JP5492760B2 - Photosensitive resin composition, method for forming cured film, cured film, organic EL display device, and liquid crystal display device - Google Patents

Description

The present invention relates to a photosensitive resin composition, a method for forming a cured film, a cured film, an organic EL display device, and a liquid crystal display device.
More specifically, a positive-type photosensitive resin composition suitable for forming a planarizing film, a protective film, and an interlayer insulating film of electronic components such as a liquid crystal display device, an organic EL display device, an integrated circuit element, and a solid-state imaging device, and the same The present invention relates to a method for forming a cured film using the above.

  Conventionally, in an electronic component such as a liquid crystal display element, an integrated circuit element, a solid-state imaging element, and an organic EL, generally, a planarizing film for imparting flatness to the surface of the electronic component, and for preventing deterioration and damage of the electronic component A photosensitive resin composition is used when forming a protective film or an interlayer insulating film for maintaining insulation. For example, a TFT type liquid crystal display element is provided with a polarizing plate on a glass substrate, a transparent conductive circuit layer such as indium tin oxide (ITO) and a thin film transistor (TFT) are formed, and covered with an interlayer insulating film to form a back plate. On the other hand, a polarizing plate is provided on a glass substrate, a pattern of a black matrix layer and a color filter layer is formed as necessary, and a transparent conductive circuit layer and an interlayer insulating film are sequentially formed as a top plate, and this back plate and The liquid crystal is manufactured by enclosing the liquid crystal between the two plates with the upper plate facing the spacer.

  As a highly sensitive photosensitive resin composition for an interlayer insulating film, for example, Patent Documents 1 and 2 include an acetal structure and a resin containing an epoxy group or a crosslinkable group, and an acid generator. A chemically amplified radiation sensitive resin composition has been proposed.

JP 2004-264623 A JP 2009-98616 A

The interlayer insulating film is a member deeply related to the reliability of the display device. As a result of investigations by the present inventors, in display devices such as organic EL display devices and liquid crystal display devices, if the electrical stability of the interlayer insulating film is insufficient, the reliability of the display device may be adversely affected. I found.
The present inventors have found that the residual DC characteristics of an interlayer insulating film can be used as an index of electrical stability, and that a display device with excellent reliability can be manufactured by using an interlayer insulating film with good residual DC characteristics. It was.
However, in the conventional photosensitive resin composition, no means for improving the residual DC characteristics of the interlayer insulating film has been known.
In addition, the photosensitive resin composition used when forming the interlayer insulating film is required to have excellent sensitivity in order to improve productivity.

The problem to be solved by the present invention is to provide a photosensitive resin composition capable of forming a cured film having excellent residual DC characteristics.
Another problem to be solved by the present invention is a method for forming a cured film using the photosensitive resin composition, a cured film formed by the forming method, and an organic EL display device including the cured film. And a liquid crystal display device.

The above-mentioned problems of the present invention have been solved by means described in the following <1>, <7>, <9>, <11> or <12>. It is described below together with <2> to <6>, <8> and <10> which are preferred embodiments.
<1> (Component A) Copolymer having at least structural units represented by formula (a1) to formula (a4), (Component B) Oxime sulfonate compound represented by formula (B), (Component C) solvent And (Component D) a photosensitive resin composition comprising a compound represented by formula (D-1) and / or a compound represented by formula (D-2),

（式中、Ｒ¹は水素原子又はメチル基を表し、Ｒ²は炭素数１〜６のアルキル基又は炭素数４〜７のシクロアルキル基を表し、Ｒ³は水素原子又はメチル基を表し、Ｒ⁴は水素原子又はメチル基を表し、Ｘは炭素数２〜１１のアルキレン基を表す。）

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 7 carbon atoms, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a hydrogen atom or a methyl group, and X represents an alkylene group having 2 to 11 carbon atoms.)

（式中、Ｒ^B1は、炭素数１〜６のアルキル基、炭素数１〜４のハロゲン化アルキル基、フェニル基、ビフェニル基、ナフチル基、２−フリル基、２−チエニル基、炭素数１〜４のアルコキシ基、フルオレニル基又はシアノ基を表し、Ｒ^B1が、フェニル基、ビフェニル基、ナフチル基又はアントラ二ル基である場合、これらの基は、ハロゲン原子、水酸基、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基及びニトロ基よりなる群から選ばれた置換基によって置換されていてもよい。Ｒ^B2は、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、炭素数１〜５のハロゲン化アルキル基、炭素数１〜５のハロゲン化アルコキシ基、Ｗで置換されていてもよいフェニル基、Ｗで置換されていてもよいナフチル基又はＷで置換されていてもよいアントラニル基、ジアルキルアミノ基、モルホリノ基又はシアノ基を表す。Ｒ^B1とＲ^B2とは互いに結合して５員環又は６員環を形成してもよく、該５員環又は６員環は１個又は２個の任意の置換基を有してもよいベンゼン環と連結していてもよい。Ｒ^B3は、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、炭素数１〜５のハロゲン化アルキル基、炭素数１〜５のハロゲン化アルコキシ基、Ｗで置換されていてもよいフェニル基、Ｗで置換されていてもよいナフチル基又はＷで置換されていてもよいアントラニル基を表す。Ｗは、ハロゲン原子、シアノ基、ニトロ基、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、炭素数１〜５のハロゲン化アルキル基又は炭素数１〜５のハロゲン化アルコキシ基を表す。）

(In the formula, R ^B1 is an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a phenyl group, a biphenyl group, a naphthyl group, a 2-furyl group, a 2-thienyl group, or a carbon number of 1; Represents an alkoxy group of ˜4, a fluorenyl group or a cyano group, and when R ^B1 is a phenyl group, a biphenyl group, a naphthyl group or an anthranyl group, these groups are a halogen atom, a hydroxyl group, and a carbon number of 1 to 4 And may be substituted with a substituent selected from the group consisting of an alkoxy group having 1 to 4 carbon atoms and a nitro group, and R ^B2 is an alkyl group having 1 to 10 carbon atoms and 1 to 10 carbon atoms. An alkoxy group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group that may be substituted with W, a naphthyl group that may be substituted with W, or W Replaced There may be an anthranyl group, a dialkylamino group, may form a 5- or 6-membered ring bonded to each other with .R ^B1 and R ^B2 representing the morpholino group or a cyano group, said 5- or 6-membered The ring may be connected to a benzene ring which may have one or two arbitrary substituents, and R ^B3 is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, A halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group optionally substituted with W, a naphthyl group optionally substituted with W, or W substituted. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a carbon number. 1 to 5 halogenated alkoxy groups Represent.)

（式（Ｄ−１）中、Ｒ^D1は水素原子又はｔ−ブトキシカルボニル基を表す。）

(In formula (D-1), R ^D1 represents a hydrogen atom or a t-butoxycarbonyl group.)

<2> The photosensitive resin composition according to <1>, which is a chemically amplified positive photosensitive resin composition,
<3> The photosensitive resin composition according to <1> or <2>, wherein R ² is an ethyl group or a cyclohexyl group.
<4> The photosensitive composition according to any one of <1> to <3>, wherein the oxime sulfonate compound represented by the formula (B) is an oxime sulfonate compound represented by the following formula (B-1). Functional resin composition,

（式中、Ｒ^B4は水素原子又はメチル基を表し、Ｒ^B5は炭素数１〜８のアルキル基、ｐ−トルイル基、フェニル基、カンホリル基、トリフルオロメチル基又はノナフルオロブチル基を表す。）

(In the formula, R ^B4 represents a hydrogen atom or a methyl group, and R ^B5 represents an alkyl group having 1 to 8 carbon atoms, a p-toluyl group, a phenyl group, a camphoryl group, a trifluoromethyl group, or a nonafluorobutyl group. )

<5> The photosensitivity according to any one of <1> to <3>, wherein the oxime sulfonate compound represented by the formula (B) is an oxime sulfonate compound represented by the following formula (B-2). Functional resin composition,

（式中、Ｒ^B6は水素原子、メチル基又はメトキシ基を表し、Ｒ^B7は炭素数１〜８のアルキル基、ｐ−トルイル基、フェニル基、カンホリル基、トリフルオロメチル基又はノナフルオロブチル基を表す。）

(In the formula, R ^B6 represents a hydrogen atom, a methyl group or a methoxy group, and R ^B7 represents an alkyl group having 1 to 8 carbon atoms, a p-toluyl group, a phenyl group, a camphoryl group, a trifluoromethyl group or a nonafluorobutyl group. Represents.)

<6> The photosensitive resin composition according to any one of <1> to <5>, including a sensitizer.
<7> (1) Application step of applying the photosensitive resin composition according to any one of <1> to <6> on a substrate, (2) removing the solvent from the applied photosensitive resin composition A solvent removal step, (3) an exposure step of exposing the photosensitive resin composition from which the solvent has been removed with actinic rays, (4) a development 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, a method for forming a cured film,
<8> The method for forming a cured film according to <7>, including a step of exposing the entire surface of the developed photosensitive resin composition after the developing step and before the post-baking step.
<9> A cured film formed by the method according to <7> or <8>,
<10> The cured film according to <9>, which is an interlayer insulating film,
<11> An organic EL display device comprising the cured film according to <9> or <10>,
<12> A liquid crystal display device comprising the cured film according to <9> or <10>.

ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition which can form the cured film excellent in a residual DC characteristic was able to be provided.
Moreover, according to this invention, the formation method of the cured film using the said photosensitive resin composition, the cured film formed by the said formation method, the organic electroluminescent display apparatus and liquid crystal display device containing the said cured film are provided. We were able to.

It is typical sectional drawing which shows the structure of an example of the organic electroluminescence display which applied the cured film using the photosensitive resin composition of this invention as an insulating film and a planarization film | membrane. It is typical sectional drawing which shows the structure which shows an example of the liquid crystal display device to which the cured film using the photosensitive resin composition of this invention is applied.

Hereinafter, the photosensitive resin composition of the present invention will be described in detail.
In the present invention, the description of “lower limit to upper limit” representing a numerical range represents “lower limit or higher and lower limit or lower”, and the description of “upper limit to lower limit” represents “lower limit or higher and lower limit or higher”. That is, it represents a numerical range including an upper limit and a lower limit.
In the present invention, “(component A) a copolymer having at least the structural units represented by formula (a1) to formula (a4)” or the like is also simply referred to as “component A” or the like.

(Photosensitive resin composition)
The photosensitive resin composition of the present invention comprises (component A) a copolymer having at least structural units represented by formulas (a1) to (a4), and (component B) an oxime sulfonate represented by formula (B). It contains a compound, (Component C) solvent, and (Component D) a compound represented by Formula (D-1) and / or a compound represented by Formula (D-2).

（式中、Ｒ¹は水素原子又はメチル基を表し、Ｒ²は炭素数１〜６のアルキル基又は炭素数４〜７のシクロアルキル基を表し、Ｒ³は水素原子又はメチル基を表し、Ｒ⁴は水素原子又はメチル基を表し、Ｘは炭素数２〜１１のアルキレン基を表す。）

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 7 carbon atoms, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a hydrogen atom or a methyl group, and X represents an alkylene group having 2 to 11 carbon atoms.)

（式中、Ｒ^B1及びＲ^B2はそれぞれ独立に一価の有機基を表し、Ｒ^B1とＲ^B2が結合して環を形成していてもよく、Ｒ^B3は炭素数１〜８のアルキル基、ｐ−トルイル基、フェニル基、カンホリル基、トリフルオロメチル基又はノナフルオロブチル基を表す。）

(Wherein R ^B1 and R ^B2 each independently represent a monovalent organic group, R ^B1 and R ^B2 may be bonded to form a ring, and R ^B3 is an alkyl group having 1 to 8 carbon atoms. , P-toluyl group, phenyl group, camphoryl group, trifluoromethyl group or nonafluorobutyl group.)

（式（Ｄ−１）中、Ｒ^D1は水素原子又はｔ−ブトキシカルボニル基を表す。）

(In formula (D-1), R ^D1 represents a hydrogen atom or a t-butoxycarbonyl group.)

The photosensitive resin composition of the present invention is a positive photosensitive resin composition, and is preferably a chemically amplified positive photosensitive resin composition (chemically amplified positive photosensitive resin composition).
In the present specification, the post-exposure heat treatment (Post Exposure Baking) may be referred to as PEB.

Hereinafter, each component which comprises the photosensitive resin composition is demonstrated.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what has a substituent with what does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

(Component A) Copolymer having at least structural units represented by formula (a1) to formula (a4) The photosensitive resin composition of the present invention is represented by (component A) formula (a1) to formula (a4). And a copolymer having at least the structural unit.
Component A may have one type of structural unit represented by formula (a1) or two or more types. The same applies to the structural units represented by formula (a2) to formula (a4).
In addition, Component A may have a structural unit other than the structural units represented by Formula (a1) to Formula (a4).
“Structural unit represented by formula (a1)” and the like are also referred to as “structural unit (a1)” and the like.

<Structural Unit Represented by Formula (a1)>
Component A has at least a structural unit represented by the formula (a1).

（式中、Ｒ¹は水素原子又はメチル基を表し、Ｒ²は炭素数１〜６のアルキル基又は炭素数４〜７のシクロアルキル基を表す。）

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 7 carbon atoms.)

R ¹ in the formula (a1) is preferably a methyl group from the viewpoint of uniformity of the polymerization rate of each monomer during polymerization.
R ² in the formula (a1) is preferably an alkyl group having 2 to 4 carbon atoms or a cycloalkyl group having 5 or 6 carbon atoms from the viewpoint of sensitivity, and preferably an ethyl group or a cyclohexyl group. More preferred.

The partial structure of —COOCH (CH ₃ ) OR ² in the structural unit represented by the formula (a1) is decomposed by an acid, for example, an acid generated from component B by exposure to actinic rays, and —COOH (carboxyl) Group). When a carboxy group is newly generated, alkali solubility is increased, and an exposed portion becomes soluble, and development can be performed. In the unexposed area, the partial structure is decomposed by a heat treatment in a post-bake process described later to generate a carboxy group. The resulting carboxy group can form a crosslink by reacting with the epoxy group of the structural unit represented by the formula (a2).

  Preferred examples of the monomer that forms the structural unit represented by the formula (a1) include compounds represented by the following formula (a1 ′).

（式中、Ｒ¹は水素原子又はメチル基を表し、Ｒ²は炭素数１〜６のアルキル基又は炭素数４〜７のシクロアルキル基を表す。）

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 7 carbon atoms.)

R ¹ and R ² in the formula (a1 '), the formula (a1) have the same meanings as R ¹ and R ² in preferred embodiment is also the same.
The structural unit represented by the formula (a1) may be formed by polymerizing the compound represented by the formula (a1 ′), or after polymerizing acrylic acid or methacrylic acid, and then —CH (CH ₃ ) OR ² may be introduced, but it is preferably formed by polymerizing the compound represented by the formula (a1 ′). When the compound represented by the formula (a1 ′) is formed by polymerization, the structural unit represented by the formula (a1) in the component A is also a monomer unit represented by the formula (a1).

<Structural Unit Represented by Formula (a2)>
Component A has at least a structural unit represented by the formula (a2).
The epoxy group of the structural unit represented by the formula (a2) can react with a carboxy group in the system by heat treatment in a post-bake process described later, or can react with each other to form a crosslink. .

  Preferred examples of the monomer that forms the structural unit represented by the formula (a2) include compounds represented by the following formula (a2 ′).

  The structural unit represented by the formula (a2) may be formed by polymerizing the compound represented by the formula (a2 ′), or by polymerizing methacrylic acid and then introducing a glycidyl group by a polymer reaction. However, it is preferably formed by polymerizing the compound represented by the formula (a2 ′). When the compound represented by the formula (a2 ') is formed by polymerization, the structural unit represented by the formula (a2) in the component A is also a monomer unit represented by the formula (a2).

<Structural Unit Represented by Formula (a3)>
Component A has at least a structural unit represented by the formula (a3).

（式中、Ｒ³は水素原子又はメチル基を表す。）

(In the formula, R ³ represents a hydrogen atom or a methyl group.)

R ³ in the formula (a3) is preferably a hydrogen atom from the viewpoint of the uniformity of the polymerization rate of each monomer during polymerization.
Preferred examples of the monomer that forms the structural unit represented by the formula (a3) include compounds represented by the following formula (a3 ′).

R ³ in formula (a3 ′) has the same meaning as R ³ in formula (a3), and the preferred embodiments are also the same.
The structural unit represented by the formula (a3) is preferably formed by polymerizing the compound represented by the formula (a3 ′). When the compound represented by the formula (a3 ′) is formed by polymerization, the structural unit represented by the formula (a3) in the component A is also a monomer unit represented by the formula (a3).

<Structural Unit Represented by Formula (a4)>
Component A has at least a structural unit represented by formula (a4), which is a structural unit having a hydroxy group, from the viewpoint of developability.

（式中、Ｒ⁴は水素原子又はメチル基を表し、Ｘは炭素数２〜１１のアルキレン基を表す。）

(In the formula, R ⁴ represents a hydrogen atom or a methyl group, and X represents an alkylene group having 2 to 11 carbon atoms.)

R ⁴ in the formula (a4) is preferably a methyl group from the viewpoint of uniformity of the polymerization rate of each monomer during polymerization.
X in the formula (a4) is preferably an alkylene group having 2 to 8 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, and an ethylene group being an alkylene group having 2 carbon atoms. It is particularly preferred. Moreover, the alkylene group in X may be a linear alkylene group or a branched alkylene group.

  Preferred examples of the monomer that forms the structural unit (a4) include compounds represented by the following formula (a4 ′).

R ⁴ and X in the formula (a4 '), the formula (a4) have the same meanings as R ⁴ and X in, preferable embodiments thereof are also the same.
The structural unit represented by the formula (a4) is preferably formed by polymerizing the compound represented by the formula (a4 ′). When the compound represented by the formula (a4 ′) is formed by polymerization, the structural unit represented by the formula (a4) in the component A is also a monomer unit represented by the formula (a4).

<Other structural units>
Component A may contain a structural unit other than the structural units (a1) to (a4) (hereinafter also referred to as “structural unit (a5)” as appropriate) as long as the effects of the present invention are not impaired.
Although it does not specifically limit as a radically polymerizable monomer used in order to form a structural unit (a5), For example, the compound as described in Paragraph 0021-0024 of Unexamined-Japanese-Patent No. 2004-264623 can be mentioned ( However, the structural units (a1) to (a4) are excluded.
Preferred embodiments of the preferred structural unit (a5) and the radical polymerizable monomer used for forming the structural unit (a5) will be specifically described.

[Structural unit having alicyclic structure (a5-1)]
Component A preferably has a structural unit (a5-1) having an alicyclic structure from the viewpoint of electrical characteristics.
The structural unit (a5-1) having an alicyclic structure is preferably a structural unit represented by the following formula (a5-1).

（式中、Ｒ⁵は水素原子又はメチル基を表し、Ｒ⁶は脂環基を表し、Ｌは単結合、アルキレン基又はアルキレンオキシ基を表す。）

(In the formula, R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents an alicyclic group, and L represents a single bond, an alkylene group or an alkyleneoxy group.)

R ⁵ in the formula (a5-1) is preferably a methyl group from the viewpoint of uniformity of the polymerization rate of each monomer during polymerization.
R ⁶ in the formula (a5-1) is preferably an alicyclic group having 5 to 18 carbon atoms, more preferably an alicyclic group having 5 to 12 carbon atoms, a cyclohexyl group, 2- A methylcyclohexyl group, a tricyclo [5.2.1.0 ^2,6 ] decan-8-yl group or an isobornyl group is particularly preferable.
The aliphatic ring in the alicyclic group is preferably a condensed ring and / or a bridged ring, and particularly preferably a tricyclo [5.2.1.0 ^2,6 ] decane ring.
L in the formula (a5-1) is preferably a single bond, an alkylene group having 1 to 10 carbon atoms, an ethyleneoxy group or a propyleneoxy group, and more preferably a single bond, a methylene group or an ethyleneoxy group. preferable.

  As a monomer which forms the structural unit (a5-1) having the alicyclic structure, a (meth) acrylate compound having an alicyclic structure can be preferably exemplified, and a compound represented by the following formula (a5′-1) is more preferable. Preferred examples can be given.

R ^5, R ⁶ and L in the formula (a5'-1), the formula (a5-1) is R ^5, respectively R ⁶ and L synonymous in, preferable embodiments thereof are also the same.
Specific examples of the compound represented by formula (a5′-1) include cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, and tricyclo [5.2.1.0 ^2,6 ] decane-8-. Yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yloxyethyl (meth) acrylate, isobornyl (meth) acrylate, and the like.
Of these, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate is most preferable.
In the present invention, “(meth) acryl” is a term including one or both of “acryl” and “methacryl”, and “(meth) acrylate” means “acrylate” and It is a term that includes either “methacrylate” or both.

[Structural Unit Having Carboxylic Acid Alkyl Ester Residue (a5-2)]
Component A preferably has a structural unit (a5-2) having a carboxylic acid alkyl ester residue from the viewpoint of transparency.
The structural unit (a5-2) having a carboxylic acid alkyl ester residue is preferably a structural unit represented by the following formula (a5-2).

（式中、Ｒ⁷は水素原子又はメチル基を表し、Ｒ⁸は炭素数１〜１２のアルキル基を表す。）

(In the formula, R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ represents an alkyl group having 1 to 12 carbon atoms.)

R ⁷ in the formula (a5-2) is preferably a methyl group from the viewpoint of uniformity of the polymerization rate of each monomer during polymerization.
R ⁸ in the formula (a5-2) is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group. Moreover, the alkyl group in R ⁸ may be linear or branched.

  As a monomer which forms the structural unit (a5-2) having a carboxylic acid alkyl ester residue, an alkyl (meth) acrylate compound can be preferably exemplified, and a compound represented by the following formula (a5′-2) is more preferable. It can be illustrated.

R ⁷ and R ⁸ in formula (a5'-2), the formula (a5-2) have the same meanings as R ⁷ and R ⁸ in, preferable embodiments thereof are also the same.

[Structural Unit Having Maleimide Residue (a5-3)]
Component A preferably has a structural unit (a5-3) having a maleimide residue from the viewpoint of thermosetting.
The structural unit (a5-3) having a maleimide residue is preferably a structural unit represented by the following formula (a5-3).

（式中、Ｒ⁹は、アルキル基、シクロアルキル基、アリール基又は下記式（Ｓ）で表される基を表す。）

(In the formula, R ⁹ represents an alkyl group, a cycloalkyl group, an aryl group, or a group represented by the following formula (S).)

（式中、ｘは２〜１０の整数を表し、波線部分は式（ａ４−３）における窒素原子との結合位置を表す。）

(In the formula, x represents an integer of 2 to 10, and the wavy line represents the bonding position with the nitrogen atom in formula (a4-3).)

R ⁹ in the formula (a5-3) is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a group represented by the formula (S). It is preferable that it is a benzyl group, a cyclohexyl group, a phenyl group, or a group represented by the above formula (S).
X in the formula (S) is preferably 2 to 8, and more preferably 2 to 7.
Preferred examples of the monomer forming the structural unit (a5-3) having a maleimide residue include compounds represented by the following formula (a5′-3).

R ⁹ in the formula (a5'-3) has the same meaning as R ⁹ in the formula (A5-3), preferable embodiments thereof are also the same.
Specific examples of the compound represented by the formula (a5′-3) include phenylmaleimide, cyclohexylmaleimide, benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl- Examples include 6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, and N- (9-acridinyl) maleimide. Of these, N-cyclohexylmaleimide and N-phenylmaleimide are particularly preferable.

[Structural unit having polyether structure (a5-4)]
Component A preferably has a structural unit (a5-4) having a polyether structure from the viewpoint of developability.
The structural unit (a5-4) having a polyether structure is preferably a structural unit represented by the following formula (a5-4-1) or formula (a5-4-2).

（式中、Ｒ¹⁰は水素原子又はメチル基を表し、Ｒ¹¹は水素原子、炭素数１〜１２のアルキル基又はフェニル基を表し、Ｙは単結合又は二価の連結基を表し、ｍ及びｎはそれぞれ独立に、０〜５０の整数を表す。ただし、ｍとｎとが共に０となることはない。）

(Wherein R ¹⁰ represents a hydrogen atom or a methyl group, R ¹¹ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a phenyl group, Y represents a single bond or a divalent linking group, m and n independently represents an integer of 0 to 50, provided that m and n are not both 0.)

R ¹⁰ in the formula (a5-4-1) and the formula (a5-4-2) is preferably a methyl group from the viewpoint of uniformity of the polymerization rate of each monomer during polymerization.
R ¹¹ in the formula (a5-4-1) and the formula (a5-4-2) is preferably an alkyl group having 1 to 8 carbon atoms or a phenyl group, and an alkyl group having 1 to 4 carbon atoms. More preferably, it is more preferably a methyl group. Moreover, the alkyl group in R ¹¹ may be linear or branched.
Y in the formula (a5-4-1) and the formula (a5-4-2) is preferably a single bond or a divalent linking group having 1 to 50 carbon atoms. More preferably, it is 20 alkylene groups, and more preferably a single bond.
M and n in the formula (a5-4-1) and the formula (a5-4-2) are each independently preferably an integer of 0 to 40, and more preferably an integer of 0 to 20. .
In the formula (a5-4-1) and the formula (a5-4-2), —C ₃ H ₆ O— represents —CH (CH ₃ ) CH ₂ O— or —CH ₂ CH (CH ₃ ). O- is preferred.

  As a monomer which forms the structural unit (a5-4) having the polyether structure, a compound represented by the following formula (a5′-4-1) or formula (a5′-4-2) can be exemplified more preferably. .

R ¹⁰ , R ¹¹ , Y, m, and n in formula (a5′-4-1) and formula (a5′-4-2) are the same as those in formula (a5-4-1) and formula (a5-4-2). ) Are the same as R ¹⁰ , R ¹¹ , Y, m and n, respectively, and the preferred embodiments are also the same.

[Structural Unit Having Carboxy Group (a5-5)]
Component A preferably has a structural unit (a5-5) having a carboxy group.
Examples of the monomer that forms the structural unit (a5-5) having a carboxy group include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and the like.
Among these, (meth) acrylic acid is preferable, and methacrylic acid is particularly preferable.
Further, the structural unit (a5-5) having a carboxy group is preferably a structural unit represented by the following formula (a5-5-1) or formula (a5-5-2). The structural unit represented by -5-1) is particularly preferable.

  These structural units (a5) may be contained alone or in combination of two or more in Component A.

  As long as the whole of component A can be developed by exposure to actinic rays, introduction of acidic groups is not excluded. Examples of the case where an acidic group is introduced into Component A include, for example, the case where the structural unit (a5-5-1) and the structural unit (a-5-5-2) are included.

From the viewpoint of improving the residual DC characteristics, the content of the monomer units forming the structural unit (a1) to the structural unit (a4) in the component A is preferably in the following range.
10-60 mol% is preferable, as for the content rate of the monomer unit which forms a structural unit (a1) in all the monomer units which comprise component A, 20-60 mol% is more preferable, and 30-50 mol% is further more preferable. .
The content of the monomer units forming the structural unit (a2) in all monomer units constituting Component A is preferably 5 to 50 mol%, more preferably 10 to 50 mol%, still more preferably 20 to 50 mol%. .
The content of monomer units forming the structural unit (a3) in all monomer units constituting Component A is preferably 1 to 50 mol%, more preferably 5 to 50 mol%, and even more preferably 10 to 30 mol%. .
The content of monomer units forming the structural unit (a4) in all monomer units constituting Component A is preferably 1 to 50 mol%, more preferably 5 to 50 mol%, and even more preferably 10 to 30 mol%. .
The content of the monomer units forming the structural unit (a5) in all monomer units constituting Component A is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, still more preferably 0 to 10 mol%. .
Moreover, it is preferable that the polystyrene conversion weight average molecular weight (Mw) measured by the gel permeation chromatography (GPC) of the component A is 2,000-100,000, more preferably 3,000-50,000. 30,000 to 30,000 is particularly preferred.

The photosensitive resin composition of this invention can contain the component A individually by 1 type or in combination of 2 or more types.
The content of Component A in the photosensitive resin composition of the present invention is preferably 20 to 99% by weight, and preferably 40 to 97% by weight, based on the total solid content of the photosensitive resin composition. More preferably, it is 60 to 95% by weight. When the content of component A is within this range, the pattern formability when developed is good. In addition, the solid content amount of the photosensitive resin composition represents an amount excluding volatile components such as a solvent.
In addition, the photosensitive resin composition of this invention may use together resin other than the component A in the range which does not prevent the effect of this invention. However, the content of the resin other than Component A is preferably smaller than the content of Component A from the viewpoint of developability.

(Component B) Oxime sulfonate compound represented by formula (B) The photosensitive resin composition of the present invention contains (Component B) an oxime sulfonate compound represented by formula (B).

（式中、Ｒ^B1は、炭素数１〜６のアルキル基、炭素数１〜４のハロゲン化アルキル基、フェニル基、ビフェニル基、ナフチル基、２−フリル基、２−チエニル基、炭素数１〜４のアルコキシ基、フルオレニル基又はシアノ基を表し、Ｒ^B1が、フェニル基、ビフェニル基、ナフチル基又はアントラ二ル基である場合、これらの基は、ハロゲン原子、水酸基、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基及びニトロ基よりなる群から選ばれた置換基によって置換されていてもよい。Ｒ^B2は、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、炭素数１〜５のハロゲン化アルキル基、炭素数１〜５のハロゲン化アルコキシ基、Ｗで置換されていてもよいフェニル基、Ｗで置換されていてもよいナフチル基又はＷで置換されていてもよいアントラニル基、ジアルキルアミノ基、モルホリノ基又はシアノ基を表す。Ｒ^B1とＲ^B2とは互いに結合して５員環又は６員環を形成してもよく、該５員環又は６員環は１個又は２個の任意の置換基を有してもよいベンゼン環と連結していてもよい。Ｒ^B3は、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、炭素数１〜５のハロゲン化アルキル基、炭素数１〜５のハロゲン化アルコキシ基、Ｗで置換されていてもよいフェニル基、Ｗで置換されていてもよいナフチル基又はＷで置換されていてもよいアントラニル基を表す。Ｗは、ハロゲン原子、シアノ基、ニトロ基、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、炭素数１〜５のハロゲン化アルキル基又は炭素数１〜５のハロゲン化アルコキシ基を表す。）

(In the formula, R ^B1 is an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a phenyl group, a biphenyl group, a naphthyl group, a 2-furyl group, a 2-thienyl group, or a carbon number of 1; Represents an alkoxy group of ˜4, a fluorenyl group or a cyano group, and when R ^B1 is a phenyl group, a biphenyl group, a naphthyl group or an anthranyl group, these groups are a halogen atom, a hydroxyl group, and a carbon number of 1 to 4 And may be substituted with a substituent selected from the group consisting of an alkoxy group having 1 to 4 carbon atoms and a nitro group, and R ^B2 is an alkyl group having 1 to 10 carbon atoms and 1 to 10 carbon atoms. An alkoxy group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group that may be substituted with W, a naphthyl group that may be substituted with W, or W Replaced There may be an anthranyl group, a dialkylamino group, may form a 5- or 6-membered ring bonded to each other with .R ^B1 and R ^B2 representing the morpholino group or a cyano group, said 5- or 6-membered The ring may be connected to a benzene ring which may have one or two arbitrary substituents, and R ^B3 is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, A halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group optionally substituted with W, a naphthyl group optionally substituted with W, or W substituted. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a carbon number. 1 to 5 halogenated alkoxy groups Represent.)

The alkyl group in R ^B1 and R ^B2 of the formula (B) may be linear or branched, or may have a ring structure. Further, the alkyl group in R ^B1 and R ^B2 may have a substituent.
The substituent is not particularly limited, but is a halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, acyl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic group, cyano group. Preferably an alkoxysulfonyl group or an aryloxysulfonyl group. If possible, the substituent may further have a substituent.
Further, the 5-membered or 6-membered ring formed by linking R ^B1 and R ^B2 in the formula (B) is not particularly limited, and a hydrocarbon ring and a heterocyclic ring can be preferably exemplified. Further, the 5-membered or 6-membered hydrocarbon ring and the 5-membered or 6-membered heterocyclic ring may have an unsaturated bond at an arbitrary position. The ring may have a substituent. Preferred examples of the substituent include those described above.

In the formula (B), R ^B1 and R ^B2 each independently represent a cyano group, or a phenyl group having 6 to 10 carbon atoms which is unsubstituted or substituted with an alkyl or alkoxy having 1 to 4 carbon atoms, or It is preferable that they are bonded to each other to form 5 or 6 rings. The ring is preferably a 5-membered or 6-membered heterocyclic ring containing at least one of an oxygen atom, a nitrogen atom and a sulfur atom, more preferably a 5-membered ring containing a sulfur atom.
In the formula (B), R ^B3 is preferably an alkyl group having 1 to 8 carbon atoms, a p-toluyl group, a phenyl group, a camphoryl group, a trifluoromethyl group or a nonafluorobutyl group.
The nonafluorobutyl group and the alkyl group having 1 to 8 carbon atoms in R ^B3 may be linear or branched.
Further, the position of bonding with the sulfur atom of the camphoryl group in R ^B3 is not particularly limited, but is preferably the 10th position. That is, the camphoryl group is preferably a 10-camphoryl group.

  The oxime sulfonate compound represented by the formula (B) is preferably an oxime sulfonate compound represented by the formula (B-1) or an oxime sulfonate compound represented by the formula (B-2).

（式中、Ｒ^B4は水素原子又はメチル基を表し、Ｒ^B5は炭素数１〜８のアルキル基、ｐ−トルイル基、フェニル基、カンホリル基、トリフルオロメチル基又はノナフルオロブチル基を表す。）

(In the formula, R ^B4 represents a hydrogen atom or a methyl group, and R ^B5 represents an alkyl group having 1 to 8 carbon atoms, a p-toluyl group, a phenyl group, a camphoryl group, a trifluoromethyl group, or a nonafluorobutyl group. )

R ^B4 in the formula (B-1) is preferably a methyl group.
The alkyl group having 1 to 8 carbon atoms and nonafluorobutyl group in R ^B5 of the formula (B-1) may be linear or branched. Moreover, it is preferable that carbon number of the alkyl group in said ^RB5 is 1-4, and it is more preferable that it is 1-3.
Further, the bonding position between the camphoryl group and the sulfur atom in R ^B5 is not particularly limited, but is preferably the 10th position. That is, the camphoryl group is preferably a 10-camphoryl group.
R ^B5 in the formula (B) is preferably a methyl group, an n-propyl group, an n-octyl group, a p-toluyl group or a camphoryl group, and an n-propyl group, an n-octyl group, a p-toluyl group or a camphoryl group. It is more preferable that it is n-propyl group or p-toluyl.

（式中、Ｒ^B6は水素原子、メチル基又はメトキシ基を表し、Ｒ^B7は炭素数１〜８のアルキル基、ｐ−トルイル基、フェニル基、カンホリル基、トリフルオロメチル基又はノナフルオロブチル基を表す。）

(In the formula, R ^B6 represents a hydrogen atom, a methyl group or a methoxy group, and R ^B7 represents an alkyl group having 1 to 8 carbon atoms, a p-toluyl group, a phenyl group, a camphoryl group, a trifluoromethyl group or a nonafluorobutyl group. Represents.)

R ^B6 in the formula (B) is preferably a hydrogen atom.
R ^B7 in the formula (B) is preferably a methyl group, an n-propyl group, an n-octyl group or a p-toluyl group, a camphoryl group, a phenyl group or a trifluoromethyl group. It is more preferably a group, an n-octyl group, a p-toluyl group or a camphoryl group.
The nonafluorobutyl group and the alkyl group having 1 to 8 carbon atoms in R ^B7 may be linear or branched.
Further, the bonding position with the sulfur atom of the camphoryl group in R ^B7 is not particularly limited, but is preferably the 10th position. That is, the camphoryl group is preferably a 10-camphoryl group.

The content of the oxime sulfonate compound represented by the formula (B) in the photosensitive resin composition of the present invention is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the component A. More preferably, it is 0.5-10 weight part, and it is still more preferable that it is 2-7 weight part.
Moreover, (Component B) may be used individually by 1 type, and may use 2 or more types together.

(Component C) Solvent The photosensitive resin composition of the present invention contains (Component C) a solvent.
It is preferable that the photosensitive resin composition of the present invention is prepared as a solution in which components A and B, which are essential components, and optional components described below are dissolved in a (component C) solvent.
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, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether Examples include acetates, esters, ketones, amides, lactones and the like.
Furthermore, as a solvent used for the photosensitive resin composition of this invention, the solvent of Paragraph 0074 of Unexamined-Japanese-Patent No. 2009-258722 is mentioned, for example.
These solvents can be used alone or in combination of two or more.
The solvent that can be used in the present invention is preferably a single type or a combination of two types, more preferably a combination of two types, and a combination of propylene glycol monoalkyl ether acetates and diethylene glycol dialkyl ethers. Is more preferable.

  The content of Component C in the photosensitive resin composition of the present invention is preferably 50 to 3,000 parts by weight, more preferably 100 to 2,000 parts by weight, with respect to 100 parts by weight of Component A. More preferably, it is 150 to 1,500 parts by weight.

(Component D) Compound represented by formula (D-1) and / or compound represented by formula (D-2) The photosensitive resin composition of the present invention is represented by the following formula (D-1). It contains a compound and / or a compound represented by the following formula (D-2) (hereinafter also referred to as a specific basic compound).

（式（Ｄ−１）中、Ｒ^D1は水素原子又はｔ−ブトキシカルボニル基を表す。）

(In formula (D-1), R ^D1 represents a hydrogen atom or a t-butoxycarbonyl group.)

The specific basic compound used for this invention is used individually by 1 type or in combination of 2 or more types.
The content of Component E in the photosensitive resin composition of the present invention is preferably 0.0001 to 1 part by weight, more preferably 0.001 to 1 part by weight with respect to 100 parts by weight of Component A. 0.002 to 0.2 parts by weight is most preferable.

  The photosensitive resin composition of the present invention may contain optional components in addition to the above components A to D as essential components. As optional components, (Component E) cross-linking agent, (Component F) adhesion improver, (Component G) surfactant, (Component H) sensitizer, (Component I) development accelerator, (Component J) oxidation Inhibitors, (Component K) plasticizers, (Component L) thermal radical generators, (Component M) thermal acid generators, (Component N) acid multipliers, and the like. The additives that can be used in the present invention are not limited to these, and various additives known in the art can be used.

(Component E) Crosslinking agent The photosensitive resin composition of the present invention preferably contains (Component E) a crosslinking agent as required. (Component E) By adding a cross-linking agent, the cured film can be made stronger.
(Component E) As the crosslinking agent, for example, a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, an alkoxymethyl group-containing crosslinking agent, or at least one ethylenically unsaturated double bond A compound having can be added.
Among these crosslinking agents, particularly preferred are compounds having two or more epoxy groups or oxetanyl groups in the molecule.

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

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

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

As specific examples of the compound having two or more oxetanyl groups in the molecule, Aron oxetane OXT-121, OXT-221, OX-SQ, and PNOX (manufactured by Toagosei Co., Ltd.) can be used.
Moreover, the compound containing an oxetanyl group can be used individually or in mixture with the compound containing an epoxy group.
The amount of the compound having two or more epoxy groups or oxetanyl groups in the molecule to the photosensitive resin composition is preferably 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight per 100 parts by weight of Component A. Part is more preferable, and 1 to 10 parts by weight is still more preferable.

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

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

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

<Compound having at least one ethylenically unsaturated double bond>
As the compound having at least one ethylenically unsaturated double bond, a (meth) acrylate compound such as a monofunctional (meth) acrylate, a bifunctional (meth) acrylate, or a trifunctional or higher (meth) acrylate is preferably used. be able to.

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

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

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

These compounds having at least one ethylenically unsaturated double bond are used singly or in combination of two or more.
The proportion of the compound having at least one ethylenically unsaturated double bond in the photosensitive resin composition of the present invention is preferably 50 parts by weight or less, and 30 parts by weight or less with respect to 100 parts by weight of Component A. It is more preferable that By containing at least one compound having an ethylenically unsaturated double bond in such a ratio, the heat resistance and surface hardness of the cured film obtained from the photosensitive resin composition of the present invention can be improved. it can. When adding a compound having at least one ethylenically unsaturated double bond, it is preferable to add a thermal radical generator described later.

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

Preferred silane coupling agents include, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriacoxysilane, γ-glycidoxypropyl dialkoxysilane, γ-methacrylate. Roxypropyltrialkoxysilane, γ-methacryloxypropyl dialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane Is mentioned.
Of these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, and γ-glycidoxypropyltrimethoxysilane is still more preferable.

These can be used alone or in combination of two or more. These are effective in improving the adhesion to the substrate and are also effective in adjusting the taper angle with the substrate.
0.1-20 weight part is preferable with respect to 100 weight part of component A, and, as for content of the (component F) contact | adherence improving agent in the photosensitive resin composition of this invention, 0.5-10 weight part is more preferable.

(Component G) Surfactant (fluorine surfactant, silicone surfactant, etc.)
The photosensitive resin composition of the present invention preferably contains (Component G) a surfactant (such as a fluorine-based surfactant or a silicone-based surfactant).
As a surfactant, a copolymer (3) containing the structural unit A and the structural unit B shown below can be given as a preferred example. The weight average molecular weight (Mw) of the copolymer is preferably 1,000 or more and 10,000 or less, and more preferably 1,500 or more and 5,000 or less. The weight average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography (GPC).

In the copolymer (3), R ²¹ and R ²³ each independently represent a hydrogen atom or a methyl group, R ²² represents a linear alkylene group having 1 to 4 carbon atoms, and R ²⁴ represents a hydrogen atom or carbon number. 1 represents an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are weight percentages representing a polymerization ratio, and p is a numerical value of 10% to 80% by weight. Q represents a numerical value of 20% by weight to 90% by weight, r represents an integer of 1 to 18 and n represents an integer of 1 to 10.
L in the structural unit B is preferably an alkylene group represented by the following formula (4).

In the formula (4), R ²⁵ represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the coated surface. More preferred is an alkyl group of 3.
The sum of p and q (p + q) is preferably p + q = 100, that is, 100% by weight.

  Specific examples of fluorine surfactants and silicone surfactants include JP-A Nos. 62-36663, 61-226746, 61-226745, and 62-170950. , JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, JP-A-2001-330953, etc. An activator can be mentioned and a commercially available surfactant can also be used. Commercially available surfactants that can be used include, for example, F-top EF301, EF303 (Mitsubishi Materials Electronics Kasei Co., Ltd.), Florard FC430, 431 (Sumitomo 3M Co., Ltd.), MegaFuck F171, F173 , F176, F189, R08 (above, manufactured by DIC Corporation), Surflon S-382, SC101, 102, 103, 104, 105, 106 (above, manufactured by Asahi Glass Co., Ltd.), PolyFox series (produced by OMNOVA), Fluorine-based surfactants or silicone-based surfactants such as KF-6012 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be mentioned. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone surfactant.

These surfactants can be used individually by 1 type or in mixture of 2 or more types. Moreover, you may use together a fluorine-type surfactant and a silicone type surfactant.
The amount of (Component G) surfactant (fluorine-based surfactant, silicone-based surfactant, etc.) added to the photosensitive resin composition of the present invention is 10 parts by weight or less with respect to 100 parts by weight of Component A. Is preferably 0.01 to 10 parts by weight, more preferably 0.01 to 1 part by weight.

(Component H) Sensitizer The photosensitive resin composition of the present invention is preferably added with (Component H) a sensitizer in order to promote its decomposition in combination with Component B described above.
The sensitizer is a photosensitizer that absorbs actinic rays or radiation and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with a photoacid generator such as Component B, 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 the 350 nm to 450 nm region.

  Polynuclear aromatics (eg, pyrene, perylene, triphenylene, anthracene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), xanthones (eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone) ), Cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), rhodocyanines, oxonols, thiazines (eg, thionine, methylene blue, toluidine blue), acridines ( For example, acridine orange, chloroflavin, acriflavine), acridones (eg, acridone, 10-butyl-2-chloroacridone), anthraquinones (eg, Ntorakinon), squaryliums (e.g., squarylium), styryl compounds, base styryl, coumarins (e.g., 7-diethylamino-4-methylcoumarin). Among these sensitizers, sensitizers that absorb an actinic ray or radiation to be in an electronically excited state and have an electron transfer action to a photoacid generator are preferred, especially polynuclear aromatics, acridones, coumarins, bases Styryls are preferred and anthracenes are most preferred.

A commercially available sensitizer may be used, or it may be synthesized by a known synthesis method.
The addition amount of the sensitizer is preferably 20 to 300 parts by weight and more preferably 30 to 200 parts by weight with respect to 100 parts by weight of Component B from the viewpoint of achieving both sensitivity and transparency.

(Component I) Development accelerator The photosensitive resin composition of the present invention preferably contains (Component I) a development accelerator.
(Component I) As the development accelerator, any compound having a development acceleration effect can be used, but a compound having at least one structure selected from the group consisting of a carboxy group, a phenolic hydroxyl group, and an alkyleneoxy group The compound having a carboxy group or a phenolic hydroxyl group is more preferable, and the compound having a phenolic hydroxyl group is particularly preferable.
The molecular weight of (Component I) the development accelerator is preferably from 100 to 2,000, more preferably from 150 to 1,500, particularly preferably from 150 to 1,000.

Examples of development accelerators having an alkyleneoxy group include polyethylene glycol, polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, polyethylene glycol glyceryl ester, polypropylene glycol glyceryl ester, polypropylene glycol diglyceryl ester, polybutylene glycol, Examples thereof include polyethylene glycol-bisphenol A ether, polypropylene glycol-bisphenol A ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, and compounds described in JP-A-9-222724.
Examples of compounds having a carboxy group include compounds described in JP-A 2000-66406, JP-A 9-6001, JP-A 10-20501, JP-A 11-338150, and the like.
Examples of those having a phenolic hydroxyl group include JP-A No. 2005-346024, JP-A No. 10-133366, JP-A No. 9-194415, JP-A No. 9-222724, JP-A No. 11-171810, Examples thereof include compounds described in JP 2007-121766, JP-A-9-297396, JP-A 2003-43679, and the like. Among these, a phenol compound having 2 to 10 benzene rings is preferable, and a phenol compound having 2 to 5 benzene rings is more preferable. Particularly preferred is a phenolic compound disclosed as a dissolution accelerator in JP-A-10-133366.

(Component I) The development accelerator may be used alone or in combination of two or more.
The addition amount of (Component I) development accelerator in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of Component A, from the viewpoint of sensitivity and remaining film ratio. -20 parts by weight is more preferable, and 0.5-10 parts by weight is particularly preferable.

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

  As a commercial item of a phenolic antioxidant, ADK STAB AO-60, ADK STAB AO-80 (above, the product made from ADEKA), and Irganox 1098 (made by Ciba Japan Co., Ltd.) are mentioned, for example.

The content of (Component J) antioxidant is preferably 0.1 to 6% by weight, more preferably 0.2 to 5% by weight, based on the total solid content of the photosensitive resin composition. It is preferably 0.5 to 4% by weight. By setting it within this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation can be improved.
As additives other than antioxidants, various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators, and the like are used in the present invention. You may add to a resin composition.

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

(Component L) Thermal Radical Generator The photosensitive resin composition of the present invention may contain (Component L) a thermal radical generator, which is a compound having at least one ethylenically unsaturated double bond as described above. When such an ethylenically unsaturated compound is contained, it is preferable to contain (Component L) a thermal radical generator.
As the thermal radical generator in the present invention, a known thermal radical generator can be used.
The thermal radical generator is a compound that generates radicals by heat energy and initiates or accelerates the polymerization reaction of the polymerizable compound. By adding a thermal radical generator, the obtained cured film becomes tougher and heat resistance and solvent resistance may be improved.
Preferred thermal radical generators include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, carbon Examples thereof include compounds having a halogen bond, azo compounds, and bibenzyl compounds.
(Component L) A thermal radical generator may be used alone or in combination of two or more.
The content of the (component L) thermal radical generator in the photosensitive resin composition of the present invention is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of component A, from the viewpoint of improving film properties, 20 parts by weight is more preferable, and 0.5 to 10 parts by weight is most preferable.

(Component M) Thermal acid generator In the present invention, (Component M) a thermal acid generator may be used in order to improve film physical properties and the like at low temperature curing.
The thermal acid generator is a compound that generates an acid by heat, and is usually a compound having a thermal decomposition point in the range of 130 ° C. to 250 ° C., preferably 150 ° C. to 220 ° C., for example, sulfonic acid, It is a compound that generates a low nucleophilic acid such as carboxylic acid or disulfonylimide.
As the generated acid, sulfonic acid, an alkylcarboxylic acid substituted with an electron withdrawing group or an arylcarboxylic acid having a strong pKa of 2 or less, and a disulfonylimide substituted with an electron withdrawing group are also preferable. Examples of the electron withdrawing group include a halogen atom such as a fluorine atom, a haloalkyl group such as a trifluoromethyl group, a nitro group, and a cyano group.

In the present invention, it is also preferable to use a sulfonic acid ester that does not substantially generate an acid by exposure to exposure light and generates an acid by heat.
The fact that acid is not substantially generated by exposure light exposure can be determined by no change in the spectrum by measuring IR spectrum and NMR spectrum before and after exposure of the compound.
The molecular weight of the thermal acid generator is preferably 230 to 1,000, and more preferably 230 to 800.

As the sulfonic acid ester usable in the present invention, a commercially available one may be used, or one synthesized by a known method may be used. The sulfonic acid ester can be synthesized, for example, by reacting a sulfonyl chloride or sulfonic acid anhydride with a corresponding polyhydric alcohol under basic conditions.
0.5-20 weight part is preferable with respect to 100 weight part of component A, and, as for content to the photosensitive resin composition of a thermal acid generator, 1-15 weight part is more preferable.

(Component N) Acid Proliferator The photosensitive resin composition of the present invention can use (Component N) an acid multiplier for the purpose of improving sensitivity.
The acid proliferating agent 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. In such a compound, since one or more acids increase in one reaction, the reaction proceeds at an accelerated rate as the reaction proceeds. However, the generated acid itself induces self-decomposition, and is generated here. The strength of the acid is preferably 3 or less, particularly preferably 2 or less, as the acid dissociation constant, pKa.
Specific examples of the acid proliferating agent include paragraphs 0203 to 0223 of JP-A-10-1508, paragraphs 0016 to 0055 of JP-A-10-282642, and page 39, line 12 of JP-T 9-512498. Examples of the compounds described in the first to page 47, line 2 are listed.

  Examples of the acid proliferating agent that can be used in the present invention include pKa such as dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, and phenylphosphonic acid, which are decomposed by an acid generated from the acid generator. Examples include compounds that generate 3 or less acids.

  The content of the acid proliferating agent in the photosensitive resin composition is preferably 10 to 1,000 parts by weight with respect to 100 parts by weight of Component B from the viewpoint of dissolution contrast between the exposed part and the unexposed part. It is more preferable to set it to -500 weight part.

(Method for forming cured film)
Next, the formation method of the cured film in this invention is demonstrated.
The method for forming a cured film in the present invention is not particularly limited as long as it is a method for forming a film using the photosensitive resin composition of the present invention and forming a cured film by applying at least one of light and heat. However, it is preferable to include the following steps (1) to (5).
(1) Application process for applying the photosensitive resin composition of the present invention onto a substrate (2) Solvent removal process for removing the solvent from the applied photosensitive resin composition (3) Photosensitive resin composition from which the solvent has been removed (4) Development step of developing the exposed photosensitive resin composition with an aqueous developer (5) Post-bake step of thermosetting the developed photosensitive resin composition The steps will be described in order.

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

  In the exposure step (3), the obtained coating film is irradiated with actinic rays having a wavelength of 300 nm or more and 450 nm or less. In this step, component B is decomposed and acid is generated. By the catalytic action of the generated acid, the acid-decomposable group in the structural unit (a1) contained in the component A is decomposed to generate a carboxy group.

  In order to accelerate the decomposition reaction in the region where the acid catalyst is generated, PEB (post-exposure heat treatment) can be performed as necessary. PEB can promote the formation of a carboxy 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 90 ° C. or lower.

In the developing step (4), the component A having a liberated carboxy group is developed using an alkaline developer. A positive image is formed by removing an exposed area containing a resin composition having a carboxy group that is easily dissolved in an alkaline developer.
In the post-baking step of (5), the obtained positive image is heated to thermally decompose the acid-decomposable group in the structural unit (a1) to generate a carboxy group, and to cure by crosslinking with an epoxy group. A film can be formed. This heating is preferably performed at a high temperature of 150 ° C. or more, more preferably 180 to 250 ° C., and particularly preferably 200 to 250 ° C. The heating time can be appropriately set depending on the heating temperature or the like, but is preferably in the range of 10 to 90 minutes.

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

<Method for preparing photosensitive resin composition>
Component A, component B, and essential components of component C are mixed at a predetermined ratio and by any method, and stirred and dissolved to prepare a photosensitive resin composition. The photosensitive resin composition thus prepared can be used after being filtered using a filter having a pore diameter of about 0.1 μm.

<Coating process and solvent removal process>
A desired dry coating film can be formed by applying the photosensitive resin composition to a predetermined substrate and removing the solvent by reducing pressure and / or heating (pre-baking). Examples of the substrate include a polarizing plate, a glass plate provided with a black matrix layer and a color filter layer as necessary, and further a transparent conductive circuit layer in manufacturing a liquid crystal display device.
The coating method to a board | substrate is not specifically limited, For example, methods, such as a slit coat method, a spray method, a roll coat method, a spin coat method, can be used. Among them, the slit coating method is preferable from the viewpoint of being suitable for a large substrate. Here, the large substrate means a substrate having a size of 1 m or more and 5 m or less on each side.

  In addition, (2) the heating conditions in the solvent removal step are such that the acid-decomposable group is decomposed in the structural unit (a1) in the component A in the unexposed area and the component A is not soluble in the alkaline developer. Yes, and depending on the type and blending ratio of each component, it is preferably about 30 to 300 seconds at 70 to 120 ° C.

<Exposure process>
(3) In the exposure step, the substrate provided with the dry coating film is irradiated with an actinic ray having a predetermined pattern. Exposure may be performed through a mask, or a predetermined pattern may be drawn directly. Actinic rays having a wavelength of 300 nm to 450 nm can be preferably used. After the exposure process, PEB is performed as necessary.
For exposure with actinic rays, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, an LED light source, a chemical lamp, a laser generator, or the like can be used.
When a mercury lamp is used, actinic rays having wavelengths such as g-line (436 nm), i-line (365 nm), and h-line (405 nm) can be preferably used. Mercury lamps are preferred in that they are suitable for large area exposure compared to lasers.

In the case of using a laser, 343 nm and 355 nm are used for a solid (YAG) laser, 351 nm (XeF) is used for an excimer laser, and 375 nm and 405 nm are used for a semiconductor laser. Among these, 355 nm and 405 nm are more preferable from the viewpoint of stability and cost. The coating can be irradiated with the laser once or multiple times.
The energy density per pulse of the laser is preferably 0.1 mJ / cm ² or more and 10,000 mJ / cm ² or less. In order to sufficiently cure the coating film, 0.3 mJ / cm ² or more is more preferable, and 0.5 mJ / cm ² or more is most preferable. To prevent the coating film from being decomposed by an ablation phenomenon, 1,000 mJ / cm ² is preferable. cm ² or less is more preferable, and 100 mJ / cm ² or less is most preferable.

  The pulse width is preferably 0.1 nsec or more and 30,000 nsec or less. In order not to decompose the color coating film due to the ablation phenomenon, 0.5 nsec or more is more preferable, and 1 nsec or more is most preferable, and in order to improve the alignment accuracy at the time of scanning exposure, 1,000 nsec or less is more preferable, Most preferred is 50 nsec or less.

Furthermore, the frequency of the laser is preferably 1 Hz or more and 50,000 Hz or less. In order to shorten the exposure processing time, 10 Hz or more is more preferable, and 100 Hz or more is most preferable. In order to improve the alignment accuracy at the time of scanning exposure, 10,000 Hz or less is more preferable, and 1,000 Hz or less is most preferable.
Compared with a mercury lamp, a laser is preferable in that the focus can be easily reduced and a mask for forming a pattern in the exposure process is not necessary and the cost can be reduced.
There are no particular restrictions on the exposure apparatus that can be used in the present invention, but commercially available devices include Callisto (buoy technology), AEGIS (buoy technology), and DF2200G (large). Nippon Screen Manufacturing Co., Ltd.) can be used. Further, devices other than those described above are also 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.

<Development process>
(4) In the developing step, the exposed area is removed using an alkaline developer to form an image pattern. Examples of the alkaline developer include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkalis such as sodium bicarbonate and potassium bicarbonate Metal bicarbonates; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.

The pH of the developer is preferably 10.0 to 14.0.
The development time is preferably 30 to 180 seconds, and the development method may be any of a liquid piling method, a dip method, a shower method, and the like. After the development, washing with running water is performed for 10 to 90 seconds to form a desired pattern.

<Post-bake process (crosslinking process)>
For a pattern corresponding to an unexposed area obtained by development, a heating device such as a hot plate or oven is used for a predetermined time, for example, 180 to 250 ° C., for example, 5 to 60 minutes on the hot plate. In the case of an oven, by performing heat treatment for 30 to 90 minutes, the acid-decomposable group in component A is decomposed to generate a carboxy group, and the epoxy group and / or oxetanyl group in component A is crosslinkable. By reacting with a group and crosslinking, a protective film and an interlayer insulating film excellent in heat resistance, hardness, and the like can be formed. In addition, when heat treatment is performed, the transparency can be improved by performing the heat treatment in a nitrogen atmosphere.
Prior to heat treatment, the substrate on which the pattern has been formed is re-exposed with actinic rays and then post-baked (re-exposure / post-bake) to generate acid from component B present in the unexposed area and promote crosslinking. It is preferable to function as a catalyst.
That is, it is preferable that the method for forming a cured film of the present invention includes a re-exposure step in which re-exposure is performed with active light between the development step and the post-bake step.
The exposure in the re-exposure step may be performed by the same means as in the exposure step. In the re-exposure step, the entire surface of the substrate on which the film is formed by the photosensitive resin composition of the present invention is exposed. It is preferable. The exposure amount in the re-exposure step is preferably 100 to 1,000 mJ / cm ² .

The organic EL (electroluminescence) display device and the liquid crystal display device of the present invention are not particularly limited except for having a flattening film or an interlayer insulating film formed using the photosensitive resin composition of the present invention, Examples include various known organic EL display devices and liquid crystal display devices having various structures.
Moreover, the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, It can be used for various uses. For example, in addition to the planarization film and interlayer insulating film, a color filter protective film, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a microlens provided on the color filter in the solid-state imaging device, etc. Can be suitably used.

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

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

  Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” and “%” are based on weight.

<Synthesis Example 1>
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethyl methyl ether. Subsequently, 63.3 parts by weight of 1-ethoxyethyl methacrylate, 42.6 parts by weight of glycidyl methacrylate, 15.6 parts by weight of styrene, 19.5 parts by weight of 2-hydroxyethyl methacrylate, and 3 parts by weight of α-methylstyrene dimer Was added, and the mixture was purged with nitrogen. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-1). The copolymer (A-1) had a polystyrene equivalent weight average molecular weight (Mw) of 12,000.
Table 1 shows the composition ratio (mol%) of the synthesized polymer.

<Synthesis Examples 2-44>
Copolymers (A-2) to (A-36) and (a-1) to (a-1) to (a) shown in Tables 1 and 2 are the same as in Synthesis Example 1 except that the monomers used and the amounts thereof are changed. Each of -8) was synthesized. The composition ratio (mol%) and Mw of each copolymer synthesized are as shown in Tables 1 and 2.

Abbreviations in Table 1 and Table 2 are as follows.
MAEVE: 1-ethoxyethyl methacrylate MACHOE: 1- (cyclohexyloxy) ethyl methacrylate GMA: glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
St: Styrene (Wako Pure Chemical Industries, Ltd.)
α-St: α-methylstyrene HEMA: 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
HEA: 2-hydroxyethyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
HBMA: 4-Hydroxybutyl methacrylate HBA: 4-Hydroxybutyl acrylate MATH: Tetrahydro-2H-pyran-2-yl methacrylate MAA: Methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
MMA: Methyl methacrylate BzMA: Benzyl methacrylate PME: Methoxypolyethyleneglycol methacrylate (manufactured by NOF Corporation, Blenmer PME-200)
n-HMA: n-hexyl methacrylate PMI: N-phenylmaleimide p-VBGE: vinylbenzyl glycidyl ether Cl-St: p-chlorostyrene

(Examples 1-216 and Comparative Examples 1-13)
The amount (solid content) described in Tables 3 to 6 was dissolved in a mixed solvent of diethylene glycol methyl ethyl ether: propylene glycol monomethyl ether acetate = 1: 1 (weight ratio) so that the solid content concentration was 20% by weight. Thereafter, the mixture was filtered through a membrane filter having a pore diameter of 0.2 μm to prepare photosensitive resin compositions of Examples 1 to 216 and Comparative Examples 1 to 13, respectively.

The unit of the usage-amount in each component of Table 3-Table 6 is a weight part.
The abbreviations in Tables 3 to 6 are as follows.

b1: 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate b2: trifluoromethylsulfonyloxybicyclo [2.2.1] -hept-5-ene-dicarboximide

E1: JER-157S70 (polyfunctional novolac type epoxy resin (epoxy equivalent: 200 to 220 g / eq), manufactured by Japan Epoxy Resins Co., Ltd.)
F1: 3-glycidoxypropyltrimethoxysilane (KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.))
G1: PolyFox PF-6320 (fluorine surfactant, manufactured by OMNOVA)
G2: Compound W-3 having the following structure

G3: polyether modified silicone surfactant (KF-6012, manufactured by Shin-Etsu Chemical Co., Ltd.)
H1: Dibutoxyanthracene (manufactured by Kawasaki Chemical Industry Co., Ltd.)

<Evaluation of residual DC>
-Sample preparation-
After applying the material on the substrate on which ITO was deposited, the material was dried at 90 ° C. for 2 minutes, exposed to 300 mJ with an ultrahigh pressure mercury lamp, and heated in an oven at 230 ° C. for 30 minutes to form a cured film having a thickness of 3 μm. A sample obtained by depositing aluminum on the cured film was used as a residual DC measurement sample.
-Measurement-
After the electrode part of the residual DC measurement sample was conditioned at 23 ° C., 60% RH for 24 hours, residual DC measurement was performed using “Residual DC measurement system RDC-1 type” manufactured by Toyo Corporation. . The voltage was held for 1 minute at an applied voltage of 3 V, and the voltage (V) after 1 second from the short circuit was measured. The measured value (V) after one minute was defined as the residual DC of the material.
The smaller the residual DC, the better, and A to C are practical. (Unit V)
A: 0.01 or less (best)
B: 0.01 or more and less than 0.05 (good)
C: 0.05 or more and less than 0.1 (allowable range)
D: 0.1 or more (impossible)

<Production and evaluation of display device>
According to Japanese Patent No. 3362008, a liquid crystal display device was produced using a cured film formed of the photosensitive resin composition of each example as an interlayer insulating film. Furthermore, the performance was evaluated by a display switching test.
The display device was repeated 20 times for white display for 1 second and subsequently black display for 1 second, and then switched to gray display to observe unevenness. The evaluation criteria are as follows. AC is a practical range.
A: Unevenness is not observed (best).
B: Slight unevenness is observed only when viewed obliquely (good).
C: Slight unevenness is observed when viewed from the front and obliquely (allowable range).
D: Unevenness is clearly observed when viewed from the front or diagonal (unsuitable)

<Evaluation of sensitivity>
Each photosensitive resin composition is slit-coated on a glass substrate (Corning 1737, 0.7 mm thick (Corning)), then pre-baked on a hot plate at 90 ° C. for 120 seconds to volatilize the solvent, and the film thickness A photosensitive resin composition layer having a thickness of 3.0 μm was formed.
Next, the obtained photosensitive resin composition layer was exposed through a predetermined mask using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. The exposed photosensitive composition layer was developed with an alkali developer (0.4 wt% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds.
By these operations, the optimum i-line exposure amount (Eopt) when resolving 15 μm line and space at 1: 1 was defined as sensitivity. The evaluation criteria are as follows. A and B are levels that have no practical problem.
A: 50mJ / cm ² less B: 50mJ / cm ² or more 80 mJ / cm ² less than C: 80mJ / cm ² or more

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

Claims (12)

(Component A) a copolymer having at least structural units represented by formula (a1) to formula (a4),
(Component B) an oxime sulfonate compound represented by formula (B),
(Component C) solvent, and
(Component D) A photosensitive resin composition comprising a compound represented by formula (D-1) and / or a compound represented by formula (D-2).

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 7 carbon atoms, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a hydrogen atom or a methyl group, and X represents an alkylene group having 2 to 11 carbon atoms.)

(In the formula, R ^B1 is an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a phenyl group, a biphenyl group, a naphthyl group, a 2-furyl group, a 2-thienyl group, or a carbon number of 1; Represents an alkoxy group of ˜4, a fluorenyl group or a cyano group, and when R ^B1 is a phenyl group, a biphenyl group, a naphthyl group or an anthranyl group, these groups are a halogen atom, a hydroxyl group, and a carbon number of 1 to 4 And may be substituted with a substituent selected from the group consisting of an alkoxy group having 1 to 4 carbon atoms and a nitro group, and R ^B2 is an alkyl group having 1 to 10 carbon atoms and 1 to 10 carbon atoms. An alkoxy group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group that may be substituted with W, a naphthyl group that may be substituted with W, or W Replaced There may be an anthranyl group, a dialkylamino group, may form a 5- or 6-membered ring bonded to each other with .R ^B1 and R ^B2 representing the morpholino group or a cyano group, said 5- or 6-membered The ring may be connected to a benzene ring which may have one or two arbitrary substituents, and R ^B3 is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, A halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group optionally substituted with W, a naphthyl group optionally substituted with W, or W substituted. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a carbon number. 1 to 5 halogenated alkoxy groups Represent.)

(In formula (D-1), R ^D1 represents a hydrogen atom or a t-butoxycarbonyl group.)   The photosensitive resin composition of Claim 1 which is a chemically amplified positive photosensitive resin composition. The photosensitive resin composition of Claim 1 or ² whose said R < ² > is an ethyl group or a cyclohexyl group. The photosensitive resin composition of any one of Claims 1-3 whose oxime sulfonate compound represented by the said Formula (B) is an oxime sulfonate compound represented by a following formula (B-1).

(In the formula, R ^B4 represents a hydrogen atom or a methyl group, and R ^B5 represents an alkyl group having 1 to 8 carbon atoms, a p-toluyl group, a phenyl group, a camphoryl group, a trifluoromethyl group, or a nonafluorobutyl group. ) The photosensitive resin composition of any one of Claims 1-3 whose oxime sulfonate compound represented by the said Formula (B) is an oxime sulfonate compound represented by a following formula (B-2).

(In the formula, R ^B6 represents a hydrogen atom, a methyl group or a methoxy group, and R ^B7 represents an alkyl group having 1 to 8 carbon atoms, a p-toluyl group, a phenyl group, a camphoryl group, a trifluoromethyl group or a nonafluorobutyl group. Represents.)   The photosensitive resin composition of any one of Claims 1-5 containing a sensitizer. (1) The application | coating process which apply | coats the photosensitive resin composition of any one of Claims 1-6 on a board | substrate,
(2) a solvent removal step of removing the solvent from the applied photosensitive resin composition;
(3) An exposure process in which the photosensitive resin composition from which the solvent has been removed is exposed to actinic rays,
(4) a developing 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;
A method for forming a cured film comprising:   The method for forming a cured film according to claim 7, comprising a step of exposing the entire surface of the developed photosensitive resin composition after the developing step and before the post-baking step.   A cured film formed by the method according to claim 7 or 8.   The cured film according to claim 9, which is an interlayer insulating film.   An organic EL display device comprising the cured film according to claim 9.   A liquid crystal display device comprising the cured film according to claim 9.

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