JP2013130816A - Resin composition for permanent film and electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for a permanent film, which is used for forming a permanent film provided in various electronic components, capable of giving a permanent film which is high in sensitivity to radiation, can be developed with an aqueous alkali solution, is excellent in pattern forming properties by development and is excellent in flatness and surface conditions.SOLUTION: There is provided a resin composition for a permanent film which comprises: a binder resin (A); a radiation sensitive compound (B); a phenol compound (C); a solvent (D) and a crosslinking agent (E) and in which the ratio of the radiation sensitive compound (B) to the phenol compound (C) (the radiation sensitive compound (B)/the phenol compound (C)) is 1 to 10 in weight ratio, in which the resin composition for a permanent film for forming a permanent film is obtained by forming a resin film composed of the resin composition and removing a part of the resin film and then leaving the remainder as a patterned film.

Description

  The present invention relates to a permanent film resin composition used for forming a permanent film provided in various electronic parts, and a permanent film and an electronic part obtained by using the permanent film resin composition, and sensitivity to radiation. Resin composition for permanent film capable of providing a permanent film having a high thickness, excellent pattern formation by development, and excellent flatness and surface condition, and a permanent film obtained using this permanent film resin composition The present invention relates to a film and an electronic component.

  Radiation-sensitive resins whose solubility in alkaline solutions and the like change when irradiated with radiation such as ultraviolet rays and electron beams are used in various applications. In recent years, in addition to the usual photoresist applications used in photolithography. Then, it is also used as a permanent film that remains in a patterned state in an electronic component such as a semiconductor element as a final product.

  When such a radiation sensitive resin is used for a normal photoresist application, the patterned resin film obtained using the radiation sensitive resin is peeled and removed after the etching process. On the other hand, when the radiation-sensitive resin is used for a permanent film, the patterned resin film obtained using the radiation-sensitive resin is not peeled and removed even after the etching process, and becomes a final product. It will be used as a functionally patterned resin film in electronic components such as semiconductor elements. Such permanent films are used, for example, as protective films, insulating films, passivation films, sealing materials, spacers, etc. for semiconductor elements.

  Specific examples include various display elements such as organic EL elements and liquid crystal display elements, integrated circuit elements, solid-state image sensors, color filters, protective films for preventing deterioration and damage to electronic components such as color filters and black matrices. A flattening film for flattening the element surface and wiring, an electric insulating film for maintaining electric insulation, and the like are provided, and these are usually formed of the above-described permanent film. Further, elements such as thin film transistor type liquid crystal display elements and integrated circuit elements are provided with a resin film as an interlayer insulating film in order to insulate between wirings arranged in layers. Usually, it is formed of the permanent film described above.

  Furthermore, the organic EL element generally has a configuration including an anode / hole injection layer / hole transport layer / organic light emission layer / electron transport layer / electron injection layer / cathode as the light emitter. Around the light-emitting body portion, a partition wall (also referred to as a pixel separation film, a pixel definition film, or an element separation film) for electrical insulation from other elements and wiring, between an active element such as a transistor and an anode, A planarizing film is provided, and these are usually formed of the permanent film described above.

  On the other hand, in addition to the properties as a photoresist such as heat resistance and developability, such a permanent film has excellent electrical and mechanical properties, durability to semiconductor manufacturing processes, etc. Therefore, depending on the application, characteristics as product constituent materials such as transparency and low outgassing are also required.

  Conventionally, thermosetting resin materials such as epoxy resins have been widely used as a resin material for forming such a permanent film. In recent years, with the increasing density of wiring and devices, these resin materials are also required to be developed with new resin materials that have excellent heat resistance, mechanical properties, etc. in addition to electrical properties such as low dielectric properties. .

  In order to meet these demands, for example, Patent Document 1 discloses an aqueous alkali-soluble polymer having an alicyclic structure and a chain structure in the main chain at the same time, an aryl group having an acidic group in the side chain, and an imide group. A positive photosensitive resin composition comprising (A), a compound (B) that generates an acid by light, and a solvent (C) is disclosed. However, the resin film obtained using the resin composition described in Patent Document 1 is not necessarily sufficient in terms of pattern formation by development, particularly in terms of film surface state and flatness and sensitivity at the time of development. It was desired.

JP 2007-334018 A

  The present invention has been made to solve the above-described problems, and is a permanent film resin composition used for forming a permanent film provided in various electronic components. A permanent film resin composition that can be developed, has excellent pattern formability by development, and can provide a permanent film with excellent flatness and surface condition, and such a permanent film resin composition is used. An object of the present invention is to provide a permanent film and an electronic component obtained in this way.

  As a result of diligent research to achieve the above object, the present inventors have blended the binder resin with a radiation sensitive compound, a phenol compound, a solvent, and a crosslinking agent, and the radiation sensitive compound with a blending ratio of the phenol compound. The inventors have found that the above object can be achieved by controlling to a predetermined range, and have completed the present invention.

  That is, according to the present invention, it comprises a binder resin (A), a radiation sensitive compound (B), a phenol compound (C), a solvent (D), and a crosslinking agent (E), and the radiation sensitive compound (B). The resin composition for a permanent film in which the ratio of the phenolic compound (C) is “radiation sensitive compound (B) / phenolic compound (C)” = 1 to 10 in terms of weight ratio, and consists of the resin composition There is provided a permanent film resin composition for forming a permanent film obtained by forming a resin film, removing a part of the resin film and leaving the remainder as a patterned film.

Preferably, the solvent (D) contains a high-boiling solvent having a boiling point of 180 ° C. to 240 ° C. under normal pressure.
Preferably, the binder resin (A) is a resin having an acid value of 50 to 70 mgKOH / g and containing a protic polar group.

Further, according to the present invention, there is provided a permanent film obtained by forming a resin film comprising any one of the above permanent film resin compositions, removing a part of the resin film, and then causing a crosslinking reaction. The
Furthermore, according to this invention, an electronic component provided with the said permanent film is provided.

  According to the present invention, a permanent film resin composition capable of providing a permanent film having high sensitivity to radiation, excellent pattern formation by development, and excellent flatness and surface condition, and such a permanent film. A permanent film and an electronic component obtained using the resin composition can be provided.

  The resin composition for a permanent film of the present invention comprises a binder resin (A), a radiation sensitive compound (B), a phenol compound (C), a solvent (D), and a crosslinking agent (E). The ratio of (B) to phenolic compound (C) is “radiation sensitive compound (B) / phenolic compound (C)” = 1 to 10 in weight ratio, and is a composition for forming a permanent film.

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

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

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

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

Specific examples of the cyclic olefin monomer (a) having a protic polar group (hereinafter, appropriately referred to as “monomer (a)”) include 2-hydroxycarbonylbicyclo [2.2.1] hept- 5-ene, 2-methyl-2-hydroxycarbonylbicyclo [2.2.1] hept-5-ene, 2-carboxymethyl-2-hydroxycarbonylbicyclo [2.2.1] hept-5-ene, 2 -Hydroxycarbonyl-2-methoxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-ethoxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxy Carbonyl-2-propoxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-butoxycarbonyl Tyrbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-pentyloxycarbonylmethyl bicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-hexyloxycarbonylmethyl Bicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-cyclohexyloxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-phenoxycarbonylmethylbicyclo [2.2.1] Hept-5-ene, 2-hydroxycarbonyl-2-naphthyloxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-biphenyloxycarbonylmethylbicyclo [2.2.1] Hept-5-ene, 2-hydroxyca Bonyl-2-benzyloxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-hydroxyethoxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2,3 -Dihydroxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3-methoxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3-ethoxycarbonylbicyclo [2.2.1] Hept-5-ene, 2-hydroxycarbonyl-3-propoxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3-butoxycarbonylbicyclo [2.2 .1] Hept-5-ene, 2-hydroxycarbonyl-3-pentyloxycarbonylbi Cyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3-hexyloxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3-cyclohexyloxycarbonylbicyclo [ 2.2.1] Hept-5-ene, 2-hydroxycarbonyl-3-phenoxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3-naphthyloxycarbonylbicyclo [2.2 .1] Hept-5-ene, 2-hydroxycarbonyl-3-biphenyloxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3-benzyloxycarbonylbicyclo [2.2.1]. ] Hept-5-ene, 2-hydroxycarbonyl-3-hydroxyethoxycarbonylbi Chlo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3-hydroxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 3-methyl-2-hydroxycarbonylbicyclo [2. 2.1] hept-5-ene, 3-hydroxymethyl-2-hydroxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyltricyclo [5.2.1.0 ^2,6 ] Deca-3,8-diene, 4-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-methyl-4-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4,5-dihydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-carboxymethyl-4-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, N- (hydroxycarbonylmethyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (hydroxycarbonylethyl) bicyclo [2 2.1] hept-5-ene-2,3-dicarboximide, N- (hydroxycarbonylpentyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (Dihydroxycarbonylethyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (dihydroxycarbonylpropyl) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (hydroxycarbonylphenethyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2- ( -Hydroxyphenyl) -1- (hydroxycarbonyl) ethyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (hydroxycarbonylphenyl) bicyclo [2.2.1] Carboxy group-containing cyclic olefins such as hept-5-ene-2,3-dicarboximide; 2- (4-hydroxyphenyl) bicyclo [2.2.1] hept-5-ene, 2-methyl-2- ( 4-hydroxyphenyl) bicyclo [2.2.1] hept-5-ene, 4- (4-hydroxyphenyl) tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-methyl-4- (4-hydroxyphenyl) tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 2-hydroxybicyclo [2.2.1] hept-5-ene, 2-hydroxymethylbicyclo [2.2.1] hept-5-ene, 2-hydroxyethyl Bicyclo [2.2.1] hept-5-ene, 2-methyl-2-hydroxymethylbicyclo [2.2.1] hept-5-ene, 2,3-dihydroxymethylbicyclo [2.2.1] Hept-5-ene, 2- (hydroxyethoxycarbonyl) bicyclo [2.2.1] hept-5-ene, 2-methyl-2- (hydroxyethoxycarbonyl) bicyclo [2.2.1] hept-5 Ene, 2- (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) bicyclo [2.2.1] hept-5-ene, 2- (2-hydroxy-2-trifluoro Mechi 3,3,3-trifluoropropyl) bicyclo [2.2.1] hept-5-ene, 3-hydroxy-tricyclo [5.2.1.0 ^{2, 6]} deca-4,8-diene, 3-hydroxymethyltricyclo [5.2.1.0 ^2,6 ] deca-4,8-diene, 4-hydroxytetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-hydroxymethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4,5-dihydroxymethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4- (hydroxyethoxycarbonyl) tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-methyl-4- (hydroxyethoxycarbonyl) tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, N- (hydroxyethyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (hydroxyphenyl) bicyclo [2.2 .1] Hydroxyl-containing cyclic olefins such as hept-5-ene-2,3-dicarboximide and the like. Among these, a carboxy group-containing cyclic olefin is preferable from the viewpoint that adhesion of the resulting permanent film is high, 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 (A1) is preferably 10 to 90 mol%, more preferably 40 to 70 mol%, further based on the total monomer units. Preferably it is 50-60 mol%. By setting the content ratio of the unit of the monomer (a) within the above range, radiation sensitivity can be made sufficient, and furthermore, generation of dissolved residues during development can be effectively suppressed. .

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

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

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

（上記式（２）中、Ｒ^２は炭素数１〜３の２価のアルキレン基、Ｒ^３は、炭素数１〜１０の１価のアルキル基、又は、炭素数１〜１０の１価のハロゲン化アルキル基を表す。） Examples of the cyclic olefin having an N-substituted imide group include a monomer represented by the following 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. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, n -Pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n -Linear alkyl groups such as pentadecyl group and n-hexadecyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group , Norbornyl group, bornyl group, isobornyl group, decahydronaphthyl group, tricyclodecanyl group, adamantyl group, etc. Alkyl group; 2-propyl group, 2-butyl group, 2-methyl-1-propyl group, 2-methyl-2-propyl group, 1-methylbutyl group, 2-methylbutyl group, 1-methylpentyl group, 1-ethylbutyl Groups, branched alkyl groups such as 2-methylhexyl group, 2-ethylhexyl group, 4-methylheptyl group, 1-methylnonyl group, 1-methyltridecyl group, 1-methyltetradecyl group, and the like. Specific examples of the aryl group include a benzyl group. Among these, since it is excellent in heat resistance and solubility in a polar solvent, a C6-C14 alkyl group and an aryl group are preferable, and a C6-C10 alkyl group and an aryl group are more preferable. When the carbon number is 4 or less, the solubility in a polar solvent is poor, when the carbon number is 17 or more, the heat resistance is poor, and when the resin film is patterned, the pattern is lost by melting with heat. There is a problem.

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

On the other hand, in the above formula (2), R ² is a divalent alkylene group having 1 to 3 carbon atoms. Examples of the divalent alkylene group having 1 to 3 carbon atoms include a methylene group, an ethylene group, a propylene group, and an iso 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- And hydroxycarbonylbicyclo [2.2.1] hept-5-ene anhydride.

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 (A1) is preferably 10 to 90 mol%, more preferably 30 to 60, based on all monomer units. It is mol%, More preferably, it is 40-50 mol%. By making the content ratio of the copolymerizable monomer (b) unit in the above range, the radiation sensitivity is improved while the solubility of the cyclic olefin polymer (A1) in the polar solvent is sufficient. Furthermore, the generation of dissolution residues during development can be effectively suppressed.

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

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

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

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

  Since the cyclic olefin polymer (A1) used in the present invention has a protic polar group, various properties of the permanent film obtained by performing a curing reaction after the etching step by the action of the protic polar group ( For example, electrical characteristics and mechanical characteristics) can be improved. In particular, in the present invention, it has a hydroxyl group, a carboxy group (hydroxycarbonyl group), or a sulfonic acid group as a protic polar group from the viewpoint that the properties of the permanent film after the curing reaction can be made particularly good. The cyclic olefin polymer (A1) is preferably used in combination with an epoxy-based or melamine-based crosslinking agent (E).

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

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

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

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

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

  As the acrylic resin (A2) used in the present invention, various characteristics (for example, electrical characteristics and mechanical characteristics) of the permanent film obtained by performing a curing reaction after the etching step can be improved. In addition, a polymer having an carboxylic acid having an acrylic group or a carboxylic acid anhydride having an acrylic group as an essential component is preferable, and in particular, the properties of the permanent film after the curing reaction can be particularly improved. Further, as an acrylic resin (A2), a polymer having (meth) acrylic acid, maleic anhydride, glycidyl (meth) acrylate, methacrylic acid-6,7-epoxyheptyl as an essential component is an epoxy-based or melamine-based polymer. The crosslinking agent (E) is preferably used in combination.

The polyimide (A3) used by this invention can be obtained by heat-processing the polyimide precursor obtained by making tetracarboxylic dianhydride and diamine react. Examples of the precursor for obtaining polyimide include polyamic acid, polyamic acid ester, polyisoimide, and polyamic acid sulfonamide.
Specific examples of the tetracarboxylic dianhydride that can be used as a raw material for obtaining the polyimide (A3) include pyromellitic dianhydride and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride. 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic Acid dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 2,2-bis [3-[(3,4-dicarboxybenzoyl) amino] -4-hydroxyphenyl] hexafluoropropane dianhydride, 1,1-bis ( 3,4-di Ruboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-di Carboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid Dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride Products, aromatic tetracarboxylic dianhydrides such as 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride Examples thereof include water, aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-cyclopentanetetracarboxylic dianhydride. These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

  Specific examples of the diamine that can be used as a raw material for obtaining the polyimide (A3) include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'- Diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 1,4-bis (4-aminophenoxy) Benzene, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4- Aminophenoxy) biphenyl, {4- (4-aminophenoxy) phenyl} ether, 1,4-bis (4-aminophenoxy) benzene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-diethyl-4 , 4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2 ', 3,3'-tetramethyl- 4,4′-diaminobiphenyl, 3,3 ′, 4,4′-tetramethyl-4,4′-diaminobiphenyl, 2,2′-di (trifluoromethyl) -4,4′-diaminobiphenyl; or Compounds in which the aromatic ring of these compounds is substituted with an alkyl group or a halogen atom; aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, bis [(3-aminopropyl) di Tylsilyl] ether; 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,6-diamino-1,3-benzenedicarboxylic acid, 2,5-diamino-1, 4-benzenedicarboxylic acid, bis (4-amino-3-carboxyphenyl) ether, bis (4-amino-3,5-dicarboxyphenyl) ether, bis (4-amino-3-carboxyphenyl) sulfone, bis ( 4-amino-3,5-dicarboxyphenyl) sulfone, 4,4′-diamino-3,3′-dicarboxybiphenyl, 4,4′-diamino-3,3′-dicarboxy-5,5′- Dimethylbiphenyl, 4,4′-diamino-3,3′-dicarboxy-5,5′-dimethoxybiphenyl, 1,4-bis (4-amino-3-carboxypheno) Xy) benzene, 1,3-bis (4-amino-3-carboxyphenoxy) benzene, bis [4- (4-amino-3-carboxyphenoxy) phenyl] sulfone, bis [4- (4-amino-3-) Diamine compounds having a carboxyl group such as carboxyphenoxy) phenyl] propane, 2,2-bis [4- (4-amino-3-carboxyphenoxy) phenyl] hexafluoropropane; 2,4-diaminophenol, 3,5- Diaminophenol, 2,5-diaminophenol, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, bis (3-amino-4-hydroxyphenyl) ether, bis (4-amino-3-hydroxyphenyl) ether, Bis (4-amino-3,5-dihydroxyphenyl) ether, bis ( -Amino-4-hydroxyphenyl) methane, bis (4-amino-3-hydroxyphenyl) methane, bis (4-amino-3,5-dihydroxyphenyl) methane, bis (3-amino-4-hydroxyphenyl) sulfone Bis (4-amino-3-hydroxyphenyl) sulfone, bis (4-amino-3,5-dihydroxyphenyl) sulfone, bis (2-hydroxy-5-aminoanilide) isophthalate, 2- (4-aminobenzoyl) Amino) -4-aminophenol, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 2,2- Bis (4-amino-3,5-dihydroxyphenyl) hexafluoropropane 4,4′-diamino-3,3′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxy-5,5′-dimethylbiphenyl, 4,4′-diamino-3,3′-dihydroxy -5,5'-dimethoxybiphenyl, 1,4-bis (3-amino-4-hydroxyphenoxy) benzene, 1,3-bis (3-amino-4-hydroxyphenoxy) benzene, 1,4-bis (4 -Amino-3-hydroxyphenoxy) benzene, 1,3-bis (4-amino-3-hydroxyphenoxy) benzene, bis [4- (3-amino-4-hydroxyphenoxy) phenyl] sulfone, bis [4- ( 3-amino-4-hydroxyphenoxy) phenyl] propane, 2,2-bis [4- (3-amino-4-hydroxyphenoxy) phenyl] hexaph Fluoropropane, 2,2-bis [N- (2-hydroxy-5-aminophenyl) benzamido-4-yl] hexafluoropropane, 2,2-bis [3-[(3-aminobenzoyl) amino] -4- Diamine compounds having a phenolic hydroxy group such as hydroxyphenyl] hexafluoropropane, 2,2-bis [3-[(4-aminobenzoyl) amino] -4-hydroxyphenyl] hexafluoropropane; 1,3-diamino- 4-mercaptobenzene, 1,3-diamino-5-mercaptobenzene, 1,4-diamino-2-mercaptobenzene, bis (4-amino-3-mercaptophenyl) ether, 2,2-bis (3-amino- 4-Mercaptophenyl) hexafluoropropane and other diamine compounds having a thiophenol group 1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-5-sulfonic acid, 1,4-diaminobenzene-2-sulfonic acid, bis (4-aminobenzene-3-sulfonic acid) Ether, 4,4′-diaminobiphenyl) 3,3′-disulfonic acid, diamine compounds having a sulfonic acid group such as 4,4′-diamino-3,3′-dimethylbiphenyl-6,6′-disulfonic acid; Etc. These diamines can be used alone or in combination of two or more.

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

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

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

  As the polyimide (A3) used in the present invention, various properties (for example, electrical properties and mechanical properties) of the permanent film obtained by performing a curing reaction after the etching step can be made particularly good. A polyamic acid obtained by reacting pyromellitic dianhydride with a diamine compound having a carboxyl group is used as a precursor, and a heat-treated product is combined with an epoxy-based or melamine-based crosslinking agent (E). It is preferable to use it.

Although it does not specifically limit as polysiloxane (A4) used by this invention, Preferably the polymer obtained by mixing and making 1 type (s) or 2 or more types of the organosilane represented by following formula (3) mention is mentioned. It is done.
_{^{(R 4) m -Si- (OR}} 5) 4-m (3)

In said formula (3), R < ⁴ > is a hydrogen atom, a C1-C10 alkyl group, a C2-C10 alkenyl group, or a C6-C15 aryl group, and several R < ⁴ > is the same, respectively. Or different. These alkyl groups, alkenyl groups, and aryl groups may all have a substituent or may be an unsubstituted form having no substituent, and are selected according to the characteristics of the composition. it can. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, n-decyl group, trifluoromethyl group, 2,2 , 2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 3-glycidoxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3-aminopropyl group, 3-mercaptopropyl Group, 3-isocyanatopropyl group. Specific examples of the alkenyl group include a vinyl group, a 3-acryloxypropyl group, and a 3-methacryloxypropyl group. Specific examples of the aryl group include phenyl group, tolyl group, p-hydroxyphenyl group, 1- (p-hydroxyphenyl) ethyl group, 2- (p-hydroxyphenyl) ethyl group, 4-hydroxy-5- (p -Hydroxyphenylcarbonyloxy) pentyl group, naphthyl group.

In the above formula (3), R ⁵ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and a plurality of R ⁷ are Each may be the same or different. In addition, both of these alkyl groups and acyl groups may have a substituent or may be an unsubstituted form having no substituent, and can be selected according to the characteristics of the composition. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Specific examples of the acyl group include an acetyl group. Specific examples of the aryl group include a phenyl group.

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

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

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

As polysiloxane (A4) used in the present invention, various characteristics (for example, electrical characteristics and mechanical characteristics) of a permanent film obtained by performing a curing reaction after the etching step can be made particularly good. More preferably, R ⁶ and R ⁷ are each a methyl group, an ethyl group or a vinyl group in combination with an epoxy-based or melamine-based crosslinking agent (E).

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

  Further, the binder resin (A) preferably has an acid value of 50 to 70 mgKOH / g, more preferably 55 to 65 mgKOH / g. Here, an acid value means the content rate of the total amount of the acidic component in binder resin (A). If the acid value is too low, it is difficult to dissolve in a developer composed of an aqueous alkali solution, and pattern formation by development may be difficult. On the other hand, if the acid value is too high, it is too soluble in a developer composed of an alkaline aqueous solution, so that the pattern after development becomes too thin and it may be difficult to form a normal pattern. Further, the pattern may be dissolved or peeled off by the developer without distinction between the exposed part and the unexposed part.

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

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

  As the quinonediazide compound, for example, an ester compound of a quinonediazidesulfonic acid halide and a compound having a phenolic hydroxyl group can be used. Specific examples of the quinonediazidesulfonic acid halide include 1,2-naphthoquinonediazide-5-sulfonic acid chloride (also known as 6-diazo-5,6-dihydro-5-oxo-naphthalene-1-sulfonic acid chloride), 1, Examples include 2-naphthoquinonediazide-4-sulfonic acid chloride and 1,2-benzoquinonediazide-5-sulfonic acid chloride. Typical examples of the compound having a phenolic hydroxyl group include 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 ′-[1- [4- [1. -[4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and the like. Other compounds having a phenolic hydroxyl group include 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2-bis (4-hydroxyphenyl) propane, tris (4- Hydroxyphenyl) methane, 1,1,1-tris (4-hydroxy-3-methylphenyl) ethane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, novolac resin oligomer, phenolic hydroxyl group Examples thereof include oligomers obtained by copolymerizing one or more compounds and dicyclopentadiene.

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

  The content of the radiation sensitive compound (B) in the resin composition for a permanent film of the present invention is preferably 20 to 100 parts by weight, more preferably 25 to 70 parts per 100 parts by weight of the binder resin (A). Part by weight, more preferably 30 to 50 parts by weight. If the content of the radiation sensitive compound (B) is within this range, the radiation sensitivity of the resin film made of the permanent film resin composition can be increased, and thus, when the resin film is patterned, radiation irradiation is performed. The difference in solubility (solubility contrast) in the developer between the part (exposed part) and the non-radiated part (unexposed part) can be increased, and patterning by development can be facilitated.

(Phenol compound (C))
The phenol compound (C) used in the present invention can be easily dissolved in an alkaline aqueous solution such as tetramethylammonium hydroxide (TMAH) generally used as a developer for a photoresist, and the permanent film of the present invention. It is a compound that has the effect of increasing the dissolving power of the exposed portion in the developer when a resin film is formed using the resin composition and exposed to radiation. Therefore, in the present invention, by adding the phenol compound (C) to the resin composition for permanent film of the present invention, the difference in solubility (solubility contrast) between the exposed portion and the unexposed portion due to radiation irradiation is efficiently obtained. Can be made larger.

  In the present invention, by including the phenol compound (C), by increasing the solubility difference between the exposed portion and the unexposed portion, the exposed portion is easily dissolved in the developer, while the unexposed portion. Since it becomes difficult to dissolve in a developing solution, the patterning property by exposure and development can be improved, and the accuracy of the resulting pattern can be improved.

  In particular, in the present invention, by containing the phenol compound (C), the acid generated in the exposed portion by exposure by irradiation for pattern formation is deacetalized (de) talized with the phenol compound (C) during development. By acting on the (deprotection) reaction, the dissolving power of the exposed portion in the developer increases. On the other hand, since no acid is generated in the non-exposed area, an increase in the dissolving power due to the phenol compound (C) does not appear. Therefore, in the present invention, as a result of these, the exposed area and the unexposed area And the solubility difference becomes large. In addition, since the phenol compound (C) is contained, the dissolution rate in the developer can be increased by about 1.1 to 2 times compared to the case where the phenol compound (C) is not used. It is also possible to shorten the time required for the process. In addition, the time required for the development process can be shortened, so that productivity can be improved and the contact time with the developer in the unexposed area can be shortened. Improvement is possible.

  The phenol compound (C) used in the present invention is not particularly limited as long as it is a compound containing a phenol group in the molecule. For example, 4-hydroxy-γ- (4-hydroxyphenyl) -γ-methylbenzene Examples include butanoic acid, 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, polyvinylphenol, and phenol resin. In addition, examples of the phenol resin include those obtained by dehydration condensation of phenol and formaldehyde using an acidic catalyst, and the weight average molecular weight (Mw) is preferably 1000 or less.

  The content of the phenol compound (C) is in the range of 1 to 10 in terms of the weight ratio of “radiation sensitive compound (B) / phenol compound (C)” with respect to the content of the radiation sensitive compound (B). The amount is preferably 1.5 to 9 and more preferably 2 to 8. In the present invention, the radiation sensitive compound (B) and the phenolic compound (C) described above are blended into the resin composition, and by setting these ratios within the above ranges, the dissolution rate and the dissolution amount during development, etc. Thus, the sensitivity to radiation is high, the development with an alkaline aqueous solution is possible, and the pattern forming property by development can be excellent. The flatness is high and the surface state can be improved. If the weight ratio of “radiation sensitive compound (B) / phenolic compound (C)” is less than 1, that is, if the content of phenolic compound (C) is too small, The effect of increasing the dissolving power becomes insufficient, and a development residue is generated. On the other hand, if the weight ratio of “radiation sensitive compound (B) / phenolic compound (C)” exceeds 10, that is, if the content of the phenolic compound (C) is too large, it will be excessively dissolved during development and before development. The ratio of the thickness of the developed resin film to the resin film, that is, the remaining film ratio is deteriorated. Also, the pattern shape after exposure and development may be inferior in rectangularity, or cracks, wrinkles, surface cracks, etc. may occur after exposure, development, drying after development, post-baking, etc. .

(Solvent (D))
The solvent (D) used in the present invention is not particularly limited, and is known as a resin composition solvent, for example, acetone, methyl ethyl ketone, cyclopentanone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone. , 4-heptanone, 2-octanone, 3-octanone, 4-octanone and other linear ketones; n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, cyclohexanol and other alcohols; ethylene glycol dimethyl ether, ethylene glycol Ethers such as 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 Esters such as ethyl propionate, methyl butyrate, ethyl butyrate, methyl lactate, and 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 glycols such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl Diethylene glycols such as ether; 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 A polar solvent such as dimethylacetamide, dimethylformamide, N-methylacetamide, and the like. These solvents (D) may be used alone or in combination of two or more.

  The content of the solvent is preferably 10 to 10,000 parts by weight, more preferably 50 to 5,000 parts by weight, and further preferably 100 to 1,000 parts by weight with respect to 100 parts by weight of the binder resin (A). It is a range. The solvent (D) is usually removed after the resin film is formed.

  Moreover, as an organic solvent (D) used for this invention, it was mentioned above from a viewpoint that each structural component (the above-mentioned and below-mentioned) in a resin composition for permanent films is easy to melt | dissolve, and this resin composition is excellent in applicability | paintability. A composite solvent in which a solvent is combined with a high boiling solvent having a boiling point in the range of 180 ° C. to 240 ° C. under normal pressure is preferable, and a combination of diethylene glycol monomethyl ether and such a high boiling solvent is particularly preferable. . Such a high boiling point solvent is not particularly limited as long as it is a solvent capable of dissolving the binder resin (A) and the radiation sensitive compound (B). For example, an alkylene glycol solvent, an ester solvent, a hydrocarbon solvent. And amide solvents. Hereinafter, specific examples of the high boiling point solvent will be given. In the following, the boiling point of each compound under normal pressure is shown in parentheses.

Examples of the alkylene glycol solvent include diethylene glycol monoalkyl ethers such as diethylene glycol monoethyl ether (202 ° C.) and diethylene glycol monobutyl ether (230 ° C.); diethylene glycol diethyl ether (189 ° C.), diethylene glycol butyl methyl ether (212 ° C.) and the like. Diethylene glycol dialkyl ether; propylene glycol alkyl ether such as dipropylene glycol monomethyl ether (190 ° C.); ethylene glycol monoalkyl ether acetate such as ethylene glycol (197.3 ° C.) ethylene glycol monobutyl ether acetate (188 ° C.); ethylene glycol (197 .3 ° C.);
Examples of the ester solvent include γ-butyrolactone (204 ° C.). Examples of the hydrocarbon solvent include aromatic hydrocarbons such as decalin (194 ° C.), 1-chlorooctane (182 ° C.), 4-ethylcyclohexane (194 ° C.), and butylbenzene (183 ° C.). it can.
Examples of the amide solvent include N-methylpyrrolidone (202 ° C.).
In addition to the above, dimethyl sulfoxide (189 ° C.) and the like can also be mentioned.
These high boiling point solvents may be used alone or in combination of two or more.

  In the case where diethylene glycol monomethyl ether and a high boiling point solvent are used in combination as the organic solvent (D), these ratios are 6: 4 to 9.5: by weight ratio of “diethylene glycol monomethyl ether: high boiling point solvent”. It is preferable to set it to 0.5. By setting these ratios within the above range, it is possible to improve the applicability of the permanent film resin composition while keeping various characteristics favorable.

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

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

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

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

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

  The content of the crosslinking agent (E) in the permanent film resin composition of the present invention is not particularly limited, but the degree of heat resistance required for the permanent film obtained using the permanent film resin composition of the present invention is determined. Although it should just set arbitrarily in consideration, it is 5-80 weight part normally with respect to 100 weight part of binder resin (A), Preferably it is 20-75 weight part, More preferably, it is 25-70 weight part. By making content of a crosslinking agent (E) into the said range, the heat resistance of the permanent film obtained can be made favorable.

(Other ingredients)
In addition, the resin composition of the present invention is a surfactant, a compound having an acidic group, a coupling agent or a derivative thereof, a sensitizer, an antioxidant, if desired, as long as the effects of the present invention are not inhibited. It may contain other compounding agents such as 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, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether Polyoxyethylene aryl ethers such as: Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Fluorine surfactants; Silicone surfactants; Methacrylic acid Copolymeric surfactants; acrylic acid copolymeric surfactants; and the like.

  The compound having an acidic group is not particularly limited as long as it has an acidic group, but is preferably an aliphatic compound having an acidic group, an aromatic compound or a heterocyclic compound, and an aromatic compound having an acidic group or a heterocyclic ring. Compounds are more preferred. In addition, as a compound which has an acidic group, what is described in [0099]-[0105] of Unexamined-Japanese-Patent No. 2011-75610 etc. can be used, for example.

  Moreover, as a compound which has an acidic group, since the same effect is acquired, a latent acid generator can be used. 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.

  The coupling agent or a derivative thereof has an effect of further improving the adhesion between the permanent film made of the permanent film resin composition and each layer such as a semiconductor layer constituting the electronic component. 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 the coupling agent or a derivative thereof, for example, those described in [0104] to [0106] of JP2011-75609A can be used.

  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.

Although it does not specifically limit as antioxidant, For example, the phenolic antioxidant, phosphorus antioxidant, sulfur antioxidant, amine antioxidant, lactone type oxidation which are used for the usual polymer are used. An inhibitor or the like can be used. A conventionally well-known thing can be used as a phenolic antioxidant, for example, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2 , 4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate and the like, and JP-A No. 1-168633. Acrylate compounds described in Japanese Patent Publication No. 2; 2,6-di-t-butyl-4-methylphenol, 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- ( '-T-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 4,4'-butylidene-bis- (3-methyl-6-t-butylphenol), 4,4'- Examples thereof include thio-bis (3-methyl-6-tert-butylphenol), pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], alkylated bisphenol, and the like.
Examples of the phosphorus antioxidant include triphenyl phosphite and tris phosphite (nonylphenyl), and examples of the sulfur antioxidant include dilauryl thiodipropionate.

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

The preparation method of the resin composition for permanent membranes of this invention is not specifically limited, What is necessary is just to mix each component which comprises the resin composition for permanent membranes 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 permanent film resin composition in a solvent. Thereby, the resin composition for permanent films is obtained with the form of a solution or a dispersion liquid.

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

  The solid content concentration of the permanent film 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 permanent film, flatness, etc. can be highly balanced.

(Permanent film)
The permanent film of the present invention is obtained by using the above-described permanent film resin composition of the present invention, and forms a pre-patterned resin film comprising the permanent film resin composition of the present invention. It is a film obtained by removing a part of the resin film and subjecting it to a cross-linking reaction, and remains inside the electronic component as the final product and functions as a functional patterned film. In particular, the permanent film of the present invention is used by remaining inside an electronic component as a final product, and is subjected to a crosslinking reaction by the action of the crosslinking agent (E) contained in the permanent film resin composition of the present invention. For the production of electronic components such as various developing solutions and stripping solutions such as alkali developing solutions and amide-based solvents, glycol-based solvents and other resist stripping solutions used in subsequent processes after the formation of the permanent film. It has resistance to various solutions used and has the property of not dissolving in them.

  The permanent film of the present invention is used as a pixel separation film of an organic EL element, in addition to a protective film, a planarizing film, and an electrical insulating film of various electronic components.

Next, a method for forming the permanent film of the present invention will be described.
First, after forming into a film by the apply | coating method or a film lamination method on a board | substrate, the resin film before patterning is formed by heat-drying (prebaking).

  The coating method is, for example, a method of removing a solvent by applying a resin composition for a permanent film and then drying by heating (prebaking). Examples of the method for applying the permanent film 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, the permanent film resin composition is applied on a B-stage film-forming substrate such as a resin film or a metal film, and then the solvent is removed by heat drying (pre-baking) to obtain a B-stage film. This is a method of laminating this B stage film. The heating and drying conditions can be appropriately selected according to the type and mixing ratio of each component, but the heating temperature is usually 30 to 150 ° C., and the heating time is usually 0.5 to 90 minutes. . Film lamination can be performed using a pressure laminator, a press, a vacuum laminator, a vacuum press, a roll laminator or the like.

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

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

  Next, the resin film before patterning obtained in this way is patterned by photolithography to obtain a permanent film. Specifically, the latent image pattern is formed by irradiating the resin film before patterning with actinic radiation, and then the pattern is revealed by bringing a developer into contact with the resin film having the latent image pattern. A permanent film is obtained.

The actinic radiation can activate the radiation-sensitive compound (B) contained in the permanent film resin composition and change the alkali solubility of the permanent film resin composition containing the radiation-sensitive compound (B). If it is, it will not specifically limit. 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 are appropriately selected according to the active radiation to be used. For example, when a light beam having a wavelength of 200 to 450 nm is used, the irradiation amount is usually 10 to 1,000 mJ / cm ² , preferably 50 to 500 mJ /. It is a range of cm ² and is determined according to irradiation time and illuminance. After irradiation with actinic radiation in this manner, the resin film is heat-treated at a temperature of about 60 to 130 ° C. for about 1 to 2 minutes as necessary.

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

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

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

  The permanent film thus obtained may be subjected to a crosslinking reaction as necessary. Crosslinking may be performed according to the method described above.

  And when the case where the permanent film of this invention is used as a pixel separation film of an organic EL element is illustrated, the resin composition for permanent films of this invention is applied on a transparent substrate having a transparent electrode layer (anode), A resin film is formed by heat drying (pre-baking), and the resin film is formed into a pattern corresponding to the pixel separation film by photolithography, and then baked (post-baked) to form a skirt-open shape (tapered shape) ) Pixel separation film (permanent film).

  Alternatively, as another example, when the permanent film of the present invention is used as a planarizing layer for planarizing a substrate, the resin composition for a permanent film of the present invention is used as a transparent electrode layer (anode). A flattening layer is formed by coating on a transparent substrate having heat, drying (pre-baking) to form a resin film, forming a pattern corresponding to a contact hole by photolithography, for example, and baking (post-baking) (Permanent film) can be formed.

(Electronic parts)
The electronic component of the present invention comprises a permanent film made of the above-described permanent film resin composition 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, These Of these, the active matrix substrate and the organic EL element substrate are preferable from the viewpoint that the effect of improving the properties by the permanent film made of the above-described permanent film resin composition of the present invention is particularly remarkable.

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

  Furthermore, as an organic EL element substrate as an example of the electronic component of the present invention, for example, an anode, a hole injection layer, a hole transport layer, an organic light emitting layer as a semiconductor layer, an electron transport layer, an electron injection on the substrate. Examples include those having a structure including a light emitting portion composed of a layer, a cathode, and the like, and a pixel separation film for separating the light emitting portion. The organic EL element substrate is preferably formed with a switching element (TFT) for controlling display (light emission) of the organic EL element. Further, a planarization layer for planarizing the substrate is preferably formed so as to cover the switching element, and a contact for connecting the switching element and the transparent electrode layer (anode) to the planarization layer. It is preferable that holes are further formed.

  When the electronic component of the present invention is an active matrix substrate, the permanent film made of the above-described permanent film resin composition of the present invention is a protective film formed on the surface of the active matrix substrate or an active matrix. A gate insulating film formed in contact with a semiconductor layer (for example, an amorphous silicon layer) of a thin film transistor that forms a substrate can be used. Alternatively, when the 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 layer, a hole transport layer, an organic light emitting layer as a semiconductor layer, an electron transport layer, an electron injection layer, and a cathode).

Next, a general manufacturing procedure of an organic EL element as an example of the electronic component of the present invention will be described.
First, a switching element (TFT) is formed on a substrate, and an insulating layer including an insulating film and a planarizing film is stacked thereon. The flattening film is used to relieve surface irregularities (steps) generated during the formation of switching elements (TFTs) and to flatten the surface. In addition, a contact hole for electrically connecting the switching element (TFT) and the electrode is formed in the insulating film and the planarizing film.

  Further, a transparent electrode (anode) is formed on this pixel by pixel, and a pixel separation film is formed so as to cover the periphery of each pixel in order to separate each pixel. The pixel separation film is provided for the purpose of preventing a short circuit between the electrodes (between the anode and the cathode) and for the purpose of preventing a mask used when the organic EL layer is formed by vapor deposition from coming into contact with the vapor deposited organic EL layer. Next, thin film layers such as a hole injection layer, a hole transport layer, an organic light emitting layer, an electron transport layer, and an electron injection layer are sequentially stacked on the pixel separation film, and an organic EL layer corresponding to each pixel region is formed. To do. The organic EL layer is formed so as to cover the transparent electrode (anode).

  And the transparent electrode (cathode) which is a counter electrode is formed so that these upper sides may be covered. Further, a passivation film is formed so as to completely cover the electrode (cathode), the organic EL layer, the pixel separation film, and the planarization film. Then, the upper part of the passivation film is covered with a cover glass, and the periphery of the cover glass is sealed with a sealing material. The organic EL element as an example of the electronic component of the present invention is generally produced by such a procedure.

  Here, a method for forming each layer of the organic EL element as an example of the electronic component of the present invention will be specifically described.

  First, an insulating layer composed of an insulating film and a planarizing film is formed by, for example, applying the resin composition for permanent film of the present invention and heating and drying (pre-baking) to form a resin film. A pattern corresponding to the hole can be formed and baked (post-baked), and the insulating layer formed of the insulating film and the planarizing film can be formed of the permanent film of the present invention.

  The transparent electrode (anode) can be formed, for example, by forming an ITO thin film by sputtering and patterning the formed ITO thin film in a matrix by, for example, photolithography (exposure, development) and etching.

  Further, the pixel separation film can be formed using the permanent film resin composition of the present invention in the same manner as the insulating film composed of the insulating film and the planarizing film described above, and is constituted by the permanent film of the present invention. Can do.

  An organic EL layer such as a hole injection layer, a hole transport layer, an organic light emitting layer, an electron transport layer, or an electron injection layer is formed by, for example, placing an evaporation mask having an opening corresponding to a desired pixel on the pixel separation film. It can be formed by vacuum deposition while holding.

  The organic EL layer is formed over the entire region including the upper surface of the vapor deposition mask. However, when the vapor deposition mask is removed from the pixel separation film, the EL layer can be formed only in a portion corresponding to a desired pixel. It is difficult to form an organic EL layer with a uniform film thickness when the underlying surface of the film formation portion is not sufficiently flat. On the other hand, since the pixel separation film is composed of the permanent film made of the above-described permanent film resin composition of the present invention, the permanent film of the present invention is excellent in flatness, which is preferable.

  The electrode (cathode) can be formed, for example, by forming an Al thin film by vacuum deposition, and patterning the Al thin film by, for example, photolithography (exposure, development) and etching.

  Next, after the formation of the above-described permanent film, the insulating layer composed of the insulating film and the flattening film, and the pixel isolation film are formed of the permanent film composed of the permanent film resin composition of the present invention. The process will be described.

  That is, as described above, as described above, for example, a metal thin film such as ITO is formed on the insulating layer made of the insulating film and the planarizing film or the pixel isolation film by sputtering or the like. A photolithography process is performed in which a normal photoresist is coated on the substrate, processed by exposure and development, and patterned. Thereafter, an etching process is performed to remove an unnecessary metal thin film in the resist removal portion patterned as described above with an etching solution. Then, after the etching, an unnecessary resist on the pattern is removed with a stripping solution, and a substrate cleaning process is performed.

  Here, since it is necessary to peel off and remove unnecessary portions in a post-process as described above, a normal photoresist does not need to be cross-linked, so it is common not to use a compound that acts as a cross-linking agent. is there. Or even if the compound which acts as a crosslinking agent is contained, it is a very small amount.

  On the other hand, the resin composition for permanent film of the present invention contains the crosslinking agent (E) as described above, and therefore, the resulting permanent film (insulating layer and pixel separation comprising an insulating film and a planarizing film) is obtained. Film) also contains a cross-linking agent (E), and the cross-linking reaction is sufficiently performed after baking due to the action of the cross-linking agent (E). It is resistant to the developer and stripping solution, and remains in the electronic component in the final product without being stripped or removed in a subsequent process, and functions as a functional pattern film.

  The resin composition for a permanent film of the present invention comprises a binder resin (A), a radiation sensitive compound (B), a phenol compound (C), a solvent (D), and a crosslinking agent (E). Since the blending ratio of (B) and phenolic compound (C) is controlled within a predetermined range, the permanent film resin composition of the present invention has high sensitivity to radiation and can be developed with an aqueous alkaline solution. The permanent film obtained by using the resin composition for a permanent film of the present invention is excellent in flatness and surface condition. According to the present invention, such a permanent film is applied to various electronic components, for example, a semiconductor element substrate such as an active matrix substrate or an organic EL element substrate, whereby a resin film (permanent film) contained in the electronic component is obtained. ) Can be patterned with high precision, and this makes it possible to improve the performance of electronic components.

  In addition, a protective film for an active matrix substrate or a resin film as a permanent film such as a pixel separation film, a planarization film, or a sealing film for an organic EL element substrate has a developer and a peeling solution that are also used in a later process. Tolerance against such factors is required. Specifically, these protective films, pixel separation films, planarization films, sealing films, and the like are sometimes developed in subsequent processes, and thus are required to have resistance to an alkaline developer. Alternatively, since the photoresist and the residue may be removed after the etching process, resistance to a resist stripping liquid or the like that is a cleaning liquid is also required. On the other hand, the permanent film made of the permanent film resin composition of the present invention contains a crosslinking agent (E) and does not dissolve in a developer, a stripping solution or the like after crosslinking. It has resistance to various developing solutions such as resist stripping solutions such as solvent based solvents and glycol based solvents and various solutions used in the manufacture of electronic components such as stripping solutions, and functions well as a permanent film.

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.

<Surface condition of resin film>
A resin composition was spin-coated on a 4-inch silicon wafer and then pre-baked at 110 ° C. for 2 minutes using a hot plate to form a resin film having a thickness of 2.5 μm. Next, the resin film was immersed in a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds, then washed with ultrapure water for 30 seconds, and then the light intensity at 365 nm. Was irradiated in the air for 20 seconds with an ultraviolet ray of 5 mW / cm ² . And the test sample which consists of a silicon wafer in which the resin film was formed was performed about the resin film which irradiated the ultraviolet-ray by performing the post-baking heated for 60 minutes at 230 degreeC using oven. And about the obtained test sample, the surface state of the resin film was observed using the optical microscope, and the following reference | standard evaluated.
○: Neither cracks nor wrinkles were observed.
X: Cracks and wrinkles were observed.

<Flatness>
For the resin film obtained in the same manner as the evaluation of the surface state, the flatness of the resin film was measured using an atomic force microscope (AFM) and evaluated according to the following criteria.
A: The surface roughness Ra was less than 3 nm.
X: The surface roughness Ra was 3 nm or more.

<Residue during development>
A resin composition was spin-coated on a 4-inch silicon wafer and then pre-baked at 110 ° C. for 2 minutes using a hot plate to form a 2.5 μm thick resin film. Next, the resin film was irradiated with ultraviolet rays having a light intensity at 365 nm of 5 mW / cm ² in the air for 20 seconds through a mask having a hole pattern of 5 μm × 5 μm. Next, a 2.38 wt% tetramethylammonium hydroxide aqueous solution was used for development processing at 23 ° C. for 60 seconds, followed by rinsing with ultrapure water for 30 seconds to form a contact hole pattern.
And about the resin film which has the pattern of the contact hole obtained in this way, the presence or absence of the melt | dissolution residue in a contact hole was confirmed using the scanning electron microscope (SEM), and the following references | standards evaluated. It is preferable that no dissolution residue is observed because the pattern forming property by development is excellent.
○: No development residue was observed.
X: Development residue was observed.

<Sensitivity to radiation>
A resin composition was spin-coated on a 4-inch silicon wafer and then pre-baked at 110 ° C. for 2 minutes using a hot plate to form a 2.5 μm thick resin film. Next, the resin film was exposed with an ultrahigh pressure mercury lamp through a 10 μm line and space mask. Next, a 2.38 wt% tetramethylammonium hydroxide aqueous solution was used for development processing at 23 ° C. for 60 seconds, followed by rinsing with ultrapure water for 30 seconds to form a pattern. The line width of the formed pattern was measured with a digital microscope, the exposure amount having a length of 10 μm, which was the same as the mask design, was determined, and the sensitivity to radiation was evaluated based on the following criteria. A smaller value is preferable because the time required for the exposure process is shortened, energy can be reduced, and pattern formation as a permanent film is improved.
A: The exposure amount was less than 100 mJ / cm ² .
X: The exposure amount was 100 mJ / cm ² or more.

<< Synthesis Example 1 >>
<Preparation of Cyclic Olefin Polymer (A-1)>
N-phenylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide 40 mol%, and 4-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 100 parts of a monomer mixture consisting of 60 mol% of 0 ^2,7 ] dodec-9-ene, 2 parts of 1,5-hexadiene, (1,3-dimesityrylimidazoline-2-ylidene) (tricyclohexylphosphine) benzylidene 0.02 part of ruthenium dichloride (synthesized by the method described in Org. Lett., Vol. 1, page 953, 1999) and 200 parts of diethylene glycol ethyl methyl ether were charged into a nitrogen pressure-substituted glass pressure-resistant reactor. The mixture was reacted for 4 hours at 80 ° C. with stirring to obtain a polymerization reaction solution.

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

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

<< Synthesis Example 3 >>
<Preparation of photosensitive polyimide precursor (A-3)>
In a reactor, 2,2'-di (p-aminophenyl) -6,6'-bisbenzoxazole 28.11 g (0.0672 mol), solvent 200 g [dimethylacetamide (DMAc) 100 g and N-methyl-2- Pyrrolidone (NMP) 100 g] was added to prepare a mixed solution. To this solution, 15.26 g (0.07 mol) of pyromellitic dianhydride was added in the form of powder while stirring on ice, and washed with 20 g of solvent (10 g of DMAc and 10 g of NMP).

  Subsequently, after stirring for 2 hours under ice cooling, the reaction temperature was raised to 30 ° C. and the reaction was allowed to proceed for 2 hours. When the reaction solution becomes almost homogeneous, the reaction solution is cooled to 10 ° C., and then 2.57 g (0.0056 mol) of p-aminobenzoic acid [tris (methacryloyl) pentaerythritol] ester is added to the solvent. 20 g (10 g DMAc and 10 g NMP) was added by washing. The reaction was carried out at 10 ° C. for 2 hours and then at 25 ° C. for 12 hours to synthesize a photosensitive polyimide precursor (polyamic acid) (A-3) at a resin concentration of 16% by weight. The terminal modification rate of this photosensitive polyimide precursor was 8%.

<< Synthesis Example 4 >>
<Preparation of alkali-soluble phenol resin>
Phenol and formaldehyde were subjected to dehydration condensation using oxalic acid as a catalyst to obtain an alkali-soluble phenol resin having a weight average molecular weight of 620 and a molecular weight distribution of 1.21.

Example 1
<Preparation of resin composition>
As binder resin (A), 100 parts of cyclic olefin polymer (A-1) obtained in Synthesis Example 1, and as radiation sensitive compound (B), 2,3,4,4′-tetrahydroxybenzophenone (1 mol) 30 parts of a condensate (B-1) of 6-diazo-5,6-dihydro-5-oxo-naphthalene-1-sulfonic acid chloride (2 mol), 4-hydroxy-γ as the phenol compound (C) 4- (4-hydroxyphenyl) -γ-methylbenzenebutanoic acid (C-1) 4 parts, solvent (D) as diethylene glycol ethyl methyl ether (D-1) 550 parts, crosslinker (E) as epoxidized butane After mixing and dissolving 50 parts of tetrakis (tetracyclohex (3-cyclohexenylmethyl) -modified ε-caprolactone, polytetrafluoroethylene having a pore size of 0.45 μm. The resin composition was prepared by filtration through a lens made filter.

  And each evaluation of the surface state of a resin film, flatness, the residue at the time of image development, and the sensitivity was performed using the resin composition obtained above. The results are shown in Table 1.

<< Examples 2 to 4 >>
Instead of 4 parts of 4-hydroxy-γ- (4-hydroxyphenyl) -γ-methylbenzenebutanoic acid (C-1) as the phenol compound (C), 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol (C-2) 5 parts (Example 2), polyvinylphenol (C-3) 10 parts (Example 3), synthesis example A resin composition was obtained in the same manner as in Example 1 except that 10 parts of the phenol resin (C-4) obtained in 4 (Example 4) was used, and evaluation was performed in the same manner. The results are shown in Table 1.

Example 5
As the radiation-sensitive compound (B), 2,3,4,4′-tetrahydroxybenzophenone (1 mol) and 6-diazo-5,6-dihydro-5-oxo-naphthalene-1-sulfonic acid chloride (2 mol) 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1 , 2-Naphthoquinonediazide-5-sulfonic acid chloride (2 mol) and 4-hydroxy-γ- (4-hydroxyphenyl) -γ as a phenol compound (C) -Resin compositions were obtained and evaluated in the same manner as in Example 1 except that the amount of methylbenzenebutanoic acid (C-1) was changed from 4 parts to 5 parts. The results are shown in Table 1.

<< Examples 6 to 8 >>
Instead of 5 parts of 4-hydroxy-γ- (4-hydroxyphenyl) -γ-methylbenzenebutanoic acid (C-1) as the phenol compound (C), 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol (C-2) 10 parts (Example 6), polyvinylphenol (C-3) 10 parts (Example 7), synthesis example A resin composition was obtained and evaluated in the same manner as in Example 5 except that 15 parts (Example 8) of the phenol resin (C-4) obtained in 4 was used. The results are shown in Table 1.

Example 9
2,3,4,4′-tetrahydroxybenzophenone (1 mol) and 6-diazo-5,6-dihydro-5-oxo-naphthalene-1-sulfonic acid chloride (2 mol) as radiation-sensitive compound (B) The amount of the condensate (B-1) is changed from 30 parts to 40 parts, and 4-hydroxy-γ- (4-hydroxyphenyl) -γ-methylbenzenebutanoic acid (C) as the phenol compound (C) is changed. -1) was changed from 4 parts to 5 parts, and a solvent consisting of 90% diethylene glycol monomethyl ether (D-1) and 10% N-methylpyrrolidone (D-2) was used as the solvent (D). Except for the above, a resin composition was obtained in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1.

Example 10
As a phenol compound (C), instead of 5 parts of 4-hydroxy-γ- (4-hydroxyphenyl) -γ-methylbenzenebutanoic acid (C-1), 4,4 ′-[1- [4- [1 A resin composition was obtained in the same manner as in Example 9 except that 10 parts of-(4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol (C-2) were used, and evaluation was performed in the same manner. went. The results are shown in Table 1.

Example 11
4,4 ′-[1- [4- [1- (4-Hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinonediazide as radiation sensitive compound (B) The blending amount of the condensate (B-2) with -5-sulfonic acid chloride (2 mol) is changed from 30 parts to 40 parts, and the blending amount of polyvinylphenol (C-3) as the phenol compound (C) is changed. Except that the solvent was changed from 10 parts to 15 parts and a solvent consisting of 90% diethylene glycol monomethyl ether (D-1) and 10% dipropylene glycol monomethyl ether (D-3) was used as the solvent (D). In the same manner as in Example 7, a resin composition was obtained and evaluated in the same manner. The results are shown in Table 1.

Example 12
As a phenol compound (C), instead of 15 parts of polyvinylphenol (C-3), except that 20 parts of the phenol resin (C-4) obtained in Synthesis Example 4 was used, the same as in Example 11, A resin composition was obtained and evaluated in the same manner. The results are shown in Table 1.

Example 13
Resin in the same manner as in Example 3 except that the acrylic polymer (A-2) obtained in Synthesis Example 2 was used instead of the cyclic olefin polymer (A-1) as the binder resin (A). A composition was obtained and evaluated in the same manner. The results are shown in Table 1.

Example 14
As the binder resin (A), instead of the cyclic olefin polymer (A-1), the same procedure as in Example 6 was used except that the photosensitive polyimide precursor (A-3) obtained in Synthesis Example 3 was used. A resin composition was obtained and evaluated in the same manner. The results are shown in Table 1.

<< Comparative Example 1 >>
Resin composition in the same manner as in Example 1 except that 4-hydroxy-γ- (4-hydroxyphenyl) -γ-methylbenzenebutanoic acid (C-1) as a phenol compound (C) was not blended. Were similarly evaluated. The results are shown in Table 1.

<< Comparative Example 2 >>
4,4 ′-[1- [4- [1- (4-Hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinonediazide as radiation sensitive compound (B) A resin composition was obtained in the same manner as in Example 5 except that the blending amount of the condensate (B-2) with -5-sulfonic acid chloride (2 mol) was changed from 30 parts to 60 parts. Was evaluated. The results are shown in Table 1.

<< Comparative Example 3 >>
Except having changed the compounding quantity of polyvinyl phenol (C-3) as a phenolic compound (C) from 10 parts to 40 parts, it carried out similarly to Example 3, obtained the resin composition, and evaluated similarly. . The results are shown in Table 1.

<< Comparative Example 4 >>
2,3,4,4′-tetrahydroxybenzophenone (1 mol) and 6-diazo-5,6-dihydro-5-oxo-naphthalene-1-sulfonic acid chloride (2 mol) as radiation-sensitive compound (B) A resin composition was obtained and evaluated in the same manner as in Example 13 except that the blending amount of the condensate (B-1) was changed from 30 parts to 5 parts. The results are shown in Table 1.

<< Comparative Example 5 >>
The blending amount of 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol (C-2) as the phenol compound (C) is from 10 parts. Except having changed into 2 parts, it carried out similarly to Example 14, and obtained the resin composition, and evaluated it similarly. The results are shown in Table 1.

  It contains a binder resin (A), a radiation sensitive compound (B), a phenol compound (C), a solvent (D), and a crosslinking agent (E), and the ratio of the radiation sensitive compound (B) to the phenol compound (C) is The resin composition with “radiation sensitive compound (B) / phenolic compound (C)” = 1 to 10 by weight ratio does not generate a residue during development, is excellent in pattern formation by development, and has sensitivity to radiation. Moreover, the resin film obtained using this resin composition had high flatness and good surface condition, and was suitable as a permanent film (Examples 1 to 14).

On the other hand, when the phenol compound (C) was not blended, the sensitivity to radiation was low, and therefore it was not suitable for use as a permanent film (Comparative Example 1).
Moreover, when there are too many compounding quantities of a radiation sensitive compound (B) and when there are too few, the resin film obtained is inferior to a surface state, the residue at the time of image development generate | occur | produces, and flatness is also inadequate. Furthermore, the sensitivity to radiation was low, and therefore it was not suitable for use as a permanent film (Comparative Examples 2 and 4).
Moreover, when there is too much compounding quantity of a phenol compound (C), there exists a tendency for the solubility with respect to a developing solution to become high too much, and the obtained resin film has surface roughness, such as wrinkles, and is inferior to a surface state In addition, a residue was generated during development, the flatness was insufficient, and the sensitivity to radiation was low, so that it was not suitable for use as a permanent film (Comparative Example 3).
Furthermore, when the blending amount of the phenol compound (C) is too small, the solubility in the developer tends to be too low, a development residue is generated, and the sensitivity to radiation is low, so that as a permanent film It was not suitable for use (Comparative Example 5).

Claims (5)

Binder resin (A), radiation sensitive compound (B), phenolic compound (C), solvent (D), crosslinker (E), the ratio of the radiation sensitive compound (B) and phenolic compound (C) Is a resin composition for a permanent film in which, by weight ratio, “radiation sensitive compound (B) / phenol compound (C)” = 1 to 10,
A permanent film resin composition for forming a permanent film obtained by forming a resin film made of the resin composition, removing a part of the resin film, and leaving the remainder as a patterned film.   The said solvent (D) contains the high boiling-point solvent which has a boiling point of 180 to 240 degreeC under a normal pressure, The resin composition for permanent films of Claim 1 characterized by the above-mentioned.   The resin composition for a permanent film according to claim 1, wherein the binder resin (A) is a resin having an acid value of 50 to 70 mg KOH / g and containing a protic polar group. .   A permanent film obtained by forming a resin film comprising the resin composition for a permanent film according to any one of claims 1 to 3 and removing a part of the resin film, followed by a crosslinking reaction.   An electronic component comprising the permanent film according to claim 4.