × 100”. The rate was calculated and evaluated according to the following criteria. In addition, since the pattern development property by image development is excellent, it is preferable that the image development residual film rate is high.
○: Development residual film ratio is 90% or more.
X: Development residual film ratio is less than 90%.

<Development residue>
A negative photosensitive resin composition is applied onto a glass substrate (trade name “Eagle XG”, manufactured by Corning) manufactured by Corning, using a spin coater, and then pre-baked at 100 ° C. for 2 minutes using a hot plate. did. Next, in order to pattern the resin film, using a contact hole pattern having a size different from 0.5 μm to 5.0 μm and a mask capable of forming each contact hole pattern of 10 μm, 25 μm, and 50 μm, light intensity at 365 nm An exposure process was performed by irradiating with ultraviolet rays having a power of 5 mW / cm ² for a desired time. Thereafter, development processing was performed at 23 ° C. for 60 seconds using a 2.38 wt% tetramethylammonium hydroxide aqueous solution to obtain a laminate including a resin film having a contact hole pattern and a glass substrate.
And about the resin film of the obtained laminated body, the presence or absence of the melt | dissolution residue in a contact hole was confirmed using the scanning electron microscope (SEM), and the following reference | standard evaluated. In addition, it is preferable that no dissolution residue is observed because the pattern forming property by development is excellent.
○: Development residue was not observed.
X: Development residue was observed.

<Heat resistant transparency>
In the same manner as the evaluation of the development residue, a negative photosensitive resin composition is used to obtain a resin film, and exposure and development are performed in the same manner, and a resin film having a contact hole pattern and a glass substrate are formed. A laminate was obtained, and the obtained laminate was heat-treated at 230 ° C. for 1 hour in a nitrogen atmosphere using a clean oven. And about the resin film of the laminated body after a heating, the transmittance | permeability measurement in wavelength 400nm was performed using the spectrophotometer (The JASCO Corporation make, ultraviolet visible spectrophotometer V560), and it converted into the film thickness of 2 micrometers. The transmittance in each case was calculated and evaluated according to the following criteria.
A: The transmittance is 80% or more and 100% or less.
○: The transmittance is 75% or more and less than 80%.
Δ: The transmittance is 70% or more and less than 75%.
X: The transmittance is less than 70%.

<Heat resistance>
In the same manner as the evaluation of the development residue, a negative photosensitive resin composition is used to obtain a resin film, and exposure and development are performed in the same manner, and a resin film having a contact hole pattern and a glass substrate are formed. A laminate was obtained. And about the resin film of the obtained laminated body, the length (L1) of the longest part of a 5-micrometer contact hole pattern was measured using the optical microscope. Next, the obtained laminate was heat-treated at 230 ° C. for 1 hour in a nitrogen atmosphere using a clean oven. Thereafter, the resin film of the laminate after heating is observed using an optical microscope, the length (L2) of the longest part is measured for the contact hole pattern observed before heating, and the length of the longest part before heat treatment is measured. From the length (L1) and the length (L2) of the longest part after the heat treatment, the pattern retention after heating is calculated according to “pattern retention (%) = (L2 / L1) × 100”. Evaluated by criteria. In addition, since the heat resistance is excellent, it is preferable that the pattern retention after heating is high.
○: Pattern retention is 80% or more.

<Outgas>
In the same manner as in the evaluation of the development residual film, spin coating, exposure and development were performed in the same manner using the negative photosensitive resin composition to obtain a resin film formed on the silicon wafer. Then, the obtained resin film was heat-treated at 230 ° C. for 1 hour in a nitrogen atmosphere using a clean oven. Thereafter, the heated resin film is heated at 220 ° C. for 30 minutes using a temperature-programmed desorption analyzer (manufactured by Electronic Science Co., Ltd., WA1000S / W type). The outgas amount was calculated from the amount and evaluated according to the following criteria.
A: Outgas amount is less than 10 ppm.
○: Outgas amount is 10 ppm or more and less than 20 ppm.
(Triangle | delta): Outgas amount is 20 ppm or more and less than 30 ppm.
X: Outgas amount is 30 ppm or more.

<< Synthesis Example 1 >>
<Preparation of Cyclic Olefin Polymer (A-1)>
9-Hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene 60.0 parts, N- (2-ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide (NEHI) 40.0 Parts, 1,5-hexadiene 2.0 parts, (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride 400 parts, and diethylene glycol ethyl methyl ether 400 parts It charged to the substituted pressure | voltage resistant glass reactor, and it superposed | polymerized at 80 degreeC for 4 hours, stirring, and obtained the polymerization reaction solution containing a ring-opening metathesis polymer.

  And the obtained polymerization reaction liquid was put into an autoclave, it stirred at 150 degreeC and the hydrogen pressure of 4 Mpa for 5 hours, hydrogenation reaction was performed, and the polymer solution containing a cyclic olefin polymer (A-1) was obtained. . The resulting cyclic olefin polymer (A-1) had a polymerization conversion of 99.7%, a weight average molecular weight of 7,150, a number average molecular weight of 4,690, a molecular weight distribution of 1.52, and a hydrogenation rate of 99. 9%.

<< Synthesis Example 2 >>
<Preparation of cyclic olefin polymer (A-2)>
9-Hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . The amount of 0 ^2,7 ] dodec-4-ene used is changed from 60.0 parts to 65.0 parts to N- (2-ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3. -Except having changed the usage-amount of dicarboximide from 40.0 parts to 35.0 parts, respectively, it superposed | polymerized and hydrogenated similarly to the synthesis example 1, and produced the cyclic olefin polymer (A-2). A polymer solution containing was obtained. The polymerization conversion rate of the obtained cyclic olefin polymer (A-2) was 99.5%, the weight average molecular weight was 5,670, the number average molecular weight was 3,520, the molecular weight distribution was 1.61, and the hydrogenation rate was 99. 9%.

<< Synthesis Example 3 >>
<Preparation of Cyclic Olefin Polymer (A-3)>
Instead of 40.0 parts N- (2-ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-phenylbicyclo [2.2.1] hept- Synthesis Example 1 except that 40.0 parts of 5-ene-2,3-dicarboximide (NBPI) were used and the amount of 1,5-hexadiene was changed from 2.0 parts to 2.8 parts. In the same manner, polymerization and hydrogenation were performed to obtain a polymer solution containing the cyclic olefin polymer (A-3). The resulting cyclic olefin polymer (A-3) had a polymerization conversion rate of 99.8%, a weight average molecular weight of 5,098, a number average molecular weight of 3,227, a molecular weight distribution of 1.58, and a hydrogenation rate of 99. 9%.

<< Synthesis Example 4 >>
<Preparation of polyimide (A'-4)>
In a four-necked flask under a dry air stream, 9.61 parts of 4,4′-diaminodiphenyl ether, 17.3 parts of bis [4- (4-aminophenoxy) phenyl] sulfone, bis (3-aminopropyl) tetramethyl 1.24 parts of disiloxane and 102.5 parts of cyclopentanone were charged and dissolved at 40 ° C. Then, pyromellitic anhydride 6.54 parts, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride 9.67 parts, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride 12.41 parts and 30 parts of cyclopentanone were added and reacted at 50 ° C. for 3 hours. This solution was concentrated by a rotary evaporator to obtain a polymer solution containing polyimide (A′-4) having a solid concentration of 35%.

<< Synthesis Example 5 >>
<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 pipe, and subsequently, low boiling point components were distilled off at a temperature of 80 ° C. and normal pressure for 30 minutes, and then the temperature was 100 ° C. and the pressure was 0.3 KPa. 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) and unreacted silane. The content of the compound and low condensate was 7% or less (GPC area percentage).

<< Synthesis Example 6 >>
<Preparation of silane-modified epoxy resin (C-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 5 and 2.3 parts of dibutyltin laurate as a catalyst were added and subjected to a demethanol reaction at 80 ° C. for 5 hours. A silane-modified epoxy resin (C-1) solution was obtained. The obtained silane-modified epoxy resin has an active ingredient (after curing) of 50%, a weight in terms of silica / a weight (weight ratio) of bisphenol type epoxy resin of 0.51, and an epoxy equivalent of 1400 g / eq. there were. 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 7 >>
<Preparation of silane-modified phenol resin (C-2)>
In a reaction apparatus equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas introduction tube, 800 parts of a novolak type phenol resin (manufactured by Arakawa Chemical Industry Co., Ltd., trade name Tamanoru 759), and 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. By distilling off 80 parts of methanol, a silane-modified phenol resin (C-2) was obtained. .

<< Synthesis Example 8 >>
<Preparation of epoxy group-containing methoxysilane partial condensate>
1400 parts of glycidol and 9,140 parts of poly (methyltrimethoxysilane) obtained in Synthesis Example 6 were charged into a reactor equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas introduction tube, and stirred under a nitrogen stream. Then, the temperature was raised to 90 ° C., and 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 9 >>
<Preparation of silane-modified polyamic acid (C-3)>
After adding 112 parts of 4,4′-diaminodiphenyl ether and 1,170 parts of N-methylpyrrolidone to a 2 L three-necked flask equipped with a stirrer, a condenser, a thermometer, and a nitrogen gas inlet tube, mix well at room temperature. While cooling to 60 ° C. or lower, 118 parts of pyromellitic dianhydride was added and stirred for 30 minutes to synthesize polyamic acid. The obtained polyamic acid had a polyimide equivalent solid residue of 15%. 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 8, and 0.24 part of 2-methylimidazole as a catalyst. And reacted at 80 ° C. for 4 hours. And after reaction for 4 hours, it cooled to room temperature and obtained the silane modification | denaturation polyamic acid (C-3) of 12% of hardening residue.

<< Synthesis Example 10 >>
<Preparation 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. The mixture was heated to 90 ° C. with stirring in a nitrogen stream, and then 2.0 parts of dibutyltin dilaurate as a catalyst was added. 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 11 >>
<Preparation of silane-modified acrylic resin (C-4)>
A reactor equipped with a stirrer, a cooling pipe, a thermometer, and a gas introduction pipe was charged with 1,461 parts of diethylene glycol dimethyl ether, heated to 100 ° C. under a nitrogen stream, and then 417 parts of butyl methacrylate and 83.3 of hydroxyethyl acrylate. 25 parts of mixed monomer and ditertiary butyl peroxide were added dropwise over 1 hour, and further mixed monomer of 250 parts of methyl methacrylate and 83.3 parts of methacrylic acid and 10 parts of ditertiary butyl peroxide, respectively. The solution was dropped in 1 hour, and further 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 10 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 (C-4) having a cured residue of 38.3 wt% was obtained.

Example 1
40 parts (in terms of solid content) of the cyclic olefin polymer (A-1) obtained in Synthesis Example 1, 60 parts (in terms of solid content) of the cyclic olefin polymer (A-2) obtained in Synthesis Example 2, and unsaturated As the group-containing compound (B), 100 parts of 3,4-epoxycyclohexylmethyl methacrylate (trade name “Cyclomer M100”, manufactured by Daicel Chemical Industries, Ltd.) and also as the unsaturated group-containing compound (B), ethylene glycol dimethacrylate (Product name “NK Ester 1G”, manufactured by Shin-Nakamura Chemical Co., Ltd.) 33.3 parts, silane-modified organic-inorganic hybrid compound (C), 5 parts of silane-modified epoxy resin (C-1) obtained in Synthesis Example 6 As a radical-generating photopolymerization initiator (D), 1,7-bis (9-acridyl) -heptane (trade name “N1717”, manufactured by ADEKA) 13.3 parts In addition, 0.05 part of a silicone-based surfactant (trade name “KP-341”, manufactured by Shin-Etsu Chemical Co., Ltd.) and diethylene glycol ethyl methyl ether as an organic solvent so that the solid part concentration becomes 40% After adding, stirring and dissolving, the solution was filtered through a polytetrafluoroethylene filter having a pore size of 0.45 μm to prepare a negative photosensitive resin composition.

  And according to the said method, each evaluation of the image development residual film, heat-resistant transparency, heat resistance, and outgas was performed using the obtained negative photosensitive resin composition. The results are shown in Table 1.

Example 2
As the unsaturated group-containing compound (B), trimethylolpropane triacrylate (trade name “NKATMPT”, manufactured by Shin-Nakamura Chemical Co., Ltd.) 33.3 instead of 3,4-epoxycyclohexylmethyl methacrylate and ethylene glycol dimethacrylate A negative photosensitive resin composition was prepared and evaluated in the same manner as in Example 1, except that the parts were used. The results are shown in Table 1.

Example 3
As the unsaturated group-containing compound (B), 3,4-epoxycyclohexylmethyl methacrylate is not used, and the blending amount of ethylene glycol dimethacrylate is changed from 33.3 parts to 75.0 parts. Example 1 except that 5 parts of the silane-modified phenol resin (C-2) obtained in Synthesis Example 7 was used as the organic-inorganic hybrid compound (C) instead of the silane-modified epoxy resin (C-1). Similarly, a negative photosensitive resin composition was prepared and evaluated in the same manner. The results are shown in Table 1.

Example 4
Other than using 100 parts (in terms of solid content) of the cyclic olefin polymer (A-3) obtained in Synthesis Example 3 instead of the cyclic olefin polymer (A-1) and the cyclic olefin polymer (A-2). In the same manner as in Example 1, a negative photosensitive resin composition was prepared and evaluated in the same manner. The results are shown in Table 1.

Example 5
Except having changed the compounding quantity of 1,7-bis (9-acridyl) -heptane as a radical generation type photoinitiator (D) from 13.3 parts to 6.7 parts, it is the same as that of Example 4. A negative photosensitive resin composition was prepared and evaluated in the same manner. The results are shown in Table 1.

Example 6
The amount of 1,7-bis (9-acridyl) -heptane as the radical-generating photopolymerization initiator (D) was changed from 13.3 parts to 3.3 parts, and a radical-generating photopolymerization initiator ( D) as ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime) (manufactured by BASF, OXE-02) 8 A negative photosensitive resin composition was prepared and evaluated in the same manner as in Example 4 except that 3 parts was further used. The results are shown in Table 1.

Example 7
Example except that 5 parts of the silane-modified phenol resin (C-2) obtained in Synthesis Example 7 was used as the silane-modified organic-inorganic hybrid compound (C) instead of the silane-modified epoxy resin (C-1). In the same manner as in Example 4, a negative photosensitive resin composition was prepared and evaluated in the same manner. The results are shown in Table 1.

Example 8
Example except that 5 parts of the silane-modified polyamic acid (C-3) obtained in Synthesis Example 9 was used as the silane-modified organic-inorganic hybrid compound (C) instead of the silane-modified epoxy resin (C-1). In the same manner as in Example 4, a negative photosensitive resin composition was prepared and evaluated in the same manner. The results are shown in Table 1.

Example 9
Example except that 5 parts of the silane-modified acrylic resin (C-4) obtained in Synthesis Example 11 were used as the silane-modified organic-inorganic hybrid compound (C) instead of the silane-modified epoxy resin (C-1). In the same manner as in Example 4, a negative photosensitive resin composition was prepared and evaluated in the same manner. The results are shown in Table 1.

Example 10
Implemented except that 3,4-epoxycyclohexylmethyl methacrylate was not used as the unsaturated group-containing compound (B), and the blending amount of ethylene glycol dimethacrylate was changed from 33.3 parts to 100.0 parts. In the same manner as in Example 4, a negative photosensitive resin composition was prepared and evaluated in the same manner. The results are shown in Table 1.

Example 11
The amount of 1,7-bis (9-acridyl) -heptane as radical generating photopolymerization initiator (D) was changed from 13.3 parts to 6.7 parts, and radical generating photopolymerization initiator ( D) as 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (manufactured by BASF, Irgacure 379EG) 8.3 parts A negative photosensitive resin composition was prepared and evaluated in the same manner as in Example 4 except that was further used. The results are shown in Table 1.

Example 12
As an unsaturated group-containing compound (B), 1,6-hexanediol diacrylate (trade name “NKAHDN”) was used instead of ethylene glycol dimethacrylate without changing the blending amount of 3,4-epoxycyclohexylmethyl methacrylate. A negative photosensitive resin composition was prepared and evaluated in the same manner as in Example 4 except that 33.3 parts of Shin Nakamura Chemical Co., Ltd.) were used. The results are shown in Table 1.

Example 13
As an unsaturated group-containing compound (B), without changing the blending amount of 3,4-epoxycyclohexylmethyl methacrylate, instead of ethylene glycol dimethacrylate, trimethylolpropane triacrylate (trade name “NKATMPT”, Shin-Nakamura A negative photosensitive resin composition was prepared in the same manner as in Example 4 except that 33.3 parts by Chemical Co., Ltd. were used, and evaluated in the same manner. The results are shown in Table 1.

<< Comparative Example 1 >>
A negative photosensitive resin composition was prepared in the same manner as in Example 4 except that 3,4-epoxycyclohexylmethyl methacrylate and ethylene glycol dimethacrylate as the unsaturated group-containing compound (B) were not used. The same evaluation was performed. The results are shown in Table 1.

<< Comparative Example 2 >>
A negative photosensitive resin composition was prepared in the same manner as in Example 4 except that 1,7-bis (9-acridyl) -heptane was not used as the radical-generating photopolymerization initiator (D). The same evaluation was performed. The results are shown in Table 1.

<< Comparative Example 3 >>
Instead of 1,7-bis (9-acridyl) -heptane as the radical-generating photopolymerization initiator (D), 13.3 parts of a cation-generating photopolymerization initiator (ADEKA OPTMER SP300, manufactured by ADEKA) A negative photosensitive resin composition was prepared and evaluated in the same manner as in Example 4 except that it was used. The results are shown in Table 1.

<< Comparative Example 4 >>
Negative type in the same manner as in Example 4 except that 100 parts of polyimide (A′-4) obtained in Synthesis Example 4 (in terms of solid content) was used instead of the cyclic olefin polymer (A-3). A photosensitive resin composition was prepared and evaluated in the same manner. The results are shown in Table 1.

  As shown in Table 1, a cyclic olefin polymer having a protic polar group (A), an unsaturated group-containing compound (B), a silane-modified organic-inorganic hybrid compound (C), and a radical-generating photopolymerization initiator (D The negative photosensitive resin compositions of Examples 1 to 13 that contain) have excellent pattern formability during development (high development residual film ratio and suppression of development residue), and excellent It had heat transparency and heat resistance, and outgas generation was effectively prevented. In particular, according to the negative photosensitive resin compositions of Examples 1 to 13, even if the process of irradiating active radiation to the entire surface of the obtained resin film was not performed in order to deactivate the photopolymerization initiator. The resulting resin film can be finely patterned without development residue, has a high development residual film ratio, excellent heat-resistant transparency and heat resistance, and can effectively prevent outgassing. Met.

On the other hand, Comparative Example 1 in which the unsaturated group-containing compound (B) was not used, Comparative Example 2 in which the radical-generating photopolymerization initiator (D) was not used, and a radical-generating photopolymerization initiator (D) In Comparative Example 3 using a cation-generating photopolymerization initiator instead, the residual film ratio is extremely low, so that a resin film is obtained that is extremely inferior in film formability and can be evaluated in various ways. I couldn't.
Moreover, in the comparative example 4 which uses a polyimide instead of the cyclic olefin polymer (A) which has a protic polar group, the resin film obtained was inferior to heat-resistant transparency and low outgas property.

Claims (5)

Cyclic olefin polymer having a protic polar groups (A), an unsaturated group-containing compound (B), the silane modified organic-inorganic hybrid compound (C), and Ri Na contain radical-forming photopolymerization initiator (D) ,
The silane-modified organic-inorganic hybrid compound (C) has an organic part and an inorganic part in a state in which they are chemically bonded to each other, and contains a silicon atom in the inorganic part, the organic portion is der polymeric material having an inorganic portion and chemically bondable functional group Ru negative photosensitive resin composition.   The negative photosensitive resin composition according to claim 1, wherein the unsaturated group-containing compound (B) is a (meth) acrylic ester.   The radical generating photopolymerization initiator (D) is a compound having sensitivity to light having a wavelength of 400 nm or less, and the content of the radical generating photopolymerization initiator (D) has the protic polar group. The negative photosensitive resin composition of Claim 1 or 2 which is 1-30 weight part with respect to 100 weight part of cyclic olefin polymers (A).   The resin film obtained using the negative photosensitive resin composition in any one of Claims 1-3.   An electronic component comprising the resin film according to claim 4.