WO2015087831A1

WO2015087831A1 - Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device and organic el display device

Info

Publication number: WO2015087831A1
Application number: PCT/JP2014/082413
Authority: WO
Inventors: 幸一杉原; 豪安藤; 雨宮　拓馬
Original assignee: 富士フイルム株式会社
Priority date: 2013-12-11
Filing date: 2014-12-08
Publication date: 2015-06-18
Also published as: KR20160085304A; KR101807630B1; JPWO2015087831A1; TW201527877A; CN105814488A; CN105814488B; TWI650609B; JP6279614B2

Abstract

Provided are: a photosensitive resin composition which has excellent adhesion to a base, high transmittance, high heat resistance and high sensitivity; a method for producing a cured film; a cured film; a liquid crystal display device; and an organic EL display device. A photosensitive resin composition which contains (A) a polybenzoxazole precursor containing a repeating unit represented by general formula (1), (B) a photoacid generator which generates an acid having a pKa of 4 or less, (C) a solvent and (D) a crosslinking agent having two or more crosslinkable groups which are reactive with a benzene ring and/or a phenolic hydroxyl group. In the formula, R¹ and/or R² is an acid-decomposable group. AA General formula (1)

Description

Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device, and organic EL display device

The present invention relates to a photosensitive resin composition (hereinafter sometimes simply referred to as “the composition of the present invention”). Moreover, it is related with the manufacturing method of the cured film using the said photosensitive resin composition, the cured film formed by hardening | curing the photosensitive resin composition, and various image display apparatuses using the said cured film.
More specifically, a photosensitive resin composition suitable for forming a flattening film, a protective film and an interlayer insulating film of an electronic component such as a liquid crystal display device, an organic EL (organic electroluminescence) display device, an integrated circuit element, and a solid-state imaging element. The present invention relates to an article and a method for producing a cured film using the article.

Organic EL display devices, liquid crystal display devices, and the like are provided with a patterned interlayer insulating film. In forming the interlayer insulating film, photosensitive resin compositions are widely used because the number of steps for obtaining a required pattern shape is small and sufficient flatness is obtained.

The photosensitive resin composition for interlayer insulating films and interlayer insulating films in the display device are required to have high sensitivity, high resolution, high transparency, and solvent resistance. As a typical material, an attempt has been made to use an acrylic resin as a film forming component. For example, those described in

Patent Documents

1 and 2 are known.

In recent years, attempts have been made to perform heat treatment and film formation at a higher temperature (eg, about 300 ° C.) than in the past in order to increase production efficiency and display device performance.

Polybenzoxazole (PBO) is known as a material having higher heat resistance than acrylic resin. Attempts have been made to prepare photosensitive resin compositions using PBO precursors and form various fine patterns (Patent Documents 3 to 5).

JP 2011-209681 A JP 2011-221471 A JP 2008-224970 A Special table 2011-512552 gazette JP 2004-170611 A

However, the conventional photosensitive compositions as disclosed in Patent Documents 3 to 5 have a problem that the adhesion to the substrate is lowered when exposed to a chemical solution used in the subsequent process of the insulating film. Further, it cannot be said that the transmittance is sufficiently high as a material for a display device.

The present invention has been made in order to solve the above problems, and has excellent adhesion to a substrate, high transmittance, high heat resistance, and high sensitivity photosensitive resin composition, a method for producing a cured film, An object is to provide a cured film, a liquid crystal display device, and an organic EL display device.

Under such circumstances, as a result of intensive studies by the inventor, the present invention contains a polybenzoxazole precursor having an acid-decomposable group, a photoacid generator having a pKa of 4 or less, and a predetermined crosslinking agent. As a result, it has been found that the adhesiveness to the substrate is excellent, the transmittance is high, the heat resistance is high, and the sensitivity is high, and the present invention has been completed.
Specifically, the above problem has been solved by the following means <1>, preferably <2> to <14>.
<1> (A) a polybenzoxazole precursor containing a repeating unit represented by the general formula (1),
(B) a photoacid generator in which the generated acid has a pKa of 4 or less,
(C) A photosensitive resin composition containing a solvent and (D) a crosslinking agent having two or more crosslinking groups that react with a benzene ring and / or a phenolic hydroxyl group.
General formula (1)

(In General Formula (1), X represents a tetravalent organic group, Y represents a divalent organic group. R ¹ and R ² are each independently a hydrogen atom, an alkyl group, an acid-decomposable group, or -CORc, wherein Rc represents an alkyl group or an aryl group, and at least one of R ¹ and R ² is an acid-decomposable group.
<2> (D) The photosensitive resin composition as described in <1> in which the crosslinkable group which a crosslinking agent has is selected from an epoxy group, a methylol group, an alkoxymethyl group, and a blocked isocyanate group.
<3> (A) The photosensitive resin composition according to <1> or <2>, wherein the terminal of the polybenzoxazole precursor is a group represented by the general formula (1-1).
General formula (1-1)

(In the general formula (1-1), Z represents a single bond, a carbon atom or a sulfur atom, R ¹¹ represents a monovalent organic group, n represents 0 or 1, and when Z is a single bond, a Is 0, when Z is a carbon atom, a is 1, and when Z is a sulfur atom, a is 2. When n is 0, two R ¹¹ 's are bonded together to form a ring. May be.)
<4> (A) The polybenzoxazole precursor includes m repeating units represented by the general formula (1-2) and n repeating units represented by the general formula (3), and m is 3 The photosensitive resin composition according to any one of <1> to <3>, wherein n represents 0 to 1000, n represents 0 to 1000, and m + n is 3 to 1000.
Formula (1-2)

General formula (3)

(In the general formulas (1-2) and (3), Y ¹ is independently an arylene group, divalent cycloaliphatic group, divalent heterocyclic group, or these, —CH ₂ —, oxygen Represents a group consisting of a combination of at least one of an atom, a sulfur atom, —SO ₂ —, —CO—, —NHCO—, and —C (CF ₃ ) ₂ —, and X ¹ represents an aromatic ring or a heterocyclic ring , An aliphatic ring, or a combination thereof with at least one of —CH ₂ —, oxygen atom, sulfur atom, —SO ₂ —, —CO—, —NHCO—, and —C (CF ₃ ) ₂ — Each of Ra and Rb independently represents a hydrogen atom, an acid-decomposable group, an alkyl group or —CORc, and at least one of Ra or Rb is an acid-decomposable group. .X ² represents an alkyl group or an aryl group, an arylene group, 2 Heterocyclic group, a divalent cyclic aliphatic group or a thereof, -CH ₂ -, an oxygen atom, a sulfur _{atom, -SO 2 -, - CO -} , - NHCO-, and -C (CF ₃₎ ₂ Represents a group consisting of a combination of at least one of-.)
<5> The photosensitive resin composition according to any one of <1> to <4>, further comprising an adhesion promoter.
<6> (B) The photosensitive resin composition according to any one of <1> to <5>, wherein the photoacid generator is an oxime sulfonate photoacid generator and / or an imide sulfonate photoacid generator. .
<7> The photosensitive resin composition according to any one of <1> to <6>, wherein the acid-decomposable group is a group capable of leaving by the action of an acid, or —C (R ⁵ ) ₂ —COOR ⁴ . R ⁵ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁴ represents a group capable of leaving by the action of an acid.
<8> The photosensitive resin composition according to <7>, wherein the group capable of leaving by the action of an acid is a vinyl ether-based substituent.
<9> The photosensitive resin composition according to <7>, wherein the group leaving by the action of an acid is an alkoxycarbonyl group, an alkoxyalkyl group, an alkylsilyl group, a group constituting an acetal, or a group constituting a ketal. object.
<10> (1) A step of applying the photosensitive resin composition according to any one of <1> to <9> to at least one surface of a substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition;
(3) A step of exposing the photosensitive resin composition from which the solvent has been removed with actinic rays,
(4) a step of developing the exposed photosensitive resin composition with an aqueous developer, and (5) a post-baking step of thermosetting the developed photosensitive resin composition,
The manufacturing method of the cured film containing this.
<11> (4) The method for producing a cured film according to <10>, comprising a step of exposing the entire surface of the developed photosensitive resin composition after the step of (4) developing and before the step of (5) post-baking.
<12> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <9> or a cured film formed by the method according to <10> or <11>.
<13> The cured film according to <12>, which is an interlayer insulating film.
<14> A liquid crystal display device or an organic EL display device having the cured film according to <12> or <13>.

According to the present invention, a photosensitive resin composition having excellent adhesion to a substrate, high transmittance, high heat resistance, and high sensitivity, a method for producing a cured film, a cured film, a liquid crystal display device, and an organic EL display device It became possible to provide.

1 is a conceptual diagram of a configuration of an example of a liquid crystal display device. 1 is a schematic cross-sectional view of an active matrix substrate in a liquid crystal display device. 1 shows a conceptual diagram of a configuration of an example of an organic EL display device. 1 is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

In addition, in the description of group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what has a substituent with what does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
Furthermore, (meth) acrylic acid means acrylic acid and / or methacrylic acid.
The solid content concentration in the present invention refers to the solid content concentration at 25 ° C.
In this specification, a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value by GPC measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6) as a column. 0.0 mm ID × 15.0 cm can be determined by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as the eluent.

Photosensitive resin composition The photosensitive resin composition of the present invention is (A) a polybenzoxazole precursor containing a repeating unit represented by the general formula (1), and (B) the generated acid has a pKa of 4 or less. A photoacid generator, (C) a solvent, and (D) a crosslinking agent having two or more crosslinkable groups that react with a benzene ring and / or a phenolic hydroxyl group.
General formula (1)

(In General Formula (1), X represents a tetravalent organic group, Y represents a divalent organic group. R ¹ and R ² are each independently a hydrogen atom, an alkyl group, an acid-decomposable group, or -CORc, wherein Rc represents an alkyl group or an aryl group, and at least one of R ¹ and R ² is an acid-decomposable group.

By using the composition of the present invention, excellent adhesion to the substrate, high transmittance, high heat resistance, and high sensitivity are obtained. Although the details about this mechanism are unknown, by blending a crosslinking agent, the benzene ring or hydroxyl group of (A) polybenzoxazole precursor reacts with the crosslinking group of the crosslinking agent to produce a polymer. It is considered that high heat resistance can be achieved by forming a cross-linked structure between them. In Patent Document 3 (Japanese Patent Laid-Open No. 2008-224970), an oxetane group is used as a crosslinkable group. However, since the ring structure of the oxetane group is stable, (A) it does not react with the polyvinylbenzoxazole precursor. . In this document, the compounds containing an oxetane group simply react to each other and play a role of bundling (A) the polyvinylbenzoxazole precursor.

The photosensitive resin composition of the present invention is preferably used as a chemically amplified positive photosensitive resin composition. Hereinafter, the composition of the present invention will be described in detail.

<(A) Polybenzoxazole precursor having acid-decomposable group>
The composition of the present invention comprises (A) a polybenzoxazole precursor (hereinafter simply referred to as “(A) polybenzoxazole precursor”, “component (A)”) containing a repeating unit represented by the general formula (1). Sometimes). The repeating unit represented by the general formula (1) is a repeating unit having an acid-decomposable group. The (A) polybenzoxazole precursor used in the present invention preferably has a crosslinkable group at the terminal. The terminal may be one terminal, but more preferably has a crosslinkable group at both terminals. In the present invention, the terminal of the polybenzoxazole precursor means the main chain terminal of the polybenzoxazole precursor.

<< (a-1) Repeating Unit Having Acid-Decomposable Group >>
In the present invention, the repeating unit (a-1) having an acid-decomposable group is a repeating unit represented by the general formula (1). The polybenzoxazole precursor (A) used in the present invention may contain only one type of repeating unit represented by the general formula (1), or may contain two or more types. (A) The polybenzoxazole precursor preferably contains 70 mol% or more, more preferably 80 mol% or more of the repeating unit represented by the general formula (1) with respect to all repeating units. Preferably it is 90 mol% or more.
(A) The polybenzoxazole precursor preferably contains a repeating unit containing an acid-decomposable group in a proportion of 50 to 100 mol%, more preferably 10 to 50 mol% of all repeating units.

General formula (1)

(In General Formula (1), X represents a tetravalent organic group, Y represents a divalent organic group. R ¹ and R ² are each independently a hydrogen atom, an alkyl group, an acid-decomposable group, or -CORc, wherein Rc represents an alkyl group or an aryl group, and at least one of R ^{1 and} R ² is an acid-decomposable group.

X represents a tetravalent organic group. The tetravalent organic group represented by X is not particularly limited, but preferably has at least one or more cyclic structures, more preferably 1 to 2 cyclic structures. The cyclic structure may be any of an aromatic ring, a heterocyclic ring, and an aliphatic ring, and preferably includes an aromatic ring and / or a heterocyclic ring, and more preferably includes an aromatic ring. By setting it as such a cyclic structure, the effect of this invention is exhibited more effectively.
Examples of the aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring. As the heterocyclic ring, furan ring, thiophene ring, pyrrole ring, pyrroline ring, pyrrolidine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, imidazoline ring, imidazolidine ring, pyrazole ring, pyrazoline ring, Examples include pyrazolidine ring, triazole ring, furazane ring, tetrazole ring, pyran ring, thiyne ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring and triazine ring. It is done. Examples of the aliphatic ring include a cyclopentane ring, a cyclohexane ring, and a cycloheptane ring.
In the case of having a plurality of cyclic structures, the ring may be condensed, —O—, —S—, a fluorine-substituted alkylene group (preferably —C (CF ₃ ) ₂ —), —CH ₂ — , —SO ₂ —, or —NHCO— may be bonded to a plurality of cyclic structures via a linking group. The linking group is preferably —O—, —S—, —C (CF ₃ ) ₂ —, —CH ₂ —, —SO ₂ —, or —NHCO—, where —C (CF ₃ ) ₂ — is More preferred.
In the present invention, the X moiety preferably contains a fluorine-substituted alkylene group. By including a fluorine-substituted alkylene group, the transparency of the composition of the present invention tends to be further improved.

Specific examples of X include, but are not limited to, the following. In the formula, X ¹ represents a linking group.

NH and R ¹ bonded to X, and NH and R ² are preferably bonded so as to be in the ortho position (adjacent position) in the cyclic structure.
X is preferably (2) or (10), more preferably (2). In particular, it is preferable that X ¹ is a fluorine-substituted alkylene group (preferably —C (CF ₃ ) ₂ —), since the transparency of the composition of the present invention is further improved.

R ¹ and R ² each independently represents a hydrogen atom, an alkyl group, an acid-decomposable group, or —CORc. At least one of R ¹ and R ² is an acid-decomposable group.
The alkyl group may or may not have a substituent.
The alkyl group may be linear, branched or cyclic, and in the case of a linear or branched alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, and an alkyl group having 1 to 15 carbon atoms Is more preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable. In the case of a cyclic alkyl group, an alkyl group having 3 to 15 carbon atoms is preferable, an alkyl group having 5 to 15 carbon atoms is more preferable, and an alkyl group having 5 to 10 carbon atoms is more preferable. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group. Examples of the substituent include a halogen atom, a cyano group, an amide group, and a sulfonylamide group.

An acid-decomposable group is a group capable of leaving by the action of an acid, or a group that leaves by the action of an acid to generate an alkali-soluble group such as a hydroxyl group or a carboxyl group, such as —C (R ⁵ ) ₂ —COOR ^4. Represents.
R ⁵ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁴ represents a group capable of leaving by the action of an acid. Here, the acid acting as an acid usually means an acid generated from an acid generator described later.
Examples of the group capable of leaving by the action of an acid include vinyl ether substituents, alkoxycarbonyl groups (preferably having 2 to 5 carbon atoms), alkoxyalkyl groups (preferably having 2 to 5 carbon atoms), alkylsilyl groups (preferably carbon atoms). And a group constituting an acetal or a ketal. From the viewpoint of sensitivity, an acetal group or a ketal group is preferable.
As group which comprises acetal or ketal, what has the following structure is mentioned, for example.

(In the formula, R ^1x and R ^2x each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R ^1x and R ^2x represents an alkyl group or an aryl group. R ^3x represents an alkyl group. Alternatively, it represents an aryl group, and R ^1x or R ^2x and R ^3x may be linked to form a cyclic ether.
The alkyl group represented by R ^1x and R ^2x is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. The aryl group represented by R ^1x and R ^2x is preferably an aryl group having 6 to 10 carbon atoms, and more preferably a phenyl group. R ^1x and R ^2x are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R ^3X represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 16 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 10 carbon atoms is more preferable.

Specific examples of the group capable of leaving by the action of an acid include alkoxycarbonyl groups such as t-butoxycarbonyl group, alkoxyalkyl groups such as methoxymethyl group and ethoxyethyl group, alkylsilyl groups such as methylsilyl group and ethylsilyl group, tetrahydro Pyranyl group, tetrahydrofuranyl group, alkoxy-substituted tetrahydropyranyl group, alkoxy-substituted tetrahydrofuranyl group and the like are exemplified as typical examples, but are not limited thereto. The most preferable group as a group capable of leaving by the action of an acid is an ethoxyethyl group, a tetrahydropyranyl group or a tetrahydrofuranyl group. These may be used alone or in combination of two or more.
The structure of a group preferable as a group capable of leaving by the action of an acid is shown.

Rc represents an alkyl group or an aryl group, and these groups may or may not have a substituent.
The alkyl group represented by Rc has the same meaning as the alkyl group represented by R ¹ and R ² , and the preferred range is also the same.
The aryl group represented by Rc is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and further preferably an aryl group having 6 to 10 carbon atoms. Specific examples of the aryl group include a phenyl group, a toluyl group, a mesityl group, and a naphthyl group. The substituent that the aryl group may have is the same as the substituent that the alkyl group may have.

Y represents a divalent organic group. The divalent organic group represented by Y is not particularly limited, but preferably has at least one cyclic structure, and more preferably has 1 to 2 cyclic structures. The cyclic structure may be any of an arylene group, a divalent cyclic aliphatic group, and a divalent heterocyclic group, and preferably includes an arylene group and / or a divalent heterocyclic ring, and includes an arylene group. It is more preferable. Specifically, the divalent organic group represented by Y includes an arylene group, a divalent cycloaliphatic group, a divalent heterocyclic group, or a methylene group, an oxygen atom, a sulfur atom, —SO _2. It preferably represents a group consisting of a combination of at least one of-, -CO-, -NHCO-, and -C (CF ₃ ) _2- .
As the arylene group, an arylene group having 6 to 20 carbon atoms is preferable, an arylene group having 6 to 14 carbon atoms is more preferable, and an arylene group having 6 to 10 carbon atoms is more preferable. Specific examples of the arylene group include a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, a naphthylene group, and an anthracenylene group.
Examples of the divalent cyclic aliphatic group include a cyclic alkylene group, a cyclic alkenylene group, and a cyclic alkynylene group. As the cyclic alkylene group, an alkylene group having 3 to 20 carbon atoms is preferable, a cyclic alkylene group having 3 to 18 carbon atoms is more preferable, and a cyclic alkylene group having 3 to 15 carbon atoms is more preferable. The cyclic alkenylene group is preferably an alkenylene group having 3 to 20 carbon atoms, more preferably a cyclic alkenylene group having 3 to 18 carbon atoms, and further preferably a cyclic alkenylene group having 3 to 15 carbon atoms. As the cyclic alkynylene group, a cyclic alkynylene group having 3 to 20 carbon atoms is preferable, a cyclic alkynylene group having 3 to 18 carbon atoms is more preferable, and a cyclic alkynylene group having 3 to 15 carbon atoms is more preferable. Specific examples of the divalent cycloaliphatic group include 1,4-cyclohexylene group, 1,3-cyclohexylene group, 1,2-cyclohexylene group, and octylene group.
The divalent heterocyclic group preferably has a 5-membered, 6-membered or 7-membered heterocyclic ring. A 5-membered ring or a 6-membered ring is more preferable, and a 6-membered ring is more preferable. As the hetero atom constituting the heterocyclic ring, a nitrogen atom, an oxygen atom and a sulfur atom are preferable. The heterocycle is preferably an aromatic heterocycle. The aromatic heterocyclic ring is generally an unsaturated heterocyclic ring, and an unsaturated heterocyclic ring having the most double bond is more preferable. Specific heterocycles include furan ring, thiophene ring, pyrrole ring, pyrroline ring, pyrrolidine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, imidazoline ring, imidazolidine ring, pyrazole ring, Pyrazoline ring, pyrazolidine ring, triazole ring, furazane ring, tetrazole ring, pyran ring, thiyne ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring and triazine ring Is included.
Y represents an arylene group, a divalent cycloaliphatic group, a divalent heterocyclic group, or a methylene group, an oxygen atom, a sulfur atom, —SO ₂ —, —CO—, —NHCO—, and — C (CF ₃₎ ₂ - in can be a group comprising a combination of at least one, and specific examples thereof include the following groups. In the formula, A represents a methylene group, an oxygen atom, a sulfur atom, —SO ₂ —, —CO—, —NHCO—, or —C (CF ₃ ) ₂ —.

Among these, Y is preferably 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group or octylene group.

The repeating unit represented by the general formula (1) is more preferably represented by the general formula (1-2).
Formula (1-2)

(In the general formula (1-2), each Y ¹ independently represents an arylene group, a divalent cycloaliphatic group, a divalent heterocyclic group, or these, —CH ₂ —, an oxygen atom, or a sulfur atom. , —SO ₂ —, —CO—, —NHCO—, and a group consisting of at least one of —C (CF ₃ ) ₂ —, wherein X ¹ is an aromatic ring, heterocyclic ring, or aliphatic ring Or a tetravalent composed of a combination of these with at least one of —CH ₂ —, oxygen atom, sulfur atom, —SO ₂ —, —CO—, —NHCO—, and —C (CF ₃ ) ₂ —. Ra and Rb each independently represents a hydrogen atom, an alkyl group, an acid-decomposable group or —CORc, and at least one of Ra or Rb is an acid-decomposable group, where Rc is an alkyl group or an aryl group Represents a group.)

Y ¹ is independently an arylene group, divalent cycloaliphatic group, divalent heterocyclic group, or a methylene group, oxygen atom, sulfur atom, —SO ₂ —, —CO—, —NHCO. And a group consisting of a combination with at least one of — and —C (CF ₃ ) ₂ —.
As the arylene group, an arylene group having 6 to 20 carbon atoms is preferable, an arylene group having 6 to 14 carbon atoms is more preferable, and an arylene group having 6 to 10 carbon atoms is more preferable. Specific examples of the arylene group include a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, a naphthylene group, and an anthracenylene group.
The divalent heterocyclic group preferably has a 5-membered, 6-membered or 7-membered heterocyclic ring. A 5-membered ring or a 6-membered ring is more preferable, and a 6-membered ring is more preferable. As the hetero atom constituting the heterocyclic ring, a nitrogen atom, an oxygen atom and a sulfur atom are preferable. The heterocycle is preferably an aromatic heterocycle. The aromatic heterocycle is generally an unsaturated heterocycle. An unsaturated heterocyclic ring having the most double bond is more preferable. Specific heterocycles include furan ring, thiophene ring, pyrrole ring, pyrroline ring, pyrrolidine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, imidazoline ring, imidazolidine ring, pyrazole ring, Pyrazoline ring, pyrazolidine ring, triazole ring, furazane ring, tetrazole ring, pyran ring, thiyne ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring and triazine ring Is included.
Examples of the divalent cyclic aliphatic group include a cyclic alkylene group, a cyclic alkenylene group, and a cyclic alkynylene group. As the cyclic alkylene group, a cyclic alkylene group having 3 to 20 carbon atoms is preferable, a cyclic alkylene group having 3 to 18 carbon atoms is more preferable, and a cyclic alkylene group having 3 to 15 carbon atoms is more preferable. As the cyclic alkenylene group, a cyclic alkenylene group having 3 to 20 carbon atoms is preferable, a cyclic alkenylene group having 3 to 18 carbon atoms is more preferable, and a cyclic alkenylene group having 3 to 15 carbon atoms is more preferable. As the cyclic alkynylene group, a cyclic alkynylene group having 3 to 20 carbon atoms is preferable, a cyclic alkynylene group having 3 to 18 carbon atoms is more preferable, and a cyclic alkynylene group having 3 to 15 carbon atoms is more preferable. Specific examples of the divalent cycloaliphatic group include 1,4-cyclohexylene group, 1,3-cyclohexylene group, 1,2-cyclohexylene group, and octylene group.
Y ¹ represents an arylene group, a divalent heterocyclic group, a divalent cycloaliphatic group, or a methylene group, an oxygen atom, a sulfur atom, —SO ₂ —, —CO—, —NHCO—, and -C (CF ₃₎ ₂ - in can be a group comprising a combination of at least one of these and, -C (CF ₃₎ ₂ -, more preferably a group consisting of an arylene group And more preferably a group consisting of a combination of —C (CF ₃ ) ₂ —.
Y ¹ is preferably a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, an octylene group, or the following exemplified compounds, and includes a 1,4-phenylene group, a 1,3-phenylene group, , 2-phenylene group and octylene group are more preferable.

X ¹ represents an aromatic ring, a heterocyclic ring, an aliphatic ring, or these, and —CH ₂ —, an oxygen atom, a sulfur atom, —SO ₂ —, —CO—, —NHCO—, and —C (CF ₃ ₂ ) represents a tetravalent group consisting of a combination of at least one of-. X ¹ preferably has at least one of an aromatic ring, a heterocyclic ring, and an aliphatic ring, and more preferably has one or two of an aromatic ring, a heterocyclic ring, and an aliphatic ring. preferable. X ¹ preferably contains an aromatic ring and / or a heterocyclic ring, and more preferably contains an aromatic ring.
Examples of the aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring. As the heterocyclic ring, furan ring, thiophene ring, pyrrole ring, pyrroline ring, pyrrolidine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, imidazoline ring, imidazolidine ring, pyrazole ring, pyrazoline ring, Examples include pyrazolidine ring, triazole ring, furazane ring, tetrazole ring, pyran ring, thiyne ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring and triazine ring. It is done. Examples of the aliphatic ring include a cyclopentane ring, a cyclohexane ring, and a cycloheptane ring.
In addition, when the tetravalent group represented by X ¹ has a plurality of cyclic structures, the ring may be condensed, and —O—, —S—, —C (CF ₃ ) ₂ —, —CH ₂ — , —SO ₂ —, or —NHCO— may be bonded to a plurality of cyclic structures via a linking group. The linking group is preferably —O—, —S—, —C (CF ₃ ) ₂ —, —CH ₂ —, —SO ₂ —, or —NHCO—, where —C (CF ₃ ) ₂ — is More preferred.

Ra and Rb each independently represent a hydrogen atom, an alkyl group, an acid-decomposable group, or —CORc, and are synonymous with R ¹ and R ² in the general formula (1), and their preferred ranges are also the same.

Specific examples of —X ¹ (ORa) (ORb) — in the repeating unit represented by the general formula (1-2) include, but are not limited to, the following. In the formula, X ¹ represents a methylene group, an oxygen atom, a sulfur atom, —SO ₂ —, —CO—, —NHCO—, or —C (CF ₃ ) ₂ —, and —C (CF ₃ ) ₂ — is preferable. R represents one of Ra and Rb.

NH and ORa, which are bonded to X, and NH and ORb are preferably bonded so as to be in the ortho position (adjacent position) in the cyclic structure.
X is preferably (2) or (10), more preferably (2).

<< (a-2) Other repeating unit >>
The polybenzoxazole precursor having an acid-decomposable group may contain other repeating units in addition to (a-1) the repeating unit having an acid-decomposable group.
Examples of other repeating units include a repeating unit represented by the general formula (2), a repeating unit represented by the general formula (3), and a repeating unit represented by the general formula (4).
<<< Repeating unit represented by formula (2) >>>
General formula (2)

(In the general formula (2), X represents a tetravalent organic group and Y represents a divalent organic group. R ³ and R ⁴ each independently represents a hydrogen atom, an alkyl group, or —CORc. Rc represents an alkyl group or an aryl group, except that R ³ and R ⁴ are acid-decomposable groups.)

In general formula (2), X, Y, R ³ , R ⁴ , and Rc have the same meanings as X, Y ¹ , Ra, Rb, and Rc in general formula (1-2), and the preferred ranges are also the same. It is.

<<< Repeating unit represented by formula (3) >>>
General formula (3)

(In General Formula (3), Y ¹ is independently an arylene group, a divalent cycloaliphatic group, a divalent heterocyclic group, or these, —CH ₂ —, an oxygen atom, a sulfur atom, — Represents a group composed of a combination with at least one of SO ₂ —, —CO—, —NHCO—, and —C (CF ₃ ) ₂ —, and X ² represents an arylene group, a divalent heterocyclic group, a divalent group, Or a cyclic aliphatic group of the above, or at least one of —CH ₂ —, oxygen atom, sulfur atom, —SO ₂ —, —CO—, —NHCO—, and —C (CF ₃ ) ₂ —. Represents a group consisting of a combination.)
In the general formula (3), Y ¹ have the same meanings as defined in formula (1-2) Y ¹ in the preferred range is also the same.
In the general formula (3), X ² represents an arylene group, a divalent heterocyclic group, a divalent cycloaliphatic group, or a methylene group, an oxygen atom, a sulfur atom, —SO ₂ —, —CO -, - NHCO-, and -C (CF ₃₎ ₂ - of a group consisting of a combination of at least one, these radicals may contain a silicon atom.
An arylene group represented by X ² , a divalent heterocyclic group, and a divalent cyclic aliphatic group are an arylene group represented by Y ¹ in formula (1-2), a divalent heterocyclic group, and a divalent cyclic group. It is synonymous with an aliphatic group, and its preferable range is also the same.

X ² represents an arylene group, a divalent cycloaliphatic group, a divalent heterocyclic group, or a methylene group, an oxygen atom, a sulfur atom, —SO ₂ —, —CO—, —NHCO—, and The group may be a combination of at least one of —C (CF ₃ ) ₂ —, and specific examples thereof include the following groups. In the formula, A represents a methylene group, an oxygen atom, a sulfur atom, —SO ₂ —, —CO—, —NHCO—, or —C (CF ₃ ) ₂ —.

<<< Repeating unit represented by formula (4) >>>
General formula (4)

(In the above formula, Y ¹ represents an arylene group, divalent cycloaliphatic group, divalent heterocyclic group, or these, —CH ₂ —, oxygen atom, sulfur atom, —SO ₂ —, —CO Represents a group composed of a combination of at least one of —, —NHCO—, and —C (CF ₃ ) ₂ —, and X ³ represents a group containing a silicon atom.)
Here, Y ¹ has the same meaning as Y ¹ in formula (1-2), and the preferred range is also the same. X ³ is preferably a group represented by the following.

(R ⁵ and R ⁶ each independently represent a divalent organic group, and R ⁷ and R ⁸ each independently represent a monovalent organic group.)

The divalent organic group represented by R ⁵ and R ⁶ is not particularly limited, but may be a linear or branched alkylene group having 1 to 20 carbon atoms and a substituent, which may have a specific substituent. Represents an arylene group having 6 to 20 carbon atoms which may have a divalent cyclic aliphatic group having 3 to 20 carbon atoms which may have a substituent, or a combination thereof.
As the linear or branched alkylene group having 1 to 20 carbon atoms, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 6 carbon atoms is more preferable. Specific examples include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, and a t-butylene group.
As the arylene group having 6 to 20 carbon atoms, an arylene group having 6 to 14 carbon atoms is more preferable, and an arylene group having 6 to 10 carbon atoms is more preferable. Specific examples of the arylene group include a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, a naphthylene group, and an anthracenylene group.
The divalent cycloaliphatic group having 3 to 20 carbon atoms is preferably a divalent cycloaliphatic group having 3 to 10 carbon atoms, and more preferably a divalent cycloaliphatic group having 5 to 6 carbon atoms. Examples of the divalent cycloaliphatic group include a 1,4-cyclohexylene group, a 1,3-cyclohexylene group, and a 1,2-cyclohexylene group.
These linear or branched alkylene groups having 1 to 20 carbon atoms, arylene groups having 6 to 20 carbon atoms, and divalent cyclic aliphatic groups having 3 to 20 carbon atoms may have a substituent. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a halogen atom, a cyano group, an amide group, and a sulfonylamide group.

The group formed by combining a straight chain or branched alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a divalent cyclic aliphatic group having 3 to 20 carbon atoms is not particularly limited. A group formed by combining groups formed by combining divalent cycloaliphatic groups having 3 to 20 carbon atoms is preferable. Specific examples of the group formed by combining a linear or branched alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a divalent cyclic aliphatic group having 3 to 20 carbon atoms are as follows: Although the following are mentioned, it is not limited to these.

The monovalent organic group represented by R ⁷ and R ⁸ represents a linear or branched alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms which may have a substituent. .
The linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group.
The aryl group which may have a substituent is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and further preferably an aryl group having 6 to 10 carbon atoms. Specific examples of the aryl group include a phenyl group, a toluyl group, a mesityl group, and a naphthyl group.
These linear or branched alkyl groups and aryl groups having 1 to 20 carbon atoms may have a substituent. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a halogen atom, a cyano group, an amide group, and a sulfonylamide group.

Specific examples of X ³ include the following, but are not limited thereto.

The polybenzoxazole precursor (A) used in the present invention includes m repeating units represented by the general formula (1-2) and n repeating units represented by the general formula (3). , M represents 3 to 1000, preferably 5 to 300, and more preferably 10 to 100. n represents 0 to 1000, preferably 0 to 300, and more preferably 0 to 100. However, m + n represents 3 to 1000, preferably 5 to 600, and more preferably 10 to 200. Here, the repeating unit represented by the general formula (1-2) and the repeating unit represented by the general formula (3) may be so-called random polymers.

The repeating unit represented by the general formula (1-2) and the repeating unit represented by the general formula (3) may each include one type or two or more types. Further, a repeating unit other than the repeating unit represented by the general formula (1-2) and the repeating unit represented by the general formula (3) may be included. However, such other repeating units are preferably 5 mol% or less of all repeating units.

The polybenzoxazole precursor in the present invention can have an embodiment having a crosslinkable group at the terminal. By setting it as such an aspect, film | membrane physical properties, such as film | membrane hardness, can be improved. The terminal having a crosslinkable group may be one terminal, but is preferably both terminals.

(A) Although the terminal of a polybenzoxazole precursor is not specifically limited, It is preferable that a crosslinkable group is included. The crosslinkable group is preferably a group containing at least one selected from an epoxy group, an oxetanyl group, a carbon-carbon unsaturated bond group, and a blocked isocyanate group. The terminal of the (A) polybenzoxazole precursor in the present invention is preferably a group represented by the general formula (1-1).
General formula (1-1)

(In the general formula (1-1), Z represents a single bond, a carbon atom or a sulfur atom, R ¹¹ represents a monovalent organic group, n represents 0 or 1, and when Z is a single bond, a Is 0, when Z is a carbon atom, a is 1, and when Z is a sulfur atom, a is 2. When n is 0, two R ¹¹ 's are bonded together to form a ring. May be.)

Z represents a single bond, a carbon atom or a sulfur atom, preferably a single bond or a carbon atom.

R ¹¹ represents a monovalent organic group. The monovalent organic group represented by R ¹¹ is not particularly limited, and examples thereof include those having a formula weight of 20 to 500 per molecule. The atom constituting the monovalent organic group represented by R ¹¹ is preferably selected from a carbon atom, an oxygen atom, a nitrogen atom, a hydrogen atom, and a sulfur atom, and a carbon atom, an oxygen atom, a nitrogen atom, and a hydrogen atom More preferably, it is selected from.
Specifically, R ¹¹ is an alkyl group (preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms) or an alkenyl group (preferably having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms). An alkynyl group (preferably having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms), an aryl group (preferably having 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms), an alkoxy group (preferably having a carbon number) 1 to 10, more preferably 1 to 6 carbon atoms), carboxyl group, crosslinkable group, oxygen atom, carbonyl group, sulfonyl group, arylene group (preferably 6 to 20 carbon atoms, more preferably 6 to 6 carbon atoms) 10) an alkylene group (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), an alkenylene group (preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms), A nylene group (preferably having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms) and an alkenyl group, alkynyl group, aryl group, carbonyl group, carboxyl group, crosslinkable group, oxygen atom, alkylene group, alkynylene group or It is more preferably a group consisting of a combination with an arylene group.
The crosslinkable group represented by R ¹¹ is synonymous with the crosslinkable group described above, and the preferred range is also the same.
These groups may have a substituent, and examples of the substituent include a hydroxyl group, an alkyl group, a halogen atom, a cyano group, an amide group, and a sulfonylamide group.

Specific examples of the group represented by the general formula (1-1) include the following, but are not limited thereto. In the formula, Ph represents a phenyl group.

(A) When the terminal of the polybenzoxazole precursor is not a crosslinkable group, it may be sealed with a sealing group. An example of the sealing group in this case is an acetyl group.

On the other hand, in the present invention, it is also preferable that the polybenzoxazole precursor has no crosslinkable group at the terminal. By setting it as such an aspect, control of the molecular weight of a polybenzoxazole precursor becomes easy and it becomes easy to obtain resin which has a more uniform molecular weight.

The polybenzoxazole precursor (A) has a weight average molecular weight of preferably 3000 to 200,000, more preferably 4000 to 100,000, and most preferably 5000 to 50000. By setting it as this range, the lithography performance and the cured film physical properties can be made excellent. Here, the weight average molecular weight is defined by a polystyrene conversion value of gel permeation chromatography.
The number average molecular weight of the (A) polybenzoxazole precursor is preferably 1000 to 50000, more preferably 2000 to 40000, and still more preferably 3000 to 30000. Here, the number average molecular weight is defined as a polystyrene equivalent value of gel permeation chromatography.
The polybenzoxazole precursor (A) used in the present invention can be configured to contain substantially no crosslinkable group other than the terminal. “Substantially free” means that the repeating unit containing a crosslinkable group is 1 mol% or less of all repeating units.

The content of the (A) polybenzoxazole precursor in the composition of the present invention is preferably 50% by mass or more, more preferably 60% by mass, and particularly preferably 70% by mass or more in terms of solid content. When using 2 or more types of polybenzoxazole precursor, the total amount becomes the said range.

<< Method for Producing Polybenzoxazole Precursor >>
The polybenzoxazole precursor used in the present invention can be synthesized in consideration of the description in JP-A-2008-224907. Further, in the present invention, it is preferable to seal the polybenzoxazole precursor with a group represented by the general formula (1-1), but such terminal blocking was performed by synthesizing a resin having a terminal amino group. Later, the terminal amino group is bonded through a carbonyl group or a sulfonyl group, capped as an amide with an acid anhydride or acid derivative, or a monofunctional amine or acid chloride is mixed in the polymerization reaction. Can be synthesized at once.

<(B) Photoacid generator in which pKa of generated acid is 4 or less>
The photosensitive resin composition of the present invention contains a photoacid generator (B) that generates an acid having a pKa of 4 or less. By using such an acid generator, a highly transparent cured film can be obtained. The photoacid generator used in the present invention is preferably a compound that reacts with an actinic ray having a wavelength of 300 nm or more, preferably 300 to 450 nm and generates an acid having a pKa of 4 or less, but is limited by its chemical structure. It is not something. 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. As the photoacid generator used in the present invention, a photoacid generator that generates an acid having a pKa of 3 or less is more preferable, and a photoacid generator that generates an acid of 2 or less is more preferable. Further, when a strong acid having a pKa of 2 or less is used, there is an effect of improving heat resistance.
In the present invention, pKa basically refers to pKa in water at 25 ° C. Those that cannot be measured in water refer to those measured after changing to a solvent suitable for measurement. Specifically, the pKa described in the chemical handbook can be referred to.

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 or an imide sulfonate compound from the viewpoints of sensitivity and insulating properties. These photoacid generators can be used singly or in combination of two or more. Specific examples of trichloromethyl-s-triazines, diaryliodonium salts, triarylsulfonium salts, quaternary ammonium salts, imidosulfonate compounds, and diazomethane derivatives include paragraph numbers 0083 to 0088 of JP2011-212494A, The compounds described in paragraph Nos. 0065 to 0072 of WO11 / 087011 can be exemplified, and the contents thereof are incorporated in the present specification. As the triarylsulfonium salt, a triarylsulfonium salt having the following structure can be preferably used.

Moreover, as an imide sulfonate compound, the imide sulfonate compound of the following structure can be used preferably. In addition, it is preferable to use an imide sulfonate compound with the sensitizer mentioned later.

(In the formula, each R independently represents a group consisting of a hydrogen atom and a carbon atom and / or an oxygen atom (excluding other than C, H and O), and the sum of the carbon atom and the oxygen atom is 16 or less. R ¹ represents a monovalent organic group having 16 or less carbon atoms.)
R independently represents a group consisting of a hydrogen atom and a carbon atom and / or an oxygen atom (excluding other than C, H and O), and the sum of the carbon atom and the oxygen atom is 16 or less. R is preferably a hydrogen atom or an alkylene oxide group having 8 or less carbon atoms.
R ¹ represents a monovalent organic group having 16 or less carbon atoms. R ¹ preferably does not contain other than C, H, O, and F. Examples of R ¹ include a methyl group, a trifluoromethyl group, a propyl group, a phenyl group, and a tosyl group.

Specific examples of such compounds include the following compounds.

In addition, specific examples of the imide sulfonate compound include the compounds described in paragraph numbers 0065 to 0075 of WO2011 / 087011, and the following compounds.

Preferred examples of the oxime sulfonate compound, that is, a compound having an oxime sulfonate structure include compounds having an oxime sulfonate structure represented by the following general formula (B1-1).
General formula (B1-1)

(In the general formula (B1-1), R ²¹ represents an alkyl group or an aryl group. The wavy line represents a bond with another group.)

In general formula (B1-1), any group may be substituted, and the alkyl group in R ²¹ may be linear, branched or cyclic. Acceptable substituents are described below.
The alkyl group for R ²¹ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group represented by R ²¹ has a halogen atom, an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group). It may be substituted with a bridged alicyclic group, preferably a bicycloalkyl group or the like.
As the aryl group for R ^21, 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 ²¹ may be substituted with a lower alkyl group, an alkoxy group, or a halogen atom.

The compound containing the oxime sulfonate structure represented by the general formula (B1-1) is preferably an oxime sulfonate compound represented by the following general formula (B1-2).
General formula (B1-2)

(In the formula (B1-2), R ⁴² represents an optionally substituted alkyl group or aryl group, X represents an alkyl group, an alkoxy group, or a halogen atom, and m4 represents 0-3. Represents an integer, and when m4 is 2 or 3, a plurality of Xs may be the same or different.

Preferred ranges of R ^42, the same as the preferable range of the R ^21.
The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. Further, the alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom as X is preferably a chlorine atom or a fluorine atom.
m4 is preferably 0 or 1. In the general formula (B1-2), m4 is 1, X is a methyl group, the substitution position of X is an ortho position, R ⁴² is a linear alkyl group having 1 to 10 carbon atoms, 7, A compound which is a 7-dimethyl-2-oxonorbornylmethyl group or a p-toluyl group is particularly preferred.

The compound containing an oxime sulfonate structure represented by the general formula (B1-1) is also preferably an oxime sulfonate compound represented by the following general formula (B1-3).
General formula (B1-3)

(In the formula (B1-3), R ⁴³ has the same meaning as R ⁴² in the formula (B1-2), and X ¹ is a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. Represents an alkoxy group, a cyano group or a nitro group, and n4 represents an integer of 0 to 5.)

R ⁴³ in the above general formula (B1-3) is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n—. A propyl group, a perfluoro-n-butyl group, a p-tolyl group, a 4-chlorophenyl group or a pentafluorophenyl group is preferable, and an n-octyl group is particularly preferable.
X ¹ is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
n4 is preferably from 0 to 2, particularly preferably from 0 to 1.
As specific examples of the compound represented by the above general formula (B1-3) and preferable examples of the oxime sulfonate compound, the description in paragraphs 0080 to 0082 of JP2012-163937A can be referred to. Incorporated in the description.

The compound containing an oxime sulfonate structure represented by the general formula (B1-1) is also preferably a compound represented by the following general formula (OS-1).

In the general formula (OS-1), R ¹⁰¹ 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 Represents a heteroaryl group. ^R102 represents an alkyl group or an aryl group.
X ¹⁰¹ represents —O—, —S—, —NH—, —NR ¹⁰⁵ —, —CH ² —, —CR ¹⁰⁶ H—, or —CR ¹⁰⁵ R ¹⁰⁷ —, wherein R ¹⁰⁵ to R ¹⁰⁷ are alkyl groups. Or an aryl group.
R ¹²¹ to R ¹²⁴ each independently represents 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 ¹²¹ to R ¹²⁴ may be bonded to each other to form a ring.
R ¹²¹ to R ¹²⁴ are preferably a hydrogen atom, a halogen atom and an alkyl group, and an embodiment in which at least two of R ¹²¹ to R ¹²⁴ are bonded to each other to form an aryl group is also preferred. Among these, an embodiment in which R ¹²¹ to R ¹²⁴ 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 general formula (OS-1) is, for example, a compound represented by the general formula (OS-2) described in paragraph numbers 0087 to 0089 of JP2012-163937A Which is incorporated herein by reference.

Specific examples of the compound represented by the general formula (OS-1) that can be suitably used in the present invention include compounds described in paragraph numbers 0128 to 0132 of JP2011-221494A (exemplified compounds b-1 to b-34), but the present invention is not limited thereto.
In the present invention, the compound containing the oxime sulfonate structure represented by the general formula (B1-1) is represented by the following general formula (OS-3), the following general formula (OS-4), or the following general formula (OS- The oxime sulfonate compound represented by 5) is preferred.

(In the general formula (OS-3) to general formula (OS-5), R ²² , R ²⁵ and R ²⁸ each independently represents an alkyl group, an aryl group or a heteroaryl group; R ²³ , R ²⁶ and R ²⁹ Each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group. X ¹ to X ³ each independently represents an oxygen atom or a sulfur atom, n ¹ to n ³ each independently represents 1 or 2, and m ¹ to m ³ each independently represents an integer of 0 to 6 Represents.)
With respect to the above general formulas (OS-3) to (OS-5), for example, the descriptions in paragraph numbers 0034 to 0071 of JP2013-47765A can be referred to, and the contents thereof are incorporated in the present specification.

In addition, the compound containing an oxime sulfonate structure represented by the above general formula (B1-1) is, for example, a compound represented by the general formula (OS-6) described in paragraph 0117 of JP2012-163937A. Particularly preferred is a compound represented by any of (OS-11), the contents of which are incorporated herein.
Preferred ranges in the above general formulas (OS-6) to (OS-11) are preferred ranges of (OS-6) to (OS-11) described in paragraph numbers 0110 to 0112 of JP2011-221494A. The contents of which are incorporated herein by reference.
Specific examples of the oxime sulfonate compound represented by the general formula (OS-3) to the general formula (OS-5) include compounds described in paragraph numbers 0114 to 0120 of JP2011-221494A. The contents of which are incorporated herein by reference. The present invention is not limited to these.

The compound containing an oxime sulfonate structure represented by the general formula (B1-1) is also preferably an oxime sulfonate compound represented by the following general formula (B1-4).
General formula (B1-4)

(In the general formula (B1-4), R ¹ represents an alkyl group or an aryl group, R ² represents an alkyl group, an aryl group, or a heteroaryl group. R ³ to R ⁶ each represents a hydrogen atom. Represents an alkyl group, an aryl group, or a halogen atom, provided that R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ may combine to form an alicyclic ring or aromatic ring. , -O- or S-.

R ¹ represents an alkyl group or an aryl group. The alkyl group is preferably a branched alkyl group or a cyclic alkyl group.
The alkyl group preferably has 3 to 10 carbon atoms. In particular, when the alkyl group has a branched structure, an alkyl group having 3 to 6 carbon atoms is preferable. When the alkyl group has a cyclic structure, an alkyl group having 5 to 7 carbon atoms is preferable.
Examples of the alkyl group include propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, 1,1-dimethylpropyl group, hexyl group. 2-ethylhexyl group, cyclohexyl group, octyl group and the like, preferably isopropyl group, tert-butyl group, neopentyl group, and cyclohexyl group.
The aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms, and still more preferably 6 to 7 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is preferable.
The alkyl group and aryl group represented by R ¹ may have a substituent. Examples of the substituent include a halogen atom (a fluorine atom, a chloro atom, a bromine atom, an iodine atom), a linear, branched or cyclic alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.), an alkenyl group, an alkynyl group, Aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, cyano group, carboxyl group, hydroxyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, heterocyclic oxy group, acyloxy group, amino group, A nitro group, a hydrazino group, a heterocyclic group, etc. are mentioned. Further, these groups may be further substituted. Preferably, they are a halogen atom and a methyl group.

In the photosensitive resin composition of the present invention, R ¹ is preferably an alkyl group from the viewpoint of transparency, and R ¹ has a branched structure having 3 to 6 carbon atoms from the viewpoint of achieving both storage stability and sensitivity. An alkyl group, an alkyl group having a cyclic structure having 5 to 7 carbon atoms, or a phenyl group is preferable, and an alkyl group having a branched structure having 3 to 6 carbon atoms or an alkyl group having a cyclic structure having 5 to 7 carbon atoms is more preferable. . By adopting such a bulky group (particularly a bulky alkyl group) as R ¹ , it becomes possible to further improve the transparency.
Among the bulky substituents, an isopropyl group, a tert-butyl group, a neopentyl group, and a cyclohexyl group are preferable, and a tert-butyl group and a cyclohexyl group are more preferable.

R ² represents an alkyl group, an aryl group, or a heteroaryl group. The alkyl group represented by R ² is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, and a cyclohexyl group. It is a group.
As the aryl group, an aryl group having 6 to 10 carbon atoms is preferable. Examples of the aryl group include a phenyl group, a naphthyl group, a p-toluyl group (p-methylphenyl group), and a phenyl group and a p-toluyl group are preferable.
Examples of the heteroaryl group include a pyrrole group, an indole group, a carbazole group, a furan group, and a thiophene group.
The alkyl group, aryl group, and heteroaryl group represented by R ² may have a substituent. As a substituent, it is synonymous with the substituent which the alkyl group and aryl group which R < ¹ > may have.
R ² is preferably an alkyl group or an aryl group, more preferably an aryl group, and more preferably a phenyl group. As the substituent for the phenyl group, a methyl group is preferred.

R ³ to R ⁶ each represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom (a fluorine atom, a chloro atom, a bromine atom, or an iodine atom). The alkyl group represented by R ³ to R ⁶ has the same meaning as the alkyl group represented by R ² , and the preferred range is also the same. The aryl group represented by R ³ to R ⁶ has the same meaning as the aryl group represented by R ¹ , and the preferred range is also the same.
Among R ³ to R ⁶ , R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ may combine to form a ring, and the ring may form an alicyclic ring or an aromatic ring. It is preferable that a benzene ring is more preferable.
R ³ to R ⁶ are each a hydrogen atom, an alkyl group, a halogen atom (fluorine atom, chloro atom, bromine atom), or R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ^6. A benzene ring is preferably formed, and a hydrogen atom, a methyl group, a fluorine atom, a chloro atom, a bromine atom, or R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ are combined to form a benzene ring Is more preferable.
Preferred embodiments of R ³ to R ⁶ are as follows.
(Aspect 1) At least two are hydrogen atoms.
(Aspect 2) The number of alkyl groups, aryl groups, or halogen atoms is one or less.
(Aspect 3) R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ are combined to form a benzene ring.
(Aspect 4) An aspect satisfying the

above aspects

1 and 2 and / or an aspect satisfying the

above aspects

1 and 3.
X represents —O— or S—.

Specific examples of the general formula (B1-4) include the following compounds, but the present invention is not particularly limited thereto. In the exemplified compounds, Ts represents a tosyl group (p-toluenesulfonyl group), Me represents a methyl group, Bu represents an n-butyl group, and Ph represents a phenyl group.

In the photosensitive resin composition of the present invention, the content of the (B) photoacid generator is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the total solid components in the photosensitive resin composition. 5 to 10 parts by mass is more preferable, and 0.5 to 5 parts by mass is even more preferable. Only 1 type may be used for a photo-acid generator, and it can also use 2 or more types together. A photo-acid generator may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of photo-acid generators, the total amount becomes the said range.

<(C) Solvent>
The photosensitive resin composition of the present invention contains (C) a solvent. The photosensitive resin composition of the present invention is preferably prepared as a solution in which the essential components of the present invention and further optional components described below are dissolved in a solvent. As a solvent used for the preparation of the composition of the present invention, a solvent that uniformly dissolves essential components and optional components and does not react with each component is used.
As the 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 such as propylene glycol monomethyl ether acetate, diethylene glycol dialkyl ethers such as diethylene glycol ethyl methyl ether, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, Dipropylene glycol dialkyl ethers, dipropylene glycol mono Ruki ether acetates, esters, ketones, amides, lactones such as γ- butyrolactone, pyrrolidones and the like. Specific examples of the solvent used in the photosensitive resin composition of the present invention include the solvents described in paragraph numbers 0174 to 0178 of JP2011-221494A, and paragraph numbers 0167 to of JP2012-194290A. Also included are the solvents described in 0168, the contents of which are incorporated herein.

In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonal as necessary for these solvents , Benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate and the like can also be added. These solvents can be used alone or in combination of two or more. The solvent that can be used in the present invention is a single type or a combination of two or more types, more preferably a combination of two types, propylene glycol monoalkyl ether acetates or dialkyl ethers, diacetates. It is more preferable to use a combination of styrene and diethylene glycol dialkyl ether or an ester and butylene glycol alkyl ether acetate.

Further, the solvent is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof.
Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), propylene glycol An example is methyl-n-propyl ether (boiling point 131 ° C.).
Solvents having a boiling point of 160 ° C or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), dipropylene glycol methyl ether acetate. (Boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (Boiling point 220 ° C.), dipropylene glycol dimethyl ether (boiling point 175 ° C.), 1,3-butylene glycol diacetate (boiling point 232 ° C.), N Methyl-2-pyrrolidone (boiling point 204 ° C.), gamma-butyrolactone (boiling point 204 ° C.) can be exemplified.

The content of the solvent in the photosensitive resin composition of the present invention is preferably 50 to 98 parts by mass and more preferably 60 to 95 parts by mass with respect to 100 parts by mass of all components in the photosensitive resin composition. It is preferably 70 to 90 parts by mass. A solvent may be used individually by 1 type, or may use 2 or more types together. When two or more kinds of solvents are used, the total amount falls within the above range.

<(D) Crosslinking agent>
The photosensitive resin composition of the present invention has at least one cross-linking agent (hereinafter also referred to as “(D) cross-linking agent”) having two or more cross-linkable groups composed of groups that react with a benzene ring and / or a phenolic hydroxyl group. Contains seeds. In the present invention, the crosslinking agent reacts with a benzene ring or a phenolic hydroxyl group contained in the polybenzoxazole precursor to form a crosslinked structure between the polybenzoxazoles.
The crosslinkable group composed of a group that reacts with a benzene ring or a phenolic hydroxyl group is not particularly limited, and examples thereof include an epoxy group, a methylol group, an alkoxymethyl group, and a blocked isocyanate group. In the present invention, as long as two or more such crosslinkable groups are contained in one molecule, each crosslinkable group may be the same or different. Preferably, the crosslinkable groups contained in one molecule are the same.
The (D) crosslinking agent used in the present invention is preferably a crosslinking agent having two or more crosslinking groups selected from an epoxy group, a methylol group, an alkoxymethyl group, and a blocked isocyanate group, and an epoxy group and / or More preferably, it has an alkoxymethyl group. More specifically, (D) the crosslinking agent includes a compound having two or more epoxy groups in the molecule, a crosslinking agent containing two or more alkoxymethyl groups and / or methylol groups in the molecule, Preferred examples include compounds containing two or more blocked isocyanate groups. These (D) crosslinking agents can react with the phenolic hydroxyl group or benzene ring of component (A) to crosslink components (A), and this crosslinking reaction is caused by the acid generated from the acid generator. Since it accelerates | cures, the cured film obtained by the photosensitive resin composition of this invention can be made into a firmer film | membrane.
The molecular weight of the crosslinking agent used in the present invention is preferably 150 to 30000, and more preferably 200 to 10000. By setting it as such a range, the effect of this invention is exhibited more effectively.
The content of the crosslinking agent (D) in the photosensitive resin composition of the present invention is preferably 1 to 50 parts by mass with respect to 100 parts by mass in total of the component (A), and 3 to 30 parts by mass. More preferred is 5 to 20 parts by mass. By adding in this range, a cured film having excellent mechanical strength and solvent resistance can be obtained. A plurality of (D) crosslinking agents can be used in combination. In that case, the content is calculated by adding all (D) crosslinking agents.
The photosensitive resin composition of this invention can also use together crosslinking agents other than the said (D) crosslinking agent. In that case, the proportion of the (D) crosslinking agent in the entire crosslinking agent is preferably 50% by mass or more, and more preferably 80% by mass or more.

<< Compound having two or more epoxy groups in the molecule >>
In the photosensitive resin composition of this invention, the compound which has a 2 or more epoxy group in a molecule | numerator can be used as (D) crosslinking agent. Specific examples of compounds having two or more epoxy groups in the molecule include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, aliphatic epoxy resins, and epoxy group containing An acrylic resin having a structural unit can be given.

These are available as commercial products. For example, JER152, JER157S70, JER157S65, JER806, JER828, JER1007 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.), and the like are commercially available products described in paragraph No. 0189 of JP2011-221494, etc. EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX- 321L, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212L, EX-214L, X-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402 (manufactured by Nagase Chemtech), YH-300 YH-301, YH-302, YH-315, YH-324, YH-325 (manufactured by NS Etc.). These can be used alone or in combination of two or more.
Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin and aliphatic epoxy resin are more preferable, and bisphenol A type epoxy resin is particularly preferable.

<< Crosslinking agent containing two or more alkoxymethyl groups or methylol groups in the molecule >>
In the photosensitive resin composition of the present invention, a crosslinking agent containing an alkoxymethyl group or a methylol group can be used as the (D) crosslinking agent. The crosslinking agent containing two or more alkoxymethyl groups or methylol groups in the molecule is a crosslinking agent having two or more structures represented by the following general formula (1) or general formula (2) in the molecule. , One or both of an alkoxymethyl group and a methylol group are contained in the molecule in a total of two or more.
-CH ₂ OR ¹ (1)
(In the formula, R ¹ represents an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.)
—CH ₂ OH (2)

The alkoxymethyl group or methylol group is preferably bonded to a nitrogen atom or a carbon atom forming an aromatic ring.

Examples of the crosslinking agent in which an alkoxymethyl group or a methylol group is bonded to a nitrogen atom include alkoxymethylated melamine, methylolated melamine, alkoxymethylated benzoguanamine, methylolated benzoguanamine, alkoxymethylated glycoluril, methylolated glycoluril, alkoxy Methylated urea and methylolated urea are preferred. Alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril, and alkoxymethylated urea convert methylolated melamine, methylolated benzoguanamine, methylolated glycoluril, or methylol group of methylolated urea to alkoxymethyl group, respectively. Can be obtained. Examples of the alkoxymethyl group include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group, and the methoxymethyl group is particularly preferable from the viewpoint of outgas generation amount.
Among these crosslinkable compounds, alkoxymethylated melamine, methylolated melamine, alkoxymethylated benzoguanamine, methylolated benzoguanamine, alkoxymethylated glycoluril, methylolated glycoluril are mentioned as preferred crosslinkable compounds, from the viewpoint of transparency Alkoxymethylated glycoluril and methylolated glycoluril are particularly preferred.
In the present invention, the alkoxymethyl group-containing crosslinking agent described in paragraph No. 0107 of JP2012-8223A can be preferably used, and the contents thereof are incorporated in the present specification.

Preferred structures of the crosslinking agent containing two or more alkoxymethyl groups or methylol groups in the molecule include compounds represented by the following formulas (8-1) to (8-4).

(In the above formulas (8-1) to (8-4), R ⁷ and R each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ⁸ to R ¹¹ each independently represents Represents a hydrogen atom, a hydroxyl group, an alkyl group or an alkoxyl group, and X ² represents a single bond, a methylene group or an oxygen atom.)

The alkyl group represented by R ⁷ and R has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group. The alkyl group represented by R ⁸ to R ¹¹ preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group. The alkoxyl group represented by R ⁸ to R ¹¹ preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, and a propoxy group. X ² is preferably a single bond or a methylene group. R ⁷ to R ¹¹ and X ² may be substituted with an alkyl group such as a methyl group or an ethyl group, or a halogen atom. A plurality of R ⁷ , R, and R ⁸ to R ¹¹ may be the same or different.

Specific examples of the compound represented by the formula (8-1) include the compounds shown below.

Specific examples of the compound represented by the formula (8-2) include N, N, N, N-tetramethylolglycoluril, N, N, N, N-tetramethylolglycoluril having 1 to 1 methylol groups. 4 methoxymethylated compounds, N, N, N, N-tetramethylolglycoluril methylol group having 1 to 4 ethoxymethylated compounds, N, N, N, N-tetramethylolglycoluril methylol N-propoxymethylated compounds having 1 to 4 groups, isopropoxymethylated compounds having 1 to 4 methylol groups in N, N, N, N-tetramethylolglycoluril, N, N, N, N -N-butoxymethylated compound having 1 to 4 methylol groups of tetramethylol glycoluril, N, N, N, N-tetramethylolglycol Methylol groups Ruuriru can be exemplified such as 1-4 tert- butoxy methylated compound. Of these, compounds having 1 to 4 methoxymethylated methylol groups of N, N, N, N-tetramethylolglycoluril are particularly preferred.

Specific examples of the compound represented by the formula (8-3) include the compounds shown below.

Specific examples of the compound represented by the formula (8-4) include N, N, N, N, N, N-hexamethylol melamine, N, N, N, N, N, N-hexamethylol melamine. 1-6 methoxymethylated methylol groups, 1-6 methoxymethylated methylol groups of N, N, N, N, N, N-hexamethylolmelamine, N, N, N, N , N, N-hexamethylolmelamine 1-6 methylol groups n-propoxymethylated, N, N, N, N, N, N-hexamethylolmelamine 1-6 methylol groups isopropoxymethyl Compound, N, N, N, N, N, N-hexamethylol compound in which 1 to 6 methylol groups of melamine are n-butoxymethylated, N, N, N, N, N, N-hexamethylol Mela Methylol groups of the emission can be cited 1-6 tert- butoxy methylated compounds were like. Among these, N, N, N, N, N, N-hexa (methoxymethyl) melamine is particularly preferable.

Examples of the crosslinking agent in which an alkoxymethyl group or a methylol group is bonded to a carbon atom that forms an aromatic ring include those represented by the following general formulas (4) to (5).

(In the formula (4), X represents a single bond or a monovalent to tetravalent organic group, R ¹¹ and R ¹² each independently represents a hydrogen atom or a monovalent organic group, and n is an integer of 1 to 4. And p and q are each independently an integer of 0 to 4.)

(In the formula (5), two Y's are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and may contain an oxygen atom or a fluorine atom, and R ¹³ to R ¹⁶ are each independently a hydrogen atom. Or a monovalent organic group, m and n are each independently an integer of 1 to 3, and p and q are each independently an integer of 0 to 4.)

Specific examples of the compounds represented by the general formulas (4) to (5) include the following compounds. Me represents a methyl group.

Crosslinking agents containing two or more alkoxymethyl groups or methylol groups in these molecules are also available as commercial products, for example, Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), Nicalac MX-750, -032, -706, -708, -40 , -31, -270, -280, -290, -750LM, Nicarak MS-11, Nicarak MW-30HM, -100LM, -270, -390 (above, manufactured by Sanwa Chemical Co., Ltd.) can do. These can be used alone or in combination of two or more.

<< Compound containing two or more blocked isocyanate groups in the molecule >>
In the photosensitive resin composition of the present invention, a compound containing two or more blocked isocyanate groups in the molecule can be used as the (D) crosslinking agent.
The blocked isocyanate group in the present invention is a group capable of generating an isocyanate group by heat. For example, a group obtained by reacting a blocking agent with an isocyanate group to protect the isocyanate group can be preferably exemplified. The blocked isocyanate group is preferably a group capable of generating an isocyanate group by heat at 90 ° C. to 250 ° C.
Further, the skeleton of the blocked isocyanate compound is not particularly limited, and any skeleton having two or more isocyanate groups in one molecule may be used, and may be aliphatic, alicyclic or aromatic. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetraisocyanate Methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate 2,2'-diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane 1,4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3′-methylene ditolylene-4,4′-diisocyanate, 4,4′-diphenyl ether diisocyanate, tetrachlorophenylene diisocyanate, Isocyanates such as norbornane diisocyanate, hydrogenated 1,3-xylylene diisocyanate, hydrogenated 1,4-xylylene diisocyanate And prepolymer type skeleton compounds derived from these compounds can be suitably used. Among these, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) are particularly preferable.
Examples of the matrix structure of the blocked isocyanate compound in the photosensitive resin composition of the present invention include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.
Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. be able to. Among these, a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferable.

Examples of the oxime compound include oxime and ketoxime, and specific examples include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, benzophenone oxime, and acetoxime.
Examples of the lactam compound include ε-caprolactam and γ-butyrolactam.
Examples of the phenol compound include phenol, naphthol, cresol, xylenol, and halogen-substituted phenol.
Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.
Examples of the amine compound include primary amines and secondary amines, which may be aromatic amines, aliphatic amines, and alicyclic amines, and examples thereof include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.
Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate and the like.
Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole and the like.
Examples of the mercaptan compound include alkyl mercaptans and aryl mercaptans.

The blocked isocyanate compound that can be used in the photosensitive resin composition of the present invention is commercially available. For example, Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (or more, Nippon Polyurethane Industry Co., Ltd.), Takenate B-830, B-815N, B-820NSU, B-842N, B-84N, B-870N, B-874N, B-882N (above, manufactured by Mitsui Chemicals, Inc.) ), Duranate 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (above , Manufactured by Asahi Kasei Chemicals Corporation, Death Module B 1100, BL1265 MPA / X, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, Sumidur BL3175 (above, manufactured by Sumika Bayer Urethane Co., Ltd.) etc. are preferably used can do.

<< Compound containing two or more methacryloyl groups and / or acryloyl groups in the molecule >>
The photosensitive resin composition of the present invention may use a compound containing a methacryloyl group or an acryloyl group as a crosslinking agent other than the (D) crosslinking agent, together with the (D) crosslinking agent. The compound containing a methacryloyl group or an acryloyl group is a compound selected from the group consisting of acrylic acid esters and methacrylic acid esters. It is preferable that the acryloyl group and the methacryloyl group are compounds having two or more, more preferably trifunctional or more in one molecule.

Examples of the bifunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Examples include tetraethylene glycol di (meth) acrylate, bisphenoxyethanol full orange acrylate, and bisphenoxyethanol full orange acrylate.
Examples of the tri- or more functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (meth) acrylate. , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
Preferable commercially available products are KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd., NK ester series manufactured by Shin-Nakamura Chemical Co., Ltd., bifunctional A-200, A-400, A-600, A-1000, ABE-300, A- BPE-4, A-BPE-10, A-BPE-20, A-BPE-30, A-BPP-3, A-DOD, A-DCP, A-IBD-2E, A-NPG, 701A, A- B1206PE, A-HD-N, A-NOD-N, APG-100, APG-200, APG-400, APG-700, 1G, 2G, 3G, 4G, 9G, 14G, 23G, BG, BD, HD- N, NOD, IND, BPE-100, BPE-200, BPE-300, BPE-500, BPE-900, BPE-1300N, NPG, DCP, 1206PE, 701, 3 G, 9PG, trifunctional A-9300, AT-30E, A-TMPT-3EO, A-TMPT-9EO, A-TMPT-3PO, A-TMM-3, A-TMM-3L, A-TMM-3LM -N, TMPT, TMPT-9EO, tetra- or higher functional ATM-35E, ATM-4E, AD-TMP, AD-TMP-L, ATM-4P, A-TMMT, A-DPH and the like can be mentioned.

<< Compound containing two or more oxetane groups in the molecule >>
The photosensitive resin composition of this invention may use the compound containing an oxetane group as crosslinking agents other than (D) crosslinking agent with (D) crosslinking agent. It is preferable that there are two or more oxetane groups in the molecule. Examples of the compound having two or more oxetanyl groups in the molecule include the compounds described in paragraphs 0134 to 0145 of JP-A-2008-224970, the contents of which are incorporated herein. As specific examples, Aron Oxetane OXT-121, OXT-221, OX-SQ, and PNOX (above, manufactured by Toagosei Co., Ltd.) can be used.

<(E) Compound in which acid group is protected with acid-decomposable group>
The photosensitive resin composition of the present invention may contain a compound in which an acid group is protected with an acid-decomposable group (also referred to as “(E) compound”). The compound in which the acid group is protected with an acid-decomposable group is a compound in which the acid group is protected with an acid-decomposable group, and the protecting group is eliminated by the action of an acid to increase alkali solubility. The compound (E) plays a role of decreasing the alkali solubility in the non-exposed area and increasing the alkali solubility in the exposed area. As the acid group, a carboxy group or a phenolic hydroxyl group is preferable.
The acid-decomposable group is not particularly limited as long as it is a group that can be decomposed by the action of an acid. An acetal group, a ketal group, a silyl group, and a silyl ether group can be mentioned, and an acetal group is preferable from the viewpoint of sensitivity. Specific examples of the protecting group include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group, tert-butoxycarbonylmethyl group, And trimethylsilyl ether group. From the viewpoints of sensitivity and stability, an ethoxyethyl group and a tetrahydrofuranyl group are preferred.

The compound (E) may be a polymer (for example, more than 5000 or even more than 10,000) or a low molecule (for example, 5000 or less). More preferred. In the case of a polymer, the molecular weight is a number average molecular weight determined by polystyrene conversion. As a lower limit of molecular weight, 150 or more are preferred and 300 or more are more preferred.
Moreover, it is preferable that a compound (E) contains either an aromatic ring, a heterocyclic ring, and an alicyclic structure from a viewpoint of a dissolution inhibitory ability improvement.

The compound (E) preferably has two or more acid groups protected in the molecule from the viewpoint of improving sensitivity.
Moreover, it is preferable that a (E) compound contains an aromatic ring or a heterocyclic ring from a viewpoint of compatibility improvement with (A) component.
Hereinafter, preferred embodiments of the compound (E) will be described.

The compound (E) is preferably a compound represented by the following general formula (E-1-1).
Formula (E-1-1)

(In the general formula (E-1-1), R represents a monovalent to hexavalent organic group having a molecular weight of 2000 or less, and R ¹ and R ² each independently represents a hydrogen atom, an alkyl group, or an aryl group. , R ¹ and R ² are an alkyl group or an aryl group, and R ³ represents an alkyl group or an aryl group, and may combine with R ¹ or R ² to form a cyclic ether. N1 represents an integer of 1 to 6.)

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.
As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable. preferable. The alkyl group may have a substituent. The alkyl group may be linear, branched or cyclic, but is preferably a linear alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group, and a cyclohexyl group.
As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 14 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is further preferable. The aryl group may have a substituent. As an aryl group, a phenyl group, a naphthyl group, an anthracenyl group etc. are mentioned, for example, A phenyl group is especially preferable.

R ³ represents an alkyl group or an aryl group, and may combine with R ¹ or R ² to form a cyclic ether. The alkyl group is preferably an alkyl group having 1 to 16 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, and further an alkyl group having 1 to 4 carbon atoms. preferable. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a neopentyl group, and a hexyl group. As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 14 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is further preferable. Specific examples of the aryl group include a phenyl group, a toluyl group, a mesityl group, and a naphthyl group.

R ³ may be linked to R ¹ or R ² to form a cyclic ether. The cyclic ether formed by linking to R ¹ or R ² is preferably a 3- to 6-membered cyclic ether, more preferably a 5- to 6-membered cyclic ether.

R ¹ and R ² are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ³ is preferably bonded to an alkyl group having 1 to 4 carbon atoms, R ¹ or R ² to form a tetrahydrofuranyl group.

R ¹ to R ³ may have a substituent. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms and a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), and these substituents may further have a substituent.

R represents a monovalent to hexavalent organic group having a molecular weight of 2000 or less. The organic group represented by R is a 1 to 6 valent organic group having a molecular weight of 2000 or less, preferably a 1 to 6 valent organic group having a molecular weight of 1500 or less, and a 1 to 6 valent organic group having a molecular weight of 1000 or less. More preferred. The organic group represented by R is preferably an organic group containing an aromatic ring or a heterocyclic ring and containing no atoms other than C, H, O, and N atoms, and is an organic group containing a cyclic structure and / or a carbonyl group. Are more preferable, and a group composed of a combination of an aromatic group, a cycloaliphatic group, a carbonyl group, an alkylene group, a phenylene group, and an oxygen atom is more preferable.

Specifically, R is preferably the following organic group when the acid group is a phenolic hydroxy group. In the formula, a wavy line represents a bonding site with an oxygen atom, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and m and n each independently represents 0 to 4 Represents an integer.

Specifically, R is preferably the following organic group when the acid group is a carboxy group. In the formula, a wavy line represents a bonding site with an oxygen atom, and R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (preferably an alkyl group having 1 to 8 carbon atoms). , M and n each independently represents an integer of 0 to 4 (preferably 0).

Specific examples of the compound represented by the general formula (E-1-1) include the following compounds, but the present invention is not particularly limited thereto.

The compound (E) is preferably a compound represented by the following general formula (E-1-2).
Formula (E-1-2)

(In general formula (E-1-2), R ¹ represents an n1-valent organic group, Ar represents an optionally substituted aryl group, a represents an integer of 0 or more, and n1 represents 2) (An integer greater than or equal to 1 is shown, where n1-a is an integer greater than or equal to 1.)

R ¹ represents an n1-valent organic group, preferably a 2- to 8-valent organic group, more preferably a 2- to 6-valent organic group. R ¹ is preferably a hydrocarbon group having 2 to 15 carbon atoms, or a group mainly having a hydrocarbon group in which 1 to 2 oxygen atoms form an ether bond in the hydrocarbon group. Specifically, R ¹ represents an aliphatic hydrocarbon structure (for example, a linear alkylene structure, a branched alkylene structure, a cycloalkylene structure, a norbornane structure, a norbornene structure, a norbornane skeleton, or a structure in which a norbornene skeleton and a cycloalkylene skeleton are condensed). ), Aromatic hydrocarbon structures (eg, benzene structures), aralkyl structures, structures in which these structures are combined, structures in which these structures are combined through ether bonds, and other tetrahydropyran structures The structure can be mentioned. As R ¹ , an alkylene structure, an alicyclic structure, an ether structure, an aralkyl structure, or a combination of these is particularly preferable as a basic skeleton.

Ar represents an optionally substituted aryl group. As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 14 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is further preferable. Specific examples of the aryl group include a phenyl group, a toluyl group, a mesityl group, and a naphthyl group.

a represents an integer of 0 or more, preferably an integer of 0 to 3, and more preferably 0. n represents an integer of 2 or more, preferably an integer of 2 to 8, more preferably an integer of 2 to 6, and more preferably 2.
In the synthesis step of the compound represented by the general formula (E-1-2), a mixture having a distribution of 0 to n may be obtained, but the mixture can be preferably used as it is. Na is an integer of 1 or more, preferably 1-7. Ar represents an optionally substituted aryl group, and specific examples thereof include a phenyl group and a naphthyl group. Examples of the substituent include a halogen atom such as a chlorine atom; a methyl group, a tert-butyl group and the like. Preferred examples include alkyl groups; alkoxy groups such as methoxy groups.

The compound represented by the general formula (E-1-2) preferably contains no atoms other than C, H, O, and N atoms from the viewpoint of improving compatibility with the component (A).

Specific examples of the compound represented by the general formula (E-1-2) include the following, but are not limited thereto.

In addition, specific examples of the compound represented by the general formula (E-1-2) include compounds described in paragraphs 0018 to 0025 of JP-A-2001-83709. It is incorporated herein.

The compound (E) is preferably a compound having a repeating unit represented by the following general formula (E-1-3).
General formula (E-1-3)

(In the general formula (E-1-3), R ¹ and R ² each independently represents a hydrogen atom, an alkyl group, or an aryl group, and ^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 may combine with R ¹ or R ² to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents 2 Represents a valent organic group.)

R ¹ and R ² has the same meaning as R ¹ and R ² in the general formula (E-1-1), and preferred ranges are also the same.
R ³ has the same meaning as R ³ in formula (E-1-1), and the preferred range is also the same.

X represents a divalent organic group. Examples of the divalent organic group represented by X include a phenylene group, a carbonyl group, and a p-phenylenecarbonyl group.

Preferable specific examples of the compound having a repeating unit represented by the general formula (E-1-3) include a polymer having any one of the following structural units. R ⁴ represents a hydrogen atom or a methyl group.

The weight average molecular weight of the compound having a repeating unit represented by the general formula (E-1-3) is preferably 2000 to 50000, more preferably 3000 to 20000. Here, the weight average molecular weight is defined by a polystyrene conversion value of gel permeation chromatography.

When a compound having a repeating unit represented by the general formula (E-1-3) is used as the compound (E), other components may be copolymerized from the viewpoint of compatibility with the component (A) and developability. preferable. Other components are not particularly limited as long as they can be copolymerized with a compound having a repeating unit represented by formula (E-1-3).

The other component is preferably a compound having a repeating unit represented by the following general formula (E-1-4).
General formula (E-1-4)

(In the general formula (E-1-4), R ⁴¹ represents a hydrogen atom or a methyl group, X represents a single bond or a divalent organic group, and R ⁴² may have a substituent. Represents an aryl group or a hydroxyl group.)

X represents a single bond or a divalent organic group, and examples of the divalent organic group represented by X include a phenylene group, a carbonyl group, a carboxyl group, and a p-phenylenecarbonyl group.

R ⁴² represents an aryl group which may have a substituent or a hydroxyl group, and the aryl group which may have a substituent includes an aryl represented by R ¹ in formula (E-1-1) It is synonymous with group, and its preferable range is also the same. The aryl group may have a substituent. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a hydroxyl group, and the like, and these substituents may further have a substituent. Good.

Preferable specific examples of the compound having a repeating unit represented by the general formula (E-1-4) include a polymer having any one of the following structural units. R ⁴ represents a hydrogen atom or a methyl group.

As the compound having a repeating unit represented by the general formula (E-1-4), the compounds (1) to (3) are preferably used from the viewpoint of compatibility with the component (A). From the viewpoint, it is preferable to use the compounds (4) to (5) having an acid group.

The ratio (% by mass) of the compound having the repeating unit represented by the general formula (E-1-3) and other components is (E-1-3) component / other components = 30/70 to 100 / 0 is preferable, and 40/60 to 80/20 is preferable. A plurality of other components may be used in combination.

When blended, the content of the compound (E) is 5 to 50 parts by mass, and more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the (A) polybenzoxazole precursor. By setting the content to 5 to 50 parts by mass, film physical properties and sensitivity can be improved. Moreover, 2 or more types of (E) compounds can be used, and when using 2 or more types, the total amount becomes the said range.
Moreover, in this invention, since (A) polybenzoxazole precursor contains an acid-decomposable group, (E) compound can also be made into 1 mass% or less of the total solid of the composition of this invention.

<Other ingredients>
To the photosensitive resin composition of the present invention, in addition to the above components, an adhesion improver (alkoxysilane compound), a sensitizer, a basic compound, a surfactant, and an antioxidant are preferably added as necessary. Can do. Furthermore, the photosensitive resin composition of the present invention includes an acid proliferation agent, a development accelerator, a plasticizer, a thermal radical generator, a thermal acid generator, an ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor. Known additives such as can be added. Further, as these compounds, for example, compounds described in paragraph numbers 0201 to 0224 of JP2012-8859A can be used, and the contents thereof are incorporated in the present specification.

<< Adhesion improver >>
The photosensitive resin composition of the present invention may contain an alkoxysilane compound as an adhesion improving agent. When an alkoxysilane compound is used, the adhesion between the film formed from the photosensitive resin composition of the present invention and the substrate can be improved, or the properties of the film formed from the photosensitive resin composition of the present invention can be adjusted. Can do. The alkoxysilane compound that can be used in the photosensitive resin composition of the present invention is a base material, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, or a metal such as gold, copper, molybdenum, titanium, or aluminum. Preferably, the compound improves the adhesion between the insulating film and the insulating film. Specifically, a known silane coupling agent or the like is also effective.
Examples of silane coupling agents include γ-glycid such as γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltrimethoxysilane. Γ-methacryloxypropyltrialkoxysilane such as xylpropyltrialkoxysilane, γ-glycidoxypropyl dialkoxysilane, 3-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyl dialkoxysilane, γ-chloropropyltrialkoxy Examples thereof include silane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, and vinyltrialkoxysilane. Of these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, γ-glycidoxypropyltrialkoxysilane is more preferable, and γ-glycidoxypropyltrimethoxysilane is more preferable. Further preferred. These can be used alone or in combination of two or more.

A well-known thing can be used for an alkoxysilane compound, without specifically limiting to these.
When the photosensitive resin composition of the present invention contains an alkoxysilane compound, the content of the alkoxysilane compound is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. 0.5 to 20 parts by mass is more preferable. An alkoxysilane compound may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of alkoxysilane compounds, the total amount becomes the said range.

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

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

When the photosensitive resin composition of the present invention contains a sensitizer, the content of the sensitizer is 0.001 to 100 parts by mass with respect to 100 parts by mass of the total solid components in the photosensitive resin composition. It is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 20 parts by mass. Two or more sensitizers can be used in combination. When two or more kinds of sensitizers are used, the total amount is within the above range.

<< basic compound >>
The photosensitive resin composition of the present invention may contain a basic compound. The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples thereof include compounds described in paragraph numbers 0204 to 0207 of JP2011-221494A and compounds described in paragraph numbers 0141 to 0145 of JP2012-133301A. It is incorporated herein.

Specific examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and the like. Examples include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea, 1,5-diazabicyclo [4.3.0 ] -5-Nonene, 1,8-di And azabicyclo [5.3.0] -7-undecene and 1,8-diazabicyclo [5.4.0] -7-undecene.
Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexylammonium hydroxide, and the like.
Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate and the like.
The basic compounds that can be used in the present invention may be used singly or in combination of two or more.

When the photosensitive resin composition of the present invention contains a basic compound, the content of the basic compound is 0.001 to 3 parts by mass with respect to 100 parts by mass of the total solid component in the photosensitive resin composition. The amount is preferably 0.005 to 1 part by mass. When using 2 or more types of basic compounds, the total amount becomes the said range.

<< Surfactant >>
The photosensitive resin composition of the present invention may contain a surfactant. As the surfactant, any of anionic, cationic, nonionic, or amphoteric can be used, but a preferred surfactant is a nonionic surfactant. Examples of the surfactant used in the composition of the present invention include those described in paragraph Nos. 0201 to 0205 in JP2012-88459A, and paragraphs 0185 to 0188 in JP2011-215580A. Can be used and these descriptions are incorporated herein.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. . The following trade names are KP-341, X-22-822 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 99C (manufactured by Kyoeisha Chemical Co., Ltd.), F Top (manufactured by Mitsubishi Materials Kasei Co., Ltd.), MegaFac (manufactured by DIC Corporation), Florard Novec FC-4430 (manufactured by Sumitomo 3M Co., Ltd.), Surflon S-242 (Manufactured by AGC Seimi Chemical Co., Ltd.), PolyFox PF-6320 (manufactured by OMNOVA), SH-8400 (Toray Dow Corning Silicone), Footgent FTX-218, FTX-218G (manufactured by Neos), and the like.
Further, the surfactant is measured by gel permeation chromatography using the structural unit A and the structural unit B represented by the following general formula (I-1-1) and using tetrahydrofuran (THF) as a solvent. A preferred example is a copolymer having a polystyrene-reduced weight average molecular weight (Mw) of 1,000 or more and 10,000 or less.

Formula (I-1-1)

(In the formula (I-1-1), R ⁴⁰¹ and R ⁴⁰³ each independently represent a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴⁰⁴ represents hydrogen. Represents an atom or an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p is 10 mass% to 80 mass%. The following numerical values are represented, q represents a numerical value of 20% to 90% by mass, r represents an integer of 1 to 18, and s represents an integer of 1 to 10.

L is preferably a branched alkylene group represented by the following general formula (I-1-2). R ⁴⁰⁵ in formula (I-1-2) represents an alkyl group having 1 to 4 carbon atoms, and preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability with respect to the coated surface. And an alkyl group having 2 or 3 carbon atoms is more preferred. The sum (p + q) of p and q is preferably p + q = 100, that is, 100% by mass.

Formula (I-1-2)

The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
These surfactants can be used individually by 1 type or in mixture of 2 or more types.
When the photosensitive resin composition of the present invention contains a surfactant, the content of the surfactant is preferably 10 parts by mass or less with respect to 100 parts by mass of the total solid components in the photosensitive resin composition. 0.001 to 10 parts by mass is more preferable, and 0.01 to 3 parts by mass is even more preferable. Surfactant may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of surfactant, the total amount becomes the said range.

<< Acid Proliferator >>
In the photosensitive resin composition of the present invention, an acid proliferating agent can be used for the purpose of improving sensitivity.
The acid proliferating agent that can be used in the present invention is a compound that can further generate an acid by an acid-catalyzed reaction to increase the acid concentration in the reaction system, and is a compound that exists stably in the absence of an acid. is there.
Specific examples of such an acid proliferating agent include the acid proliferating agents described in paragraph numbers 0226 to 0228 of JP2011-221494A, the contents of which are incorporated herein.

When the composition of the present invention contains an acid proliferating agent, the content of the acid proliferating agent in the photosensitive composition should be 10 to 1,000 parts by mass with respect to 100 parts by mass of the photoacid generator. From the viewpoint of dissolution contrast between the exposed part and the unexposed part, it is preferably 20 to 500 parts by mass. The acid proliferating agent may be used alone or in combination of two or more. When two or more kinds of acid proliferating agents are used, the total amount is within the above range.

<< Development accelerator >>
The photosensitive resin composition of the present invention can contain a development accelerator.
As the development accelerator, those described in paragraphs 0171 to 0172 of JP2012-042837A can be referred to, and the contents thereof are incorporated in the present specification.
A development accelerator may be used individually by 1 type, and can also use 2 or more types together.
When the photosensitive resin composition of the present invention contains a development accelerator, the content of the development accelerator is 0 with respect to 100 parts by mass of the total solid content of the photosensitive resin composition from the viewpoint of sensitivity and residual film ratio. Is preferably 30 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and most preferably 0.5 to 10 parts by mass. When two or more types of development accelerators are used, the total amount is within the above range.

<< Antioxidant >>
The photosensitive resin composition of the present invention may contain an antioxidant. As an antioxidant, a well-known antioxidant can be contained. By containing the antioxidant, there is an advantage that coloring of the cured film can be prevented, or the film thickness reduction due to decomposition by light or heat can be reduced, and the heat-resistant transparency is excellent.
Examples of the antioxidant include phosphorus antioxidants, amides, hydrazides, sulfur antioxidants, phenolic antioxidants, ascorbic acids, zinc sulfate, saccharides, nitrites, sulfites, thiosulfates, Examples include hydroxylamine derivatives. Among these, a phenolic antioxidant, a phosphorus antioxidant, and a sulfur antioxidant are preferable, and a phenolic antioxidant is more preferable from the viewpoints of coloring the cured film by light and heat and reducing the film thickness. These may be used individually by 1 type and may mix 2 or more types. When two or more kinds are used in combination, there is no particular limitation, but from the viewpoint of coloring the cured film by light or heat and reducing the film thickness, the combined use of a phenol-based antioxidant and a sulfur-based antioxidant is preferable.
Preferred commercial products include ADK STAB AO-15, ADK STAB AO-18, ADK STAB AO-20, ADK STAB AO-23, ADK STAB AO-30, ADK STAB AO-37, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-51, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-330, ADK STAB AO-412S, ADK STAB AO-503, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-8W, ADK STAB PEP-24G, ADK STAB PEP-36, Examples include ADK STAB PEP-36Z and ADK STAB HP-10 (above, manufactured by ADEKA Corporation).
When the photosensitive resin composition of the present invention has an antioxidant, the content of the antioxidant is 0.1 to 10 parts by mass with respect to 100 parts by mass of the total solid components of the photosensitive resin composition. The amount is preferably 0.2 to 5 parts by mass, and particularly preferably 0.5 to 4 parts by mass. When using 2 or more types of antioxidant, the total amount becomes the said range.
In addition, as other additives, thermal radical generators described in paragraphs 0120 to 0121 of JP2012-8223A, nitrogen-containing compounds and thermal acid generators described in WO2011-133604A1, can be used. Is incorporated herein by reference.

<Method for preparing photosensitive resin composition>
Each component is mixed in a predetermined ratio and by any method, stirred and dissolved to prepare a photosensitive resin composition. For example, a resin composition can be prepared by preparing a solution in which components are dissolved in a solvent in advance and then mixing them in a predetermined ratio. The composition solution prepared as described above can be used after being filtered using a filter having a pore size of 0.2 μm or the like.

The solid content concentration of the composition of the present invention at 25 ° C. is preferably 1 to 60% by mass, more preferably 3 to 40% by mass, further preferably 5 to 30% by mass, and particularly preferably 5 to 17% by mass.
The viscosity at 25 ° C. of the composition of the present invention is preferably 1 to 100 mPa · s, more preferably 2 to 60 mPa · s, and most preferably 3 to 40 mPa · s. By setting the solid content concentration and viscosity within the above ranges, high-quality coating can be achieved. The viscosity can be measured, for example, using a viscometer RE85L (rotor: 1 ° 34 ′ × R24 measurement range 0.6 to 1200 mPa · s) manufactured by Toki Sangyo Co., Ltd., with the temperature adjusted to 25 ° C. .

(Method for producing cured film)
The method for producing a cured film of the present invention preferably includes the following steps (1) to (5).
(1) A step of applying the photosensitive resin composition of the present invention to at least one surface of a substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition;
(3) A step of exposing the photosensitive resin composition from which the solvent has been removed with actinic rays,
(4) a step of developing the exposed photosensitive resin composition with an aqueous developer, and (5) a post-baking step of thermosetting the developed photosensitive resin composition,
The manufacturing method of the cured film containing this.
Each step will be described below in order.

In the application step (1), the photosensitive resin composition of the present invention is preferably applied onto a substrate to form a wet film containing a solvent. Before applying the photosensitive resin resin composition to the substrate, it is preferable to perform substrate cleaning such as alkali cleaning or plasma cleaning, and it is more preferable to treat the substrate surface with hexamethyldisilazane after substrate cleaning. By performing this treatment, the adhesiveness of the photosensitive resin composition to the substrate tends to be improved. The method for treating the substrate surface with hexamethyldisilazane is not particularly limited, and examples thereof include a method in which the substrate is exposed to hexamethyldisilazane vapor.
Examples of the substrate include inorganic substrates, resins, and resin composite materials.
Examples of the inorganic substrate include glass, quartz, silicone, silicon nitride, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited on such a substrate.
The resins include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, poly Fluorine resins such as benzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, aromatic Made of synthetic resin such as aromatic ether, maleimide-olefin, cellulose, episulfide compound And the like.
These substrates are rarely used in the above-described form, and usually a multilayer laminated structure such as a TFT element is formed depending on the form of the final product.
The photosensitive resin composition can be applied onto the substrate by a known coating method such as slit coating, spin coating, or inkjet coating. Of these, slit coating is preferred. Since the slit coat can be efficiently applied to a large substrate, the productivity is high. And large-sized substrate refers to a substrate area of 300000Mm ² more 12000000Mm ² or less. When applying the slit, the relative movement speed of the substrate and the slit die is preferably 20 to 180 mm / sec. It is also possible to combine spin coating after slit coating.
The coating film thickness (dry film thickness) is not particularly limited, and can be applied with a film thickness according to the application, but is usually used in the range of 0.5 to 10 μm.

(2) In the solvent removal step (2), the solvent is removed from the applied film by vacuum (vacuum) and / or heating to form a dry coating film on the substrate. The heating conditions for the solvent removal step are preferably 70 to 130 ° C. and about 30 to 300 seconds. When the temperature and time are in the above ranges, the pattern adhesiveness is better and the residue tends to be further reduced.

In the exposure step (3), the substrate provided with the coating film is irradiated with an actinic ray having a predetermined pattern. In this step, the photoacid generator is decomposed to generate an acid. Due to the catalytic action of the generated acid, the acid-decomposable group contained in the coating film component is hydrolyzed to generate a carboxyl group or a phenolic hydroxyl group.
As an exposure light source using actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, and the like can be used, and i-line (365 nm), h-line (405 nm), Actinic rays having a wavelength of 300 nm to 450 nm, such as 436 nm), can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed. The exposure amount is preferably 1 to 500 mJ / cm ² .
As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, a lens scanner, laser exposure, and immersion exposure can be used.

Also, exposure using so-called super-resolution technology can be performed. Examples of the super-resolution technique include multiple exposure in which exposure is performed a plurality of times, a method using a phase shift mask, and an annular illumination method. By using these super-resolution techniques, it is possible to form a higher definition pattern, which is preferable.

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 in order to accelerate the hydrolysis reaction. PEB can promote the formation of a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group. The temperature for performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C. or higher and 100 ° C. or lower.

In the developing step (4), a copolymer having a liberated carboxyl group or phenolic hydroxyl group is developed using an alkaline developer. A positive image is formed by removing an exposed area containing a resin composition having a carboxyl group or a phenolic hydroxyl group that is easily dissolved in an alkaline developer.
The developer used in the development step preferably contains an aqueous solution of a basic compound. Examples of basic compounds include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; sodium bicarbonate, potassium bicarbonate Alkali metal bicarbonates such as: tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, diethyldimethylammonium hydroxide, and other tetraalkylammonium hydroxides: Alkyl) trialkylammonium hydroxides; silicates such as sodium silicate and sodium metasilicate; ethylamine, propylamine, diethylamine, triethylammonium Alkylamines such as diamine; alcohol amines such as dimethylethanolamine and triethanolamine; 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0 ] Cycloaliphatic amines such as 5-nonene can be used.
Of these, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide) are preferable.
An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
The pH of the developer is preferably 10.0 to 14.0.
The development time is preferably 30 to 500 seconds, and the development method may be any of a liquid piling method (paddle method), a shower method, a dipping method, and the like.
A rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like. A known method can be used as the rinsing method. For example, shower rinse and dip rinse can be mentioned.

In the post-baking step of (5), the obtained positive image is heated to thermally decompose the acid-decomposable group to generate a carboxyl group or a phenolic hydroxyl group, to crosslink the crosslinkable group, the crosslinking agent, and the like. A cured film can be formed by promoting cyclized PBO. This heating is performed using a heating device such as a hot plate or an oven at a predetermined temperature, for example, 180 to 400 ° C. for a predetermined time, for example, 5 to 120 minutes on a hot plate, 30 to 360 minutes for an oven. It is preferable to By proceeding with the crosslinking reaction and the cyclization reaction in this way, a protective film and an interlayer insulating film that are superior in heat resistance, hardness and the like can be formed. In addition, when the heat treatment is performed in a nitrogen atmosphere, the transparency can be further improved.
Prior to post-baking, post-baking can be performed after baking at a relatively low temperature (addition of a middle baking process). When middle baking is performed, it is preferable to post-bake at a high temperature of 200 ° C. or higher after heating at 90 to 150 ° C. for 1 to 60 minutes. Moreover, middle baking and post-baking can be heated in three or more stages. The taper angle of the pattern can be adjusted by devising such middle baking and post baking. These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.
Prior to post-baking, the entire surface of the patterned substrate was re-exposed with actinic rays (post-exposure), and then post-baked to generate an acid from the photoacid generator present in the unexposed portion, thereby performing a crosslinking step. It can function as a catalyst to promote, and can accelerate the curing reaction of the film. The preferred exposure amount in the case of including a post-exposure step, preferably 100 ~ 3,000mJ / cm ^2, particularly preferably 100 ~ 500mJ / cm ^2.

Furthermore, the cured film obtained from the photosensitive resin composition of the present invention can also be used as an etching resist. In the case where a cured film obtained by thermal curing in a post-baking process is used as a dry etching resist, dry etching processes such as ashing, plasma etching, and ozone etching can be performed as the etching process.

(Cured film)
The cured film of the present invention is a cured film obtained by curing the above-described photosensitive resin composition.
The cured film of the present invention can be suitably used as an interlayer insulating film. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the formation method of the cured film of this invention mentioned above.
With the photosensitive resin composition of the present invention, an interlayer insulating film having excellent insulation and high transparency even when baked at high temperatures can be obtained. Since the interlayer insulating film using the photosensitive resin composition of the present invention has high transparency and excellent cured film properties, it is useful for liquid crystal display devices and organic EL display devices.

The transmittance of the cured film of the present invention at a wavelength of 400 nm is preferably 85 to 100%, more preferably 90 to 100%, and still more preferably 95 to 100%. The transmittance at a wavelength of 400 nm can be measured, for example, with a spectrophotometer (U-3000: manufactured by Hitachi, Ltd.).

(Liquid crystal display device)
The liquid crystal display device of the present invention comprises the cured film of the present invention.
The liquid crystal display device of the present invention is not particularly limited except that it has a protective film, a planarizing film, and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and is known in various structures. The liquid crystal display device can be mentioned.
For example, specific examples of TFT (Thin-Film Transistor) included in the liquid crystal display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
In addition, as a liquid crystal driving method that can be adopted by the liquid crystal display device of the present invention, a TN (Twisted Nematic) method, a VA (Virtual Alignment) method, an IPS (In-Place-Switching) method, an FFS (Frings Field Switching) method, an OCB (Optical) method. Compensated Bend) method and the like.
In the panel configuration, the cured film of the present invention can also be used in a COA (Color Filter on Array) type liquid crystal display device. For example, the organic insulating film (115) of JP-A-2005-284291, -346054 can be used as the organic insulating film (212). Specific examples of the alignment method of the liquid crystal alignment film that the liquid crystal display device of the present invention can take include a rubbing alignment method and a photo alignment method. Further, the polymer orientation may be supported by a PSA (Polymer Sustained Alignment) technique described in JP-A Nos. 2003-149647 and 2011-257734.
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, it can be suitably used for a color filter protective film, 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, or the like.
FIG. 1 is a conceptual cross-sectional view showing an example of an active matrix liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two

glass substrates

14 and 15 having a polarizing film attached thereto. The elements of the TFT 16 corresponding to are arranged. Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.
The light source of the backlight is not particularly limited, and a known light source can be used. For example, a white LED, a multicolor LED such as blue, red, and green, a fluorescent lamp (cold cathode tube), and an organic EL can be used.
Further, the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type. Further, it can be made flexible, and used as the second interlayer insulating film (48) described in Japanese Patent Application Laid-Open No. 2011-145686 and the interlayer insulating film (520) described in Japanese Patent Application Laid-Open No. 2009-258758. Can do.
Further, even in a static drive type liquid crystal display device, a pattern with high designability can be displayed by applying the present invention. As an example, the present invention can be applied as an insulating film of a polymer network type liquid crystal as described in JP-A-2001-125086.

(Organic EL display device)
The organic EL display device of the present invention includes the cured film of the present invention.
The organic EL display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and various known structures having various structures. Examples thereof include an organic EL display device and a liquid crystal display device.
For example, specific examples of TFT (Thin-Film Transistor) included in the organic EL display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
FIG. 2 is a conceptual diagram of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
A bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si 3 N 4 is formed so as to cover the TFT 1. A contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. The wiring 2 is for connecting 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. 2, 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 second 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.

Since the photosensitive resin composition of the present invention is excellent in curability and cured film characteristics, a resist pattern formed using the photosensitive resin composition of the present invention as a structural member of a MEMS device can be used as a partition wall or mechanically driven. Used as part of the part. Examples of such MEMS devices include parts such as SAW filters, BAW filters, gyro sensors, display micro shutters, image sensors, electronic paper, inkjet heads, biochips, sealants, and the like. More specific examples are exemplified in JP-T-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.

Since the photosensitive resin composition of the present invention is excellent in flatness and transparency, for example, the bank layer (16) and the planarization film (57) described in FIG. 2 of JP-A-2011-107476, JP-A-2010- The partition wall (12) and the planarization film (102) described in FIG. 4 (a) of Japanese Patent No. 9793, the bank layer (221) and the third interlayer insulating film (216b) described in FIG. 10 of Japanese Patent Application Laid-Open No. 2010-27591. ), The second interlayer insulating film (125) and the third interlayer insulating film (126) described in FIG. 4A of JP-A-2009-128577, and the flatness described in FIG. 3 of JP-A-2010-182638. It can also be used to form a chemical film (12) and a pixel isolation insulating film (14). In addition, spacers for maintaining the thickness of the liquid crystal layer in liquid crystal display devices, imaging optical systems for on-chip color filters such as facsimiles, electronic copying machines, solid-state image sensors, and micro lenses for optical fiber connectors are also used. It can be used suitably.

The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.

Synthesis Example A-1: Synthesis of Resin A-1 In a three-necked flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube, 293 g (0.8 mol) of hexafluoro-2,2-bis (3-amino- 4-Hydroxyphenyl) propane (Nippon Kayaku Co., Ltd.), 158.2 g (2.0 mol) of pyridine and 1.2 kg of N-methyl-2-pyrrolidone (NMP) were added. This was stirred at room temperature and then cooled to −25 ° C. with a dry ice / acetone bath. To this solution, while maintaining the reaction temperature at −20 ° C. to −30 ° C., 73.9 g (0.364 mol) of isophthaloyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), 107.4 g (0.364 mol) of Mixing of 4,4′-oxybisbenzoyl chloride (obtained by converting 4,4′-oxybisbenzoic acid (manufactured by Aldrich) to acid chloride by a conventional method) and 700 g of NMP (1-methyl-2-pyrrolidone) The solution was added dropwise. After the addition was complete, the resulting mixture was stirred at room temperature for 16 hours.
Next, the reaction solution was cooled to −5 ° C. or lower with an ice / methanol bath, and 17.0 g (0.217 mol) of acetyl chloride was added dropwise while maintaining the reaction temperature at −0 ° C. or lower. After completion of the dropwise addition, the mixture was further stirred for 16 hours.
The reaction solution is diluted with 2 L of acetone, poured into 20 L of deionized water with vigorous stirring, the precipitated white powder is recovered by filtration, and deionized water and a water / methanol (50/50 mass ratio) mixture. Washed. The polymer was dried under vacuum at 40 ° C. for 24 hours to obtain Resin A-1.

Synthesis Examples A-2 to A-14: Synthesis of Resins A-2 to 14 Resins A-2 to A-14 were synthesized in the same manner as Resin A-1. The apparatus used in these syntheses, the amount of pyridine, the amount of solvent, the method for taking out the polymer, etc. are all the same apparatus and conditions as in Synthesis Example A-1. In all cases, all of the acid dichloride was mixed and placed on the dropping liquid side. The amount of monomer used and the molecular weight of the resulting polymer are shown in the table below.

In the table, bis-APAF represents hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane, ODC represents 4,4′-oxybisbenzoyl chloride, and IC represents isophthalic acid chloride. Seb-C represents sebacic acid dichloride (manufactured by ALDRICH), Adi-C represents adipic acid dichloride (manufactured by ALDRICH), and CHD-C represents 1,4-cyclohexanedicarboxylic acid dichloride (manufactured by Tokyo Chemical Industry 1, 4-cyclohexanedicarboxylic acid obtained by acidification by a conventional method), and AcCl represents acetyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.).
A molecular weight (GPC) represents the numerical value x1000 in a table | surface. The molecular weight is an Mw value measured by gel permeation chromatography in terms of polystyrene, and represents a numerical value x 1000 in the table (hereinafter the same as the molecular weight of the resin).

Synthesis Example A-101a: Synthesis of Resin A-101a In a three-necked flask, 150 g of the polymer (A-1) obtained in Synthesis Example A-1 and propylene glycol-1-monomethyl ether-2-acetate (PGMEA) 2.4 L was added, and the contents were concentrated to 1.35 kg. Using a thermometer, a stirrer, and a nitrogen inlet tube, 17.4 g (2.25 mmol) of camphorsulfonic acid (3 mass% PGMEA solution) and 12.99 g (0.169 mol) of 2,3-dihydrofuran were added, Stir at room temperature for 4 hours. Next, 5.68 g (5.62 mmol) of triethylamine (10 mass% PGMEA solution) was added to stop the reaction.
The reaction solution was diluted with 1.5 L of acetone, poured into 20 L of hexane that was vigorously stirred, and the precipitated white powder was collected by filtration. The polymer was dried under vacuum at 40 ° C. for 4 hours, 120 g of this polymer was dissolved in 2 L acetone, poured into 10 L of vigorously stirred water, and deionized water and water / methanol (50/50 mass ratio) ) Washed with the mixture. The polymer was dried under vacuum at 40 ° C. for 24 hours to obtain Resin A-101a.

Synthesis Examples A-101b to A-114c: Synthesis of Resins A-101b to A-114c Resins A-101b to A-114c were synthesized in the same manner as Resin A-101a. The equipment used in these syntheses, the amount of solvent, the method of taking out the polymer, etc. are all the same equipment and conditions as in Synthesis Example A-101a. The amount of monomer used and the molecular weight of the resulting polymer are shown in the table below.

In the table, DHF represents 2,3-dihydrofuran, 3% CSA represents camphorsulfonic acid (3% by mass PGMEA solution), and 10% NEt ₃ represents triethylamine (10% by mass PGMEA solution).

Synthesis Example A-201a: Synthesis of Resin A-201a Synthesis Example A-101a except that 12.99 g of 2,3-dihydrofuran in Synthesis Example A-101a was changed to 12.19 g (0.169 mol) of ethyl vinyl ether. The reaction, polymer reprecipitation, and drying were performed in the same manner as described above. The polymer obtained at this time had an OH group protection rate of 30% and a molecular weight of 6,700.

Synthesis Example A-301a: Synthesis of Resin A-301a Synthesis Example A-101a except that 12.99 g of 2,3-dihydrofuran in Synthesis Example A-101a was changed to 21.3 g (0.169 mol) of cyclohexyl vinyl ether. The reaction, polymer reprecipitation, and drying were performed in the same manner as described above. The polymer obtained at this time had an OH group protection rate of 30% and a molecular weight of 6,800.

<Preparation of photosensitive resin composition>
Each component was weighed so as to have a solid content ratio described in the following table, and filtered through a polytetrafluoroethylene filter having a diameter of 0.2 μm to obtain photosensitive resin compositions of various examples and comparative examples. The numerical value which does not attach | subject especially the unit in a table | surface is a mass part.

The details of the abbreviations indicating the compounds used in Examples and Comparative Examples are as follows.
B. Photoacid generator B-1: structure shown below (PAG-103, manufactured by BASF), pKa of generated acid is 2 or less

B-2: Structure shown below (PAI-101, manufactured by Midori Chemical Co., Ltd.), Me represents a methyl group. The pKa of the acid generated is 2 or less

B-3: Structure shown below (synthesis example will be described later). The pKa of the acid generated is 2 or less

B-4: Structure shown below (synthesis example will be described later). Ts represents a tosyl group. The pKa of the acid generated is 2 or less

B-5: Structure shown below (synthesis example will be described later). The pKa of the acid generated is 2 or less

B-6: Structure shown below (synthesized as described in paragraph 0249 of WO11 / 087011). The pKa of the acid generated is 2 or less

B-7: Structure shown below (GSID-26-1, triarylsulfonium salt, manufactured by BASF). The pKa of the acid generated is 2 or less

NQD: Structure shown below (synthesized according to Example 2 of JP 2000-39714 A). The acid generated has a pKa greater than 4.

C. Solvent GBL: Gamma butyrolactone (Mitsubishi Chemical Corporation)
PGMEA: Propylene glycol monomethyl ether acetate (Showa Denko)

D. Crosslinking agent D-1: Structure shown below (JER828, manufactured by Mitsubishi Chemical Holdings Corporation)

D-2: Structure shown below (JER157S65, manufactured by Mitsubishi Chemical Holdings Corporation)

D-3: Structure shown below (Denacol EX-321L, manufactured by Nagase Chemtech)

D-4: Structure shown below (Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd.)

D-5: Structure shown below

D-6: Structure shown below (Nikarak MW-100LM, manufactured by Sanwa Chemical Co., Ltd.)

D-7: Structure shown below (Nicalak MW-270, manufactured by Sanwa Chemical Co., Ltd.)

D-8: Structure shown below (Duranate 17B-60P, manufactured by Asahi Kasei Chemicals)

D-9: Structure shown below (Takenate B870N, manufactured by Mitsui Chemicals)

D-10: Structure shown below (Compound O-1 described in JP-A-2008-224970)

D-11: Structure shown below (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)

Adhesion improver E-1: γ-glycidoxypropyltrimethoxysilane E-2: γ-glycidoxypropyltriethoxysilane

Basic compound H-1: Compound having the following structure

H-2: 1,8-diazabicyclo [5.4.0] -7-undecene

(Surfactant)
W-1: Compound having the following structure

W-2: Mega Fuck F-554 (manufactured by DIC)

(Sensitizer)
DBA: 9,10-butoxyanthracene

<< Synthesis of benzoxazole precursor polymer (PBO-1) (polymer of Example 2 of JP 2000-39714 A) >>
Under a dry nitrogen stream, 11.0 g of BAHF (0.03 mol), 4.0 g (0.02 mol) of 4,4′-diaminodiphenyl ether, 30 g of acetone and 58 g of propylene oxide (1.0 mol) in a four-necked flask. ) And cooled to -10 ° C. A solution prepared by dissolving 21.1 g (0.1 mol) of trimellitic anhydride chloride in 40 g of acetone was gradually added dropwise so that the temperature of the reaction solution did not exceed 0 ° C. After completion of the dropwise addition, the reaction was carried out at −5 ° C. or lower for 1 hour, and 9.0 g (0.045 mol) of 4,4′-diaminodiphenyl ether and 1,3-bis (3-aminopropyl) tetramethyldisiloxane A solution prepared by dissolving 24 g (0.005 mol) in 80 g of N-methylpyrrolidone (NMP) was added and reacted at 0 ° C. for 1 hour and then at 30 ° C. for 4 hours.
After completion of the reaction, the solution was poured into 10 L of water to form a polyhydroxyamic acid precipitate. The precipitate was collected by filtration, washed with water and dried in a vacuum dryer at 50 ° C. for 20 hours to obtain a comparative polybenzoxazole precursor PBO-1 (PBO precursor having no crosslinking group). .

<< Synthesis of acrylic polymer >>
A mixed solution of 66 parts of 1-ethoxyethyl methacrylate, 50 parts of GMA, 20 parts of 2-hydroxyethyl methacrylate and 132.5 parts of PGMEA was heated to 70 ° C. in a nitrogen stream. While stirring this mixed solution, it was added dropwise over 2.5 hours to a mixed solution of radical polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd., 12.4 parts) and 100.0 parts of PGMEA. After completion of the dropping, an acrylic polymer was synthesized by reacting at 70 ° C. for 4 hours. Reprecipitation was performed according to a conventional method to obtain a powder.

<< Synthesis of B-3 >>
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, and the crystals were diluted with diisopropyl ether (10 mL). The slurry was reslurried, filtered and dried to obtain a ketone compound (6.5 g).
Acetic acid (7.3 g) and a 50 mass% aqueous hydroxylamine 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-3 (2.3 g).
The ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-3 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 B-4 >>
After 4.0 g of 1-amino-2-naphthol hydrochloride (manufactured by Tokyo Kasei) is suspended in 16 g of N-methylpyrrolidone (Wako Pure Chemical Industries), 3.4 g of sodium hydrogen carbonate (manufactured by Wako Pure Chemical Industries) is added, 4.9 g of methyl 4,4-dimethyl-3-oxovalerate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise and heated at 120 ° C. for 2 hours in a nitrogen atmosphere. After allowing to cool, water and ethyl acetate were added to the reaction mixture and the phases were separated, and the organic phase was dried over magnesium sulfate, filtered and concentrated to obtain crude B-1-2A. Crude B-1-2A was purified by silica gel column chromatography to obtain 1.7 g of intermediate B-1-2A.
B-1-2A (1.7 g) and p-xylene (6 mL) were mixed, 0.23 g of p-toluenesulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added and heated at 140 ° C. for 2 hours. . After allowing to cool, water and ethyl acetate were added to the reaction mixture and the phases were separated. The organic phase was dried over magnesium sulfate, filtered and concentrated to give crude B-1-2B.
THF (2 mL) and the entire amount of crude B-1-2B were mixed, and 2 mL hydrochloric acid / THF solution 6.0 mL was added dropwise under ice cooling, and then isopentyl nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) (0.84 g) was added dropwise. The mixture was stirred for 2 hours after warming. Water and ethyl acetate were added to the obtained reaction mixture for liquid separation, and the organic layer was washed with water, dried over magnesium sulfate, filtered and concentrated to obtain Intermediate Intermediate B-1-2C.
The whole amount of intermediate crude B-1-2C was mixed with acetone (10 mL), and triethylamine (Wako Pure Chemical Industries, Ltd.) (1.2 g) and p-toluenesulfonyl chloride (Tokyo Kasei Co., Ltd.) (1.4 g) were cooled with ice. Then, the mixture was warmed to room temperature and stirred for 1 hour. Water and ethyl acetate were added to the obtained reaction mixture to separate it, and the organic phase was dried over magnesium sulfate, filtered and concentrated to obtain crude B-4. Crude B-4 was reslurried with cold methanol, filtered and dried to obtain B-4 (1.2 g).
The ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-4 is δ = 8.5-8.4 (m, 1H), 8.0-7.9 (m, 4H), 7.7. -7.6 (m, 2H), 7.6-7.5 (m, 1H), 7.4 (d. 2H), 2.4 (s, 3H), 1.4 (s, 9H) there were.

<< Synthesis of B-5 >>
A separable flask equipped with a stirrer and a thermometer was charged with 33.6 g of N-hydroxynaphthalimide sodium salt, 0.72 g of 4-dimethylaminopyridine and 300 ml of tetrahydrofuran, and the mixture was stirred and dissolved at room temperature of 25 ° C. Next, (+) 10-camphorsulfonyl chloride (42 g) was added and stirred for 3 hours, and then 15 g of triethylamine was added and stirred at room temperature for 10 hours. Subsequently, the reaction solution was put into 300 ml of distilled water, and the deposited precipitate was separated by filtration. This precipitation was repeated several times with acetone and hexane to obtain N-camphorsulfonyloxy-1,8-naphthalimide (12 g).

<Evaluation of viscosity>
Using the prepared composition, a viscometer RE85L (rotor: 1 ° 34 ′ × R24 measurement range 0.6 to 1200 mPa · s) manufactured by Toki Sangyo Co., Ltd. was used, and the viscosity was measured with the temperature adjusted to 25 ° C.
A: Less than 2 mPa · s B: 2 mPa · s or more and less than 15 mPa · s C: 15 mPa · s or more and less than 30 mPa · s D: 30 mPa · s or more

<Reactivity evaluation of crosslinking agent>
2 parts by mass of the crosslinking agent used in each Example / Comparative Example and 2 parts by mass of Marcalinker M (manufactured by Maruzen Petroleum, number average molecular weight 1500) were dissolved in 100 parts by mass of THF.

Confirmation before heating When this solution was subjected to GPC analysis, it was confirmed that two peaks (crosslinker peak and phenol peak) were observed. In addition, the retention time of Marcalinker was recorded.

Evaluation of reactivity The solution was slit-coated on a glass substrate, the solvent was volatilized by vacuum drying, and then prebaked on a hot plate at 90 ° C. for 120 seconds to form a resin layer having a thickness of 2.0 μm. This glass substrate was heated in an oven at 200 ° C. for 30 minutes. 0.1 mass parts of the heated film was scraped off, 10 mass parts of PGMEA was added, and GPC analysis was performed in the same manner.
The case where the polymer peak detected by this analysis deviates from the retention time of the first markalinker M is A, and the case where it does not deviate is B.
In the case of A, the benzene ring or phenolic hydroxyl group of Marca Linker M and the crosslinking agent reacted. As a result, it means that the polymer has a higher molecular weight.
In the case of B, it means that the benzene ring or phenolic hydroxyl group of Marcalinker M did not react with the crosslinking agent.

<Evaluation of sensitivity>
A glass substrate (OA-10 (manufactured by Nippon Electric Glass Co., Ltd.)) was exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and each photosensitive resin composition was slit coated, and then the solvent was volatilized by vacuum drying. Then, it prebaked on a 120 degreeC / 120 second hotplate, and formed the photosensitive resin composition layer with a film thickness of 2.0 micrometers.
Next, the obtained photosensitive resin composition layer was exposed through a predetermined mask using MPA 5500CF manufactured by Canon Inc. After the exposure, the photosensitive resin composition layer heated on an 80 ° C. hot plate for 60 seconds was developed with an alkali developer (2.38% tetramethylammonium hydroxide aqueous solution) at 23 ° C./80 seconds, and then ultrapure. Rinse with water for 20 seconds. The optimum i-line exposure (Eopt) when resolving a 5 μm hole by these operations was taken as the sensitivity. A and B are practical levels.
A: Less than 100 mJ / cm ² B: 100 mJ / cm ² or more, less than 200 mJ / cm ² C: 200 mJ / cm ² or more, less than 400 mJ / cm ² D: 400 mJ / cm ² or more

The composition of Example 104 was evaluated in the same manner as the above sensitivity except that heating was not performed for 60 seconds at 80 ° C. after the pattern exposure.

<Evaluation of transmittance>
A glass substrate (OA-10 (manufactured by Nippon Electric Glass Co., Ltd.)) was exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and each photosensitive resin composition was slit coated, and then the solvent was volatilized by vacuum drying. Then, it prebaked on a 120 degreeC / 120 second hotplate, and formed the photosensitive resin composition layer with a film thickness of 2.0 micrometers. Subsequently, exposure was performed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm ² (energy intensity: 20 mW / cm ² ), and the substrate was heated in an oven at 300 ° C./60 minutes in a nitrogen atmosphere. The transmittance of the cured film was measured at a wavelength of 400 nm using a spectrophotometer (U-3000: manufactured by Hitachi, Ltd.). The unit is expressed in%. A, B and C are practical levels.
A: 95% or more B: 90% or more and less than 95% C: 85% or more and less than 90% D: Less than 85%

<Heat resistance>
The glass substrate was exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds. Each photosensitive resin composition was spin-coated and then pre-baked on a hot plate at 120 ° C. for 120 seconds to volatilize the solvent to form a photosensitive resin composition layer having a thickness of 2.0 μm. Subsequently, exposure is performed using an ultra-high pressure mercury lamp so that the integrated irradiation amount is 300 mJ / cm ² (energy intensity: 20 mW / cm ² ), and then the substrate is heated in an oven at 300 ° C./60 minutes in a nitrogen atmosphere. Thus, a cured film was obtained.
Next, the cured film was scraped off, heated from room temperature to 300 ° C. at 20 ° C./min, and held at 300 ° C. for 60 minutes, and the thermal weight loss was evaluated. Evaluation was carried out in a nitrogen atmosphere. The results are shown in the following table. The smaller the numerical value, the higher the heat resistance, and A or B is a practical level.
A: Weight reduction rate of less than 3% B: Weight reduction rate of 3% or more and less than 5% C: Weight reduction rate of 5% or more and less than 10% D: Weight reduction rate of 10% or more

<Curing film adhesion>
The glass substrate on which the Mo (molybdenum) thin film was formed was exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds. Each photosensitive resin composition was spin-coated and then pre-baked on a hot plate at 120 ° C. for 120 seconds to volatilize the solvent to form a photosensitive resin composition layer having a thickness of 2.0 μm. Subsequently, exposure is performed using an ultra-high pressure mercury lamp so that the integrated irradiation amount is 300 mJ / cm ² (energy intensity: 20 mW / cm ² ), and then the substrate is heated in an oven at 300 ° C./60 minutes in a nitrogen atmosphere. Thus, a cured film was obtained. The substrate on which this cured film was formed was immersed in N-methyl-2-pyrrolidone (NMP) whose temperature was controlled at 80 ° C. for 30 minutes.
After immersion, the cured film was cut using a cutter at intervals of 1 mm vertically and horizontally, and a tape peeling test (100 mask loss cut method: conforming to JIS 5600) was performed using a scotch tape. The adhesion between the cured film and the substrate was evaluated from the area of the cured film transferred to the back surface of the tape. The results are shown in the following table. The smaller the numerical value, the higher the adhesion to the base substrate, and A or B is a practical level.
A: The transferred area is less than 10% B: The transferred area is 10% or more and less than 50% C: The transferred area is 50% or more

From the above table, it was found that Examples 1 to 109 using the photosensitive resin composition of the present invention were all good in reactivity, sensitivity, transmittance, heat resistance and adhesion. On the other hand, Comparative Examples 1 to 6 that do not satisfy the requirements of the present invention were found to be inferior to Examples in terms of reactivity, sensitivity, transmittance, heat resistance, and adhesion. Specifically, it was found that (D) Comparative Example 1 which does not contain a crosslinking agent is extremely inferior in adhesion. (D) It was found that Comparative Examples 2 to 3 containing a crosslinking agent other than the crosslinking agent were significantly inferior to the examples in terms of reactivity, transmittance, heat resistance and adhesion. It turned out that the comparative example 4 which does not contain a photo-acid generator is remarkably inferior to an Example in a sensitivity and adhesiveness. It was found that Comparative Example 5 using a photoacid generator having a pKa of the acid generated exceeding 4 has significantly lower sensitivity, transmittance, heat resistance, and adhesion than the examples. Moreover, it turned out that the comparative example 6 which does not contain a polybenzoxazole precursor is remarkably inferior to the Example in the transmittance | permeability and heat resistance.

(355nm laser exposure)
Furthermore, the photosensitive resin compositions of Examples 1 to 109 were subjected to pattern formation in the same manner as the sensitivity evaluation except that the exposure was changed as follows in the sensitivity evaluation. That is, a predetermined photomask was set through a 150 μm interval from the coating film, and a laser having a wavelength of 355 nm was irradiated. The laser device used was “AEGIS” manufactured by Buoy Technology Co., Ltd. (wavelength 355 nm, pulse width 6 nsec).
In any of the examples, it was found that the pattern could be formed in the same manner as MPA5500CF.

(UV-LED exposure)
Further, the photosensitive resin compositions of Examples 1 to 109 were evaluated in the same manner as the sensitivity evaluation (without PEB) except that the exposure was changed to a UV-LED light source exposure machine. Similarly, it was found that pattern formation was possible.

(Example 200)
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, after forming a contact hole in the insulating film 3, a wiring 2 (height of 1.0 μm) connected to the TFT 1 through the contact hole was formed on the insulating film 3.

Further, in order to flatten the unevenness due to the formation of the wiring 2, a planarizing film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarizing film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 2 on a substrate, pre-baking on a hot plate (90 ° C. × 2 minutes), and then applying high pressure from above the mask. A mercury lamp is used to irradiate i-line (365 nm) with an exposure amount corresponding to the sensitivity measured by sensitivity evaluation, heated on an 80 ° C. hot plate for 60 seconds, and then developed with an aqueous alkaline solution to form a pattern. A heat treatment was performed at 60 ° 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 level difference 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 flattening 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 at 50 ° C. using a resist stripper (remover 100, manufactured by AZ Electronic Materials). 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 using the photosensitive resin composition of Example 2 by the same method as described above.

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

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

(Example 201)
An organic EL display device was produced in the same manner as in Example 200 except that the photosensitive resin composition of Example 2 was changed to the photosensitive resin composition of Example 46. The obtained organic EL display device showed very good display characteristics and was found to be a highly reliable organic EL display device.

(Example 202)
An organic EL display device was produced in the same manner as in Example 200 except that the photosensitive resin composition of Example 2 was changed to the photosensitive resin composition of Example 91. The obtained organic EL display device showed good display characteristics and was found to be a highly reliable organic EL display device.

(Example 203)
An organic EL display device was produced in the same manner as in Example 200 except that the photosensitive resin composition of Example 2 was changed to the photosensitive resin composition of Example 97. The obtained organic EL display device showed good display characteristics and was found to be a highly reliable organic EL display device.

(Example 204)
In the active matrix type 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 204 was obtained.
That is, using the photosensitive resin composition of Example 2, 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 200.

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

(Example 205)
A liquid crystal display device was produced in the same manner as in Example 204 except that the photosensitive resin composition of Example 2 was changed to the photosensitive resin composition of Example 46. The obtained liquid crystal display device showed very good display characteristics and was found to be a highly reliable liquid crystal display device.

(Example 206)
A liquid crystal display device was produced in the same manner as in Example 204 except that the photosensitive resin composition of Example 2 was changed to the photosensitive resin composition of Example 91. The obtained liquid crystal display device showed good display characteristics and was found to be a highly reliable liquid crystal display device.

(Example 207)
A liquid crystal display device was produced in the same manner as in Example 204 except that the photosensitive resin composition of Example 2 was changed to the photosensitive resin composition of Example 97. The obtained liquid crystal display device showed good display characteristics and was found to be a highly reliable liquid crystal display device.

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

Claims

A polybenzoxazole precursor containing a repeating unit represented by the general formula (1);
A photoacid generator in which the generated acid has a pKa of 4 or less;
Solvent,
A photosensitive resin composition comprising: a crosslinking agent having two or more crosslinking groups that react with at least one selected from a benzene ring and a phenolic hydroxyl group;
General formula (1)

In general formula (1), X represents a tetravalent organic group, Y represents a divalent organic group; R 1 and R 2 each independently represents a hydrogen atom, an alkyl group, an acid-decomposable group, or — Represents CORc; Rc represents an alkyl group or an aryl group; at least one of R 1 and R 2 is an acid-decomposable group.
The photosensitive resin composition of Claim 1 in which the crosslinkable group which the said crosslinking agent has is selected from an epoxy group, a methylol group, an alkoxymethyl group, and a blocked isocyanate group.
The photosensitive resin composition according to claim 1 or 2, wherein a terminal of the polybenzoxazole precursor is a group represented by the general formula (1-1);
General formula (1-1)

In the general formula (1-1), Z represents a single bond, a carbon atom or a sulfur atom, R 11 represents a monovalent organic group; n represents 0 or 1, and when Z is a single bond, a represents When 0 and Z is a carbon atom, a is 1, and when Z is a sulfur atom, a is 2; when n is 0, two R 11 are bonded to each other to form a ring. May be.
The polybenzoxazole precursor includes m repeating units represented by the general formula (1-2) and n repeating units represented by the general formula (3), m represents 3 to 1000, The photosensitive resin composition according to any one of claims 1 to 3, wherein n represents 0 to 1000, and m + n is 3 to 1000;
Formula (1-2)

General formula (3)

In general formulas (1-2) and (3), Y 1 is each independently an arylene group, divalent cycloaliphatic group, divalent heterocyclic group, or these, —CH 2 —, an oxygen atom , A sulfur atom, —SO 2 —, —CO—, —NHCO—, and a group consisting of a combination with at least one of —C (CF 3 ) 2 —, wherein X 1 represents an aromatic ring, a heterocyclic ring, From an aliphatic ring or a combination thereof with at least one of —CH 2 —, oxygen atom, sulfur atom, —SO 2 —, —CO—, —NHCO—, and —C (CF 3 ) 2 —. Each of Ra and Rb independently represents a hydrogen atom, an acid-decomposable group, an alkyl group or —CORc, and at least one of Ra or Rb is an acid-decomposable group; It represents a group or an aryl group; X 2 represents an arylene group, a divalent A heterocyclic group, a divalent cyclic aliphatic group or a thereof, -CH 2 -, an oxygen atom, a sulfur atom, -SO 2 -, - CO - , - NHCO-, and -C (CF 3) 2 - Represents a group consisting of a combination with at least one of the above.
The photosensitive resin composition according to any one of claims 1 to 4, further comprising an adhesion promoter.
6. The photosensitive resin composition according to claim 1, wherein the photoacid generator is at least one selected from an oxime sulfonate photoacid generator and an imide sulfonate photoacid generator.
The photosensitive resin composition according to claim 1, wherein the acid-decomposable group is a group capable of leaving by the action of an acid, or —C (R 5 ) 2 —COOR 4 ; R 5 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 4 represents a group capable of leaving by the action of an acid.
The photosensitive resin composition according to claim 7, wherein the group capable of leaving by the action of an acid is a vinyl ether-based substituent.
The photosensitive resin composition according to claim 7, wherein the group capable of leaving by the action of an acid is an alkoxycarbonyl group, an alkoxyalkyl group, an alkylsilyl group, a group constituting an acetal, or a group constituting a ketal.
Applying the photosensitive resin composition according to any one of claims 1 to 9 to at least one surface of a substrate;
Removing the solvent from the applied photosensitive resin composition;
Exposing the photosensitive resin composition from which the solvent has been removed with actinic rays,
A step of developing the exposed photosensitive resin composition with an aqueous developer, and a post-baking step of thermosetting the developed photosensitive resin composition;
The manufacturing method of the cured film containing this.
The manufacturing method of the cured film of Claim 10 including the process of exposing the developed photosensitive resin composition to the whole surface after the said image development process and before the said post-baking process.
A cured film formed by curing the photosensitive resin composition according to any one of claims 1 to 9, or a cured film formed by the method according to claim 10 or 11.
The cured film according to claim 12, which is an interlayer insulating film.
A liquid crystal display device having the cured film according to claim 12.
An organic EL display device having the cured film according to claim 12.