JP5517860B2 - Photosensitive resin composition, method for forming cured film, cured film, organic EL display device, and liquid crystal display device - Google Patents

Description

  The present invention relates to a photosensitive resin composition, a method for forming a cured film, a cured film, an organic EL display device, and a liquid crystal display device.

An organic EL display device, a liquid crystal display device, and the like are provided with a patterned interlayer insulating film. In forming the interlayer insulating film, photosensitive resin compositions are widely used because the number of steps for obtaining a required pattern shape is small and sufficient flatness is obtained.
In addition to the physical properties of the cured film, such as excellent insulation, solvent resistance, heat resistance, and indium tin oxide (ITO) sputtering suitability, high transparency is desired for the interlayer insulating film in the display device. For this reason, an attempt has been made to use an acrylic resin having excellent transparency as a film forming component.

  As such a photosensitive resin composition, for example, Patent Document 1 discloses (A) (a) an unsaturated carboxylic acid or unsaturated carboxylic acid anhydride, (b) a radical polymerizable compound having an epoxy group, and (c A radiation-sensitive resin composition having a resin soluble in an alkaline aqueous solution, which is a copolymer of another radical polymerizable compound, and (B) a radiation-sensitive acid generating compound has been proposed.

  Patent Document 2 discloses that the component (A) has 3 to 16 carbon atoms, has a side chain having an unsaturated bond at the terminal, and has a number average molecular weight of 2,000 to 30,000 in terms of polystyrene. A positive photosensitive resin composition containing an alkali-soluble acrylic polymer, (B) component: 1,2-quinonediazide compound, and (C) a solvent has been proposed.

  Patent Document 3 discloses that at least one selected from the group consisting of component (A): a phenolic hydroxy group, a carboxyl group, and a group that generates a carboxylic acid or a phenolic hydroxy group by the action of heat or acid. An alkali-soluble resin having a group and a number average molecular weight of 2,000 to 30,000, component (B): compound having two or more unsaturated groups at the end of one molecule, component (C): A positive photosensitive resin composition containing a photoacid generator and (D) a solvent has been proposed.

JP-A-5-165214 JP 2008-256974 A JP 2008-76739 A

  The photosensitive resin compositions described in Patent Documents 1 to 3 have a problem that sensitivity is low and stability over time is not sufficient. Moreover, the cured film formed of these photosensitive resin compositions has a problem that the transparency is not sufficient and a problem that the ITO sputtering resistance is not sufficient, and the surface is roughened when the ITO film is formed by the sputtering method.

  An object of the present invention is to provide a photosensitive resin composition having a high sensitivity, high transparency and excellent ITO sputtering resistance, a cured film having high transparency and excellent ITO sputtering resistance, and production thereof. It is an object of the present invention to provide a method and an organic EL display device and a liquid crystal display device having such a cured film as an interlayer insulating film.

  As a result of intensive studies to solve the above problems, the present inventor has (A) a monomer unit (a1) having a residue that generates a carboxy group or a phenolic hydroxyl group with an acid, and an ethylenically unsaturated bond at the terminal. A photopolymer containing a monomer unit (a2) having a group having 3 to 16 carbon atoms and having a weight average molecular weight of more than 1,000, (B) a photoacid generator, and (C) a solvent. It has been found that by using the resin composition, high sensitivity can be obtained, and a cured film having high transparency and excellent ITO sputtering resistance can be obtained.

That is, the said subject of this invention was solved by the means as described in <1>, <9>, <10>, <12> or <13> below. It describes below with <2>-<8> and <11> which are preferable embodiments.
<1> (A) a monomer unit (a1) having a residue that generates a carboxy group or a phenolic hydroxyl group with an acid, and a monomer unit having a group of 3 to 16 carbon atoms having an ethylenically unsaturated bond at the terminal ( a photosensitive resin composition comprising: a2) a polymer having a weight average molecular weight greater than 1,000, (B) a photoacid generator, and (C) a solvent;
<2> The photosensitive resin composition according to <1>, which is a chemically amplified positive photosensitive resin composition,
<3> The polymer (A) contains a monomer unit (a3) having a carboxy group, a carboxylic acid anhydride residue and / or a phenolic hydroxyl group, and the monomer unit (a3) in the polymer (A). The photosensitive resin composition according to the above <1> or <2>, wherein the ratio is 1 to 25 mol% based on the total monomer units of the polymer (A),
<4> The photosensitive resin composition according to any one of <1> to <3>, wherein the polymer (A) contains a monomer unit (a4) having an epoxy group and / or an oxetanyl group. ,
<5> The photosensitive resin composition according to any one of <1> to <4>, wherein the (B) photoacid generator is a compound having an oxime sulfonate residue,
<6> The above-mentioned <1> to <5>, wherein the (B) photoacid generator is a compound represented by the formula (OS-3), the formula (OS-4) or the formula (OS-5). Any one of the photosensitive resin compositions,

（式（ＯＳ−３）〜式（ＯＳ−５）中、Ｒ¹はアルキル基、アリール基又はヘテロアリール基を表し、Ｒ²はそれぞれ独立に、水素原子、アルキル基、アリール基又はハロゲン原子を表し、Ｒ⁶はそれぞれ独立に、ハロゲン原子、アルキル基、アルキルオキシ基、スルホン酸基、アミノスルホニル基又はアルコキシスルホニル基を表し、ＸはＯ又はＳを表し、ｎは１又は２を表し、ｍは０〜６の整数を表す。）

(In Formula (OS-3) to Formula (OS-5), R ¹ represents an alkyl group, an aryl group, or a heteroaryl group, and R ² independently represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom. R ⁶ represents each independently a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, X represents O or S, n represents 1 or 2, m Represents an integer of 0 to 6.)

<7> (D) The photosensitive resin composition according to any one of <1> to <6>, further including a thermal radical generator,
<8> (E) The photosensitive resin composition according to any one of <1> to <7>, further including a crosslinking agent,
<9> (1) Application step of applying the photosensitive resin composition according to any one of the above <1> to <8> on a substrate, (2) Solvent from the applied photosensitive resin composition. A method for forming a cured film, comprising: a solvent removing step to be removed; (3) an exposure step of exposing with actinic rays; (4) a developing step of developing with an aqueous developer; and (5) a post-baking step of thermosetting.
<10> A cured film formed by the method according to <9> above,
<11> The cured film according to <10>, which is an interlayer insulating film,
<12> An organic EL display device comprising the cured film according to <10> or <11> above,
<13> A liquid crystal display device comprising the cured film according to <10> or <11>.

  According to the present invention, a photosensitive resin composition capable of obtaining a cured film having high sensitivity, high transparency and excellent ITO sputtering resistance, cured film having high transparency and excellent ITO sputtering resistance, and production thereof It was possible to provide a method, and an organic EL display device and a liquid crystal display device having such a cured film as an interlayer insulating film.

1 shows a conceptual diagram of a configuration of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided. 1 is a conceptual diagram of a configuration of an example of a liquid crystal display device. The schematic sectional drawing of the active matrix substrate in a liquid crystal display device is shown, and it has the cured film 17 which is an interlayer insulation film.

(Photosensitive resin composition)
Hereinafter, the photosensitive resin composition of the present invention will be described in detail.
The photosensitive resin composition of the present invention comprises (A) a monomer unit (a1) having a residue that generates a carboxy group or a phenolic hydroxyl group with an acid, and a C 3-16 having an ethylenically unsaturated bond at the terminal. And a monomer unit (a2) having a group having a weight average molecular weight of greater than 1,000, (B) a photoacid generator, and (C) a solvent.
Hereinafter, these components represented by (A) to (C) are also referred to as “(A) component” to “(C) component”, respectively.

The photosensitive resin composition of the present invention is preferably a positive photosensitive resin composition.
The photosensitive resin composition of the present invention is preferably a chemically amplified photosensitive resin composition, and is a chemically amplified positive photosensitive resin composition (chemically amplified positive photosensitive resin composition). More preferably.
The photosensitive resin composition of the present invention preferably contains no 1,2-quinonediazide compound as a photoacid generator sensitive to actinic rays. A 1,2-quinonediazide compound generates a carboxy group by a sequential photochemical reaction, but its quantum yield is always 1 or less.
On the other hand, the photoacid generator (B) used in the present invention acts as a catalyst for the deprotection of the acid-protected acid group produced in response to actinic rays. The acid produced by the action contributes to many deprotection reactions, and the quantum yield exceeds 1 and becomes a large value of the power of 10. As a result of so-called chemical amplification, high sensitivity is obtained.

  The photosensitive resin composition of the present invention contains the components (A) to (C), so that it has high sensitivity and can form a cured film having high transparency and excellent ITO sputtering resistance. The resulting photosensitive resin composition.

Hereinafter, the components (A) to (C) constituting the photosensitive resin composition will be described.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what has a substituent with what does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
The method for introducing the monomer unit contained in the copolymer used in the present invention may be a polymerization method or a polymer reaction method. In the polymerization method, monomers containing a predetermined functional group are synthesized in advance, and then these monomers are copolymerized. In the polymer reaction method, after a polymerization reaction is performed, a necessary functional group is introduced into the monomer unit using a reactive group contained in the monomer unit of the obtained copolymer. Here, as a functional group, a protective group for protecting an alkali-soluble group (acidic group) such as a carboxy group or a phenolic hydroxyl group, a carboxy group or a phenolic hydroxyl group, and simultaneously decomposing and releasing them in the presence of a strong acid. And a crosslinkable group such as a group having an ethylenically unsaturated bond, an epoxy group or an oxetanyl group.
In the polymer (A), the monomer units (a1) to (a4) may be introduced into the polymer (A) by a polymerization method or a polymer reaction method, or these two methods may be used in combination.
In the polymerization method, an ethylenically unsaturated compound having a carboxy group or a phenolic hydroxyl group, an ethylenically unsaturated compound having a residue in which the carboxy group or the phenolic hydroxyl group is protected with an acid-decomposable group, and having an ethylenically unsaturated bond A bifunctional ethylenically unsaturated compound having a group and an ethylenically unsaturated compound having an epoxy group or an oxetanyl group are mixed and subjected to addition polymerization to obtain a desired copolymer.
In the polymer reaction method, methacryloyl group can be introduced by reacting methacrylic acid chloride with a copolymer obtained by copolymerizing 2-hydroxyethyl methacrylate. Thus, after copolymerizing an ethylenically unsaturated compound having a reactive group, the reactive group remaining in the side chain is utilized to perform a polymer reaction to produce a carboxy group, a phenolic hydroxyl group, a carboxy group, or a phenolic hydroxyl group. A functional group such as a residue protected with an acid-decomposable group, a group having an ethylenically unsaturated bond, and / or a crosslinkable group can be introduced into the side chain.

(A) Polymer The photosensitive resin composition of the present invention contains the (A) polymer.
The polymer (A) contained in the photosensitive resin composition of the present invention has a monomer unit (a1) having a residue that generates a carboxy group or a phenolic hydroxyl group with an acid, and an ethylenically unsaturated bond at the terminal. A polymer containing a monomer unit (a2) having a group having 3 to 16 carbon atoms and having a weight average molecular weight of more than 1,000.
(A) The polymer is preferably a resin that is insoluble in alkali and becomes alkali-soluble when the acid-decomposable group is dissociated. Here, in the present invention, the acid-decomposable group represents a functional group capable of decomposing in the presence of an acid to generate a carboxy group or a phenolic hydroxyl group.
The term “alkali-soluble” in the present invention refers to a coating film (thickness 3 μm) of the compound (resin) formed by applying a solution of the compound (resin) on a substrate and heating at 90 ° C. for 2 minutes. ) In a 0.4 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C. is 0.005 μm / second or more. “Alkali insoluble” means that the solution of the compound (resin) is a substrate The dissolution rate of a coating film (thickness: 3 μm) of the compound (resin) formed by coating on the substrate and heating at 90 ° C. for 2 minutes in a 0.4 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C. , Less than 0.005 μm / sec.
The (A) polymer does not exclude the introduction of an acidic group as long as the entire (A) polymer is kept insoluble in alkali, but a carboxy group, a carboxylic acid anhydride residue and / or a phenolic hydroxyl group described later. May have a monomer unit (a3) having

<Monomer unit (a1)>
The polymer (A) contains a monomer unit (a1) having a residue that generates a carboxy group or a phenolic hydroxyl group with an acid.
Among the monomer units (a1), as the monomer unit having a residue that generates a carboxy group with an acid, for example, a monomer unit having a structure in which a carboxy group is protected with a protecting group, known in the field of positive chemically amplified resists, is used. A monomer unit having a structure such as an acetal ester, a ketal ester or a tertiary alkyl ester of a carboxy group is preferably used.

The tertiary alkyl ester structure of the carboxy group is more preferably at least one selected from the group consisting of structures represented by the following formula (I).
-COOC (R ¹ R ² R ³ ) (I)

In formula (I), R ¹ , R ² and R ³ are each independently a chain alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or carbon. 7 represents an aralkyl group of 7 to 12, and any ^{two of} R ¹ , R ² and R ³ may be bonded to each other to form a ring together with the carbon atoms to which they are bonded.
The residue represented by the above formula (I) is directly bonded to the main chain carbon atom in the monomer unit derived from the ethylenically unsaturated bond or bonded through a divalent linking group. Is preferred.

The chain alkyl group having 1 to 12 carbon atoms of R ¹ , R ² and R ³ in the formula (I) may be linear or branched, for example, methyl group, ethyl group, n -Propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, texyl group (2,3-dimethyl group) -2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group and the like.

  Examples of the cyclic alkyl group having 3 to 12 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group.

  Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a 1-naphthyl group.

  Examples of the aralkyl group having 7 to 12 carbon atoms include a benzyl group, an α-methylbenzyl group, a phenethyl group, and a naphthylmethyl group.

R ¹ , R ² and R ³ can be bonded together to form a ring together with the carbon atom to which they are bonded. Examples of the ring structure when R ¹ and R ² , R ¹ and R ³ or R ² and R ³ are combined include, for example, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, an adamantyl group, and a tetrahydropyrani group. And the like.
Preferred examples of the tertiary alkyl ester structure of the carboxy group include a structure where R ¹ = R ² = R ³ = methyl group, a structure where R ¹ = R ² = methyl group and R ³ = benzyl group, R ¹ = structure together with the carbon atom to which R ² and R ³ a methyl group attached to form a cyclohexyl group, together with the carbon atom to which R ² and R ³ in R ¹ = methyl group is bonded 2- Examples thereof include a structure forming an adamantyl group.

The acetal ester structure of the carboxy group is more preferable than the ketal ester structure of the carboxy group.
Examples of ORae in the carboxy group acetal ester structure (—COORae) include, for example, 1-methoxyethoxy group, 1-ethoxyethoxy group, 1-n-propoxyethoxy group, 1-i-propoxyethoxy group, 1-n Butoxyethoxy group, 1-i-butoxyethoxy group, 1-sec-butoxyethoxy group, 1-t-butoxyethoxy group, 1-cyclopentyloxyethoxy group, 1-cyclohexyloxyethoxy group, 1-norbornyloxyethoxy group 1-bornyloxyethoxy group, 1-phenyloxyethoxy group, 1- (1-naphthyloxy) ethoxy group, 1-benzyloxyethoxy group, 1-phenethyloxyethoxy group, (cyclohexyl) (methoxy) methoxy group, (Cyclohexyl) (ethoxy) methoxy group, (cycl (Cyclohexyl) (n-propoxy) methoxy group, (cyclohexyl) (i-propoxy) methoxy group, (cyclohexyl) (cyclohexyloxy) methoxy group, (cyclohexyl) (phenoxy) methoxy group, (cyclohexyl) (benzyloxy) methoxy group, (Phenyl) (methoxy) methoxy group, (phenyl) (ethoxy) methoxy group, (phenyl) (n-propoxy) methoxy group, (phenyl) (i-propoxy) methoxy group, (phenyl) (cyclohexyloxy) methoxy group, (Phenyl) (phenoxy) methoxy group, (phenyl) (benzyloxy) methoxy group, (benzyl) (methoxy) methoxy group, (benzyl) (ethoxy) methoxy group, (benzyl) (n-propoxy) methoxy group, (benzyl ) (I-propoxy) me Mention of xyl group, (benzyl) (cyclohexyloxy) methoxy group, (benzyl) (phenoxy) methoxy group, (benzyl) (benzyloxy) methoxy group, 2-tetrahydrofuranyloxy group, 2-tetrahydropyranyloxy group, etc. Can do.

  Among these, 1-ethoxyethoxy group, 1-cyclohexyloxyethoxy group, 2-tetrahydropyranyloxy group, 1-n-propoxyethoxy group, and 2-tetrahydrofuranyloxy group can be mentioned as preferable examples.

  Examples of ORke in the ketal ester structure (—COORke) of the carboxy group include, for example, 1-methyl-1-methoxyethoxy group, 1-methyl-1-ethoxyethoxy group, 1-methyl-1-n-propoxyethoxy group, 1-methyl-1-i-propoxyethoxy group, 1-methyl-1-n-butoxyethoxy group, 1-methyl-1-i-butoxyethoxy group, 1-methyl-1-sec-butoxyethoxy group, 1- Methyl-1-t-butoxyethoxy group, 1-methyl-1-cyclopentyloxyethoxy group, 1-methyl-1-cyclohexyloxyethoxy group, 1-methyl-1-norbornyloxyethoxy group, 1-methyl-1 -Bornyloxyethoxy group, 1-methyl-1-phenyloxyethoxy group, 1-methyl-1- (1-naphthyloxy ) Ethoxy group, 1-methyl-1-benzyloxyethoxy group, 1-methyl-1-phenethyloxyethoxy group, 1-cyclohexyl-1-methoxyethoxy group, 1-cyclohexyl-1-ethoxyethoxy group, 1-cyclohexyl -1-n-propoxyethoxy group, 1-cyclohexyl-1-i-propoxyethoxy group, 1-cyclohexyl-1-cyclohexyloxyethoxy group, 1-cyclohexyl-1-phenoxyethoxy group, 1-cyclohexyl-1-benzyloxy Ethoxy group, 1-phenyl-1-methoxyethoxy group, 1-phenyl-1-ethoxyethoxy group, 1-phenyl-1-n-propoxyethoxy group, 1-phenyl-1-i-propoxyethoxy group, 1-phenyl -1-cyclohexyloxyethoxy group, 1-pheny -1-phenyloxyethoxy group, 1-phenyl-1-benzyloxyethoxy group, 1-benzyl-1-methoxyethoxy group, 1-benzyl-1-ethoxyethoxy group, 1-benzyl-1-n-propoxyethoxy group 1-benzyl-1-i-propoxyethoxy group, 1-benzyl-1-cyclohexyloxyethoxy group, 1-benzyl-1-phenyloxyethoxy group, 1-benzyl-1-benzyloxyethoxy group, 2- (2 -Methyltetrahydrofuranyl) oxy group, 2- (2-methyltetrahydropyranyl) oxy group, 1-methoxycyclopentyloxy group, 1-methoxy-cyclohexyloxy group and the like.

  Among these, 1-methyl-1-methoxyethoxy group and 1-methyl-1-cyclohexyloxyethoxy group can be mentioned as preferable ones.

  As the carboxylic acid having a carboxy group protected by the protecting group, any carboxylic acid can be used as long as it can be a monomer unit (a1) by protecting the carboxy group with a protecting group. For example, acrylic acid, methacrylic acid, Examples thereof include monocarboxylic acids such as crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid. As the monomer unit (a1), these carboxy groups are protected with a protecting group. Carboxylic acid-derived monomer units can be mentioned as preferred, and monomer units derived from methacrylic acid and acrylic acid are particularly preferred.

  Among the monomer units (a1), examples of the monomer unit having a residue that generates a phenolic hydroxyl group with an acid include a monomer having a structure in which a phenolic hydroxyl group is protected with a protecting group, which is known in the field of positive chemically amplified resists. A monomer unit having an acetal protection structure, a ketal protection structure, or a tertiary alkyl protection structure of a phenolic hydroxyl group can be preferably used.

  As the protecting group for the phenolic hydroxyl group, the protecting group for the carboxy group described above can be used. Particularly preferred structures include a 1-ethoxyethyl group, a 1-cyclohexyloxyethyl group, a 2-tetrahydropyranyl group, A 1-n-propoxyethyl group and a 2-tetrahydrofuranyl group can be exemplified. Moreover, as a protecting group for the phenolic hydroxyl group, a tert-butoxycarbonyl group can also be mentioned as a particularly preferred structure.

As the compound having a phenolic hydroxyl group protected by the protecting group, any compound can be used as long as the phenolic hydroxyl group can be protected by the protecting group to become a monomer unit (a1). For example, p-hydroxystyrene, Hydroxystyrenes such as α-methyl-p-hydroxystyrene, compounds described in paragraphs 0011 to 0016 of JP-A-2008-40183, and 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of Japanese Patent No. 2888454 Preferred examples include an addition reaction product of 4-hydroxybenzoic acid and glycidyl methacrylate, an addition reaction product of 4-hydroxybenzoic acid and glycidyl acrylate, and the like.
Among these, α-methyl-p-hydroxystyrene, compounds described in paragraphs 0011 to 0016 of JP-A-2008-40183, and 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of Japanese Patent No. 2888454 An addition reaction product of 4-hydroxybenzoic acid and glycidyl methacrylate and an addition reaction product of 4-hydroxybenzoic acid and glycidyl acrylate are more preferable.

  Preferable specific examples of the radical polymerizable monomer used for forming the monomer unit (a1) having a residue that generates a carboxy group or a phenolic hydroxyl group with an acid include the following.

  1-ethoxyethyl methacrylate, 1-ethoxyethyl acrylate, 1-methoxyethyl methacrylate, 1-methoxyethyl acrylate, 1-n-butoxyethyl methacrylate, 1-n-butoxyethyl acrylate, 1-isobutoxyethyl methacrylate, 1-iso Butoxyethyl acrylate, 1- (2-ethylhexyloxy) ethyl methacrylate, 1- (2-ethylhexyloxy) ethyl acrylate, 1-n-propoxyethyl methacrylate, 1-n-propoxyethyl acrylate, 1-cyclohexyloxyethyl methacrylate, 1 -Cyclohexyloxyethyl acrylate, 1- (2-cyclohexylethoxy) ethyl methacrylate, 1- (2-cyclohexylethoxy) ethyl acrylate, 1 Benzyl methacrylate, 1-benzyloxy-ethyl acrylate, methacrylic acid tetrahydrofuran-2-yl, acrylic acid tetrahydrofuran-2-yl;

  Tert-butyl methacrylate, tert-butyl acrylate, tetrahydro-2H-pyran-2-yl methacrylate, tetrahydro-2H-pyran-2-yl acrylate, 2-methyl-2-adamantyl methacrylate, 2-acrylate Methyl-2-adamantyl, 1-methylcyclohexyl methacrylate, 1-methylcyclohexyl acrylate;

  1-alkoxyalkyl protector of hydroxystyrene, tetrahydropyranyl protector of hydroxystyrene, tetrahydrofuranyl protector of hydroxystyrene, 1-alkoxyalkyl protector of α-methyl-hydroxystyrene, tetrahydropyrani of α-methyl-hydroxystyrene Protector, α-methyl-hydroxystyrene tetrahydrofuranyl protector, α-methyl-hydroxystyrene tert-butoxycarbonyl group protector, 4-hydroxyphenyl methacrylate 1-alkoxyalkyl protector, 4-hydroxyphenyl methacrylate protector Protected tetrahydropyranyl, protected tetrahydrofuranyl of 4-hydroxyphenyl methacrylate, tert-butoxycarbonyl group of 4-hydroxyphenyl methacrylate , 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester 1-alkoxyalkyl protected, 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester tetrahydropyranyl protected, 4-hydroxybenzoic acid (2 -Methacryloyloxyethyl) ester tetrahydrofuranyl protected, 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester 1-alkoxyalkyl protected, 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester tetrahydropyranyl Protected body, 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester protected tetrahydrofuranyl, 4-hydroxybenzoic acid (6-methacryloyloxyhexyl) ester 1-alkoxyalkyl Protected, 4-hydroxybenzoic acid (6-methacryloyloxyhexyl) ester tetrahydropyranyl protected, 4-hydroxybenzoic acid (6-methacryloyloxyhexyl) ester tetrahydrofuranyl protected, 4-hydroxybenzoic acid (3 -1-alkoxyalkyl protected form of methacryloyloxy-2-hydroxypropyl) ester, tetrahydropyranyl protected form of 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester, 4-hydroxybenzoic acid (3- A tetrahydrofuranyl protected form of methacryloyloxy-2-hydroxypropyl) ester.

Among these, in particular, 1-ethoxyethyl methacrylate, 1-ethoxyethyl acrylate, 1-cyclohexyloxyethyl methacrylate, 1-cyclohexyloxyethyl acrylate, tetrahydro-2H-pyran-2-yl methacrylate, tetrahydro-2H acrylate -Pyran-2-yl, tetrahydrofuran-2-yl methacrylate, tetrahydrofuran-2-yl acrylate, 1-alkoxyalkyl protector of α-methyl-hydroxystyrene, tetrahydropyranyl protector of α-methyl-hydroxystyrene, α-Methyl-hydroxystyrene protected with tetrahydrofuranyl, 4-hydroxyphenyl methacrylate with 1-alkoxyalkyl protected, 4-hydroxyphenyl methacrylate with tetrahydropyranyl protected , Tetrahydrofuranyl protector of 4-hydroxyphenyl methacrylate, 1-alkoxyalkyl protector of 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester, tetrahydropyrani of 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester Protected, 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester tetrahydrofuranyl protected, 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester 1-alkoxyalkyl protected, 4-hydroxybenzoic acid ( 3-Methacryloyloxypropyl) ester tetrahydropyranyl protected, 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester tetrahydrofuranyl protected, 4-hydroxybenzoic 1-alkoxyalkyl protector of (6-methacryloyloxyhexyl) ester, tetrahydropyranyl protector of 4-hydroxybenzoic acid (6-methacryloyloxyhexyl) ester, 4-hydroxybenzoic acid (6-methacryloyloxyhexyl) ester Protected tetrahydrofuranyl, 1-alkoxyalkyl protected 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester, tetrahydropyrani 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester Preferred is a protected hydrocarbon and a protected tetrahydrofuranyl of 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester.
These radically polymerizable monomers can be used alone or in combination of two or more.

The content of the monomer unit (a1) having a residue that generates a carboxy group or a phenolic hydroxyl group with an acid in all the monomer units constituting the polymer (A) is preferably 10 to 70 mol%, and preferably 15 to 60 More preferably, mol% is more preferable, and 20-50 mol% is still more preferable. By containing the monomer unit (a1) at the above ratio, a highly sensitive photosensitive resin composition can be obtained.
A commercially available thing may be used for the radically polymerizable monomer used in order to form a monomer unit (a1), and what was synthesize | combined by the well-known method can also be used. For example, it can be synthesized by reacting (meth) acrylic acid with a vinyl ether compound in the presence of an acid catalyst as described below.

  In addition, the monomer unit (a1) may be formed by reacting a carboxyl group or a phenolic hydroxyl group with, for example, a vinyl ether compound after polymerization with the monomer units (a2) to (a5) described below or a precursor thereof. it can. In addition, the specific example of the preferable monomer unit formed in this way is the same as the monomer unit derived from the preferable specific example of the said radical polymerizable monomer.

<Monomer unit (a2)>
(A) A component contains the monomer unit (a2) which has a C3-C16 group which has an ethylenically unsaturated bond at the terminal.

  A monomer unit (a2) will not be specifically limited if it is a monomer unit which has C3-C16 group which has an ethylenically unsaturated bond in the terminal. Among these, a monomer unit having a specific side chain represented by the following formula (1) is preferable.

In Formula (1), R ¹ is a group having 1 to 13 carbon atoms, and an organic group selected from the group consisting of an aliphatic group, an aliphatic group including a cyclic structure, and an aromatic group, or a group thereof. An organic group comprising a combination of a plurality of organic groups selected from R ¹ may contain a bond such as an ester bond, an ether bond, an amide bond, or a urethane bond. R ³ represents a hydrogen atom or a methyl group.

Specific examples of R ¹ include those represented by the following formulas (A-1) to (A-10).

  Among the specific side chains represented by the formula (1), a specific side chain which is an aliphatic side chain is preferable, and a specific side chain whose terminal is an acryloyl group or a methacryloyl group is more preferable.

  Moreover, it is preferable that 1 mol of unsaturated double bonds contained in the specific side chain represented by the formula (1) is contained with respect to 150 to 2,000 g of the polymer (A). It is more preferable that 1 mol is contained with respect to 300 g.

  The method for obtaining the monomer unit (a2) having the specific side chain as described above is not particularly limited. For example, a polymer having a specific functional group is generated in advance by a polymerization method such as radical polymerization, and the specific functional group is obtained. And a compound having an unsaturated bond at the terminal (hereinafter referred to as a specific compound) to produce a specific side chain to form a monomer unit (a2).

  Here, the specific functional group means one or more functional groups selected from the group consisting of a carboxyl group, an epoxy group, a hydroxy group, an amino group having active hydrogen, a phenolic hydroxy group, an isocyanate group, and the like. .

  Examples of the specific compound include glycidyl methacrylate, glycidyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, isocyanate ethyl methacrylate, isocyanate ethyl acrylate, methacrylic acid chloride, and acrylic acid. Examples include chloride, methacrylic acid, and acrylic acid.

  Among the monomer units (a2) thus obtained, a monomer unit (a2) having a preferred specific side chain is a monomer unit having a side chain represented by the above formula (1), that is, the following formula (2) Is a monomer unit represented by

In the formula (2), R ¹ is a group having 1 to 13 carbon atoms as defined in the above formula (1), and includes an aliphatic group, an aliphatic group containing a cyclic structure, and an aromatic group. An organic group selected from the group consisting of groups, or an organic group consisting of a combination of a plurality of organic groups selected from these groups. R ¹ may contain a bond such as an ester bond, an ether bond, an amide bond, or a urethane bond. R ² and R ³ each independently represents a hydrogen atom or a methyl group.

  In the reaction for generating the specific side chain, a preferable combination of the specific functional group and the specific compound includes a carboxyl group and an epoxy group, a carboxyl group and an oxetanyl group, a hydroxy group and an isocyanate group, a phenolic hydroxy group and an epoxy group, A combination of a carboxyl group and an isocyanate group, an amino group and an isocyanate group, a hydroxy group and an acid chloride, and the like. More specifically, a carboxyl group and glycidyl methacrylate, and a hydroxy group and isocyanate ethyl methacrylate are preferable.

The polymer having the specific functional group is a monomer having a functional group (specific functional group) for reacting with a specific compound, that is, a carboxyl group, an epoxy group, a hydroxy group, an amino group having active hydrogen, or a phenolic hydroxy group. A (co) polymer obtained by polymerizing a monomer selected from the group consisting of monomers having a group or an isocyanate group as an essential constituent, and having a number average molecular weight of 1,000 to 50,000 is there. In that case, the monomer which has a specific functional group may be individual, and if it is a combination which does not react during superposition | polymerization, you may use multiple types together.
Specific examples of the monomer having a specific functional group necessary for obtaining a polymer having a specific functional group are listed below, but the invention is not limited thereto.

  Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, and N- (carboxyphenyl). ) Maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide and the like.

  Examples of the monomer having an epoxy group include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2-epoxy-5-hexene, 1,7. -Octadiene monoepoxide, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate and the like.

  Examples of the monomer having a hydroxy group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3- Dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2- (acryloyloxy) ethyl ester, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, poly (Ethylene glycol) ethyl ether methacrylate, 5-acryloyl Shi-6-hydroxy-norbornene-2-carboxylic-6-lactone, 5-methacryloyloxy-6-hydroxy-norbornene-2-carboxylic-6-lactone and the like.

  Examples of the monomer having an amino group having active hydrogen include 2-aminoethyl acrylate and 2-aminomethyl methacrylate.

  Examples of the monomer having a phenolic hydroxy group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) maleimide and the like.

  Furthermore, as a monomer which has an isocyanate group, acryloyl ethyl isocyanate, methacryloyl ethyl isocyanate, m-tetramethyl xylene isocyanate, etc. are mentioned, for example.

  Further, in the present invention, when obtaining a polymer having a specific functional group, the monomer having the specific functional group and the monomer to be the monomer unit (a1), the monomer units (a3) to (a5) described later. The monomer which becomes can be used together.

A method for obtaining a polymer having a specific functional group used in the present invention is not particularly limited. It can be obtained by carrying out a polymerization reaction at a temperature of 110 ° C. In that case, the solvent used will not be specifically limited if it dissolves the monomer which comprises the polymer which has a specific functional group, and the polymer which has a specific functional group. As a specific example, the solvent described in the (C) solvent mentioned later is mentioned.
The polymer having the specific functional group thus obtained is usually in a solution state dissolved in a solvent.

Subsequently, a specific compound is made to react with the obtained polymer which has a specific functional group, and the monomer unit (a2) which has a C3-C16 group which has an ethylenically unsaturated bond at the terminal can be obtained. At that time, a polymer solution having a specific functional group is usually subjected to the reaction.
Specifically, for example, the monomer unit (a2) is obtained by reacting a solution of an acrylic polymer having a carboxyl group with glycidyl methacrylate at a temperature of 70 to 150 ° C. in the presence of a catalyst such as benzyltriethylammonium chloride. be able to.

Further, in order to form the monomer unit (a2), allyl methacrylate or allyl acrylate may be used as the radical polymerizable monomer in addition to the polymer reaction as described above.
These monomer units can be used alone or in combination of two or more.

  In the monomer unit constituting the polymer (A), the content of the monomer unit (a2) having a group having 3 to 16 carbon atoms having an ethylenically unsaturated bond at the terminal is preferably 15 to 80 mol%, 20-75 mol% is more preferable, and 20-65 mol% is still more preferable. By containing the monomer unit (a2) at the above ratio, transparency of the cured film obtained from the photosensitive resin composition and ITO sputtering resistance are improved.

<Monomer unit (a3) having carboxy group, carboxylic acid anhydride residue and / or phenolic hydroxyl group>
The (A) polymer preferably contains a monomer unit (a3) having a carboxy group, a carboxylic acid anhydride residue and / or a phenolic hydroxyl group as long as the (A) polymer is not alkali-soluble. .
Examples of the radical polymerizable monomer used to form a monomer unit having a carboxy group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itacone. Preferred examples include dicarboxylic acids such as acids.
Moreover, as a radically polymerizable monomer used in order to form the monomer unit which has a carboxylic anhydride residue, maleic anhydride, itaconic anhydride, etc. can be mentioned as a preferable thing, for example.
Examples of the radical polymerizable monomer used to form a monomer unit having a phenolic hydroxyl group include hydroxystyrenes such as p-hydroxystyrene and α-methyl-p-hydroxystyrene, and JP-A-2008-40183. Compounds described in paragraphs 0011 to 0016 of the above, 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of Japanese Patent No. 2888454, addition reaction product of 4-hydroxybenzoic acid and glycidyl methacrylate, 4-hydroxybenzoic acid An addition reaction product of an acid and glycidyl acrylate can be mentioned as a preferable one.

  Among these, methacrylic acid, acrylic acid, compounds described in paragraphs 0011 to 0016 of JP-A-2008-40183, 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of Japanese Patent No. 2888454, 4- An addition reaction product of hydroxybenzoic acid and glycidyl methacrylate, and an addition reaction product of 4-hydroxybenzoic acid and glycidyl acrylate are more preferable. Compounds described in paragraphs 0011 to 0016 of JP-A-2008-40183, Patent No. In particular, 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of No. 2888454, addition reaction product of 4-hydroxybenzoic acid and glycidyl methacrylate, addition reaction product of 4-hydroxybenzoic acid and glycidyl acrylate preferable. These monomer units can be used alone or in combination of two or more.

  Preferable specific examples of the monomer unit (a3) include the following monomer units.

  The content of the monomer unit (a3) in the case where the monomer unit (a3) having a carboxy group, a carboxylic acid anhydride residue and / or a phenolic hydroxyl group is contained in all the monomer units constituting the polymer (A) is as follows. 1-25 mol% is preferable, 2-25 mol% is more preferable, and 3-20 mol% is still more preferable. By containing the monomer unit (a3) having a carboxy group, a carboxylic acid anhydride residue and / or a phenolic hydroxyl group at the above ratio, high sensitivity can be obtained and developability can be improved.

<Monomer unit (a4) having epoxy group and / or oxetanyl group>
The (A) polymer may contain a monomer unit (a4) having an epoxy group and / or an oxetanyl group.
The monomer unit (a4) having an epoxy group and / or oxetanyl group is preferably a monomer unit having an alicyclic epoxy group and / or oxetanyl group, and more preferably a monomer unit having an oxetanyl group.
The alicyclic epoxy group is a group in which an aliphatic ring and an epoxy ring form a condensed ring. Specifically, for example, 3,4-epoxycyclohexyl group, 2,3-epoxycyclohexyl group, 2,3 -An epoxy cyclopentyl group etc. are mentioned preferably.
The group having an oxetanyl group is not particularly limited as long as it has an oxetane ring, but a (3-ethyloxetane-3-yl) methyl group can be preferably exemplified.
The monomer unit having an epoxy group and / or oxetanyl group may have at least one epoxy group or oxetanyl group in one monomer unit, one or more epoxy groups and one or more oxetanyl groups, two Although it may have the above epoxy groups or two or more oxetanyl groups and is not particularly limited, it preferably has a total of 1 to 3 epoxy groups and / or oxetanyl groups, and epoxy groups and / or oxetanyl groups. It is more preferable to have one or two groups in total, and it is even more preferable to have one epoxy group or oxetanyl group.

  Specific examples of the radical polymerizable monomer used to form the monomer unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, and glycidyl α-n-propyl acrylate. Glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, acrylate-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, cycloaliphatic described in paragraphs 0031 to 0035 of Japanese Patent No. 4168443 Compounds containing an epoxy skeleton It is.

  Specific examples of the radical polymerizable monomer used for forming the monomer unit having an oxetanyl group include, for example, (meth) acrylic acid having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A No. 2001-330953. Examples include esters.

  Specific examples of the radical polymerizable monomer used to form a monomer unit having an epoxy group and / or an oxetanyl group include a monomer having a methacrylic ester structure and a monomer having an acrylate structure. Is preferred.

  Among these monomers, more preferred are compounds containing an alicyclic epoxy skeleton described in paragraphs 0034 to 0035 of Japanese Patent No. 4168443 and paragraphs 0011 to 0016 of JP 2001-330953 A. (Meth) acrylic acid esters having an oxetanyl group, particularly preferred are (meth) acrylic acid esters having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A No. 2001-330953. Among these, preferred are 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, (3-ethyloxetane-3-yl) methyl acrylate, and methacrylic acid (3-ethyloxetane). -3-yl) methyl, most preferred are acrylic acid (3-ethyloxetane-3-yl) methyl and methacrylic acid (3-ethyloxetane-3-yl) methyl. These monomer units can be used singly or in combination of two or more.

  Preferable specific examples of the monomer unit (a4) include the following monomer units.

  When the monomer unit (a4) having an epoxy group and / or oxetanyl group is contained in all monomer units constituting the polymer (A), the content is preferably 1 to 50 mol%, and 5 to 50 mol%. Is more preferable, and 5-40 mol% is still more preferable. By containing the monomer unit (a4) having an epoxy group and / or an oxetanyl group in the above ratio, the physical properties of the cured film may be improved.

<Other monomer units (a5)>
The polymer (A) is a monomer unit (a5) other than the above (a1) to (a4) (hereinafter referred to as “component (a5)” or “other monomer units (a5), as long as the effects of the present invention are not hindered. ) ”))).
Examples of the radical polymerizable monomer used to form the component (a5) include the compounds described in paragraphs 0021 to 0024 of JP-A No. 2004-264623 (provided that (a1) above) To (a4) monomer units are excluded.).

Among these, (meth) acrylic acid esters containing alicyclic structure such as dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl acrylate, methyl (meth) acrylate, (meth) Preferred examples include 2-hydroxyethyl acrylate and styrene.
These (a5) components can be used individually by 1 type or in combination of 2 or more types.

  In all monomer units constituting the polymer (A), the content of the component (a5) when the component (a5) is contained is preferably 1 to 50 mol%, more preferably 5 to 40 mol%, 30 mol% is still more preferable.

  The weight average molecular weight of the polymer (A) is preferably more than 1,000, more than 1,000 and not more than 100,000, and more preferably 2,000 to 50,000. In addition, it is preferable that the weight average molecular weight in this invention is a polystyrene conversion weight average molecular weight by gel permeation chromatography (GPC).

  Various methods are also known for the synthesis method of the polymer (A). To give an example, at least a radical polymerizable monomer and a monomer used to form the monomer unit (a1) A specific functional group-containing polymer obtained by polymerizing a radical polymerizable monomer mixture containing a radical polymerizable monomer having the specific functional group used to form the unit (a2) in an organic solvent using a radical polymerization initiator Can be obtained. The polymer (A) can be obtained by adding the specific compound to the specific functional group-containing polymer by the method described above.

Hereinafter, preferred examples of the polymer (A) used in the present invention are illustrated, but the present invention is not limited thereto.
In addition, it is preferable that the weight average molecular weights of the said (A) polymer illustrated below are 2,000-50,000. The “(partial) adduct” represents a complete adduct or a partial adduct, and the partial adduct is a more preferable embodiment.
1-Ethoxyethyl methacrylate / methacrylic acid copolymer glycidyl methacrylate (part) adduct 1-ethoxyethyl methacrylate / methacrylic acid / methyl methacrylate glycidyl methacrylate (part) adduct methacrylic acid Glycidyl methacrylate (partial) adduct of 1-ethoxyethyl / methacrylic acid / dicyclopentanyl methacrylate copolymer Glycidyl methacrylate of 1-ethoxyethyl / methacrylic acid / 2-hydroxyethyl methacrylate copolymer (Part) Adduct Tetrahydrofuran-2-yl methacrylate / Methacrylic acid / Glycidyl methacrylate of 2-hydroxyethyl methacrylate copolymer (Part) Adduct Tetrahydrofuran-2-yl methacrylate / Methacrylic acid / Methacrylic acid 2 -Hydroxyethyl / Styrene copolymer glycidyl methacrylate (part) adduct 1-ethoxyethyl methacrylate / methacrylic acid / cyclohexyl methacrylate glycidyl methacrylate (part) adduct tetrahydro-2H-pyran-2 methacrylate -Glycidyl methacrylate (partially) adduct of yl / methacrylic acid / dicyclopentanyl methacrylate copolymer 1-ethoxyethyl methacrylate / methacrylic acid / methyl methacrylate copolymer 3,4-epoxycyclohexyl methacrylate Methyl (partial) adduct 1,4-ethoxyethyl methacrylate / methacrylic acid / methyl methacrylate copolymer 3,4-epoxycyclohexylmethyl acrylate (partial) adduct tetrahydro-2H-pyran-2-yl methacrylate / Methacrylic acid / methacrylic acid 1,4-Epoxycyclohexylmethyl acrylate (partial) adduct of hexyl copolymer 1-ethoxyethyl methacrylate / 3,4-epoxycyclohexylmethyl methacrylate / 4-hydroxyphenyl methacrylate / methyl methacrylate copolymer Acrylic acid (partial) adduct of 1-ethoxyethyl methacrylate / 3,4-epoxycyclohexylmethyl acrylate / 4-hydroxyphenyl methacrylate / methyl methacrylate copolymer 1-ethoxyethyl / glycidyl methacrylate / 4-hydroxyphenyl methacrylate / methacrylic acid (partial) adduct of copolymer of methyl methacrylate 1-ethoxyethyl / glycidyl methacrylate / 4-hydroxyphenyl methacrylate / methacrylic acid acid Acrylic acid (partially) adduct of methyl copolymer 1-ethoxyethyl methacrylate / glycidyl methacrylate / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / acrylic acid of dicyclopentanyl methacrylate copolymer (Partial) Adduct α-methyl-parahydroxystyrene 1-ethoxyethyl ether / methacrylic acid / methyl methacrylate copolymer glycidyl methacrylate (partial) adduct α-methyl-parahydroxystyrene 2-tetrahydro Pyranyl ether / methacrylic acid / methyl methacrylate copolymer 3,4-epoxycyclohexylmethyl methacrylate (partially) adduct α-methyl-parahydroxystyrene 2-tetrahydropyranyl ether / methacrylic acid / methyl methacrylate copolymer Combined acrylic acid 3 4-Epoxycyclohexylmethyl (partially) adduct α-methyl-parahydroxystyrene 1-ethoxyethyl ether / 3,4-epoxycyclohexylmethyl methacrylate / 4-hydroxyphenyl methacrylate / acrylic methyl methacrylate copolymer Acid (partial) adduct α-methyl-parahydroxystyrene 1-ethoxyethyl ether / acrylic acid 3,4-epoxycyclohexylmethyl / methacrylic acid 4-hydroxyphenyl / acrylic acid cyclohexyl copolymer (partial) ) Acrylic acid of 1-ethoxyethyl ether / glycidyl methacrylate / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / cyclohexyl methacrylate copolymer of adduct α-methyl-parahydroxystyrene (part) Tert-butyl methacrylate / methacrylic acid / methyl methacrylate copolymer glycidyl methacrylate (partially) adduct α-methyl-parahydroxystyrene protected tert-butoxycarbonyl group / methacrylic acid / methyl methacrylate copolymer Glycidyl methacrylate (part) adduct of polymer 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester 1-ethoxyethyl ether / methacrylic acid / methyl methacrylate copolymer glycidyl methacrylate (part) addition 4-hydroxyphenyl methacrylate 1-ethoxyethyl ether / methacrylic acid / methyl methacrylate copolymer glycidyl methacrylate (partial) adduct 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester 1 of Glycidyl methacrylate ethoxyethyl ether / methacrylic acid / methacrylic acid cyclohexyl copolymer (part) adduct (A) polymers may be used alone or in combination of two or more.

The content ratio of the monomer unit (a1) to the monomer unit (a2) in the polymer (A) is a molar ratio, and is monomer unit (a1): monomer unit (a2) = 100: 10 to 100: 500. Is more preferable, 100: 20 to 100: 200 is more preferable, and 100: 50 to 100: 150 is still more preferable.
In addition, the content ratio of the monomer unit (a1), the monomer unit (a2), and the monomer unit (a3) in the polymer (A) is a molar ratio: monomer unit (a1): monomer unit (a2): monomer unit. (A3) = 100: (10-500) :( 0-100) is preferable, 100: (20-200) :( 1-80) is more preferable, 100: (50-150) : (10-50) is more preferable.
The content of the polymer (A) in the photosensitive resin composition of the present invention is preferably 20 to 99% by weight, preferably 40 to 97% by weight, based on the total solid content of the photosensitive resin composition. It is more preferable that it is 60 to 95% by weight. When the content is within this range, the pattern formability upon development is good. In addition, the solid content amount of the photosensitive resin composition represents an amount excluding volatile components such as a solvent.
In addition, in the photosensitive resin composition of this invention, you may use together resin other than (A) polymer in the range which does not inhibit the effect of this invention. However, the content of the resin other than the polymer (A) is preferably smaller than the content of the polymer (A) from the viewpoint of the physical properties of the obtained cured film.

(B) Photoacid generator The photosensitive resin composition of the present invention contains (B) a photoacid generator.
As the photoacid generator (also referred to as “component (B)”) used in the present invention, a compound that reacts with actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid is preferable. The chemical structure is not limited. Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.
The photoacid generator used in the present invention is preferably a photoacid generator that generates an acid having a pKa of 4 or less, and more preferably a photoacid generator that generates an acid having a pKa of 3 or less.
Examples of the photoacid generator include trichloromethyl-s-triazines, iodonium salts, sulfonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, it is preferable to use an oxime sulfonate compound from the viewpoint of insulation. These photoacid generators can be used singly or in combination of two or more.

Specific examples of these include the following.
As trichloromethyl-s-triazines, 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -bis (4,6-trichloromethyl)- s-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxy-β-styryl) -bis (4,6-trichloromethyl) -s -Triazine, 2-piperonyl-bis (4,6-trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine, 2- [2- (5-Methylfuran-2-yl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methyl) Butylphenyl) ethenyl] - bis (4,6-trichloromethyl) -s-triazine, or 2- (4-methoxynaphthyl) - bis (4,6-trichloromethyl) -s-triazine and the like;

  As iodonium salts, diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, phenyl, 4- (2′-hydroxy-1 ′) -Tetradecaoxy) phenyliodonium trifluoromethanesulfonate, 4- (2'-hydroxy-1'-tetradecaoxy) phenyliodonium hexafluoroantimonate, or phenyl, 4- (2'-hydroxy-1'-tetra Decaoxy) phenyliodonium-p-toluenesulfonate and the like;

  Examples of sulfonium salts include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfone. Nato or 4-phenylthiophenyldiphenylsulfonium trifluoroacetate, etc .;

  As quaternary ammonium salts, tetramethylammonium butyltris (2,6-difluorophenyl) borate, tetramethylammonium hexyltris (p-chlorophenyl) borate, tetramethylammonium hexyltris (3-trifluoromethylphenyl) borate, benzyl Dimethylphenylammonium butyltris (2,6-difluorophenyl) borate, benzyldimethylphenylammonium hexyltris (p-chlorophenyl) borate, benzyldimethylphenylammonium hexyltris (3-trifluoromethylphenyl) borate, etc .;

  Examples of the diazomethane compound include bis (cyclohexylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, and the like;

Examples of imide sulfonate compounds include trifluoromethylsulfonyloxybicyclo [2.2.1] -hept-5-ene-dicarboximide, succinimide trifluoromethyl sulfonate, phthalimido trifluoromethyl sulfonate, N-hydroxynaphthalimide methane sulfonate, N -Hydroxy-5-norbornene-2,3-dicarboximidopropane sulfonate and the like.
The compound shown below as an oxime sulfonate compound.

  As an oxime sulfonate compound, that is, a compound having an oxime sulfonate residue, a compound containing an oxime sulfonate residue represented by the formula (4) can be preferably exemplified.

In formula (4), R ⁵ represents an alkyl group or an aryl group. Any group may be substituted, and the alkyl group in R ⁵ may be linear, branched or cyclic. Acceptable substituents are described below.
The alkyl group for R ⁵ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms.
The alkyl group of R ⁵ is an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group or other bridged type fat It may be substituted with a cyclic group, preferably a bicycloalkyl group or the like.
As the aryl group for R ^5, an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. The aryl group of R ⁵ may be substituted with a lower alkyl group, an alkoxy group or a halogen atom.
As for the said compound containing the oxime sulfonate residue represented by Formula (4), it is more preferable that it is an oxime sulfonate compound represented by following formula (5).

In formula (5), R ⁵ has the same meaning as R ⁵ in formula (4), X represents an alkyl group, an alkoxy group, or a halogen atom, m represents an integer of 0 to 3, and m represents When it is 2 or 3, a plurality of X may be the same or different.
The alkyl group represented by X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
The alkoxy group represented by X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
As the halogen atom represented by X, a chlorine atom or a fluorine atom is preferable.
m is preferably 0 or 1.
In the formula (5), m is 1, X is a methyl group, the substitution position of X is an ortho position, R ⁵ is a linear alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl- A compound that is a 2-oxonorbornylmethyl group or a p-tolyl group is particularly preferable.

  Specific examples of the oxime sulfonate compound include the following compound (i), compound (ii), compound (iii), compound (iv), and the like. These may be used alone or in combination of two or more. be able to. Compounds (i) to (iv) can be obtained as commercial products. Moreover, it can also be used in combination with another kind of (B) photo-acid generator.

  The compound containing an oxime sulfonate residue represented by formula (4) is also preferably a photoacid generator represented by formula (II).

In the formula (II), R ^4A represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group, and L is an integer of 0 to 5 Represents. R ^3A is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, or W A phenyl group which may be substituted, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W, W represents a halogen atom, a cyano group, a nitro group, 1 to 1 carbon atoms It represents a 10 alkyl group, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms.

R ^3A in the formula (II) includes methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group, perfluoro group, A fluoro-n-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferable, and a methyl group, ethyl group, n-propyl group, n-butyl group or p-tolyl group is particularly preferable. .
The halogen atom represented by R ^4A is preferably a fluorine atom, a chlorine atom or a bromine atom.
The alkyl group having 1 to 4 carbon atoms represented by R ^4A is preferably a methyl group or an ethyl group.
The alkoxy group having 1 to 4 carbon atoms represented by R ^4A is preferably a methoxy group or an ethoxy group.
As L, an integer of 0 to 2 is preferable, and 0 or 1 is particularly preferable.

As a preferred embodiment of the compound included in the photoacid generator represented by the formula (II), R ^3A represents a methyl group, an ethyl group, an n-propyl group, an n-butyl group or a 4-tolyl group, R ^4A represents a hydrogen atom or a methoxy group, and L is 0 or 1.

  Hereinafter, although the especially preferable example of the compound included by the photo-acid generator represented by Formula (II) is shown, this invention is not limited to these.

α- (Methylsulfonyloxyimino) benzyl cyanide (R ^3A = methyl group, R ^4A = hydrogen atom)
α- (Ethylsulfonyloxyimino) benzyl cyanide (R ^3A = ethyl group, R ^4A = hydrogen atom)
α- (n-propylsulfonyloxyimino) benzyl cyanide (R ^3A = n-propyl group, R ^4A = hydrogen atom)
α- (n-butylsulfonyloxyimino) benzyl cyanide (R ^3A = n-butyl group, R ^4A = hydrogen atom)
α- (4-Toluenesulfonyloxyimino) benzyl cyanide (R ^3A = 4-tolyl group, R ^4A = hydrogen atom)
α-[(Methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^3A = methyl group, R ^4A = methoxy group)
α-[(Ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^3A = ethyl group, R ^4A = methoxy group)
α-[(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^3A = n-propyl group, R ^4A = methoxy group)
α-[(n-butylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^3A = n-butyl group, R ^4A = methoxy group)
α-[(4-Toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^3A = 4-tolyl group, R ^4A = methoxy group)

  The compound containing an oxime sulfonate residue represented by the formula (4) is also preferably a compound represented by the formula (OS-1).

In the formula (OS-1), R ¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or hetero Represents an aryl group. R ² represents an alkyl group or an aryl group.
X is -O -, - S -, - NH -, - NR 5 -, - CH 2 -, - CR 6 H-, or, -CR ⁶ R ⁷ - represents, R ⁵ to R ⁷ is an alkyl group, Or an aryl group is represented.
R ^{21 to} R ²⁴ are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxy group, amino group, alkoxycarbonyl group, alkylcarbonyl group, arylcarbonyl group, amide group, sulfo group, cyano group, Or an aryl group is represented. Two of R ^{21 to} R ²⁴ may be bonded to each other to form a ring.
As R ^{21 to} R ²⁴ , a hydrogen atom, a halogen atom, and an alkyl group are preferable, and an embodiment in which at least two of R ^{21 to} R ²⁴ are bonded to each other to form an aryl group is also preferable. Among these, an embodiment in which R ^{21 to} R ²⁴ are all hydrogen atoms is preferable from the viewpoint of sensitivity.
Any of the aforementioned functional groups may further have a substituent.

  The compound represented by the formula (OS-1) is more preferably a compound represented by the following formula (OS-2).

In said formula (OS-2), R < ¹ >, R < ² >, R < ²¹ > -R < ²⁴ > is synonymous with each in formula (OS-1), and its preferable example is also the same.
Among these, the aspect in which R ¹ in the formula (OS-1) and the formula (OS-2) is a cyano group or an aryl group is more preferable, represented by the formula (OS-2), and R ¹ is a cyano group. The embodiment which is a phenyl group or a naphthyl group is most preferable.

  In the oxime sulfonate compound, the steric structure (E, Z, etc.) of the oxime or benzothiazole ring may be either one or a mixture.

  Specific examples (exemplary compounds b-1 to b-34) of the compound represented by the formula (OS-1) that can be suitably used in the present invention are shown below, but the present invention is not limited thereto. Me represents a methyl group, Et represents an ethyl group, Bn represents a benzyl group, and Ph represents a phenyl group.

  Among the above compounds, b-9, b-16, b-31, and b-33 are preferable from the viewpoint of achieving both sensitivity and stability.

  The compound containing an oxime sulfonate residue represented by the formula (4) is an oxime sulfonate compound represented by the formula (OS-3), formula (OS-4) or formula (OS-5). Is preferred.

（式（ＯＳ−３）〜式（ＯＳ−５）中、Ｒ¹はアルキル基、アリール基又はヘテロアリール基を表し、Ｒ²はそれぞれ独立に、水素原子、アルキル基、アリール基又はハロゲン原子を表し、Ｒ⁶はそれぞれ独立に、ハロゲン原子、アルキル基、アルキルオキシ基、スルホン酸基、アミノスルホニル基又はアルコキシスルホニル基を表し、ＸはＯ又はＳを表し、ｎは１又は２を表し、ｍは０〜６の整数を表す。）

(In Formula (OS-3) to Formula (OS-5), R ¹ represents an alkyl group, an aryl group, or a heteroaryl group, and R ² independently represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom. R ⁶ represents each independently a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, X represents O or S, n represents 1 or 2, m Represents an integer of 0 to 6.)

In the formulas (OS-3) to (OS-5), the alkyl group, aryl group, or heteroaryl group in R ¹ may have a substituent.
In the formulas (OS-3) to (OS-5), the alkyl group for R ¹ is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent.
Examples of the substituent that the alkyl group in R ¹ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. .

Examples of the alkyl group in R ¹ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n -Octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group, phenoxyethyl group, methylthioethyl group, phenylthioethyl group, ethoxycarbonylethyl group, Examples include phenoxycarbonylethyl group and dimethylaminocarbonylethyl group.
Among these, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, An n-decyl group, an n-dodecyl group, a trifluoromethyl group, a perfluoropropyl group, a perfluorohexyl group, and a benzyl group are preferable.

In the formulas (OS-3) to (OS-5), the aryl group for R ¹ is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.
As the substituent that the aryl group in R ¹ may have, a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an aminocarbonyl group , A sulfonic acid group, an aminosulfonyl group, and an alkoxysulfonyl group.

As the aryl group in R ¹ , a phenyl group, a p-methylphenyl group, a p-chlorophenyl group, a pentachlorophenyl group, a pentafluorophenyl group, an o-methoxyphenyl group, a p-phenoxyphenyl group, a p-methylthiophenyl group, p -Phenylthiophenyl group, p-ethoxycarbonylphenyl group, p-phenoxycarbonylphenyl group, p-dimethylaminocarbonylphenyl group.
Among these, a phenyl group, p-methylphenyl group, p-chlorophenyl group, pentachlorophenyl group, pentafluorophenyl group, o-methoxyphenyl group, and p-phenoxyphenyl group are preferable.

Further, the formula (OS-3) ~ (OS -5), as the heteroaryl group in R ^1, heteroaryl group having a total carbon number of 4-30 which may have a substituent is preferable.
Examples of the substituent that the heteroaryl group in R ¹ may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl. Group, sulfonic acid group, aminosulfonyl group and alkoxysulfonyl group.

In the formulas (OS-3) to (OS-5), at least one of the heteroaryl groups in R ¹ may be a heteroaromatic ring. For example, a heteroaromatic ring and a benzene ring are condensed. May be.
The heteroaryl group in R ¹ may have a substituent, the group consisting of a thiophene ring, a pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a benzothiophene ring, a benzothiazole ring, and a benzimidazole ring And a group in which one hydrogen atom is removed from the ring selected from the above.

In the formulas (OS-3) to (OS-5), R ² is preferably a hydrogen atom, an alkyl group, or an aryl group, and more preferably a hydrogen atom or an alkyl group.
In the formulas (OS-3) to (OS-5), it is preferable that one or two of R ² present in the compound is an alkyl group, an aryl group or a halogen atom, and one is an alkyl group. More preferably an aryl group or a halogen atom, and particularly preferably one is an alkyl group and the rest is a hydrogen atom.
In the formulas (OS-3) to (OS-5), the alkyl group or aryl group in R ² may have a substituent.
Examples of the substituent that the alkyl group or aryl group in R ² may have include the same groups as the substituent that the alkyl group or aryl group in R ¹ may have.

The alkyl group for R ² is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, and an alkyl group having 1 to 6 carbon atoms which may have a substituent. It is more preferable.
Specific examples of the alkyl group for R ² include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, allyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, perfluorohexyl group, chloromethyl group, bromomethyl group, methoxymethyl group, benzyl group, phenoxyethyl group, methylthioethyl Group, phenylthioethyl group, ethoxycarbonylethyl group, phenoxycarbonylethyl group, dimethylaminocarbonylethyl group.
Among these, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, n-hexyl group, allyl group, chloromethyl group, bromomethyl group, Methoxymethyl group and benzyl group are preferable, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group and n-hexyl group are more preferable, and methyl group , An ethyl group, an n-propyl group, an n-butyl group, and an n-hexyl group are more preferable, and a methyl group is particularly preferable.

The aryl group for R ² is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.
Specific examples of the aryl group for R ² include phenyl group, p-methylphenyl group, o-chlorophenyl group, p-chlorophenyl group, o-methoxyphenyl group, p-phenoxyphenyl group, p-methylthiophenyl group, p- Examples include a phenylthiophenyl group, a p-ethoxycarbonylphenyl group, a p-phenoxycarbonylphenyl group, and a p-dimethylaminocarbonylphenyl group.
Among these, a phenyl group, p-methylphenyl group, o-chlorophenyl group, p-chlorophenyl group, o-methoxyphenyl group, and p-phenoxyphenyl group are preferable.
Examples of the halogen atom for R ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Among these, a chlorine atom and a bromine atom are preferable.

In the formulas (OS-3) to (OS-5), X represents O or S, and is preferably O.
In formulas (OS-3) to (OS-5), the ring containing X as a ring member is a 5-membered ring or a 6-membered ring.
In the formulas (OS-3) to (OS-5), n represents 1 or 2, and when X is O, n is preferably 1, and when X is S, n is 2 is preferred.

In the formulas (OS-3) to (OS-5), the alkyl group and alkyloxy group in R ⁶ may have a substituent.
In the formulas (OS-3) to (OS-5), the alkyl group for R ⁶ is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent.
Examples of the substituent that the alkyl group in R ⁶ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. .

Examples of the alkyl group in R ⁶ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n -Octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group, phenoxyethyl group, methylthioethyl group, phenylthioethyl group, ethoxycarbonylethyl group, Examples include phenoxycarbonylethyl group and dimethylaminocarbonylethyl group.
Among these, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, An n-decyl group, an n-dodecyl group, a trifluoromethyl group, a perfluoropropyl group, a perfluorohexyl group, and a benzyl group are preferable.

In the formulas (OS-3) to (OS-5), the alkyloxy group for R ⁶ is preferably an alkyloxy group having 1 to 30 carbon atoms which may have a substituent.
Examples of the substituent that the alkyloxy group in R ⁶ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. It is done.

Examples of the alkyloxy group in R ⁶ include methyloxy group, ethyloxy group, butyloxy group, hexyloxy group, phenoxyethyloxy group, trichloromethyloxy group, ethoxyethyloxy group, methylthioethyloxy group, phenylthioethyloxy group, ethoxy Examples thereof include a carbonylethyloxy group, a phenoxycarbonylethyloxy group, and a dimethylaminocarbonylethyloxy group.
Among these, a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, a trichloromethyloxy group, or an ethoxyethyloxy group is preferable.
In the formulas (OS-3) to (OS-5), examples of the aminosulfonyl group for R ⁶ include a methylaminosulfonyl group, a dimethylaminosulfonyl group, a phenylaminosulfonyl group, a methylphenylaminosulfonyl group, and an aminosulfonyl group. It is done.
In the formulas (OS-3) to (OS-5), examples of the alkoxysulfonyl group for R ⁶ include a methoxysulfonyl group, an ethoxysulfonyl group, a propyloxysulfonyl group, and a butyloxysulfonyl group.

  In the formulas (OS-3) to (OS-5), m represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and 0. It is particularly preferred.

  The compound containing an oxime sulfonate residue represented by the formula (4) is particularly preferably an oxime sulfonate compound represented by any of the following formulas (OS-6) to (OS-11). .

（式（ＯＳ−６）〜（ＯＳ−１１）中、Ｒ¹はアルキル基、アリール基又はヘテロアリール基を表し、Ｒ⁷は、水素原子又は臭素原子を表し、Ｒ⁸は水素原子、炭素数１〜８のアルキル基、ハロゲン原子、クロロメチル基、ブロモメチル基、ブロモエチル基、メトキシメチル基、フェニル基又はクロロフェニル基を表し、Ｒ⁹は水素原子、ハロゲン原子、メチル基又はメトキシ基を表し、Ｒ¹⁰は水素原子又はメチル基を表す。）

(In the formulas (OS-6) to (OS-11), R ¹ represents an alkyl group, an aryl group or a heteroaryl group, R ⁷ represents a hydrogen atom or a bromine atom, R ⁸ represents a hydrogen atom or a carbon number. Represents an alkyl group of 1 to 8, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group; R ⁹ represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group; ¹⁰ represents a hydrogen atom or a methyl group.)

R ¹ in the formulas (OS-6) to (OS-11) has the same meaning as R ¹ in the formulas (OS-3) to (OS-5), and preferred embodiments thereof are also the same.
R ⁷ in formula (OS-6) represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
R ⁸ in the formulas (OS-6) to (OS-11) is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl. Represents a group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. Is more preferable, and a methyl group is particularly preferable.
R ⁹ in Formula (OS-8) and Formula (OS-9) represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group, and is preferably a hydrogen atom.
R ¹⁰ in formulas (OS-8) to (OS-11) represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
In the oxime sulfonate compound, the oxime steric structure (E, Z) may be either one or a mixture.

  Specific examples of the oxime sulfonate compound represented by the formula (OS-3) to the formula (OS-5) include the following exemplified compounds, but the present invention is not limited thereto.

  In the photosensitive resin composition of the present invention, the photoacid generator as the component (B) is preferably contained in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the component (A). More preferably, it is contained in an amount of 10 to 10 parts by weight.

The photosensitive resin composition of the present invention preferably contains a sensitizer in order to promote its decomposition in combination with the photoacid generator (B).
The sensitizer absorbs actinic rays or radiation and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a photo-acid generator raise | generates a chemical change and decomposes | disassembles and produces | generates an acid.
Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength ranges from 350 nm to 450 nm.

  Polynuclear aromatics (eg, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene), xanthenes (Eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), xanthones (eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines ( For example, merocyanine, carbomerocyanine), rhodocyanines, oxonols, thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine oleoresin) Di, chloroflavin, acriflavine), acridones (eg, acridone, 10-butyl-2-chloroacridone), anthraquinones (eg, anthraquinone), squariums (eg, squalium), styryls, base styryls ( For example, 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole), coumarins (for example, 7-diethylamino 4-methylcoumarin, 7-hydroxy-4-methylcoumarin, 2,3,6,7 -Tetrahydro-9-methyl-1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolidine-11-non).

  Among these sensitizers, polycyclic aromatics, acridones, styryls, base styryls and coumarins are preferable, and polycyclic aromatics are more preferable. Of the polynuclear aromatics, anthracene derivatives are most preferable.

(C) Solvent The photosensitive resin composition of the present invention contains (C) a solvent.
The photosensitive resin composition of the present invention comprises the above components (A) and (B) which are essential components, the following components (D) and / or (E) which are preferred components, and further optional components described below. (C) It is preferably prepared as a solution dissolved in a solvent.
As the solvent (C) used in the photosensitive resin composition of the present invention, known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene. Glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol Examples include monoalkyl ether acetates, esters, ketones, amides, lactones and the like.

As the (C) solvent used in the photosensitive composition of the present invention, for example,
(A) Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether;
(A) Ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether;
(C) Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate;
(D) Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
(E) propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether;

(F) Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate;
(G) Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether;
(H) Diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate;
(G) Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether;
(Co) dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether;

(Sa) Dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate;
(L) Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, isoamyl lactate;
(Su) n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, propionate Aliphatic carboxylic acid esters such as isobutyl acid, methyl butyrate, ethyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, isobutyl butyrate;
(C) ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutyl Other esters such as butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate;
(So) ketones such as methyl ethyl ketone, methyl propyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone;

(Ta) Amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone;
(H) Examples include lactones such as γ-butyrolactone.
In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonal as necessary for these solvents. Solvents such as benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, and propylene carbonate can also be added.
These solvents can be used alone or in combination of two or more.
The solvent that can be used in the present invention is preferably a single type or a combination of two types, and more preferably contains at least diethylene glycol ethyl methyl ether.

  The content of the solvent (C) in the photosensitive resin composition of the present invention is preferably 50 to 3,000 parts by weight and 100 to 2,000 parts by weight per 100 parts by weight of the component (A). Is more preferable, and it is still more preferable that it is 150-1,500 weight part.

<Other ingredients>
In addition to the components (A), (B), and (C), the photosensitive resin composition of the present invention includes (D) a thermal radical generator described below as an optional component as necessary. (E) a crosslinking agent, (F) an antioxidant, (G) an adhesion improver, (H) a basic compound, (I) a surfactant, and (J) a plasticizer, and a thermal acid generator, Known additives such as ultraviolet absorbers, thickeners, and organic or inorganic suspending agents can be added.

(D) Thermal radical generator It is preferable that the photosensitive resin composition of the present invention contains (D) a thermal radical generator.
As the thermal radical generator in the present invention, those generally known as radical generators can be used.
The thermal radical generator is a compound that generates radicals by heat energy and initiates or accelerates the polymerization reaction of the polymerizable compound. By adding a thermal radical generator, the obtained cured film becomes tougher and heat resistance and solvent resistance may be improved.

Hereinafter, (D) the thermal radical generator will be described in detail, but the present invention is not limited by these descriptions.
In the present invention, preferred (D) thermal radical generators include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocenes. Examples thereof include compounds, active ester compounds, compounds having a carbon halogen bond, azo compounds, and bibenzyl compounds.
In the present invention, from the viewpoint of heat resistance and solvent resistance of the obtained cured film, organic peroxides, azo compounds, and bibenzyl compounds are more preferable, and bibenzyl compounds are more preferable.

  Moreover, as a bibenzyl compound, the compound represented by following formula (5) is preferable.

In the formula (5), a plurality of R ³ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, a nitro group, an alkoxy group having 1 to 20 carbon atoms, or a halogen atom. Represent.

  Specific examples of the compound represented by the formula (5) include 2,3-dimethyl-2,3-diphenylbutane, α, α′-dimethoxy-α, α′-diphenylbibenzyl, α, α′- Diphenyl-α-methoxybibenzyl, α, α′-dimethoxy-α, α′dimethylbibenzyl, α, α′-dimethoxybibenzyl, 3,4-dimethyl-3,4-diphenyl-n-hexane, 2, 2,3,3-tetraphenyl succinic acid nitrile, dibenzyl and the like can be mentioned.

In the present invention, (D) the thermal radical generator may be used alone or in combination of two or more.
(D) The addition amount of the thermal radical generator to the photosensitive resin composition of the present invention is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the polymer (A) from the viewpoint of improving film properties. More preferably, it is 0.1-20 weight part, More preferably, it is 0.5-10 weight part.

(E) Crosslinking agent It is preferable that the photosensitive resin composition of this invention contains (E) crosslinking agent as needed.
(E) As a crosslinking agent, for example, a compound having two or more epoxy groups in the molecule described below, an alkoxymethyl group-containing crosslinking agent, and a compound having at least one ethylenically unsaturated double bond are added. be able to. (E) By adding a cross-linking agent, the cured film can be made stronger.

<Compound having two or more epoxy groups in the molecule>
Specific examples of compounds having two or more epoxy groups in the molecule include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, aliphatic epoxy resins, and the like. Can do.

  These are available as commercial products. For example, as bisphenol A type epoxy resin, JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1051, EPICLON1051 DIC Co., Ltd.), etc., as bisphenol F type epoxy resin, JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, Japan Epoxy Resin Co., Ltd.), EPICLON830, EPICLON835 (above, DIC Corporation) )), LCE-21, RE-602S (above, Nippon Kayaku Co., Ltd.), etc. As the enol novolac type epoxy resin, JER152, JER154, JER157S65, JER157S70 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, DIC) (Corporation) etc., as cresol novolac type epoxy resins, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (Above, manufactured by DIC Corporation), EOCN-1020 (above, manufactured by Nippon Kayaku Co., Ltd.), etc., as an aliphatic epoxy resin, ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (above, manufactured by ADEKA Corporation), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, PB 4700 (above, manufactured by Daicel Chemical Industries, Ltd.) ) And the like. In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation) and the like can be mentioned. These can be used alone or in combination of two or more.

  Among these, preferred are bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, and cresol novolac type epoxy resin. A bisphenol A type epoxy resin is particularly preferable.

  The addition amount of the compound having two or more epoxy groups in the molecule to the photosensitive resin composition is preferably 1 to 50 parts by weight, and 3 to 30 parts by weight when the total amount of the component (A) is 100 parts by weight. Is more preferable.

<Alkoxymethyl group-containing crosslinking agent>
As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril, alkoxymethylated urea and the like are preferable. These can be obtained by converting the methylol group of methylolated melamine, methylolated benzoguanamine, methylolated glycoluril, or methylolated urea to an alkoxymethyl group, respectively. The type of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. From the viewpoint of the amount of outgas generated, A methoxymethyl group is preferred.
Among these crosslinkable compounds, alkoxymethylated melamine, alkoxymethylated benzoguanamine, and alkoxymethylated glycoluril are mentioned as preferable crosslinkable compounds, and alkoxymethylated glycoluril is particularly preferable from the viewpoint of transparency.

  These alkoxymethyl group-containing crosslinking agents are available as commercial products. For example, Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), Nicarax MX-750, -032, -706, -708, -40, -31, -270, -280, -290, Nicarac MS-11, Nicarak MW-30HM, -100LM, -390, (manufactured by Sanwa Chemical Co., Ltd.) and the like can be preferably used.

  When the alkoxymethyl group-containing crosslinking agent is used in the photosensitive resin composition of the present invention, the addition amount of the alkoxymethyl group-containing crosslinking agent is preferably 0.05 to 50 parts by weight with respect to 100 parts by weight of component (A). More preferably, it is 0.5 to 10 parts by weight. By adding within this range, preferable alkali solubility during development and excellent solvent resistance of the cured film can be obtained.

<Compound having at least one ethylenically unsaturated double bond>
As the compound having at least one ethylenically unsaturated double bond, a (meth) acrylate compound such as a monofunctional (meth) acrylate, a bifunctional (meth) acrylate, or a trifunctional or higher (meth) acrylate is preferably used. be able to. In the present invention, “(meth) acryl” is a term including one or both of “acryl” and “methacryl”, and “(meth) acrylate” means “acrylate” and It is a term that includes either “methacrylate” or both.

  Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, and 2- (meth) acryloyloxyethyl. And 2-hydroxypropyl phthalate.

  Examples of the bifunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Examples include tetraethylene glycol di (meth) acrylate, bisphenoxyethanol full orange acrylate, and bisphenoxyethanol full orange acrylate.

  Examples of the tri- or more functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (meth) acrylate. , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

These compounds having at least one ethylenically unsaturated double bond are used singly or in combination of two or more.
The proportion of the compound having at least one ethylenically unsaturated double bond in the photosensitive resin composition of the present invention is preferably 50 parts by weight or less, more preferably 30 parts, per 100 parts by weight of component (A). Less than parts by weight. By including at least one compound having an ethylenically unsaturated double bond in such a ratio, the heat resistance and surface hardness of the insulating film obtained from the photosensitive resin composition of the present invention can be improved. it can.

(F) Antioxidant The photosensitive resin composition of the present invention may contain (F) an antioxidant.
(F) As antioxidant, a well-known antioxidant can be contained. (F) By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat resistant transparency is excellent.
Examples of such antioxidants include phosphorus antioxidants, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenolic antioxidants, ascorbic acids, zinc sulfate, sugars, nitrites, sulfites. Examples thereof include salts, thiosulfates, and hydroxylamine derivatives. Among these, a phenolic antioxidant is particularly preferable from the viewpoint of coloring the cured film and reducing the film thickness. These may be used alone or in combination of two or more.

Examples of commercially available phenolic antioxidants include ADK STAB AO-60 (manufactured by ADEKA), ADK STAB AO-80 (manufactured by ADEKA), and Irganox 1098 (manufactured by Ciba Japan). Can be mentioned.
(F) It is preferable that content of antioxidant is 0.1 to 6 weight% with respect to the total solid of the photosensitive resin composition, and it is more preferable that it is 0.2 to 5 weight%. More preferably, the content is 0.5% to 4% by weight. By setting it within this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation becomes good.
As additives other than antioxidants, various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators, and the like are used in the present invention. You may add to a resin composition.

(G) Adhesion improving agent The photosensitive resin composition of the present invention may contain (G) an adhesion improving agent.
The adhesion improver (G) that can be used in the photosensitive resin composition of the present invention includes an inorganic substance serving as a substrate, for example, a silicon compound such as silicon, silicon oxide, and silicon nitride, a metal such as gold, copper, and aluminum. It is a compound that improves adhesion to an insulating film. Specific examples include silane coupling agents and thiol compounds. The silane coupling agent (G) used as an adhesion improver used in the present invention is for the purpose of modifying the interface, and any known silane coupling agent can be used without any particular limitation.

Preferred silane coupling agents include, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriacoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ- Methacryloxypropyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltri An alkoxysilane is mentioned.
Of these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, and γ-glycidoxypropyltrialkoxysilane is more preferable.

These can be used alone or in combination of two or more. These are effective in improving the adhesion to the substrate and are also effective in adjusting the taper angle with the substrate.
The content of the (G) adhesion improving agent in the photosensitive resin composition of the present invention is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, relative to 100 parts by weight of the component (A). preferable.

(H) Basic compound The photosensitive resin composition of the present invention may contain (H) a basic compound.
(H) The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like.

Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and dicyclohexylamine. , Dicyclohexylmethylamine and the like.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.

  Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.3.0] -7 -Undecene and the like.

  Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.

  Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.

The basic compounds that can be used in the present invention may be used singly or in combination of two or more. However, it is preferable to use two or more in combination, and it is more preferable to use two in combination. Preferably, two kinds of heterocyclic amines are used in combination.
The content of the basic compound (H) in the photosensitive resin composition of the present invention is preferably 0.001 to 1 part by weight with respect to 100 parts by weight of the component (A), and 0.005 to 0.005. More preferably, it is 2 parts by weight.

(I) Surfactant The photosensitive resin composition of the present invention may contain (I) a surfactant.
(I) As the surfactant, any of anionic, cationic, nonionic or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. . In addition, the following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by JEMCO), MegaFac (manufactured by DIC Corporation), Florard (Sumitomo 3M) (Manufactured by Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), and the like.
In addition, as a surfactant, it contains a structural unit A and a structural unit B represented by the following formula (1), and is a weight average in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent. A preferable example is a copolymer having a molecular weight (Mw) of 1,000 or more and 10,000 or less.

（式（１）中、Ｒ¹及びＲ³はそれぞれ独立に、水素原子又はメチル基を表し、Ｒ²は炭素数１以上４以下の直鎖アルキレン基を表し、Ｒ⁴は水素原子又は炭素数１以上４以下のアルキル基を表し、Ｌは炭素数３以上６以下のアルキレン基を表し、ｐ及びｑは重合比を表す重量百分率であり、ｐは１０重量％以上８０重量％以下の数値を表し、ｑは２０重量％以上９０重量％以下の数値を表し、ｒは１以上１８以下の整数を表し、ｎは１以上１０以下の整数を表す。）

(In the formula (1), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group, R ² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴ represents a hydrogen atom or carbon number. 1 represents an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are weight percentages representing a polymerization ratio, and p is a numerical value of 10% to 80% by weight. Q represents a numerical value of 20 wt% or more and 90 wt% or less, r represents an integer of 1 or more and 18 or less, and n represents an integer of 1 or more and 10 or less.)

The L is preferably a branched alkylene group represented by the following formula (2). R ⁵ in the formula (2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the coated surface. More preferred is an alkyl group of 3. The sum (p + q) of p and q is preferably p + q = 100, that is, 100% by weight.

The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
These surfactants can be used individually by 1 type or in mixture of 2 or more types.
The addition amount of (I) surfactant in the photosensitive resin composition of the present invention is preferably 10 parts by weight or less, and 0.01 to 10 parts by weight with respect to 100 parts by weight of component (A). It is more preferable that the content is 0.01 to 1 part by weight.

(J) Plasticizer The photosensitive resin composition of the present invention may contain (J) a plasticizer.
Examples of the plasticizer (J) include dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, polyethylene glycol, glycerin, dimethyl glycerin phthalate, dibutyl tartrate, dioctyl adipate, and triacetyl glycerin.
The addition amount of the (J) plasticizer in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the component (A), and is 1 to 10 parts by weight. It is more preferable.

(Method for forming cured film)
Next, the formation method of the cured film of this invention is demonstrated.
The method for forming a cured film of the present invention includes the following steps (1) to (5).
(1) Application process for applying the photosensitive resin composition of the present invention onto a substrate (2) Solvent removal process for removing the solvent from the applied photosensitive resin composition (3) Exposure process for exposure with actinic rays (4) ) Development step for developing with aqueous developer (5) Post-bake step for thermosetting Each step will be described below in order.

In the coating step (1), the photosensitive resin composition of the present invention is coated on a substrate to form a wet film containing a solvent.
In the solvent removal step (2), the solvent is removed from the applied film by vacuum (vacuum) and / or heating to form a dry coating film on the substrate.

  In the exposure step (3), the obtained coating film is irradiated with actinic rays having a wavelength of 300 nm or more and 450 nm or less. In this step, (B) the photoacid generator is decomposed to generate an acid. Due to the catalytic action of the generated acid, the acid-decomposable group in the monomer unit (a1) contained in the polymer (A) is hydrolyzed to produce a carboxy group or a phenolic hydroxyl group.

  In order to accelerate the hydrolysis reaction in the region where the acid catalyst is generated, post-exposure heat treatment (Post Exposure Bake (hereinafter also referred to as “PEB”)) can be performed as necessary. PEB can promote the formation of a carboxy group or a phenolic hydroxyl group from an acid-decomposable group.

  In addition, by performing PEB at a relatively low temperature, hydrolysis of an acid-decomposable group can be promoted without causing a crosslinking reaction. The temperature at which PEB is performed is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C. or higher and 80 ° C. or lower.

  In the developing step (4), a polymer having a liberated carboxy group or phenolic hydroxyl group is developed using an alkaline developer. A positive image is formed by removing an exposed area containing a resin composition having a carboxyl group or a phenolic hydroxyl group that is easily dissolved in an alkaline developer.

  In the post-baking step (5), by heating the obtained positive image, the ethylenically unsaturated bond contained in the component (A) can be polymerized to form a cured film. This heating is preferably performed at a high temperature of 150 ° C. or more, more preferably 180 to 250 ° C., and particularly preferably 200 to 250 ° C. The heating time can be appropriately set depending on the heating temperature or the like, but is preferably in the range of 10 to 90 minutes.

When a step of irradiating the development pattern with actinic rays, preferably ultraviolet rays, before the post-baking step is added, the crosslinking reaction can be promoted by an acid generated by actinic ray irradiation.
Next, the formation method of the cured film using the photosensitive resin composition of this invention is demonstrated concretely.

<Method for preparing photosensitive resin composition>
The photosensitive resin composition is prepared by mixing the essential components (A) to (C) in a predetermined ratio and by any method, and stirring and dissolving. For example, the component (A) or the component (B) can be previously dissolved in the solvent (C) to prepare a solution, and then mixed at a predetermined ratio to prepare a photosensitive resin composition. The photosensitive resin composition prepared as described above can be used after being filtered using a filter having a pore size of 0.2 μm or the like.

<Coating process and solvent removal process>
A desired dry coating film can be formed by applying the photosensitive resin composition to a predetermined substrate and removing the solvent by reducing pressure and / or heating (pre-baking). As the substrate, for example, in the production of a liquid crystal display element, a polarizing plate, a glass plate provided with a black matrix layer and a color filter layer as necessary, and a transparent conductive circuit layer, and the like can be exemplified. The coating method to a board | substrate is not specifically limited, For example, methods, such as a slit coat method, a spray method, a roll coat method, a spin coat method, can be used. Among them, the slit coating method is preferable from the viewpoint of being suitable for a large substrate. Here, the large substrate means a substrate having a side of 1 m or more on each side.

  In addition, (2) the heating conditions in the solvent removal step are ranges in which the acid-decomposable group in the component (A) in the unexposed area is decomposed and the component (A) is not soluble in the alkaline developer. However, it is preferably about 80 to 130 ° C. for about 30 to 120 seconds.

<Exposure process and development process (pattern formation method)>
In the exposure step, the substrate on which the coating film is provided is irradiated with actinic rays through a mask having a predetermined pattern. After the exposure step, heat treatment (PEB) is performed as necessary, and then in the development step, the exposed area is removed using an alkaline developer to form an image pattern.
For exposure with actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, an LED light source, a chemical lamp, an excimer laser generator, or the like can be used. Actinic rays having a wavelength of 300 nm to 450 nm can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.

  A basic compound is used for the developer used in the development step. Examples of the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkalis such as sodium bicarbonate and potassium bicarbonate Metal bicarbonates; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.

The pH of the developer is preferably 10.0 to 14.0.
The development time is preferably 30 to 180 seconds, and the development method may be either a liquid piling method or a dipping method. After the development, washing with running water is performed for 30 to 90 seconds, and a desired pattern can be formed.

<Post-bake process (crosslinking process)>
For a pattern corresponding to an unexposed area obtained by development, using a heating device such as a hot plate or oven, at a predetermined temperature, for example, 180 to 250 ° C., for a predetermined time, for example, 5-60 minutes on the hot plate, If it is an oven, heat treatment is performed for 30 to 90 minutes to react and crosslink the ethylenically unsaturated bond in component (A) or the added crosslinking agent, and a protective film or interlayer insulation excellent in heat resistance, hardness, etc. A film can be formed. In addition, by performing such heat treatment, the acid-decomposable group in component (A) is decomposed to generate a carboxy group or a phenolic hydroxyl group, and react with a crosslinking agent to which these are added to cause crosslinking, heat resistance, hardness It is possible to form a protective film and an interlayer insulating film excellent in the above. In addition, when heat treatment is performed, the transparency can be improved by performing the heat treatment in a nitrogen atmosphere.
Prior to the heat treatment, the substrate on which the pattern is formed is re-exposed with actinic rays and then post-baked (re-exposure / post-bake) to generate an acid from the component (B) present in the unexposed portion, thereby crosslinking. It is preferable to function as a catalyst that accelerates the process.
That is, the method for forming a cured film of the present invention preferably includes a re-exposure step in which re-exposure is performed with actinic rays between the development step and the post-bake step.
The exposure in the re-exposure step may be performed by the same means as in the exposure step. In the re-exposure step, the entire surface of the substrate on which the film is formed by the photosensitive resin composition of the present invention is exposed. It is preferable.
A preferable exposure amount in the re-exposure step is 100 to 1,000 mJ / cm ² .

With the photosensitive resin composition of the present invention, an interlayer insulating film having excellent insulation and high transparency even when baked at high temperatures can be obtained. Since the interlayer insulating film using the photosensitive resin composition of the present invention has high transparency and excellent cured film physical properties, it is useful for applications of organic EL display devices and liquid crystal display devices.
The organic EL display device and the liquid crystal display device of the present invention are not particularly limited except that they have a flattening film, a protective film, and an interlayer insulating film formed using the photosensitive resin composition of the present invention. Examples include various known organic EL display devices and liquid crystal display devices having a simple structure.
Moreover, the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, It can be used for various uses. For example, in addition to a flattening film, a protective film, and an interlayer insulating film, it is preferably used for a spacer for maintaining a constant thickness of a liquid crystal layer in a liquid crystal display device, a microlens provided on a color filter in a solid-state imaging device, or the like. be able to.

FIG. 1 is a conceptual diagram illustrating an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
A bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ is formed so as to cover the TFT 1. A contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. The wiring 2 is used to connect the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
Further, in order to flatten the unevenness due to the formation of the wiring 2, the flattening film 4 is formed on the insulating film 3 with the unevenness due to the wiring 2 being embedded.
On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.
An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing this insulating film, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. be able to.
Further, although not shown in FIG. 1, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a first layer made of Al is formed on the entire surface above the substrate. An active matrix organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a TFT 1 for driving it. An EL display device is obtained.

  FIG. 2 is a conceptual cross-sectional view showing an example of the active matrix type liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto. The elements of the TFT 16 corresponding to are arranged. Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.

  Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

<Synthesis of acrylic copolymer: A-1>
After adding 0.5 parts by weight of phenothiazine to 144.2 parts by weight (2 molar equivalents) of ethyl vinyl ether, and dropping 86.1 parts by weight (1 molar equivalent) of methacrylic acid while cooling the reaction system to 10 ° C. or lower, Stir at room temperature (25 ° C.) for 4 hours. After adding 5.0 parts by weight of pyridinium p-toluenesulfonate, the mixture was stirred at room temperature (25 ° C.) for 2 hours and allowed to stand overnight at room temperature. To the reaction solution, 5 parts by weight of sodium bicarbonate and 5 parts by weight of sodium sulfate were added, and the mixture was stirred at room temperature (25 ° C.) for 1 hour. The insoluble material was filtered and concentrated under reduced pressure at 40 ° C. or lower. Distillation gave 134.0 parts by weight of 1-ethoxyethyl methacrylate as a colorless oily substance having a boiling point (bp.) Of 43 to 45 ° C./7 mmHg fraction.

1-Ethoxyethyl methacrylate (79.06 parts by weight (0.5 molar equivalent)), methacrylic acid (43.05 parts by weight (0.5 molar equivalent)) and diethylene glycol ethyl methyl ether (99.9 parts by weight) Part) was heated to 70 ° C. under a nitrogen stream. While stirring this mixed solution, a mixed solution of radical polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd., 4.5 parts by weight) and diethylene glycol ethyl methyl ether (90.0 parts by weight) was added to 2.5%. It was added dropwise over time. After completion of the dropwise addition, reaction was carried out at 70 ° C. for 5 hours to obtain a diethylene glycol ethyl methyl ether solution of binder a-1 (solid content concentration: 40% by weight).
Glycidyl methacrylate (56.86 parts by weight (0.4 molar equivalent)), benzyltriethylammonium (2.41 parts by weight) and diethylene glycol ethyl methyl ether (85.3 parts by weight) were further added to the binder a-1 solution. Then, by reacting at 75 ° C., a diethylene glycol ethyl methyl ether solution of binder A-1 (solid content concentration: 40% by weight) was obtained. The weight average molecular weight measured by gel permeation chromatography (GPC) of the obtained binder A-1 was 20,000.

<Acrylic copolymer: Synthesis of A-2 to A-10, A-12, A-13, and A'-11>
Acrylic copolymers A-2 to A-10, A in the same manner as the synthesis of acrylic copolymer A-1, except that each monomer used and the amount used were changed to those shown in Table 1. -12, A-13 and A'-11 were synthesized respectively.

In addition, the copolymerization ratio of Table 1 is a molar ratio, and the symbol in Table 1 is as follows.
HEMA: 2-hydroxyethyl methacrylate MAEVE: 1-ethoxyethyl methacrylate MMA: methyl methacrylate GMA: glycidyl methacrylate CHMA: cyclohexyl methacrylate DCPM: dicyclopentanyl methacrylate CHOEMA: 1- (cyclohexyloxy) ethyl methacrylate M100 : 3,4-epoxycyclohexylmethyl methacrylate (manufactured by Daicel Chemical Industries, Ltd.)
A400: 3,4-epoxycyclohexylmethyl acrylate (manufactured by Daicel Chemical Industries)
AA: Acrylic acid MAA: Methacrylic acid thpMA: Tetrahydro-2H-pyran-2-yl methacrylate MATH: Tetrahydrofuran-2-yl methacrylate St: Styrene P-Ph1: 1-Ethoxyethyl ether of α-methyl-parahydroxystyrene Protection body P-Ph2: Tetrahydropyranyl ether protection body of 4-hydroxyphenyl methacrylate P-Ph3OH: 1-ethoxyethyl ether protection body of 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester Ph-3OH : 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester C1: propylene glycol monomethyl ether acetate C2: diethylene glycol ethyl methyl ether

  Moreover, the abbreviation represented by the form of “AB” listed as the monomer 2 in Table 1 represents a monomer unit in which “B” is added to the “A” portion of the copolymer. Specifically, “MAA-GMA”, “MAA-A400”, “GMA-AA”, and “M100-AA” each represent a monomer unit having the structure shown below.

  Note that thpMA (tetrahydro-2H-pyran-2-yl methacrylate) was synthesized by the method of Synthesis Example 1 in paragraph 0018 of JP-A-5-88367. CHOEMA (1- (cyclohexyloxy) ethyl methacrylate) was synthesized in the same manner. Further, other 1-ethoxyethyl ether protection and tetrahydropyranyl ether protection were carried out in the same manner.

<Synthesis of MATHF (tetrahydrofuran-2-yl methacrylate)>
Methacrylic acid (86 g, 1 mol) was cooled to 15 ° C., and camphorsulfonic acid (4.6 g, 0.02 mol) was added. To the solution, 2,3-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was added dropwise. After stirring for 1 hour, saturated aqueous sodium hydrogen carbonate solution (500 mL) was added, extracted with ethyl acetate (500 mL), dried over magnesium sulfate, insolubles were filtered and concentrated under reduced pressure at 40 ° C. or lower to give a yellow oily residue. Was distilled under reduced pressure to obtain 125 g of tetrahydrofuran-2-yl methacrylate (MATHF) as a colorless oily substance having a boiling point (bp.) Of 54 to 56 ° C./3.5 mmHg (yield 80%).

<Synthesis of Ph-3OH (4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester)>
Ph-3OH (4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester) was synthesized by the following method.
After adding 100 parts by weight of p-hydroxybenzoic acid, 100 parts by weight of glycidyl methacrylate, and 9.7 parts by weight of tetrabutylammonium bromide to 257 parts by weight of N-methylpyrrolidone, the mixture was reacted at 90 ° C. with stirring for 6 hours, and then reacted. The mixture was poured into a water / ethyl acetate mixed solvent, and the precipitated crystals were collected by filtration and recrystallized from ethyl acetate / n-hexane to give 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester. .

(Examples 1-43 and Comparative Examples 1-4)
(1) Preparation of photosensitive resin composition The components shown in Tables 2 and 3 below were mixed to form a uniform solution, and then filtered using a polytetrafluoroethylene filter having a pore size of 0.2 μm. The photosensitive resin compositions of Examples 1 to 43 and Comparative Examples 1 to 4 were respectively prepared.
The composition used in Comparative Example 3 is the composition described in Example 1 of Patent Document 2 (Japanese Patent Laid-Open No. 2008-256974), and the composition used in Comparative Example 4 is Patent Document 3 (special This is the composition described in Example 1 of Kaikai 2008-76739).

In addition, the symbol in Table 2 and Table 3 is as follows.
B1: CGI1397 (manufactured by Ciba Japan)
B2: CGI1325 (Ciba Japan Co., Ltd.)
B3: PAI-1001 (structure shown below, manufactured by Midori Chemical Co., Ltd.)
B4: DBA (9,10-dibutoxyanthracene, structure shown below, manufactured by Kawasaki Chemical Industry Co., Ltd.)
B5: Compound having the following structure B6: Compound having the following structure

<Synthesis of B5>
1-1. Synthesis of Synthesis Intermediate B5-A 2-Aminobenzenethiol: 31.3 g (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in toluene: 100 mL (manufactured by Wako Pure Chemical Industries, Ltd.) at room temperature (25 ° C.). . Next, phenylacetyl chloride: 40.6 g (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, and the mixture was stirred at room temperature for 1 hour and then stirred at 100 ° C. for 2 hours for reaction. 500 mL of water was added to the resulting reaction solution to dissolve the precipitated salt, the toluene oil was extracted, and the extract was concentrated with a rotary evaporator to obtain a synthetic intermediate B5-A.

1-2. Synthesis of B5 2.25 g of the synthetic intermediate B5-A obtained as described above was mixed with 10 mL of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), and then placed in an ice bath to bring the reaction solution to 5 ° C. or lower. Cooled down. Next, tetramethylammonium hydroxide: 4.37 g (25% by weight methanol solution, manufactured by Alfa Acer) was added dropwise, and the mixture was stirred for 0.5 hour in an ice bath to be reacted. Furthermore, 7.03 g of isopentyl nitrite: was dropped while maintaining the internal temperature at 20 ° C. or lower, and after completion of the dropping, the reaction solution was warmed to room temperature and stirred for 1 hour.
Subsequently, after cooling the reaction liquid to 5 ° C. or lower, p-toluenesulfonyl chloride (1.9 g) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and stirred for 1 hour while maintaining 10 ° C. or lower. Thereafter, 80 mL of water was added and stirred at 0 ° C. for 1 hour. After filtering the obtained precipitate, 60 mL of isopropyl alcohol (IPA) was added, heated to 50 ° C., stirred for 1 hour, filtered while hot, and dried to obtain 1.8 g of (B5: the above structure). Obtained.
The ¹ H-NMR spectrum (300 MHz, deuterated DMSO ((D ₃ C) ₂ S═O)) of the obtained B5 is δ = 8.2 to 8.17 (m, 1H), 8.03 to 8.0. 00 (m, 1H), 7.95 to 7.9 (m, 2H), 7.6 to 7.45 (m, 9H), 2.45 (s, 3H).
From the above ¹ H-NMR measurement results, it is estimated that the obtained B5 is a single geometric isomer.

<Synthesis of B6>
Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension of 2-naphthol (10 g) and chlorobenzene (30 mL), and the mixture was heated to 40 ° C. for 2 hours. I let you. Under ice-cooling, 4N HCl aqueous solution (60 mL) was added dropwise to the reaction solution, and ethyl acetate (50 mL) was added for liquid separation. Potassium carbonate (19.2 g) was added to the organic layer, reacted at 40 ° C. for 1 hour, 2N HCl aqueous solution (60 mL) was added and separated, and the organic layer was concentrated. The slurry was reslurried, filtered and dried to obtain a ketone compound (6.5 g).
Acetic acid (7.3 g) and 50% by weight hydroxylamine aqueous solution (8.0 g) were added to a suspension of the obtained ketone compound (3.0 g) and methanol (30 mL), and the mixture was heated to reflux. After allowing to cool, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain an oxime compound (2.4 g).
The obtained oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice cooling, and the temperature was raised to room temperature. Reacted for hours. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered, reslurried with methanol (20 mL), filtered and dried to obtain B6 (2.3 g).
In addition, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B6 is δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 ( d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H) 7.3 (d, 2H), 7.1 (d.1H), 5.6 (q, 1H), 2 .4 (s, 3H), 1.7 (d, 3H).

C1: Propylene glycol monomethyl ether acetate C2: Diethylene glycol ethyl methyl ether D1: NOFMER BC-90 (manufactured by NOF Corporation)
E1: JER-157S70 (polyfunctional novolac type epoxy resin (epoxy equivalent: 200 to 220 g / eq), manufactured by Japan Epoxy Resins Co., Ltd.)
E2: Nicarak MW-100LM (manufactured by Sanwa Chemical Co., Ltd.)
Surfactant 1: Megafac R-08 (perfluoroalkyl group-containing nonionic surfactant, manufactured by DIC Corporation)
Surfactant 2: Compound W-3 having the following structure
Basic compound 1: 4-dimethylaminopyridine Basic compound 2: 1,5-diazabicyclo [4.3.0] -5-nonene Basic compound 3: triphenylimidazole Adhesion improver 1: KBM-403 (Shin-Etsu Chemical) Kogyo Co., Ltd. DPHA: KAYARAD DPHA (Nippon Kayaku Co., Ltd.)

(2) Evaluation of sensitivity After the photosensitive resin composition solution was spin-coated on a silicon wafer having a silicon oxide film, it was pre-baked on a hot plate at 90 ° C. for 110 seconds to form a coating film having a thickness of 3 μm.

Next, it exposed through the predetermined | prescribed mask using i line | wire stepper (Canon Co., Ltd. product FPA-3000i5 ^<+> ). After the exposure, the resist film was developed with a 0.4 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds and rinsed with ultrapure water for 1 minute. By these operations, the optimum exposure amount (Eopt) when resolving 10 μm line and space at 1: 1 was defined as sensitivity. It can be said that the sensitivity is high when the exposure is lower than 100 mJ / cm ² and is very high when the exposure is lower than 70 mJ / cm ² .
The evaluation results of sensitivity are shown in Tables 4 and 5. It turns out that all the photosensitive resin compositions of this invention are very highly sensitive.

(3) Evaluation of heat-resistant transparency After a photosensitive resin composition was spin-coated on a glass substrate “Corning 1737 (manufactured by Corning)”, it was pre-baked on a hot plate at 90 ° C. for 110 seconds to have a film thickness of 3 μm. Formed. The obtained coating film was exposed to a cumulative irradiation amount of 200 mJ / cm ² (illuminance: 20 mW / cm ² ) using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. Was heated in an oven at 230 ° C. for 1 hour to obtain a cured film. The obtained cured film was further heated in an oven at 230 ° C. for 2 hours, and the light transmittance was in the range of 400 to 800 nm using a spectrophotometer “150-20 type double beam (manufactured by Hitachi, Ltd.)”. Measured at a wavelength of. Tables 4 and 5 show the evaluation of the minimum light transmittance at that time. The evaluation was as follows. Evaluation “2” is good heat transparency, evaluation “1” is extremely good heat transparency, and evaluation “0” is the best heat transparency.
0: Minimum light transmittance of 90% or more 1: Minimum light transmittance of 85% or more and less than 90% 2: Minimum light transmittance of 82% or more and less than 85% 3: Minimum light transmittance of 80% or more and less than 82% 4: Minimum light transmittance The rate is less than 80% According to the evaluation results shown in Table 4 and Table 5, it can be seen that the cured film formed using the photosensitive resin composition of the present invention exhibits good or extremely good heat-resistant transparency. . Among these, it can be seen that the best heat-resistant transparency is obtained particularly when the photosensitive agent B6 is used.

(4) Evaluation of ITO Sputtering Resistance A photosensitive resin composition was spin-coated on a glass substrate “Corning 1737 (manufactured by Corning)” and then pre-baked on a hot plate at 90 ° C. for 110 seconds to form a coating film having a thickness of 3 μm. Formed. The obtained coating film was exposed to a cumulative irradiation amount of 200 mJ / cm ² (illuminance: 20 mW / cm ² ) using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. Was heated in an oven at 230 ° C. for 1 hour to obtain a cured film. The obtained cured film was subjected to ITO sputtering with SIH-3030 manufactured by ULVAC at a substrate temperature of 210 ° C. to produce an ITO film of 0.14 μm on the cured film. The surface after sputtering was observed with an optical microscope, and the presence or absence of surface roughness was evaluated. The evaluation results are shown in Tables 4 and 5. The evaluation was as follows.
1: No surface roughness observed 2: Slight surface roughness observed, but at a practically acceptable level 3: Surface roughness observed, unacceptable for practical use 4: Surface roughened significantly According to the evaluation results shown in Table 4 and Table 5, it can be seen that the cured films formed using the photosensitive resin composition of the present invention all exhibit good ITO sputtering resistance. Moreover, it turns out that ITO sputter tolerance is further improved by using a thermal radical generator and a crosslinking agent together.

(Example 44)
Using the photosensitive resin composition of Example 42, the same evaluation as in Example 42 was carried out using a UV-LED light source exposure machine instead of the ultrahigh pressure mercury lamp, and the same results as in Example 42 were obtained. Obtained.

(Example 45)
An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 1).
A bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ was formed so as to cover the TFT 1. Next, a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. . The wiring 2 is used to connect the TFT 1 to the organic EL element formed between the TFTs 1 or in a later process.

Further, in order to flatten the unevenness due to the formation of the wiring 2, the planarizing film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarization film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 4 on a substrate, pre-baking on a hot plate (90 ° C. × 2 minutes), and then applying high pressure from above the mask. After irradiating 45 mJ / cm ² (illuminance 20 mW / cm ² ) with i-line (365 nm) using a mercury lamp, a pattern was formed by developing with an alkaline aqueous solution, and heat treatment was performed at 230 ° C. for 60 minutes. The applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking. Furthermore, the average step of the wiring 2 was 500 nm, and the thickness of the prepared planarizing film 4 was 2,000 nm.

  Next, a bottom emission type organic EL element was formed on the obtained planarization film 4. First, a first electrode 5 made of ITO was formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. Thereafter, a resist was applied, prebaked, exposed through a mask having a desired pattern, and developed. Using this resist pattern as a mask, pattern processing was performed by wet etching using an ITO etchant. Thereafter, the resist pattern was stripped using a resist stripping solution (mixed solution of monoethanolamine and dimethyl sulfoxide (DMSO)). The first electrode 5 thus obtained corresponds to the anode of the organic EL element.

  Next, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. The insulating film 8 was formed by the same method as described above using the photosensitive resin composition of Example 4. By providing this insulating film 8, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in the subsequent process.

  Furthermore, a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus. Next, a second electrode made of Al was formed on the entire surface above the substrate. The obtained board | substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the glass plate for sealing, and an ultraviolet curable epoxy resin.

  As described above, an active matrix type organic EL display device in which each organic EL element is connected to the TFT 1 for driving the organic EL element was obtained. When a voltage was applied via the drive circuit, it was found that the organic EL display device showed good display characteristics and high reliability.

(Example 46)
An organic EL device was produced in the same manner as in Example 45 except that the photosensitive resin composition of Example 4 was replaced with the photosensitive resin composition of Example 28. It was found that the organic EL display device had good display characteristics and high reliability.

(Example 47)
An organic EL device was produced in the same manner as in Example 45 except that the photosensitive resin composition of Example 4 was replaced with the photosensitive resin composition of Example 42. It was found that the organic EL display device had good display characteristics and high reliability.

(Example 48)
In the active matrix type liquid crystal display device shown in FIGS. 1 and 2 of Japanese Patent No. 3321003, a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 48 was obtained.
That is, using the photosensitive resin composition of Example 4, the cured film 17 was formed as an interlayer insulating film by the same method as the method for forming the planarizing film 4 of the organic EL display device in Example 45.

  When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.

(Example 49)
A liquid crystal display device was produced in the same manner as in Example 48 except that the photosensitive resin composition of Example 4 was replaced with the photosensitive resin composition of Example 28. It was found that the liquid crystal display device had good display characteristics and high reliability.

(Example 50)
A liquid crystal display device was prepared in the same manner as in Example 48 except that the photosensitive resin composition of Example 4 was replaced with the photosensitive resin composition of Example 42. It was found that the liquid crystal display device had good display characteristics and high reliability.

1: TFT (Thin Film Transistor)
2: Wiring 3: Insulating film 4: Flattened film 5: First electrode 6: Glass substrate 7: Contact hole 8: Insulating film 10: Liquid crystal display device 12: Backlight unit 14, 15: Glass substrate 16: TFT
17: Cured film 18: Contact hole 19: ITO transparent electrode 20: Liquid crystal 22: Color filter

Claims (12)

(A) monomeric units (a1) having a residue of generating a carboxy group or a phenolic hydroxyl group with an acid, monomer units having a group of 3 to 16 carbon atoms having an ethylenic unsaturated bond end edge (a2), and A polymer containing a monomer unit (a3) having a carboxy group, a carboxylic acid anhydride residue and / or a phenolic hydroxyl group, and having a weight average molecular weight of more than 1,000,
(B) a photoacid generator, and
(C) contains a solvent ,
The ratio of the said monomer unit (a3) in the said (A) polymer is 1-25 mol% with respect to all the monomer units of the said (A) polymer, The photosensitive resin composition characterized by the above-mentioned.   The photosensitive resin composition of Claim 1 which is a chemically amplified positive photosensitive resin composition. The photosensitive resin composition of Claim 1 or 2 in which the said (A) polymer contains the monomer unit (a4) which has an epoxy group and / or an oxetanyl group. (B) the photoacid generator is a compound having an oxime sulfonate residue, the photosensitive resin composition according to any one of claims 1-3. The said (B) photo-acid generator is a compound represented by a formula (OS-3), a formula (OS-4), or a formula (OS-5), The any one of Claims 1-4. Photosensitive resin composition.

(In Formula (OS-3) to Formula (OS-5), R ¹ represents an alkyl group, an aryl group, or a heteroaryl group, and R ² independently represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom. R ⁶ represents each independently a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, X represents O or S, n represents 1 or 2, m Represents an integer of 0 to 6.) (D) The photosensitive resin composition of any one of Claims 1-5 which further contains a thermal radical generator. (E) The photosensitive resin composition of any one of Claims 1-6 which further contains a crosslinking agent. (1) coating step the photosensitive resin composition according to any one of claims 1 to 7 coated on a substrate,
(2) a solvent removal step of removing the solvent from the applied photosensitive resin composition;
(3) an exposure step of exposing with actinic rays;
(4) a development step of developing with an aqueous developer, and
(5) A method for forming a cured film, comprising a post-baking step of thermosetting. A cured film formed by the method according to claim 8 . The cured film according to claim 9 , which is an interlayer insulating film. Comprising a cured film according to claim 9 or 10, an organic EL display device. Comprising a cured film according to claim 9 or 10, the liquid crystal display device.

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