JP5528314B2 - Method for producing cured film, photosensitive resin composition, cured film, organic EL display device, and liquid crystal display device - Google Patents

Description

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

Conventionally, in an electronic component such as a liquid crystal display element, an integrated circuit element, a solid-state imaging element, and an organic EL, generally, a flattening film for imparting flatness to the surface of the electronic component, and for preventing deterioration and damage of the electronic component A photosensitive resin composition is used when forming a protective film or an interlayer insulating film for maintaining insulation. With the recent increase in the size of display devices, suitability for slit coating that can be applied and manufactured with a slit coater has been required. Furthermore, along with this increase in size, it takes time for exposure, and high sensitivity is required to shorten the exposure time.
Patent Document 1 discloses slit coating a photosensitive resin composition in which a carboxy group-containing polymer, a quinonediazide compound, and a specific onium are mixed. However, this composition is not sensitive enough. As high-sensitivity interlayer insulating film compositions, for example, Patent Documents 2 and 3 include a chemical amplification type radiation-sensitive resin composition containing an acetal structure and a resin containing an epoxy group or a crosslinkable group, and an acid generator. Things are disclosed.

JP 2009-075329 A JP 2004-254623 A JP 2009-098616 A

When the present inventors examined, when the high sensitive photosensitive resin composition of patent document 2 and 3 was slit-coated, it turned out that the sensitivity is not stabilized. Further, it has been found that when the insulating film is produced by slit coating, there is a problem that the contact hole patterning performance is not sufficient. This is a new problem when a chemically amplified photosensitive resin composition is formed into an insulating film by slit coating.
The problem to be solved by the present invention is a manufacturing method for manufacturing a cured film excellent in contact hole patterning performance, ITO sputtering suitability, and heat-resistant transparency by slit coating, which can be manufactured with high sensitivity and stable sensitivity. It is providing the photosensitive resin composition used, the cured film manufactured by the said manufacturing method, the organic electroluminescence display containing the said cured film, and a liquid crystal display device.

The above-described problems of the present invention have been solved by the means described in <1> to <12> below.
<1> (1) A low temperature treatment step for bringing the photosensitive resin composition to a temperature of 10 ° C. or lower, (2) a coating step for slit coating the photosensitive resin composition on a substrate, and (3) the coated photosensitivity. A solvent removal step of removing the solvent from the photosensitive resin composition, (4) an exposure step of exposing the photosensitive resin composition from which the solvent has been removed with actinic rays, (5) a step of allowing 45 seconds or more to pass at room temperature, (6) A development step of developing with an aqueous developer, and (7) a post-bake step of thermosetting in this order, wherein the photosensitive resin composition comprises (Component A) at least (a1) an acid group is an acid-decomposable group. A copolymer containing a structural unit having a residue protected with (a2) a structural unit having a crosslinking group, (a3) a structural unit having a carboxy group and / or a phenolic hydroxyl group, and (Component B) a photoacid Generator, and (component C Process for producing a cured film, characterized by containing a solvent, a,
<2> The method for producing a cured film according to <1>, wherein the structural unit (a1) is a structural unit having a residue in which a carboxy group is protected with an acetal or a ketal.
<3> The method for producing a cured film according to <1> or <2>, in which the structural unit (a1) is represented by the formula (A2).

（式（Ａ２）中、Ｒ¹及びＲ²は、それぞれ独立に水素原子、アルキル基又はアリール基を表し、少なくともＲ¹及びＲ²のいずれか一方がアルキル基又はアリール基であり、Ｒ³は、アルキル基又はアリール基を表し、Ｒ¹又はＲ²とＲ³とが連結して環状エーテルを形成してもよく、Ｒ⁴は、水素原子又はメチル基を表し、Ｘは単結合又はアリーレン基を表す。）

(In formula (A2), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least ^one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ is Represents an alkyl group or an aryl group, R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group. Represents.)

<4> The structural unit (a2) has at least one group selected from the group consisting of an epoxy group, an oxetanyl group, and an ethylenically unsaturated group, and any one of <1> to <3> A method for producing the cured film according to claim 1,
<5> The method for producing a cured film according to any one of <1> to <4>, wherein the structural unit (a2) has an alicyclic epoxy group and / or an oxetanyl group,
<6> The method for producing a cured film according to any one of <1> to <5>, wherein Component B is a compound having an oxime sulfonate residue,
<7> The component B is any one of <1> to <6>, which is a compound represented by the formula (OS-3), the formula (OS-4), or the formula (OS-5). A method for producing a cured film of

（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.)

<8> The method for producing a cured film according to any one of <1> to <7>, wherein the photosensitive resin composition is a chemically amplified positive photosensitive resin composition,
<9> A photosensitive resin composition used in the method for producing a cured film according to any one of <1> to <8>,
<10> A cured film produced by the method for producing a cured film according to any one of <1> to <8>,
<11> An organic EL display device comprising the cured film according to <10>,
<12> A liquid crystal display device comprising the cured film according to <10>.

  According to the present invention, a method for producing a cured film, which can be produced by slit coating, can be produced with high sensitivity and stable sensitivity, and an interlayer insulating film excellent in contact hole patterning performance, ITO sputtering suitability and heat-resistant transparency is used in the production method. It was possible to provide a photosensitive resin composition, a cured film produced by the production method, an organic EL display device including the cured film, and a liquid crystal display device.

It is a composition conceptual diagram of an example of an organic EL display. It is a conceptual sectional view showing an example of a liquid crystal display.

  The method for producing a cured film of the present invention includes (1) a low-temperature treatment step for bringing the photosensitive resin composition to a temperature of 10 ° C. or lower, (2) a coating step for slit coating the photosensitive resin composition on a substrate, 3) Solvent removal step for removing the solvent from the applied photosensitive resin composition, (4) Exposure step for exposing the photosensitive resin composition from which the solvent has been removed with actinic rays, (5) 45 seconds or more at room temperature The photosensitive resin composition comprises at least (component A) at least (a1), a step of allowing the composition to pass, (6) a developing step of developing with an aqueous developer, and (7) a post-baking step of thermosetting. A copolymer containing a structural unit having a residue in which an acid group is protected with an acid-decomposable group, (a2) a structural unit having a crosslinking group, and (a3) a structural unit having a carboxy group and / or a phenolic hydroxyl group. (Component B) Photoacid generation Agents, as well, characterized by containing the (Component C) a solvent. Hereinafter, the present invention will be described in detail. In addition, in this invention, description of "A-B" showing a numerical range means "A or more and B or less" unless there is particular notice, and means the numerical range containing A and B which are endpoints.

I. Photosensitive resin composition The photosensitive resin composition (hereinafter also referred to as the photosensitive resin composition of the present invention) used in the method for producing a cured film of the present invention contains the component A to the component C, and is necessary. Accordingly, (Component D) sensitizer, (Component E) cross-linking agent, (Component F) adhesion improver, (Component G) basic compound, (Component H) surfactant and the like are contained. Hereinafter, each component will be described.

(Component A)
The photosensitive resin composition of the present invention comprises (Component A) at least (a1) a structural unit having a residue in which an acid group is protected by an acid-decomposable group, (a2) a structural unit having a crosslinking group, (a3) carboxy A copolymer containing a structural unit having a group and / or a phenolic hydroxyl group is contained. Component A is preferably a resin that is insoluble in alkali and becomes alkali-soluble when the acid-decomposable group is decomposed. Here, the “acid-decomposable group” means a functional group that can be decomposed in the presence of an acid. “Alkali-soluble” refers to a coating film (thickness 3 μm) formed by applying a solution of a compound (resin) on a substrate and heating at 90 ° C. for 2 minutes. The dissolution rate with respect to the aqueous solution of methylammonium hydroxide is 0.01 μm / second or more. On the other hand, “alkali insoluble” means that the dissolution rate is less than 0.01 μm / second. The alkali dissolution rate of component A is more preferably less than 0.005 μm / second.

Component A is preferably an addition polymerization type resin, and more preferably a polymer containing a structural unit derived from (meth) acrylic acid and / or an ester thereof. “(Meth) acrylic acid” is synonymous with “acrylic acid and / or methacrylic acid”. In addition, the component A may have structural units other than the structural unit derived from (meth) acrylic acid and / or its ester, for example, a structural unit derived from styrene or a vinyl compound.
Component A preferably contains 50 mol% or more of monomer units derived from (meth) acrylic acid and / or its ester, more preferably 90 mol% or more, more preferably 100 mol, based on all monomer units. % Of the polymer is particularly preferable.

The method for introducing the structural unit contained in component A may be a polymerization method, a polymer reaction method, or a combination of these two methods.
In the polymerization method, for example, an ethylenically unsaturated compound having a residue in which an acid group is protected with an acid-decomposable group, an ethylenically unsaturated compound having a crosslinking group, an ethylene having a carboxy group and / or a phenolic hydroxyl group. A target copolymer can be obtained by mixing and polymerizing a unsaturated unsaturated compound.
In the polymer reaction method, an epoxy group can be introduced by reacting a copolymer obtained by copolymerizing 2-hydroxyethyl methacrylate with epichlorohydrin. Thus, after copolymerizing an ethylenically unsaturated compound having a reactive group, the reactive group remaining in the side chain is utilized to protect the phenolic hydroxyl group or carboxy group with an acid-decomposable group by a polymer reaction. Functional groups such as cross-linked groups and / or cross-linking groups can be introduced into the side chain.

(Structural unit (a1))
Component A contains (a1) a structural unit having a residue in which an acid group is protected with an acid-decomposable group. When Component A has the structural unit (a1), a highly sensitive photosensitive resin composition can be obtained. Examples of the acid group include a carboxy group and a phenolic hydroxyl group.

(A1-1) Structural unit having a residue in which a carboxy group is protected with an acid-decomposable group (a1-1) Structural unit having a residue in which a carboxy group is protected with an acid-decomposable group (hereinafter referred to as “structural unit”) (Also referred to as (a1-1) ”) is a residue in which the carboxy group contained in the constituent units described in (a1-1-1) and (a1-1-2) described later is protected by an acid-decomposable group. A structural unit having a group is preferred.

(A1-1-1) Structural unit having a carboxy group The structural unit having a carboxy group includes at least one carboxy group in the molecule, such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or an unsaturated tricarboxylic acid. Examples include structural units derived from unsaturated carboxylic acids and the like.
Examples of the unsaturated monocarboxylic acid include (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polyvalent carboxylic acid may be its acid anhydride, and specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. Further, the unsaturated polyvalent carboxylic acid may be a mono (2- (meth) acryloyloxyalkyl) ester of a polyvalent carboxylic acid, for example, succinic acid mono (2- (meth) acryloyloxyethyl). And mono (2- (meth) acryloyloxyethyl) phthalate. Further, the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both terminals, and examples thereof include ω-carboxypolycaprolactone mono (meth) acrylate. As the unsaturated carboxylic acid, (meth) acrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like can also be used. Among them, from the viewpoint of developability, in order to form a structural unit having a carboxy group, it is preferable to use (meth) acrylic acid or an anhydride of an unsaturated polyvalent carboxylic acid, and (meth) acrylic acid is used. It is more preferable.
The structural unit (a1-1-1) having a carboxy group may be composed of one kind alone, or may be composed of two or more kinds.

(A1-1-2) Structural unit having both an ethylenically unsaturated group and an acid anhydride residue The structural unit (a1-1-2) having both an ethylenically unsaturated group and an acid anhydride residue is A structural unit derived from a monomer obtained by reacting a hydroxyl group present in a compound having an ethylenically unsaturated group with an acid anhydride is preferable. In the following description, an acid anhydride residue means a residue generated by a reaction between a hydroxyl group and an acid anhydride, for example, a residue having an ester bond and a carboxy group.
As the acid anhydride, known ones can be used, and specific examples include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride and the like. Examples include basic acid anhydrides; acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, and biphenyl tetracarboxylic acid anhydride. Among these, phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride is preferable from the viewpoint of developability.
The reaction rate of the acid anhydride with respect to the hydroxyl group is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, from the viewpoint of developability.

(A1-1) Structural unit having a residue in which a carboxy group is protected with an acid-decomposable group The structural unit having a residue in which a carboxy group is protected with an acid-decomposable group is preferably the above (a1-1- 1) A structural unit having a residue in which a carboxy group contained in the structural unit described in (a1-1-2) is protected by an acid-decomposable group.
The acid-decomposable group is not particularly limited, and any known acid-decomposable group in the positive resist for KrF and the positive resist for ArF can be used. Examples of acid-decomposable groups include groups that are relatively easily decomposed by acid (for example, acetal functional groups such as tetrahydropyranyl group and ethoxyethyl group), and groups that are relatively difficult to decompose by acid (for example, t-butyl ester). Groups, t-butyl functional groups such as t-butyl carbonate groups) are known. As the structural unit (a1-1), a structural unit having a residue in which a carboxy group is protected with an acetal or a residue in which a carboxy group is protected with a ketal has sensitivity, pattern shape, or contact hole formability. It is preferable from the viewpoint.

Furthermore, among the acid-decomposable groups, it is more preferable from the viewpoint of sensitivity that the carboxy group is a residue protected with an acetal or ketal represented by the formula (A1). In addition, when the carboxy group is an acetal or ketal-protected residue represented by the formula (A1), the entire residue is —C (═O) —O—CR ¹ R ² (OR ³ ). It has a structure.

（式（Ａ１）中、Ｒ¹及びＲ²は、それぞれ独立に水素原子、アルキル基、又は、アリール基を表し、少なくともＲ¹及びＲ²のいずれか一方がアルキル基、又は、アリール基であり、Ｒ³は、アルキル基、又は、アリール基を表し、Ｒ¹又はＲ²とＲ³とが連結して環状エーテルを形成してもよい。式（Ａ１）における波線部分は、他の構造との結合位置を表す。））

(In formula (A1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, or an aryl group, and at least ^one of R ¹ and R ² is an alkyl group or an aryl group. , R ³ represents an alkyl group or an aryl group, and R ¹ or R ² and R ³ may be linked to form a cyclic ether, wherein the wavy line in formula (A1) represents other structures and Represents the bonding position of

In formula (A1), the alkyl group in R ¹ , R ² and R ³ may be linear, branched or cyclic.
The linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. Specifically, 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 Examples include -hexyl group, texyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, and n-decyl group. Of these, a methyl group and an ethyl group are preferable.
The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 4 to 6 carbon atoms. Examples of the cyclic alkyl group 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. Of these, monocyclic ones are preferable, and cyclohexyl groups are more preferable.
The alkyl group may have a substituent. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, aryl group having 6 to 20 carbon atoms, and 1 to 6 carbon atoms. The alkoxy group of can be illustrated. When it has a halogen atom as a substituent, R ¹ , R ² and R ³ become a haloalkyl group, and when it has an aryl group as a substituent, R ¹ , R ² and R ³ become an aralkyl group. As the aralkyl group, a benzyl group is preferable.

In formula (A1), the aryl group in R ¹ , R ² and R ³ preferably has 6 to 12 carbon atoms, and more preferably 6 to 10 carbon atoms. The aryl group may have a substituent, and preferred examples of the substituent include an alkyl group having 1 to 6 carbon atoms. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a 1-naphthyl group, and a phenyl group is preferable.

In formula (A1), R ¹ , R ² and R ³ can be bonded to each other 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.

In formula (A1), it is preferable that either R ¹ or R ² is a hydrogen atom or a methyl group.
As the radical polymerizable monomer used for forming the structural unit having the residue represented by the formula (A1), a commercially available one may be used, for example, paragraph 0025 of JP-A-2009-098616. Those synthesized by a known method such as the method described in ˜0026 may be used.

  As the structural unit (a1-1) having a residue in which a carboxy group is protected with an acid-decomposable group, a structural unit represented by the formula (A2) is more preferable.

（式（Ａ２）中、Ｒ¹及びＲ²は、それぞれ独立に水素原子、アルキル基又はアリール基を表し、少なくともＲ¹及びＲ²のいずれか一方がアルキル基又はアリール基であり、Ｒ³は、アルキル基又はアリール基を表し、Ｒ¹又はＲ²とＲ³とが連結して環状エーテルを形成してもよく、Ｒ⁴は、水素原子又はメチル基を表し、Ｘは単結合又はアリーレン基を表す。）

(In formula (A2), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least ^one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ is Represents an alkyl group or an aryl group, R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group. Represents.)

Wherein (A2), R ¹ ~R ³ is the same as R ¹ to R ³ in the formula (A1), and preferred ranges are also the same.
In Formula (A2), R ¹ and R ² are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group. R ³ is preferably a linear, branched or cyclic alkyl group having 6 or less carbon atoms or an aralkyl group having 7 to 10 carbon atoms, and more preferably an ethyl group, a cyclohexyl group or a benzyl group. The cyclic ether in which R ¹ or R ² and R ³ are linked is preferably a tetrahydropyranyl group or a tetrahydrofuranyl group. R ⁴ is preferably a methyl group. X is preferably a single bond or a phenylene group.

  Preferable specific examples of the structural unit (a1-1) include the following structural units. R represents a hydrogen atom or a methyl group.

The structural unit (a1-1) may be a structural unit having a residue in which a carboxy group is protected with a tertiary alkyl group represented by the formula (A3). The sensitivity is inferior to that of a residue protected with an acetal or ketal, but it is preferable in terms of excellent storage stability. When the carboxy group is a residue protected with a tertiary alkyl group represented by the formula (A3), the residue as a whole is —C (═O) —O—CR ¹ R ² R ^3. This is the structure.

In formula (A3), R ¹ , R ² and R ³ each independently represents an alkyl group or an aryl group, and any ^{two of} R ¹ , R ² and R ³ are bonded to each other to form a ring. Also good. The wavy line part in Formula (A3) represents the coupling position with another structure. Specific examples of the alkyl group and aryl group in R ^{1 to} R ³ of formula (A3) are the same as the specific examples of the alkyl group and aryl group in formula (A1).
In the formula (A3), preferred examples include a combination of R ¹ = R ² = R ³ = methyl group, and a combination of R ¹ = R ² = methyl group and R ³ = benzyl group.

(A1-2) Structural unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group (a1-2) As a structural unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group, a1-2-1) A structural unit having a residue in which the phenolic hydroxyl group of the structural unit having a phenolic hydroxyl group is protected by an acid-decomposable group is preferred.

(A1-2-1) Structural Unit Having Phenolic Hydroxyl Group Examples of the structural unit having a phenolic hydroxyl group include a hydroxystyrene structural unit and a structural unit in a novolac resin. Among these, α-methylhydroxy A structural unit derived from styrene is preferred from the viewpoint of transparency. Among the structural units having a phenolic hydroxyl group, the structural unit represented by the formula (A4) is preferable from the viewpoints of transparency and sensitivity.

（式（Ａ４）中、Ｒ²⁰は水素原子又はメチル基を表し、Ｒ²¹は単結合又は二価の連結基を表し、Ｒ²²はそれぞれ独立にハロゲン原子又はアルキル基を表し、ａは１〜５の整数を表し、ｂは０〜４の整数を表し、ａ＋ｂは５以下である。）

(In the formula (A4), R ²⁰ represents a hydrogen atom or a methyl group, R ²¹ represents a single bond or a divalent linking group, R ²² each independently represents a halogen atom or an alkyl group, 5 represents an integer of 5, b represents an integer of 0 to 4, and a + b is 5 or less.)

R ²⁰ is preferably a methyl group.
Examples of the divalent linking group for R ²¹ include an ester bond (—COO—) in which a carbon atom is bonded to the main chain, and an alkylene group. The alkylene group is preferably a linear or branched alkylene group having 1 to 6 carbon atoms. In the case of -COO-, the sensitivity can be improved and the transparency of the cured film can be further improved. Among these, R ²¹ is preferably a single bond or an ester bond. The divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group.

Moreover, although a represents the integer of 1-5, it is preferable that a is 1 or 2 from the point that manufacture is easy, and it is more preferable that a is 1.
Further, the bonding position of the hydroxyl group in the benzene ring is preferably bonded to the 4-position when the carbon atom bonded to R ²¹ is the reference (first position).
R ²² is a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom, or a linear or branched alkyl group having 1 to 5 carbon atoms. Among these, a chlorine atom, a bromine atom, a methyl group or an ethyl group is preferable because of easy production.

(A1-2) Structural unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group A structural unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group is (a1-2-1) A structural unit having a residue in which a phenolic hydroxyl group of a structural unit having a phenolic hydroxyl group is protected by an acid-decomposable group.
As the acid-decomposable group, a known group can be used as described above, and is not particularly limited.
The basic physical properties of the resist, especially the sensitivity, pattern shape, and photosensitivity, are the structural units having a residue in which the phenolic hydroxyl group is protected with an acid-decomposable group, and the residue in which the phenolic hydroxyl group is protected with an acetal or ketal. It is preferable from the viewpoint of storage stability of the resin composition and formability of contact holes. Furthermore, among the residues in which the phenolic hydroxyl group is protected with an acid-decomposable group, it is more preferable from the viewpoint of sensitivity that the phenolic hydroxyl group is a residue protected with an acetal or ketal represented by the formula (A1). . In this case, the residue as a whole has a structure of —Ar—O—CR ¹ R ² (OR ³ ). Ar represents an arylene group.
Preferable examples of the acetal ester structure of the phenolic hydroxyl group include a combination of R ¹ = R ² = R ³ = methyl group, R ¹ = R ² = methyl group and R ³ = benzyl group.

  Examples of the radical polymerizable monomer used to form a structural unit having a residue in which a phenolic hydroxyl group is protected with an acetal or ketal include, for example, a 1-alkoxyalkyl protector of hydroxystyrene, a hydroxystyrene Protected tetrahydropyranyl, 1-alkoxyalkyl protected α-methylhydroxystyrene, tetrahydropyranyl protected α-methyl-hydroxystyrene, 1-alkoxyalkyl protected 4-hydroxyphenyl methacrylate, 4-hydroxyphenyl methacrylate Tetrahydropyranyl protected form of 4-hydroxybenzoic acid (1-methacryloyloxymethyl) ester 1-alkoxyalkyl protected, 4-hydroxybenzoic acid (1-methacryloyloxymethyl) ester tetrahydride Protected ropyranyl, 1-alkoxyalkyl protected 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester, protected tetrahydropyranyl of 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester, 4-hydroxybenzoic acid 1-alkoxyalkyl protector of (3-methacryloyloxypropyl) ester, tetrahydropyranyl protector of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxy) 1-alkoxyalkyl protector of propyl) ester, tetrahydropyranyl protector of 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester, and the like. Of these, a 1-alkoxyalkyl protector of α-methyl-hydroxystyrene is preferred.

  Specific examples of the acetal protecting group and the ketal protecting group for the phenolic hydroxyl group include 1-alkoxyalkyl groups, such as 1-ethoxyethyl group, 1-methoxyethyl group, 1-n-butoxyethyl group, 1- Isobutoxyethyl group, 1- (2-chloroethoxy) ethyl group, 1- (2-ethylhexyloxy) ethyl group, 1-n-propoxyethyl group, 1-cyclohexyloxyethyl group, 1- (2-cyclohexylethoxy) Examples thereof include an ethyl group and a 1-benzyloxyethyl group, and among them, a 1-ethoxyethyl group is preferable. These can be used alone or in combination of two or more.

  A commercially available thing may be used for the radically polymerizable monomer used in order to form a structural unit (a1-2), and what was synthesize | combined by the well-known method can also be used. For example, it can be synthesized by reacting a compound having a phenolic hydroxyl group with vinyl ether in the presence of an acid catalyst. In the above synthesis, a monomer having a phenolic hydroxyl group may be previously copolymerized with another monomer, and then reacted with vinyl ether in the presence of an acid catalyst.

  Preferable specific examples of the structural unit (a1-2) include the following structural units, but the present invention is not limited thereto. R represents a hydrogen atom or a methyl group.

  A structural unit having a residue in which a carboxy group is protected with an acid-decomposable group develops faster than a structural unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group. Therefore, when it is desired to develop quickly, a structural unit having a residue in which a carboxy group is protected with an acid-decomposable group is preferable. Conversely, when it is desired to delay development, it is preferable to use a structural unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group.

  From the viewpoint of sensitivity, the content of monomer units derived from the structural unit (a1) in the monomer units constituting Component A is preferably 20 to 60 mol% in all monomer units of the copolymer of Component A. 30 -50 mol% is more preferable.

(Structural unit (a2))
Component A contains (a2) a structural unit having a crosslinking group. The crosslinking group is preferably a group that causes a crosslinking reaction by heat treatment. Preferred embodiments of the structural unit having a bridging group include a structural unit containing at least one selected from the group consisting of a 3-membered ring and / or a 4-membered cyclic ether residue and an ethylenically unsaturated group. It is done.

(A2-1) A structural unit having a 3-membered ring and / or a 4-membered cyclic ether residue The 3-membered cyclic ether residue is also called an epoxy group, and the 4-membered cyclic ether residue is an oxetanyl group. Also called. These cyclic ether residues react with a carboxy group or a phenolic hydroxyl group by heat treatment to form a covalent bond to cause a crosslinking reaction. The structural unit (a2-1) having an epoxy group and / or oxetanyl group is preferably a structural unit having an alicyclic epoxy group and / or oxetanyl group, and more preferably a structural unit having an oxetanyl group. preferable.
The structural unit having an epoxy group and / or oxetanyl group only needs to have at least one epoxy group or oxetanyl group in one structural unit, and has a total of 1 to 3 epoxy groups and / or oxetanyl groups. It is more preferable to have one or two epoxy groups and / or oxetanyl 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 structural unit having an epoxy group include, for example, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, α-ethyl ( Glycidyl acrylate, glycidyl α-n-propyl (meth) acrylate, glycidyl α-n-butyl (meth) acrylate, (meth) acrylic acid-3,4-epoxybutyl, (meth) acrylic acid-6 , 7-epoxyheptyl, α-ethyl (meth) acrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, paragraph of Japanese Patent No. 4168443 Compounds containing an alicyclic epoxy skeleton according to any one of 0031 to 0035 Etc., and the like.
Specific examples of the radical polymerizable monomer used for forming the structural unit having an oxetanyl group include, for example, a (meth) acryl having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A No. 2001-330953. Examples include acid esters.
In the present invention, the radical polymerizable monomer used for forming the structural unit (a2) is preferably a monomer containing a (meth) acrylate structure.

  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 (meth) acrylic acid 3,4-epoxycyclohexylmethyl and (meth) acrylic acid (3-ethyloxetan-3-yl) methyl, and most preferred is (meth) acrylic acid (3 -Ethyloxetane-3-yl) methyl. These structural units can be used alone or in combination of two or more.

  The structural unit (a2-1) has a residue selected from the group consisting of a residue obtained by removing one hydrogen atom from the structure represented by the formula (A5) and a residue represented by the formula (A6). preferable.

（式（Ａ６）中、Ｒ^1b及びＲ^6bはそれぞれ独立に水素原子又はアルキル基を表し、Ｒ^2b、Ｒ^3b、Ｒ^4b、Ｒ^5b、Ｒ^7b、Ｒ^8b、Ｒ^9b及びＲ^10bはそれぞれ独立に水素原子、ハロゲン原子、アルキル基、又は、アリール基を表す。式（Ａ６）における波線部分は、他の構造との結合位置を表す。）

(In formula (A6), R ^1b and R ^6b each independently represent a hydrogen atom or an alkyl group, and R ^2b , R ^3b , R ^4b , R ^5b , R ^7b , R ^8b , R ^9b and R ^10b are each independent. Represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group, and a wavy line in formula (A6) represents a bonding position with another structure.)

In formula (A6), R ^1b and R ^6b each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. More preferably, it is a group.
R ^2b , R ^3b , R ^4b , R ^5b , R ^7b , R ^8b , R ^9b and R ^10b each independently represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group.
As a halogen atom, a fluorine atom and a chlorine atom are more preferable, and a fluorine atom is still more preferable.
The alkyl group may be linear, branched or cyclic. The linear and branched alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. The cyclic alkyl group preferably has 3 to 10 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 5 to 7 carbon atoms. The linear and branched alkyl groups may be substituted with a cyclic alkyl group, and the cyclic alkyl group may be substituted with a linear and / or branched alkyl group.
The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms.
The alkyl group and aryl group may further have a substituent, and examples of the substituent that the alkyl group may have include a halogen atom and an aryl group. Examples of suitable substituents include halogen atoms and alkyl groups.
Among these, R ^2b , R ^3b , R ^4b , R ^5b , R ^7b , R ^8b , R ^9b and R ^10b are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or More preferably, it is a perfluoroalkyl group having 1 to 4 carbon atoms.
A preferred example of the residue represented by the formula (A6) is a (3-ethyloxetane-3-yl) methyl group.

  Preferable specific examples of the structural unit (a2-1) include the following structural units. R represents a hydrogen atom or a methyl group.

  In the present invention, an oxetanyl group is preferable from the viewpoint of transmittance (transparency). Moreover, an alicyclic epoxy group is preferable from the viewpoint of electrical characteristics.

(A2-3) Structural unit having an ethylenically unsaturated group As one of the structural units (a2), there may be mentioned a structural unit (a2-3) having an ethylenically unsaturated group. As the structural unit (a2-3), for example, structural units described in paragraphs 0010 to 0040 of JP-A-2008-256974 can also be used in the present invention. The structural unit (a2-3) is preferably a structural unit having an ethylenically unsaturated group in the side chain, more preferably a structural unit having an ethylenically unsaturated group at the terminal and a side chain having 3 to 16 carbon atoms. A structural unit having a side chain represented by formula (A7) is more preferable.

（式（Ａ７）中、Ｒ¹は炭素数１〜１３の二価の連結基を表し、Ｒ³は水素原子又はメチル基を表す。式（Ａ７）における波線部分は、主鎖との結合位置を表す。）

(In formula (A7), R ¹ represents a divalent linking group having 1 to 13 carbon atoms, and R ³ represents a hydrogen atom or a methyl group. The wavy line in formula (A7) represents the position of bonding with the main chain. Represents.)

R ¹ is a divalent linking group having 1 to 13 carbon atoms, and includes an alkenyl group, a cycloalkenyl group, an arylene group, or a combination thereof, and includes an ester bond, an ether bond, an amide bond, a urethane bond, and the like. Bonds may be included. The divalent linking group may have a substituent such as a hydroxy group or a carboxy group at an arbitrary position. Specific examples of R ¹ include linking groups described in paragraphs 0016 to 0017 of JP-A-2008-256974.
Moreover, it is preferable that 1 mol of ethylenically unsaturated groups contained in the side chain represented by the formula (A7) is contained with respect to Component A 150 to 2,000 g, and 1 mol with respect to 200 to 1,300 g. More preferably it is included.
In the present invention, the structural unit (a2-3) is preferably a structural unit represented by the formula (A8).

（式（Ａ８）中、Ｒ¹は、炭素数１〜１３の二価の連結基を表し、Ｒ²、Ｒ³はそれぞれ独立に、水素原子又はメチル基を表す。）
式（Ａ８）におけるＲ¹は、式（Ａ７）におけるＲ¹と同義であり、好ましい範囲も同様である。

(In formula (A8), R ¹ represents a divalent linking group having 1 to 13 carbon atoms, and R ² and R ³ each independently represent a hydrogen atom or a methyl group.)
R ¹ in formula (A8) has the same meaning as R ¹ in formula (A7), and the preferred range is also the same.

  The method for obtaining the structural unit (a2-3) having a side chain represented by the formula (A7) 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. A copolymer having a structural unit (a2-3) by reacting with a group that reacts with the specific functional group and a compound having an ethylenically unsaturated group at the terminal (hereinafter referred to as a specific compound). Can do. Specific examples of the specific functional group, the polymer having the specific functional group, and the specific compound are described in paragraphs 0019 to 0031 of JP-A-2008-256974, and can also be used in the present invention.

In the present invention, when a polymer having a specific functional group is obtained, the monomer having the specific functional group and the monomer to be the structural unit (a1), and the monomer to be the structural unit (a3) described later are further added. Combined.
A method for obtaining a polymer having a specific functional group used in the present invention and a method for obtaining a structural unit (a2-3) by reacting a polymer having a specific functional group with a specific compound are not limited, For example, reference can be made to paragraphs 0038 to 0040 of JP-A-2008-256974.

  The content of the monomer unit derived from the structural unit (a2) in all monomer units constituting Component A is 20 to 45 mol% from the viewpoint of various resistances such as ITO sputtering suitability and transparency of the formed film. Preferably, 20-40 mol% is more preferable.

(Structural unit (a3))
Component A contains (a3) a structural unit having a carboxy group and / or a phenolic hydroxyl group as long as component A is not alkali-soluble. The carboxy group also includes a carboxylic anhydride residue.
Examples of the radical polymerizable monomer used to form the structural unit having a carboxy group include monocarboxylic acids such as (meth) acrylic acid and crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, Dicarboxylic acids such as itaconic acid are preferred. Moreover, as a radically polymerizable monomer used in order to form the structural unit which has a carboxylic anhydride residue, maleic anhydride, itaconic anhydride, etc. are preferable, for example. Examples of the radical polymerizable monomer that forms a structural unit having a phenolic hydroxyl group include hydroxystyrenes such as p-hydroxystyrene and α-methyl-p-hydroxystyrene, paragraph 0011 of JP2008-40183A. To 0016, 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 and acrylic An addition reaction product with glycidyl acid is preferred. Among these, (meth) acrylic acid and hydroxystyrenes are more preferable. These structural units can be used individually by 1 type or in combination of 2 or more types.

  Preferable specific examples of the structural unit (a3) include the following structural units. R represents a hydrogen atom or a methyl group.

  Since the outstanding sensitivity and developability are obtained, the content of the monomer units derived from the structural unit (a3) is preferably 1 to 20 mol%, and preferably 5 to 15 mol, in all the monomer units constituting the component A. % Is more preferable.

(Other structural units)
Component A may contain other structural units other than the structural units (a1) to (a3) as long as the effects of the present invention are not hindered. Examples of the radical polymerizable monomer used to form other structural units include the compounds described in paragraphs 0021 to 0024 of JP-A No. 2004-264623 (provided that (a1) above) To (a3) except for the compound forming the structural unit).
Among these, (meth) acrylic acid esters containing an alicyclic structure such as dicyclopentanyl (meth) acrylate and cyclohexyl (meth) acrylate are preferable from the viewpoint of improving electric characteristics. From the viewpoint of transparency, methyl (meth) acrylate is preferred. From the viewpoint of sensitivity, 2-hydroxyethyl (meth) acrylate and alkyl-terminated polyalkylene glycol (meth) acrylate are preferred. Among these, 2-hydroxyethyl (meth) acrylate is more preferable. Other structural units can be used alone or in combination of two or more. In all the structural units constituting Component A, the content of other structural units is preferably from 0 to 30 mol%, more preferably from 5 to 25 mol%.

  The weight average molecular weight of Component A is preferably 1,000 to 100,000, and more preferably 2,000 to 50,000. In addition, the weight average molecular weight in this invention is a polystyrene conversion weight average molecular weight by gel permeation chromatography (GPC).

  Various methods for synthesizing the copolymer of the component A are known. For example, at least the structural unit (a1), the structural unit (a2), and the structural unit (a3) are formed. And a method of synthesizing a mixture of radically polymerizable monomers containing a radically polymerizable monomer used for the purpose of polymerization in an organic solvent using a radical polymerization initiator.

Hereinafter, although preferable thing is illustrated as a component A used by this invention, this invention is not limited to this.
1-ethoxyethyl methacrylate / tert-butyl methacrylate / glycidyl methacrylate / methacrylic acid copolymer 1-ethoxyethyl methacrylate / tetrahydro-2H-pyran-2-yl methacrylate / glycidyl methacrylate / methacrylic acid copolymer 1-ethoxyethyl methacrylate / 2-hydroxyethyl methacrylate / 3,4-epoxycyclohexylmethyl methacrylate / methacrylic acid copolymer 1-ethoxyethyl methacrylate / 2-hydroxyethyl methacrylate / 3,4-epoxy methacrylate Cyclohexylmethyl / 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester copolymer 1-ethoxyethyl methacrylate / 2-hydroxyethyl methacrylate / 3,4-epoxy methacrylate Xoxycyclohexylmethyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester copolymer 1-ethoxyethyl methacrylate / 2-hydroxyethyl methacrylate / 3,4-epoxycyclohexylmethyl methacrylate-4-hydroxybenzoic acid ( 3-methacryloyloxypropyl) ester copolymer 1-ethoxyethyl methacrylate / 2-hydroxyethyl methacrylate / 3,4-epoxycyclohexylmethyl methacrylate / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / methacrylic acid Methyl copolymer tetrahydro-2H-pyran-2-yl methacrylate / 3,4-epoxycyclohexylmethyl methacrylate / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester Copolymer Tetrahydro-2H-pyran-2-yl methacrylate / 3,4-epoxycyclohexylmethyl methacrylate / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / 2-hydroxyethyl methacrylate copolymer Methacrylic acid 1-ethoxyethyl / methacrylic acid (3-ethyloxetane-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester copolymer tetrahydro-2H-pyran-2-yl methacrylate / methacrylic acid ( 3-ethyloxetane-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / methacrylic acid 2-hydroxyethyl copolymer 1- (cyclohexyloxy) ethyl methacrylate / methacrylic acid / methacrylic acid 3-Ethyloxetane-3-yl) methyl / 2-hydroxyethyl methacrylate copolymer 1-ethoxyethyl methacrylate / methacrylic acid / methacrylic acid (3-ethyloxetane-3-yl) methyl / 2-hydroxyethyl methacrylate Copolymer 1-ethoxyethyl acrylate / acrylic acid / acrylic acid (3-ethyloxetane-3-yl) methyl / 2-hydroxyethyl acrylate copolymer 1-ethoxyethyl methacrylate / methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate / styrene copolymer 1-ethoxyethyl methacrylate / methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate / dicyclopentanyl methacrylate copolymer tetrahydrofuran-2-yl methacrylate / methac Rylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate copolymer Tetrahydrofuran-2-yl methacrylate / methacrylic acid / methacrylic acid (3-ethyloxetane-3-yl) methyl / 2-hydroxyethyl methacrylate copolymer Component A can be used singly or in combination of two or more.

The content of Component A in the photosensitive resin composition of the present invention is preferably 20 to 99% by weight, and preferably 40 to 97% by weight, based on the total solid content of the photosensitive resin composition. More preferably, 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 the component A in the range which does not prevent the effect of this invention. However, the content of the resin other than Component A is preferably smaller than the content of Component A from the viewpoint of developability.

(Component B) Photoacid Generator The photosensitive resin composition of the present invention contains (Component B) a photoacid generator. The photoacid generator used in the present invention is preferably a compound that reacts with actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid, but is not limited to its chemical structure. 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, sulfonium salts and iodonium 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.
Preferred examples of the oxime sulfonate compound, that is, the compound having an oxime sulfonate residue include compounds having an oxime sulfonate residue of the formula (B1).

In formula (B1), R ⁵ represents an alkyl group, an alkoxy group, an aryl group or a halogen atom. The wavy line part in Formula (B1) represents the coupling position with another structure.
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 a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, aryl group having 6 to 11 carbon atoms, alkoxy group having 1 to 10 carbon atoms, or cyclo It may be substituted with an alkyl group (including a bridged alicyclic group such as a 7,7-dimethyl-2-oxonorbornyl group, preferably a bicycloalkyl group).
The alkoxy group R ^5, preferably a linear or branched alkoxy group having 1 to 4 carbon atoms, a methoxy group or an ethoxy group is more preferable. The alkoxy group may be substituted in the same manner as the alkyl group.
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 an alkyl group having 1 to 5 carbon atoms, an alkoxy group, or a halogen atom.
The compound containing an oxime sulfonate residue represented by the formula (B1) is more preferably an oxime sulfonate compound represented by the formula (B2).

（式（Ｂ２）中、Ｒ⁵は、式（Ｂ１）におけるＲ⁵と同義であり、Ｘは、アルキル基、アルコキシ基又はハロゲン原子を表し、ｍは、０〜３の整数を表し、ｍが２又は３であるとき、複数のＸは同一でも異なっていてもよい。）

(In Formula (B2), R ⁵ has the same meaning as R ⁵ in Formula (B1), 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, the plurality of X may be the same or different.)

The alkyl group in X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom is preferably a chlorine atom or a fluorine atom.
m is preferably 0 or 1.
In the formula (B2), 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-toluyl group is particularly preferable.

  The compound containing an oxime sulfonate residue represented by the formula (B1) is also preferably an oxime sulfonate compound represented by the formula (B3).

（式（Ｂ３）中、Ｒ⁵は式（Ｂ１）におけるＲ⁵と同義であり、Ｘ’は、ハロゲン原子、水酸基、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、又はニトロ基を表し、ｌは０〜５の整数を表す。）

(In the formula (B3), R ⁵ has the same meaning as R ⁵ in the formula (B1), X 'is a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or Represents a nitro group, and l represents an integer of 0 to 5.)

R ⁵ in the formula (B3) is methyl, ethyl, n-propyl, n-butyl, n-octyl, trifluoromethyl, pentafluoroethyl, perfluoro-n-propyl, perfluoro A fluoro-n-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferred, and an n-octyl group is particularly preferred.
X ′ is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
As l, an integer of 0 to 2 is preferable, and 0 or 1 is particularly preferable.
Specific examples of the compound represented by the formula (B3) include α- (methylsulfonyloxyimino) benzyl cyanide, α- (ethylsulfonyloxyimino) benzyl cyanide, α- (n-propylsulfonyloxyimino) benzyl. Cyanide, α- (n-butylsulfonyloxyimino) benzyl cyanide, α- (4-toluenesulfonyloxyimino) benzyl cyanide, α-[(methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α- [(Ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-butylsulfonyloxyimino) -4-methoxyphenyl Acetonitrile, α-[(4-toluene Sulfo) -4-methoxyphenyl] can be mentioned acetonitrile.

  Among these, specific examples of preferred oxime sulfonate compounds include (i) to (vi), and can be used singly or in combination of two or more. Compounds (i) to (vi) can be obtained as commercial products. It can also be used in combination with other types of photoacid generators.

  The compound containing an oxime sulfonate residue represented by the formula (B1) 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.
In the formula (OS-1), X is -O -, - S -, - NH -, - NR 5 -, - CH 2 -, - CR 6 H-, or, -CR ⁶ R ⁷ - represents, R ^{5 to} R ^{7 each} represents an alkyl group or an aryl group.
In the formula (OS-1), R ^{21 to} R ²⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, An amide group, a sulfo group, a 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 (B1) is an oxime sulfonate compound represented by the formula (OS-3), formula (OS-4) or formula (OS-5). Is more preferable.

（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 and benzyl group are preferred.

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 for R ¹ , a phenyl group, a p-methylphenyl group, a p-chlorophenyl group, a pentachlorophenyl group, a pentafluorophenyl group, an o-methoxyphenyl group, and a 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.
Examples of the alkyl group in R ² include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, n-hexyl group, allyl group, and chloromethyl group. , A bromomethyl group, a methoxymethyl group, and a benzyl group are preferable, and a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, and an n-hexyl group are more preferable. A 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.
As the aryl group for R ² , a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group, and a 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, n-decyl, n-dodecyl, trifluoromethyl, perfluoropropyl, perfluorohexyl and benzyl are preferred.

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.

As the alkyloxy group for R ⁶ , 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 is preferably used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of Component A, from the viewpoint of sensitivity and transparency. It is more preferable to use parts by weight.

(Component C) Solvent The photosensitive resin composition of the present invention contains (Component C) a solvent. The photosensitive resin composition of the present invention is preferably prepared as a solution in which components A and B, which are essential components, and optional components described below are dissolved in a solvent.
As the (Component C) solvent 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 Examples include glycol monoalkyl ether acetates, esters, ketones, amides, and lactones. As specific examples of these solvents, reference can be made to paragraph 0062 of JP-A-2009-098616. Solvents that can be used in the present invention may be used singly or in combination of two or more, preferably in combination of two, and in combination with propylene glycol monoalkyl ether acetates and other solvents. More preferably, the combined use of propylene glycol monomethyl ether acetate and diethylene glycol ethyl methyl ether is more preferable.
The content of the solvent in the photosensitive resin composition of the present invention is preferably 50 to 3,000 parts by weight per 100 parts by weight of component A from the viewpoint of adjusting the viscosity to be suitable for slit coating. More preferably, it is 1,000 parts by weight, and more preferably 150 to 1,500 parts by weight.

  In addition, 1-50 mPa * s is preferable, as for the viscosity of the photosensitive resin composition, 1-30 mPa * s is more preferable, and 1-20 mPa * s is further more preferable. The viscosity is measured at 25 ± 0.2 ° C. using, for example, a RE-80L rotational viscometer manufactured by Toki Sangyo Co., Ltd. The rotation speed at the time of measurement is 100 rpm for less than 5 mPa · s, 50 rpm for 5 mPa · s to less than 10 mPa · s, 20 rpm for 10 mPa · s to less than 30 mPa · s, and 10 rpm for 30 mPa · s or more.

(Optional component)
In addition to the components A to C, the following additives can be added as optional components to the photosensitive resin composition of the present invention.

(Component D) Sensitizer In the present invention, it is preferable to add (Component D) a sensitizer in order to promote the decomposition of the photoacid generator. 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 preferable sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength ranges of 350 to 450 nm.
Specific examples of the sensitizer include 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 (eg merocyanine, carbomerocyanine), rhodocyanins, oxonols, thiazines (eg thionine, methylene blue, toluidine blue), acridines For example, acridine orange, chloroflavin, acriflavine), acridones (for example, acridone, 10-butyl-2-chloroacridone), anthraquinones (for example, anthraquinone), squaliums (for example, squalium), styryls, base Styryls and coumarins (for example, 7-diethylamino 4-methylcoumarin), polynuclear aromatics, acridones, coumarins and base styryls are particularly preferred, polynuclear aromatics and acridones are more preferred, and anthracene The derivative, 10-butyl-2-chloroacridone is more preferred.
The addition amount of the sensitizer is preferably 20 to 300 parts by weight, particularly preferably 30 to 200 parts by weight with respect to 100 parts by weight of the photoacid generator, from the viewpoint of achieving both sensitivity and transparency.

(Component E) Crosslinking agent (Component E) A crosslinking agent is added to the photosensitive resin composition of this invention as needed. Examples of the crosslinking agent include a compound having two or more epoxy groups or oxetanyl groups in the molecule, an alkoxymethyl group-containing crosslinking agent, and a compound having at least one ethylenically unsaturated double bond. By adding a crosslinking agent, the cured film can be made stronger.

Specific examples of the compound having two or more epoxy groups in the molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic epoxy resin and the like. . Specific examples include JER-157S65 (polyfunctional novolac type epoxy resin) in addition to the compound described in paragraph 0042 of JP2009-258723A. Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenol novolac type epoxy resin are preferable, and phenol novolac type epoxy resin is more preferable.
Specific examples of the compound having two or more oxetanyl groups in the molecule include aron oxetane OXT-121, OXT-221, OX-SQ, and PNOX (above, manufactured by Toagosei Co., Ltd.). Moreover, the compound containing an oxetanyl group can be used individually or in mixture with the compound containing an epoxy group.

  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.

  As the compound having at least one ethylenically unsaturated bond, a (meth) acrylate compound such as a monofunctional (meth) acrylate, a bifunctional (meth) acrylate, a trifunctional or higher (meth) acrylate, or the like is preferably used. it can. 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 trifunctional or higher functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (meth) acrylate, Examples include dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

When adding a compound having at least one ethylenically unsaturated bond, it is preferable to add a thermal radical generator. In the present invention, Component E is preferably a compound having two or more epoxy groups or oxetanyl groups in the molecule. As the thermal radical generator, a known thermal radical generator can be used, and is described, for example, in paragraph 0037 of JP-A-2009-218509.
From the viewpoint that excellent heat resistance, solvent resistance and hardness of the cured film can be obtained, the amount of component E added is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight with respect to 100 parts by weight of component A. Preferably, 5 to 20 parts by weight is more preferable.

(Component F) Adhesion Improving Agent The photosensitive resin composition of the present invention may contain (Component F) an adhesion improving agent. The adhesion improver is a compound that improves the adhesion between an inorganic material serving as a base material, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, a metal such as gold, copper, or aluminum and a cured film as an insulating film. . Specific examples include silane coupling agents and thiol compounds. The silane coupling agent as the adhesion improving agent is for the purpose of modifying the interface, and any known silane coupling agent can be used without any particular limitation.
As the silane coupling agent, the silane coupling agent described in paragraph 0048 of JP-A-2009-98616 is preferable, and γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, γ-glycidoxypropyltrialkoxysilane is more preferable, and γ-glycidoxypropyltrimethoxysilane is particularly preferable. These can be used alone or in combination of two or more. These are also effective in improving the adhesion to the substrate and adjusting the taper angle with the substrate.
0.1-20 weight part is preferable with respect to 100 weight part of component A, and, as for content of the adhesion improving agent in the photosensitive resin composition of this invention, 0.5-10 weight part is more preferable.

(Component G) Basic Compound The photosensitive resin composition of the present invention may contain (Component G) a basic compound.
The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids and the like described in paragraphs 0051 to 0056 of JP2009-098616A. Among them, a heterocyclic amine is preferable, a heterocyclic amine having a pyridine ring, a heterocyclic amine having a bicyclo ring is more preferable, and 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8 -Diazabicyclo [5.3.0] -7-undecene is more preferred.
The basic compound may be used alone or in combination of two or more. However, it is preferable to use two or more in combination, and more preferable to use two in combination. It is more preferable to use two types in combination. From the viewpoint of sensitivity stability, the content of the basic compound is preferably 0.001 to 1 part by weight and more preferably 0.005 to 0.2 part by weight with respect to 100 parts by weight of Component A. preferable.

(Component H) Surfactant The photosensitive resin composition of the present invention may contain (Component H) a surfactant.
As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant. Specific examples include nonionic surfactants described in paragraph 0058 of JP-A-2009-098616, and among these, fluorosurfactants are preferable. These surfactants can be used individually by 1 type or in mixture of 2 or more types.

  In addition, as a surfactant, the structural unit A and the structural unit B represented by the following formula (1) are included, and the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent. A preferred example is a copolymer having (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.

  From the viewpoint of suitability for slit coating, the addition amount of the surfactant in the photosensitive resin composition of the present invention is preferably 10 parts by weight or less, more preferably 0.01 to 10 parts by weight, relative to 100 parts by weight of Component A. 0.01-1 weight part is further more preferable.

(Other ingredients)
If necessary, the photosensitive resin composition of the present invention may contain other components such as a plasticizer, a thermal radical generator, a thermal acid generator, an acid multiplier, a development accelerator, and an antioxidant. it can. As these components, for example, those described in JP 2009-098616 A, JP 2009-244801 A, and other known ones can be used. In addition, various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators and the like may be added to the photosensitive resin composition of the present invention. .

(Method for preparing photosensitive resin composition)
A photosensitive resin composition is prepared by mixing the essential components of component A to component C and, if necessary, optional components at a predetermined ratio and in any manner, stirring and dissolving. For example, it is possible to prepare a photosensitive resin composition by preparing a solution in which component A or component B is previously dissolved in a solvent and then mixing them in a predetermined ratio. 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.

II. Manufacturing method of cured film The manufacturing method of the cured film of the present invention includes (1) a low-temperature treatment step for bringing the photosensitive resin composition to a temperature of 10 ° C. or lower, and (2) slitting the photosensitive resin composition on a substrate. A coating step for coating, (3) a solvent removal step for removing the solvent from the coated photosensitive resin composition, (4) an exposure step for exposing the photosensitive resin composition from which the solvent has been removed with actinic rays, (5 And (6) a development step of developing with an aqueous developer, and (7) a post-bake step of thermal curing in this order. Each step will be described below in order.

(1) Low-temperature treatment step for bringing the photosensitive resin composition to a temperature of 10 ° C. or lower In the present invention, a low-temperature treatment step for bringing the photosensitive resin composition to a temperature of 10 ° C. or lower is performed before applying the photosensitive resin composition. Although there will be no restriction | limiting in particular if the temperature of a process is 10 degrees C or less, From a viewpoint of hole formation property and ITO sputtering suitability, -50-0 degreeC is preferable and -30--10 degreeC is more preferable.
The treatment time is not particularly limited, but is preferably 20 minutes or more, more preferably 30 minutes or more, and most preferably 40 minutes or more. By setting it within this range, the performance can be further improved. The upper limit of the treatment time is not particularly limited, but is preferably 365 days or less, more preferably 180 days or less, from the viewpoint of preventing aging deterioration of the composition.

(2) Coating step of slit coating the photosensitive resin composition on the substrate In the coating step of (2), the photosensitive resin composition of the present invention is slit coated (slit coating) on the substrate and wetted with a solvent. A film is formed.
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 slit coating method is preferable from the viewpoint of being suitable for a large substrate. Here, the large substrate refers to a substrate having a size of 1 m × 1 m square to 5 m × 5 m square.

  In a conventional small substrate, a spin coater has been used. As the substrate becomes larger, it becomes difficult to rotate the substrate, and a spinless coater has been used. In particular, it is said that a substrate larger than the sixth generation substrate (approximately 1,500 × 1,800 mm) cannot be rotated with a spin coater. In addition, the slit coater is EBR (edge back rinse) because it saves liquid (about 1/3 of the slit & spin coater), shortens the tact time, does not wrap around to the fringe (thick coating area at the end of the substrate) or back. There is an advantage that processing is not necessary. In the case of a conventional spin coater, a force in the horizontal direction with respect to the substrate acts on the liquid. On the other hand, in the case of a slit coater, no external force acts on the liquid on the substrate simply by placing the liquid on the substrate. It is estimated that a difference in performance occurs due to a difference in history with respect to such a liquid (photosensitive composition). In the present invention, a commercially available slit coater can be used.

(3) Solvent removal step for removing the solvent from the applied photosensitive resin composition In the solvent removal step (3), the solvent is removed from the applied film by vacuum and / or heating. A dry coating film is formed on the substrate. In the present invention, it is preferable to form a dry coating film on the substrate by removing the solvent by heating.
The heating condition of the solvent removal step is a range in which the acid-decomposable group is decomposed in the structural unit (a1) in the component A in the unexposed area and the component A is not soluble in the alkaline developer. Although it varies depending on the blending ratio, it is preferably about 80 to 130 ° C. for 30 to 120 seconds.
The thickness of the dried coating film is preferably from 0.1 to 30 μm, more preferably from 1.0 to 8.0 μm.

(4) Exposure step of exposing the photosensitive resin composition from which the solvent has been removed with actinic rays In the exposure step (4), the obtained coating film is irradiated with actinic rays having a wavelength of 300 to 450 nm. In this step, the photoacid generator is decomposed to generate an acid. By the catalytic action of the generated acid, the acid-decomposable group in the structural unit (a1) contained in the component A is decomposed to produce an acid group.
For exposure with actinic rays, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, an LED light source, a chemical lamp, a laser generator, or the like can be used. When a mercury lamp is used, actinic rays having wavelengths such as g-line (436 nm), i-line (365 nm), and h-line (405 nm) can be preferably used. In this case, exposure is performed through a mask. Mercury lamps are preferred in that they are suitable for large area exposure compared to lasers.
In the case of using a laser, 343 nm and 355 nm are used for a solid (YAG) laser, 351 nm (XeF) is used for an excimer laser, and 375 nm and 405 nm are used for a semiconductor laser. Among these, 355 nm and 405 nm are more preferable from the viewpoint of stability and cost. The coating film can be irradiated with the laser once or a plurality of times.

The energy density per pulse of the laser is preferably 0.1 to 10,000 mJ / cm ² . In order to sufficiently cure the coating film, 0.3 mJ / cm ² or more is preferable, and 0.5 mJ / cm ² or more is more preferable. In order not to degrade the coating film by ablation phenomenon is preferably 1,000 mJ / cm ² or less, 100 mJ / cm ² or less being more preferred.
The pulse width is preferably 0.1 to 30,000 nsec. In order not to decompose the color coating film due to the ablation phenomenon, 0.5 nsec or more is more preferable, and 1 nsec or more is most preferable. In order to improve the alignment accuracy at the time of scan exposure, 1,000 nsec or less is more preferable, and 50 nsec or less is most preferable.
Furthermore, the frequency of the laser is preferably 1 to 50,000 Hz, and more preferably 10 to 1,000 Hz. When the frequency of the laser is 1 Hz or more, the exposure processing time is appropriate, and when it is 50,000 Hz or less, the alignment accuracy is improved during scan exposure. In order to shorten the exposure processing time, 10 Hz or more is more preferable, and 100 Hz or more is most preferable. In order to improve the alignment accuracy at the time of scanning exposure, 10,000 Hz or less is more preferable, and 1,000 Hz or less is most preferable.

  Compared with a mercury lamp, a laser is preferable because it is easy to focus, and a mask for pattern formation in the exposure process is unnecessary, or a small mask may be used, so that the cost can be reduced. The exposure apparatus usable in the present invention is not particularly limited, and commercially available products include Calisto (manufactured by Buoy Technology), AEGIS (manufactured by Buoy Technology), DF2200G (Dainippon Screen Manufacturing ( Etc.). 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.

  In order to accelerate the decomposition 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 accelerate the decomposition of the acid-decomposable group. In the present invention, a mode in which a positive image is formed by development without performing PEB is preferable. In addition, by performing PEB at a relatively low temperature, decomposition of the acid-decomposable group can be promoted without causing a crosslinking reaction. The temperature when performing PEB is preferably 50 to 110 ° C, more preferably 60 to 90 ° C.

(5) Step of allowing 45 seconds or more to elapse at room temperature The step (5) is a step of allowing the substrate to generally elapse for 45 seconds or more at room temperature between the (4) exposure step and the (6) development step. During this process, the substrate may be left without moving, or the substrate may be moved for reasons such as transportation. The elapsed time is 45 seconds or more from the viewpoint of sensitivity stability, preferably 60 seconds or more, more preferably 90 seconds or more, and most preferably 120 seconds or more. Although there is no particular upper limit, it is preferably 10 minutes or less, more preferably 5 minutes or less from the viewpoint of production efficiency. The room temperature (temperature) is preferably 10 to 45 ° C, more preferably 10 to 40 ° C, and still more preferably 15 to 30 ° C. Sensitivity can be stabilized by setting this range. In the case of a large substrate, if the sensitivity is unstable, a large problem such as generation of a residue can occur. The PEB may be performed before or after the process, or may be performed in between (for example, PEB is performed after 30 seconds have elapsed after exposure, and further 40 seconds have elapsed). In the present invention, from the viewpoint of simplification of the process, a mode in which PEB is not provided before or after the process of (5) is preferable.

(6) Development Step for Developing with Aqueous Developer In the development step (6), it is preferable to develop the polymer having an acid group using an alkaline developer. A positive image is formed by removing the exposed area containing an acid group-containing copolymer that is easily dissolved in an alkaline developer.
In the development step, it is preferable to use a basic developer. 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. Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to an aqueous solution of the above bases can also be used as a developing solution.
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 may be performed for 30 to 90 seconds.

(7) Post-bake process for thermosetting In the post-bake process of (7), the obtained positive image is heated to crosslink the structural unit (a2) and form a cured film excellent in heat resistance, hardness, etc. it can. In this heating, the pattern corresponding to the unexposed region obtained by development is preferably heated to a high temperature of 150 ° C. or higher using a heating device such as a hot plate or an oven, and is heated to 180 to 250 ° C. Is more preferable, and heating to 200 to 250 ° C. is particularly preferable.
The heating time can be appropriately set depending on the heating temperature or the like, but is preferably in the range of 5 to 90 minutes. For example, heat treatment is performed for 5 to 60 minutes on a hot plate and 30 to 90 minutes for an oven. In addition, when heat treatment is performed, the transparency can be improved by performing the heat treatment in a nitrogen atmosphere.

In the case where the crosslinking group of the structural unit (a2) is an epoxy group or an oxetanyl group, the substrate on which the pattern has been formed is re-exposed with actinic rays, preferably ultraviolet rays, and then post-baked prior to the heat treatment ( It is preferable to generate an acid from component B present in the unexposed portion by re-exposure / post-bake) to function as a catalyst for accelerating the crosslinking step.
The exposure in the re-exposure process may be performed by the same means as in the exposure process. However, in the re-exposure process, it is preferable that the entire surface of the substrate on which the film is formed is exposed. A preferable exposure amount in the re-exposure step is 100 to 1,000 mJ / cm ² .

III. Cured film, organic EL display device, liquid crystal display device By the method for producing a cured film of the present invention, a cured film having excellent insulation and high transparency can be obtained even when baked at a high temperature. 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 particularly limited except that they have a flattening film, a protective layer, and a cured film as an interlayer insulating film formed by using the cured film manufacturing method of the present invention. However, various known organic EL display devices and liquid crystal display devices having various structures can be used.
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 planarizing film, a protective layer, and an interlayer insulating film, it is suitably used for a spacer for keeping the thickness of a liquid crystal layer in a liquid crystal display device constant, a microlens provided on a color filter in a solid-state imaging device, 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 (thin film transistor) 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 layer 4 is formed on the insulating film 3 in a state where the unevenness due to the wiring 2 is 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 the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do.
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. This 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 is disposed between all two glass substrates 14 and 15 having a polarizing film attached thereto. Elements of the TFT 16 corresponding to the pixels 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.

  Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “% by weight”.

1. Synthesis of copolymer <Synthesis of copolymer A-1>
To 144.2 parts (2 molar equivalents) of ethyl vinyl ether, 0.5 part of phenothiazine was added, and 86.1 parts (1 molar equivalent) of methacrylic acid was added dropwise while cooling the reaction system to 10 ° C. or lower. ) For 4 hours. After adding 5.0 parts of pyridinium p-toluenesulfonate, the mixture was stirred at room temperature for 2 hours and allowed to stand overnight at room temperature. To the reaction solution, 5 parts of sodium bicarbonate and 5 parts of sodium sulfate were added, and the mixture was stirred at room temperature for 1 hour. Insoluble matter was filtered and concentrated under reduced pressure at 40 ° C. or lower, and the yellow oily residue was distilled under reduced pressure to obtain a boiling point (bp .) 134.0 parts of 1-ethoxyethyl methacrylate in the 43-45 ° C./7 mmHg fraction were obtained as a colorless oil.
1-Ethoxyethyl methacrylate (66.41 parts (0.42 mole equivalent)), methacrylic acid (6.89 parts (0.08 mole equivalent)), glycidyl methacrylate (GMA) (49.75 parts ( 0.35 molar equivalent)), 2-hydroxyethyl methacrylate (19.52 parts, (0.15 molar equivalent)) and propylene glycol monomethyl ether acetate (PGMEA) (132.5 parts) in a nitrogen stream Under heating to 70 ° C. While stirring the mixed solution, radical polymerization initiator V-65 (2,2′-azobis (2,4-dimethylvaleronitrile), Wako Pure Chemical Industries, Ltd., 12.4 parts) and PGMEA (100 0.0 part) was added dropwise over 2.5 hours. After completion of the dropwise addition, a PGMEA solution of copolymer A-1 (solid content concentration: 40% by weight) was obtained by reacting at 70 ° C. for 4 hours. The weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the obtained copolymer A-1 was 8,000.

<Synthesis of Copolymers A-2 to A-16 and A′-1 to A′-3>
Copolymers A-2 to A-16 and A′-1 to A′— were the same as the synthesis of Copolymer A-1, except that the monomer species and the amount used thereof were changed to those shown in Table 1. 3 were synthesized respectively. The amount of radical polymerization initiator V-65 added was adjusted to have the molecular weight shown in Table 1.

In addition, the copolymerization ratio of Table 1 is a molar ratio, and the symbol in Table 1 is as follows.
MAEVE: 1-ethoxyethyl methacrylate CHOEMA: 1- (cyclohexyloxy) ethyl methacrylate THPMA: tetrahydro-2H-pyran-2-yl methacrylate MATH: tetrahydrofuran-2-yl methacrylate MATHH was synthesized as follows. did.
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%).

GMA: Glycidyl methacrylate OXE-30: Methacrylic acid (3-ethyloxetane-3-yl) methyl (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
ECHMMA: 3,4-epoxycyclohexylmethyl methacrylate MAA: methacrylic acid α-MHS: α-methylhydroxystyrene HEMA: 2-hydroxyethyl methacrylate PME-400: methyl-terminated polyethylene glycol methacrylate (Blemmer PME-400, NOF Corporation ) Made)
DCPM: Dicyclopentanyl methacrylate

2. Preparation of photosensitive resin composition (Examples 1-44, Comparative Examples 1-7, Examples 101-139, Examples 201-239, and Examples 301-308)
The components shown in Tables 2 to 5 were mixed, and a 1: 1 mixed solvent of C1: propylene glycol monomethyl ether acetate and C2: diethylene glycol ethyl methyl ether was added to obtain a viscosity of 3.0 mPa · s. Filtration was performed using a polytetrafluoroethylene filter to prepare a positive photosensitive resin composition.

  In addition, the symbol in Table 2-Table 5 is as follows.

B5: α- (4-Toluenesulfonyloxyimino) benzyl cyanide (synthesized according to the method described in paragraph 0108 of JP-T-2002-528451)
B6: α-[(4-Toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile (PAI-101, manufactured by Midori Chemical Co., Ltd.)

D1: NBCA (10-butyl-2-chloroacridone, manufactured by Kurokin Kasei Co., Ltd.)
D2: DBA (9,10-dibutoxyanthracene, manufactured by Kawasaki Kasei Kogyo Co., Ltd.)
E1: JER-157S65 (polyfunctional novolac type epoxy resin (epoxy equivalent: 200 to 220 g / eq), manufactured by Japan Epoxy Resins Co., Ltd.)
F1: KBM-403 (3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)
G1: 4-dimethylaminopyridine G2: 1,5-diazabicyclo [4.3.0] -5-nonene H1: PolyFox PF-6320 (fluorine surfactant, manufactured by OMNOVA)
W-3: The following compound

(Synthesis of photoacid generator B-10)
1-1. Synthesis of Synthesis Intermediate B-10A 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 B-10A.

1-2. Synthesis of B-10 2.25 g of the synthetic intermediate B-10A obtained as described above was mixed with tetrahydrofuran: 10 mL (manufactured by Wako Pure Chemical Industries, Ltd.), and then placed in an ice bath and the reaction solution was placed at 5 ° C. Cooled to: 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 and dried while hot (B-5: the above structure). 8 g was obtained.
¹ H-NMR spectrum (300 MHz, deuterated DMSO ((D ₃ C) ₂ S═O)) of the obtained B-10 is δ = 8.2 to 8.17 (m, 1H), 8.03 to It was 8.00 (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 result, it is estimated that the obtained B-10 is a single geometric isomer.

(Synthesis of photoacid generator B-11)
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 B-11 (2.3 g).
In addition, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-11 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).

(Synthesis of photoacid generator B-11)
2-Naphthol (20 g) is dissolved in N, N-dimethylacetamide (150 mL), potassium carbonate (28.7 g) and ethyl 2-bromooctanoate (52.2 g) are added and reacted at 100 ° C. for 2 hours. It was. To the reaction solution are added water (300 mL) and ethyl acetate (200 mL), and the mixture is separated. The organic layer is concentrated, and then 48 wt% aqueous sodium hydroxide solution (23 g), ethanol (50 mL), and water (50 mL) are added. The reaction was performed for 2 hours. The reaction solution was poured into 1N HCl aqueous solution (500 mL), and the precipitated crystals were filtered and washed with water to obtain a crude carboxylic acid, and then 30 g of polyphosphoric acid was added and reacted at 170 ° C. for 30 minutes. The reaction solution was poured into water (300 mL), and ethyl acetate (300 mL) was added for liquid separation, and the organic layer was concentrated and purified by silica gel column chromatography to obtain a ketone compound (10 g).
Sodium acetate (30.6 g), hydroxylamine hydrochloride (25.9 g), and magnesium sulfate (4.5 g) were added to a suspension of the resulting ketone compound (10.0 g) and methanol (100 mL) for 24 hours. Heated to reflux. After standing to cool, water (150 mL) and ethyl acetate (150 mL) were added for liquid separation, and the organic layer was separated four times with 80 mL of water, concentrated and purified by silica gel column chromatography to obtain an oxime compound (5.8 g). Got.
The obtained oxime (3.1 g) was sulfonated in the same manner as B-11 to obtain B-12 (3.2 g).
In addition, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-12 is δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7. 8 (d, 1H), 7.6 (dd, 1H), 7.5 (dd, 1H) 7.3 (d, 2H), 7.1 (d.1H), 5.6 (dd, 1H) , 2.4 (s, 3H), 2.2 (ddt, 1H), 1.9 (ddt, 1H), 1.4 to 1.2 (m, 8H), 0.8 (t, 3H) there were.

(Synthesis of photoacid generator B-13)
B-13 was synthesized in the same manner as B-11 except that benzenesulfonyl chloride was used instead of p-toluenesulfonyl chloride in B-11.
In addition, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-13 is δ = 8.3 (d, 1H), 8.1 (d, 2H), 7.9 (d, 1H), 7. 8 (d, 1H), 7.7-7.5 (m, 4H), 7.4 (dd, 1H), 7.1 (d.1H), 5.6 (q, 1H), 1.7 (D, 3H).

B-14: 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate B-15: trifluoromethylsulfonyloxybicyclo [2.2.1] -hept-5-ene-dicarboxy Imide

3. Evaluation (Example 1)
The following evaluation was performed using the photosensitive resin composition of Example 1.
<Evaluation of sensitivity>
The prepared photosensitive resin composition was once subjected to low temperature treatment under the conditions shown in Table 6 and returned to room temperature (23 ° C.). The photosensitive resin composition was slit-coated on a 2,160 × 2,460 mm glass substrate and then pre-baked on a hot plate at 90 ° C. for 90 seconds to remove the solvent to form a coating film having a thickness of 3 μm. Next, it exposed through the predetermined mask using FX-85S (i line specification, Nikon Corporation make). After exposure, at the temperature shown in Table 6, the time shown in Table 6 was allowed to elapse, followed by shower development with a 0.4 wt% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 35 seconds, and then with ultrapure water for 1 minute. Rinse. By these operations, the optimum exposure dose (E _opt ) when resolving 10 μm line and space at 1: 1 was determined. This was repeated 10 times, and the arithmetic average was taken as the sensitivity. It can be said that the sensitivity is high when the exposure amount is lower than 50 mJ / cm ² . The results are shown in Table 6.

<Evaluation of sensitivity stability>
Of the 10 optimum exposure doses determined by sensitivity measurement, the maximum value is E _max and the minimum value is E _min , and the value of (E _max −E _min ) ÷ (sensitivity) × 100 is 0 or more and less than 5: A, 5 Above 10 and below: B, 10 and above: C. The smaller this value is, the more stable the sensitivity is, and there is no practical problem if A or B is evaluated. C evaluation is not acceptable because problems such as residue may occur. The results are shown in Table 6.

<Evaluation of heat-resistant transparency>
The prepared photosensitive resin composition was subjected to low temperature treatment under the conditions shown in Table 6 and returned to room temperature (23 ° C.).
After the photosensitive resin composition was slit-coated on a glass substrate (Corning), the solvent was removed by pre-baking on a hot plate at 90 ° C. for 120 seconds to form a coating film having a thickness of 3 μm. Using FX-85S (i-line specification, manufactured by Nikon Corporation), the entire surface is exposed with the optimum exposure amount, and after the time shown in Table 6 has elapsed at the temperature shown in Table 6, the same as in the sensitivity evaluation is performed. The film was developed and rinsed with ultrapure water for 1 minute. The resulting coating film was exposed with FX-85S so that the cumulative irradiation amount was 300 mJ / cm ² (illuminance: 20 mW / cm ² ), and this substrate was heated in an oven at 230 ° C. for 1 hour to form a cured film. Obtained. The obtained cured film was further heated in an oven at 230 ° C. for 2 hours, and the light transmittance was 400 to 800 nm using a spectrophotometer “150-20 type double beam” (manufactured by Hitachi, Ltd.). Measured at a range of wavelengths. Table 6 shows the evaluation results of the minimum light transmittance at that time (evaluation results of heat-resistant transparency). The evaluation criteria are as follows.
A: 93% or more B: 88% or more and less than 93% C: 83% or more and less than 88% D: Less than 83%

<ITO sputtering suitability>
The cured film after the final heat treatment was obtained in the same manner as in the evaluation of heat-resistant transparency. On this cured film, an ITO transparent electrode was formed by sputtering (manufactured by ULVAC, SIH-3030, sputtering temperature 200 ° C.). The surface of the cured film after sputtering was observed with an optical microscope (500 times) and evaluated according to the following criteria.
A: No wrinkle is generated on the surface of the cured film B: Slight wrinkles are visible on the surface of the cured film (allowable range)
C: Generation of wrinkles on the surface of the cured film When wrinkles are observed on the surface of the cured film after the ITO transparent electrode is formed by sputtering, the transmittance of the cured film is reduced, which is not preferable. The results are shown in Table 6.

<Evaluation of formability of contact holes>
A coating film having a thickness of 3.0 μm was formed in the same manner as the sensitivity evaluation except that the substrate was changed to a silicon wafer. Next, using an i-line stepper (FPA-3000i5 ⁺ manufactured by Canon Inc.), an optimal exposure exposure was performed with a mask having a hole pattern having a diameter of 10 μm corresponding to a contact hole.
Development and rinsing were performed in the same manner as described above to form a contact hole pattern. Here, the diameter of the bottom of the formed contact hole was measured with an electron microscope. Further, the developed coating film in which the contact hole was formed was irradiated with light of 500 mJ / cm ^{2 at} a wavelength of 365 nm using an ultrahigh pressure mercury lamp, and then heated in an oven at 220 ° C. for 60 minutes. Here, the diameter of the lower bottom of the contact hole was measured in the same manner as described above.
In this evaluation, regarding the diameter of the bottom bottom of the formed contact hole, the difference between the two measured values measured before and after heating was “A”, which was less than 0.5 μm, which was 0.5 μm or more and less than 1.0 μm. The sample was evaluated as “B”, and the sample that was 1.0 μm or more was evaluated as “C”. The smaller the difference in diameter before and after heating, the easier it is to control the contact hole diameter, which is preferable. A or B can be used practically.
Further, the hole cross section after heating was observed, and the forward tapered shape was A, the vertical one was B, and the reverse tapered one was C. A forward taper is preferred, and A can be used practically. The results are shown in Table 6.

(Examples 2 to 21, Examples 26 to 28, Examples 30 to 44, Examples 101 to 121, Examples 126 to 129, Examples 131 to 139, Examples 201 to 221 and Examples 226 to 229, Examples Examples 231 to 239 and Examples 301 to 304)
Example 1 except that the formulation of the photosensitive resin composition was changed as shown in Tables 2 to 5 and the conditions (temperature and time) for leaving the substrate after exposure were changed as shown in Tables 6 to 9. In the same manner as above, the photosensitive resin composition and the cured film were evaluated.

(Examples 22 to 25)
The conditions for leaving the substrate after exposure (temperature, time) are as follows: after exposure, PEB at 80 ° C. for 60 seconds is performed at 23 ° C. for 90 seconds, and development is performed after 35 seconds at 23 ° C. In the same manner as in Example 1, the photosensitive resin composition and the cured film were evaluated. The results are shown in Table 6.
(Example 29)
Except that the pattern exposure was changed to the following laser exposure, it was performed in the same manner as in Example 8 (the substrate size was adjusted as appropriate). A predetermined photomask was set through a 150 μm interval from a dry coating film having a thickness of 3 μm, and a laser having a wavelength of 355 nm was irradiated with an optimum exposure amount. The laser device used was “AEGIS” manufactured by Buoy Technology Co., Ltd. (wavelength 355 nm, pulse width 6 nsec), and the exposure was measured using “PE10B-V2” manufactured by OPHIR. It was found that a pattern can be formed with a laser as well as a mercury lamp.

(Examples 122 to 125)
The conditions for leaving the substrate after exposure (temperature, time) are as follows: after exposure, PEB at 80 ° C. for 60 seconds is performed at 23 ° C. for 90 seconds, and development is performed after 35 seconds at 23 ° C. In the same manner as in Example 101, the photosensitive resin composition and the cured film were evaluated. The results are shown in Table 7.
(Example 130)
Except that the pattern exposure was the following laser exposure, the same procedure as in Example 108 was performed (the substrate size was adjusted as appropriate). A predetermined photomask was set through a 150 μm interval from a dry coating film having a thickness of 3 μm, and a laser having a wavelength of 355 nm was irradiated with an optimum exposure amount. The laser device used was “AEGIS” manufactured by Buoy Technology Co., Ltd. (wavelength 355 nm, pulse width 6 nsec), and the exposure was measured using “PE10B-V2” manufactured by OPHIR. It was found that a pattern can be formed with a laser as well as a mercury lamp.

(Examples 222 to 225)
The conditions for leaving the substrate after exposure (temperature, time) are as follows: after exposure, PEB at 80 ° C. for 60 seconds is performed at 23 ° C. for 90 seconds, and development is performed after 35 seconds at 23 ° C. In the same manner as in Example 201, the photosensitive resin composition and the cured film were evaluated. The results are shown in Table 8.
(Example 230)
The pattern exposure was performed in the same manner as in Example 208 except that the following laser exposure was performed (the substrate size was adjusted as appropriate). A predetermined photomask was set through a 150 μm interval from a dry coating film having a thickness of 3 μm, and a laser having a wavelength of 355 nm was irradiated with an optimum exposure amount. The laser device used was “AEGIS” manufactured by Buoy Technology Co., Ltd. (wavelength 355 nm, pulse width 6 nsec), and the exposure was measured using “PE10B-V2” manufactured by OPHIR. It was found that a pattern can be formed with a laser as well as a mercury lamp.

(Examples 305 to 308)
The composition was changed as shown in Table 5 and the conditions (temperature, time) for leaving the substrate after exposure were changed. After 90 seconds at 23 ° C. after exposure, PEB was performed at 80 ° C. for 60 seconds on a hot plate, and further 23 ° C. The photosensitive resin composition and the cured film were evaluated in the same manner as in Example 101 except that development was performed after 35 seconds. The results are shown in Table 9.

(Comparative Examples 1-7)
Comparative examples 1, 2, 4 to 6 as in Example 1 except that the formulation was changed as shown in Table 2 and the conditions (temperature, time) for leaving the substrate after exposure were changed as shown in Table 6 were low temperature treatment. The photosensitive resin composition was prepared and the photosensitive resin composition and the cured film were evaluated in the same manner as in Example 1. In Comparative Example 3, the composition of Example 7 described in JP-A-2009-98616 was prepared using a 1: 1 mixed solvent of C1: propylene glycol monomethyl ether acetate and C2: diethylene glycol ethyl methyl ether and a viscosity of 3.0 mPa · s. In the same manner as in Example 1, the photosensitive resin composition and the cured film were evaluated. For Comparative Example 7, the photosensitive resin composition and the cured film were evaluated in the same manner as in Example 1 using the composition of Example 17 of JP-A-2009-75329.

From the results shown in Tables 6 to 9, the following can be understood.
In all of the examples, the photosensitive resin composition containing Component A, Component B, and Component C is subjected to a predetermined low-temperature treatment step and a step of allowing 45 seconds or more to elapse at room temperature, so that satisfactory performance can be achieved by slit coating. It can be seen that an interlayer insulating film can be obtained. Specifically, by adjusting the low-temperature treatment process, contact hole formability, ITO sputtering suitability, and the like can be further improved (Examples 1 to 16). In addition, it can be seen that the sensitivity is slightly improved by elongating the elapsed time at room temperature (Examples 12, 30 to 36).
It can be seen that performance can be achieved with various compositions within the range including Component A, Component B, and Component C (Examples 18 to 29). It can be seen that all the structural units are composed of (meth) acrylate, and the copolymer using the oxetanyl group as the component (a2) is excellent in heat-resistant transparency. When slit coating is performed without a low-temperature treatment process, there is no sensitivity stability, and performances such as contact hole formability and ITO sputtering suitability are not simultaneously satisfied (Comparative Examples 1 and 3). It can also be seen that if the time allowed to pass at room temperature is short, the sensitivity is not stable and the change in the contact hole diameter is large (Comparative Example 2). It can be seen that a polymer that does not have any of (a1), (a2), and (a3) cannot simultaneously satisfy various characteristics such as sensitivity, sensitivity stability, and contact hole formability (Comparative Examples 4 to 7).
It turns out that the effect of this invention is show | played also by various polymers and photo-acid generators like Examples 101-139, 201-239, and Examples 301-308. Moreover, it turns out that transparency is especially high when the photo-acid generator of a naphthofuran mother nucleus is used like Examples 201-239 and 301-304.

(Example 45)
In the sensitivity evaluation of Example 8, the same evaluation was performed except that the substrate was changed to a glass substrate surface-treated with HDMS (hexamethyldisilazane). A fine pattern could be created as in Example 8.

(Example 140)
In the sensitivity evaluation of Example 108, evaluation was performed in the same manner except that the substrate was changed to a glass substrate surface-treated with HDMS (hexamethyldisilazane). As in Example 108, a fine pattern could be created.

(Example 240)
In the sensitivity evaluation of Example 208, evaluation was performed in the same manner except that the substrate was changed to a glass substrate surface-treated with HDMS (hexamethyldisilazane). As in Example 208, a fine pattern could be created.

(Example 46)
In the sensitivity evaluation of Example 8, except that the exposure machine was changed to FX-85S (ghi line specification, manufactured by Nikon Corporation) with an i-line cut filter installed (that is, gh line exposure). evaluated. A fine pattern could be created as in Example 8.

<Evaluation of coatability>
(Examples 47 to 50)
In the preparation of the photosensitive resin composition of Example 8, the photosensitive resin composition of Example 47 was prepared in the same manner as in Example 8 except that the amount of the solvent was adjusted so that the viscosity was 18.0 mPa · s. The photosensitive resin compositions of Examples 48 to 50 were also adjusted to viscosities of 22.0 mPa · s, 29.0 mPa · s, and 31.0 mPa · s in the same manner as in Example 47.
About the photosensitive resin composition of Example 8 and Examples 47-50, applicability | paintability was evaluated as follows. Using CL1700 manufactured by Tokyo Electron Ltd., a glass substrate of 1,500 mm × 1,800 mm was slit coated so that the coating thickness after drying was 3.0 μm. Drying was performed on a hot plate at 90 ° C. for 90 seconds. The coated surface was visually observed to count the number of streaky irregularities and evaluated according to the following criteria. The results are shown in the table. A, B, and C are acceptable.
No streaky unevenness on the coated surface: A
1-3 pieces: B
4-5 pieces: C
6 or more: D

(Examples 141-144)
In the preparation of the photosensitive resin composition of Example 108, the photosensitive resin composition of Example 141 was prepared in the same manner as in Example 108 except that the amount of solvent was adjusted to a viscosity of 18.0 mPa · s. The photosensitive resin compositions of Examples 142 to 144 were also adjusted to viscosities of 22.0 mPa · s, 29.0 mPa · s, and 31.0 mPa · s in the same manner as Example 140.
About the photosensitive resin composition of Example 108 and Examples 141-144, applicability | paintability was evaluated like the above.

(Examples 241 to 244)
A photosensitive resin composition of Example 241 was prepared in the same manner as in Example 208, except that in the preparation of the photosensitive resin composition of Example 208, the amount of solvent was adjusted to a viscosity of 18.0 mPa · s. The photosensitive resin compositions of Examples 242 to 244 were also adjusted to viscosities of 22.0 mPa · s, 29.0 mPa · s, and 31.0 mPa · s in the same manner as in Example 241.
About the photosensitive resin composition of Example 208 and Examples 241 to 244, applicability was evaluated in the same manner as described above.

(Comparative Example 8)
Using the photosensitive resin composition of Example 8, the liquid-saving property of the slit coat was evaluated as follows. Using CL1700 manufactured by Tokyo Electron Ltd., a glass substrate of 1,500 mm × 1,800 mm was slit coated so that the coating thickness after drying was 3.0 μm. Drying was performed on a hot plate at 90 ° C. for 90 seconds. When converted from the solid content remaining on the substrate as a dry film, it was found that 80 wt% or more of the photosensitive resin composition used in slit coating remained on the substrate.
In the production of the photosensitive resin composition of Example 8, a composition of Comparative Example 8 for spin coating was obtained in the same manner as in Example 8 except that the amount of solvent was adjusted to a viscosity of 35.0 mPa · s. . The composition of Comparative Example 8 was spin-coated on a 150 mm × 150 mm glass substrate so that the coating thickness after drying was 3.0 μm. Drying was performed on a hot plate at 90 ° C. for 90 seconds. When converted from the solid content remaining on the substrate as a dry film, it was found that, of the photosensitive resin composition used in the spin coating, only 15 wt% or less remained on the substrate. In addition, although an attempt was made to spin coat a 1,500 mm × 1,800 mm glass substrate, the substrate could not be rotated. Thus, the slit coat is a coating method that is excellent in liquid-saving properties and large-size correspondence.

(Example 51)
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 flattening layer 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 slit-coating the photosensitive resin composition of Example 12 subjected to low temperature treatment on the substrate, prebaking (90 ° C. × 2 minutes) on a hot plate, After irradiating 20 mJ / cm ² (illuminance 20 mW / cm ² ) with i-line (365 nm) using a high-pressure mercury lamp from above, it is allowed to elapse for 125 seconds at room temperature (23 ° C.) and developed with an aqueous alkaline solution to form a pattern Then, 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 (a 1: 1 mixture 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 7. 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 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 through the drive circuit, it was found that the organic EL display device showed good display characteristics and high reliability.

(Example 145)
An organic EL display device was produced in the same manner as in Example 51 except that the insulating film 8 was formed using the composition of Example 107. When a voltage was applied through the drive circuit, it was found that the organic EL display device showed good display characteristics and high reliability.

(Example 245)
An organic EL display device was produced in the same manner as in Example 51 except that the insulating film 8 was formed using the composition of Example 207. When a voltage was applied through the drive circuit, it was found that the organic EL display device showed good display characteristics and high reliability.

(Example 52)
In the active matrix liquid crystal display device shown in FIGS. 1 and 2 of Japanese Patent No. 3312003, a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 52 was obtained.
That is, using the photosensitive resin composition of Example 12, 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 51. 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 146)
A liquid crystal display device was produced in the same manner as in Example 52 except that the cured film 17 was formed using the composition of Example 138. When a driving voltage was applied, it was found that the liquid crystal display device showed good display characteristics and high reliability.

(Example 246)
A liquid crystal display device was produced in the same manner as in Example 52 except that the cured film 17 was formed using the composition of Example 238. When a driving voltage was applied, it was found that the liquid crystal display device showed good display characteristics and high reliability.

1: TFT
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)

(1) a low-temperature treatment step for bringing the photosensitive resin composition to a temperature of 10 ° C. or lower,
(2) A coating step of slit coating the photosensitive resin composition on a substrate,
(3) a solvent removal step for removing the solvent from the applied photosensitive resin composition;
(4) An exposure step in which the photosensitive resin composition from which the solvent has been removed is exposed to actinic rays,
(5) A step of allowing 45 seconds or more to pass at room temperature,
(6) a development step of developing with an aqueous developer, and
(7) including a post-bake step of thermosetting in this order,
The photosensitive resin composition is
(Component A) at least (a1) a structural unit having a residue in which an acid group is protected by an acid-decomposable group, (a2) a structural unit having a crosslinking group, (a3) a structure having a carboxy group and / or a phenolic hydroxyl group A copolymer containing units,
(Component B) a photoacid generator, and
(Component C) Solvent, The manufacturing method of the cured film characterized by the above-mentioned.   The method for producing a cured film according to claim 1, wherein the structural unit (a1) is a structural unit having a residue in which a carboxy group is protected with an acetal or a ketal. The manufacturing method of the cured film of Claim 1 or 2 with which the said structural unit (a1) is represented by Formula (A2).

(In formula (A2), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least ^one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ is Represents an alkyl group or an aryl group, R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group. Represents.)   The cured film according to any one of claims 1 to 3, wherein the structural unit (a2) has at least one group selected from the group consisting of an epoxy group, an oxetanyl group, and an ethylenically unsaturated group. Manufacturing method.   The manufacturing method of the cured film of any one of Claims 1-4 in which the said structural unit (a2) has an alicyclic epoxy group and / or an oxetanyl group.   The manufacturing method of the cured film of any one of Claims 1-5 whose said component B is a compound which has an oxime sulfonate residue. Production of the cured film according to any one of claims 1 to 6, wherein Component B is a compound represented by Formula (OS-3), Formula (OS-4), or Formula (OS-5). Method.

(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.)   The manufacturing method of the cured film of any one of Claims 1-7 whose said photosensitive resin composition is a chemically amplified positive photosensitive resin composition.   The photosensitive resin composition used for the manufacturing method of the cured film of any one of Claims 1-8.   The cured film manufactured by the manufacturing method of the cured film of any one of Claims 1-8.   An organic EL display device comprising the cured film according to claim 10.   A liquid crystal display device comprising the cured film according to claim 10.

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